WO2012076686A2 - Procédé de préparation de résine uréthane-méthacrylate - Google Patents

Procédé de préparation de résine uréthane-méthacrylate Download PDF

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Publication number
WO2012076686A2
WO2012076686A2 PCT/EP2011/072307 EP2011072307W WO2012076686A2 WO 2012076686 A2 WO2012076686 A2 WO 2012076686A2 EP 2011072307 W EP2011072307 W EP 2011072307W WO 2012076686 A2 WO2012076686 A2 WO 2012076686A2
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WO
WIPO (PCT)
Prior art keywords
resin composition
methacrylate
isocyanate
resin
zirconium
Prior art date
Application number
PCT/EP2011/072307
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English (en)
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WO2012076686A3 (fr
Inventor
Daniel Haveman
Johan Franz Gradus Antonius Jansen
Daniel Raimann
Original Assignee
Dsm Ip Assets B.V.
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Filing date
Publication date
Application filed by Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Publication of WO2012076686A2 publication Critical patent/WO2012076686A2/fr
Publication of WO2012076686A3 publication Critical patent/WO2012076686A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen

Definitions

  • the present invention relates to a method for the preparation of an urethane methacrylate resin composition
  • an urethane methacrylate resin composition comprising (a) urethane methacrylate resin, (b) reactive diluent and (c) a transition metal compound as accelerator
  • the method comprises (1) preparing an urethane methacrylate resin by reacting at least a hydroxyl functional methacrylate and an isocyanate in the presence of a reaction catalyst, whereby a secondary hydroxyalkyl methacrylate is used as methacrylate, and the isocyanate is an aromatic and/or aliphatic di- and tri- isocyanate; (2) adding reactive diluent to the urethane methacrylate resin during and/or after its preparation, and (3) adding at least one transition metal compound to the urethane methacrylate resin.
  • a standard catalyst for the preparation of such urethane methacrylate resins are organo stannous compounds, in particular dibutyl tin dilaurate, since this catalyst is very effective in view of its rate, conversion and selectivity.
  • this catalyst has a negative toxicological profile, in other words it is poisonous and measures need to be taken to reduce or prevent environmental exposure. Consequently there is a need to replace such catalyst.
  • the reaction of an isocyanate with a secondary hydroxyl functional methacrylate is much more difficult than with a primary hydroxyl functional methacrylate.
  • the object of the present invention is to perform the urethane methacrylate resin preparation using a secondary hydroxyl functional methacrylate with a catalyst that is more environmentally benign, which catalyst has also a good selectivity, and at the same time to maintain or even improve the curing efficiency of a resin composition comprising such urethane methacrylate resin and reactive diluent.
  • the inventors have surprisingly found that by using a zirconium alkoxide and/ or zirconium carboxylate as reaction catalyst, the reaction of a secondary hydroxyalkyl methacrylate with an aromatic and/or aliphatic di- and tri- isocyanate can be executed efficiently; and at the same time by using a Co, Cu, Mn and/or Fe compound as transition metal compound, the peroxide initiated curing of a resin composition comprising such urethane methacrylate resin, reactive diluent and the transition metal compound remains efficient or can even be improved.
  • the present invention relates to a method for the preparation of an urethane methacrylate resin composition
  • an urethane methacrylate resin composition comprising (a) urethane methacrylate resin, (b) reactive diluent and (c) a transition metal compound as accelerator
  • the method comprises (1) preparing an urethane methacrylate resin by reacting at least a hydroxyl functional methacrylate and an isocyanate and optionally other alcohols in the presence of a reaction catalyst, whereby at least a secondary hydroxyalkyi methacrylate is used as methacrylate, and the isocyanate is an aromatic and/or aliphatic di- and tri- isocyanate; (2) adding reactive diluent to the urethane methacrylate resin during and/or after its preparation, and (3) adding at least one transition metal compound to the urethane methacrylate resin after its preparation, wherein a zirconium alkoxide and/ or a zirconium carboxylate is used as
  • the resin composition comprises a zirconium alkoxide and/or a zirconium carboxylate, compared with the state of the art tin catalyst, the presence of a Co, Cu, Fe or Mn compound in the resin composition results even in an improvement of the curing efficiency (as demonstrated by gel time, peak time and/or peak temperature).
  • WO-A-03074579 describes liquid resin compositions comprising (a) an urethane (meth)acrylate, a Group IV metal compound, preferably a titanium or zirconium compound, and a phosphorus containing photoinitiator for UV-initiating the curing of the liquid resin composition.
  • Non-limiting examples of secondary hydroxyalkyi methacrylate are 2- hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 2-hydroxycyclohexyl methacrylate and glycerol-1 ,3-dimethacrylate.
  • a preferred secondary hydroxyalkyi methacrylate is 2-hydroxypropyl methacrylate.
  • the methacrylate used for preparing the urethane methacrylate resin is a secondary hydroxyalkyi methacrylate.
  • 2-hydroxypropyl methacrylate is used as secondary hydroxyalkyi methacrylate.
  • the methacrylate used is 2-hydroxypropyl methacrylate.
  • Non-limiting examples of aromatic and/or aliphatic di- and tri- isocyanates used for preparing the urethane methacrylate resin are toluene
  • TDI diisocyanate
  • MDI 4,4'-methylene diphenyl diisocyanate
  • HDI hexanediisocyanate
  • IPDI isopherone diisocyanate
  • TDI trimers HDI trimers
  • pMDI polymeric MDI
  • Preferred aromatic and/or aliphatic di- and tri- isocyanates are toluene diisocyanate (TDI), 4,4'-methylene diphenyl diisocyanate (MDI), hexanediisocyanate (HDI), isopherone diisocyanate (IPDI), TDI trimers, HDI trimers, and polymeric MDI (pMDI).
  • Especially MDI and polymeric MDI are preferred diisocyanates.
  • aromatic and/or aliphatic diisocyanate is used as isocyanate compound.
  • the catalyst used for preparing the urethane methacrylate resin is a zirconium alkoxide and/or a zirconium carboxylate. More preferably, the catalyst used is a zirconium (IV) alkoxide and/or a zirconium (IV) carboxylate. Even more preferably, the catalyst used is a zirconium alkoxide and even more preferably a zirconium (IV) alkoxide.
  • the amount of zirconium catalyst used for preparing the urethane methacrylate resin is preferably from 1 to 5000 ppm (relative to the total amount of reaction components used for preparing the urethane methacrylate resin).
  • the method for preparing the urethane methacrylate resin may be performed in the presence of the reaction product of the isocyanate with a polyol, preferably a diol.
  • polyols are glycerol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene oxide, polypropylene oxide, ethoxylated bisphenol A , ethoxylated bisphenol F, propoxylated bisphenol A, propoxylated bisphenol F.
  • Preferred diols are dipropylene glycol, tripropylene glycol, ethoxylated bisphenol A , ethoxylated bisphenol F, propoxylated bisphenol A, propoxylated bisphenol F.
  • the amount of secondary hydroxyl functional methacrylate used for preparing the urethane methacrylate resin is preferably chosen such that for each mole of isocyanate group at least one mole of secondary hydroxyl functional methacrylate is present. In one embodiment, a slight stoichiometric excess of the secondary hydroxyl functional methacrylate is added to ensure that only a minimum level of isocyanate groups remain after an acceptable reaction period in order to prevent that unreacted isocyanate will copolymerize with the reactive diluent (being an ethylenically unsaturated monomer that is added to the resin during and/or after its preparation) on subsequent curing.
  • the reactive diluent being an ethylenically unsaturated monomer that is added to the resin during and/or after its preparation
  • the process of the invention preferably further comprises adding another reactive diluent than a secondary hydroxyl functional methacrylate during the preparation of the urethane methacrylate resin and optionally adding additional reactive diluent (not necessarily the same as that used during the preparation) after the preparation of the urethane methacrylate resin.
  • additional reactive diluent not necessarily the same as that used during the preparation
  • an excess of the secondary hydroxyl functional methacrylate is added, resulting in that unreacted secondary hydroxyl functional methacrylate remain after the reaction period which secondary hydroxyl functional methacrylate is a reactive diluent for the prepared resin.
  • the method according to the invention optionally further comprises adding, to the urethane methacrylate resin during and/or after its preparation, another reactive diluent than the secondary hydroxyalkyl methacrylate used for the preparation of the urethane methacrylate resin.
  • the amount of optional polyol described above used for preparing the urethane methacrylate resin can vary with in wide ranges as long as an excess of isocyanate is present.
  • the molar ratio between OH groups of the polyol and NCO groups of the isocyanate is general higher than 0.01 , more preferably higher than 0.05 and even more preferably higher than 0.1.
  • the molar ratio between OH groups of the polyol and NCO groups of the isocyanate is preferably lower than 0.95, more preferably lower than 0.9 and even more preferably lower than 0.7.
  • the method for preparing the urethane methacrylate resin comprises mixing the isocyanate component(s) with the zirconium catalyst, optionally adding the polyol to such mixture to allow reaction of the isocyanate with the polyol, preferably at a temperature of between 20 and 90°C, to obtain a first reaction product, and adding the secondary hydroxyl functional methacrylate, preferably at a temperature of between 20 and 90°C, to allow reaction with the first reaction product.
  • conventional vinyl inhibitors may be used during the preparation of the resin, for example inhibitors like for instance benzoquinone, hydroquinone, tert butyl catechol.
  • the method according to the invention further comprises adding at least one transition metal compound selected from a Co, Cu, Mn, Fe compound or mixtures thereof to the urethane methacrylate resin after its preparation, to obtain a resin composition comprising an urethane methacrylate resin diluted in reactive diluent, zirconium alkoxide and/or zirconium carboxylate, and pre-accelerated with a Co, Cu, Mn and/or Fe compound.
  • the Co, Cu, Mn and/or Fe compound are/is added to the urethane methacrylate resin diluted in reactive diluent.
  • the Co, Cu, Mn and/or Fe compound are/is preferably pre-mixed with reactive diluent and the so- obtained mixture is added to the urethane methacrylate resin.
  • thermosetting resin composition comprising (a) an urethane methacrylate resin prepared by reacting at least a hydroxyl functional methacrylate and an isocyanate and optionally other alcohols in the presence of a reaction catalyst, wherein at least a secondary
  • hydroxyalkyl methacrylate is used as methacrylate and the isocyanate is an aromatic and/or aliphatic di- and tri- isocyanate, (b) a reactive diluent and (c) a transition metal compound, wherein the resin composition comprises (c) a Co, Cu, Mn and/or Fe compound as transition metal compound and (d) a zirconium alkoxide and/or a zirconium carboxylate.
  • the amounts and types of the reaction components for obtaining the urethane methacrylate resin are preferably as described above.
  • the amount of zirconium alkoxide and zirconium carboxylate in the resin composition is preferably from 1 to 5000 ppm (relative to the urethane methacrylate resin).
  • the zirconium alkoxide is preferably a zirconium (IV) alkoxide.
  • the zirconium carboxylate is preferably a zirconium (IV) carboxylate.
  • the resin composition comprises a zirconium alkoxide and even more preferably a zirconium (IV) alkoxide.
  • the resin composition according to the invention comprises at least one transition metal compound (c) selected from the group consisting of Co, Cu, Mn, Fe compounds and mixtures thereof. More preferably, in view of curing efficiency, the resin composition comprises a Co compound, a Mn compound, and/or a Fe compound as transition metal compound. Even more preferably, the resin composition comprises a Mn compound and/or a Fe compound as transition metal compound.
  • the transition metal compound accelerates the radically curing of the resin composition.
  • the Co compound, Cu compound, Fe compound or Mn compound is preferably a salt or complex, preferably a carboxylate, more preferably a C C 30 carboxylate and even more preferably a C Ci 6 carboxylate.
  • the total amount of Co, Cu, Mn and Fe compounds in the resin composition according to the invention is preferably such that the total amount of Co, Cu, Mn and Fe in mmol per kg of the sum of the amounts of compounds (a) and (b) is preferably from 0.01 to 30, and more preferably from 0.1 to 20.
  • the resin composition may comprise a co-accelerator.
  • a co-accelerator is preferably an amine and/or a 1 ,3-dioxo compound.
  • the co-accelerator is preferably an amine, acetoacetamide, a K salt, an imidazole and/or a gallate or mixtures thereof.
  • the co-accelerator is preferably a 1 ,3-dioxo compound, a thiol and/or a K or Li salt or mixtures thereof.
  • the co-accelerator is preferably a 1 ,3-dioxo compound and/or a thiol preferably in combination with an alkali metal salt.
  • 1 ,3-dioxo compounds are acetyl acetone, acetoacetates and
  • the amount of co accelerator can vary within wide ranges and is preferably more than 0.01 wt.% and less than 10 wt.% preferably more than 0.1 wt.% and less than 5 wt.%.
  • the resin composition comprises a Co compound as transition metal compound and optionally a co-accelerator.
  • the co- accelerator is preferably an amine and/or a 1 ,3-dioxo compound.
  • the resin composition comprises a Cu compound as transition metal compound and the resin composition preferably further comprises a co- accelerator preferably selected from an amine, an acetoacetamide, a K salt, an imidazole and/or a gallate or mixtures thereof.
  • the resin composition comprises a Mn compound as transition metal compound and the resin composition preferably further comprises a co-accelerator preferably selected from a 1 ,3-dioxo compound, a thiol and/or a K or Li salt or mixtures thereof.
  • the resin composition comprises a Fe compound as transition metal compound and the resin composition preferably further comprises a co-accelerator, the co-accelerator is preferably a 1 ,3-dioxo compound and/or a thiol preferably in combination with an alkali metal salt.
  • the resin composition preferably comprises from 30 up to and including 85 wt.% of urethane methacrylate resin.
  • the amount of reactive diluent in the resin composition is in the range from 15 up to and including 70 wt.%. As used herein, all amounts in wt.% are given relative to the total weight of the urethane methacrylate resin (a) and reactive diluent (b), unless otherwise specified.
  • the urethane methacrylate resin preferably has the following structural formula (1):
  • X C1-C6 (cyclo)alkyl.
  • the urethane methacrylate resin more preferably has the following structural formula (2):
  • a reactive diluent is a diluent for the urethane methacrylate resin which diluent is able to copolymerize with the urethane methacrylate resin.
  • Ethylenically unsaturated compounds can be advantageously used as reactive diluent such as styrene, a-methylstyrene, 4-methylstyrene, (meth)acrylates, vinyl ethers, a vinyl esters, vinyl amines or vinyl amides or a mixture of at least two of these compounds.
  • styrene and/or methacrylates are used as reactive diluent. More preferably, methacrylates are used as reactive diluent.
  • Suitable examples of (meth)acrylate reactive diluents are hydroxyl ethyl (meth)acrylate, hydroxyl propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate and cyclohexyl
  • (meth)acrylate phenoxyethyl (meth)acrylate, tetrahydro furfuryl (meth)acrylate, allyl (meth)acrylate, PEG200 di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, 1 ,3- butanediol di(meth)acrylate, 2,3-butanedioldi(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate and its isomers, diethyleneglycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate neopentyl glycol di(meth)acrylate, dipropyleneglycol di(meth)acrylate, tripropyleneglycol di(meth)acryl
  • Preferred methacrylate reactive diluents are hydroxyl ethyl (meth)acrylate, hydroxyl propyl (meth)acrylate, 1 ,4- butanediol di(meth)acrylate, neopentylglycol di(meth)acrylate, PEG200
  • 2-hydroxypropyl methacylate is present as reactive diluent as in such a case an excess of 2-hydroxypropyl methacylate can be employed in the urethane synthesis.
  • Other preferred reactive diluents in view of their labeling, are butane diol di methacrylate, PEG200 dimethacrylate and
  • fillers can be present.
  • a wide variety of fillers can be applied like for instance, without being limited thereto, silica, sand, cement, mica and talc.
  • the resin composition may also be coloured by means of pigments.
  • reinforcing fibers can be present, such as for example glass fibres, natural fibres and carbon fibres.
  • other additives may be present in the resin compositions according to the invention such as for instance low profile additives.
  • the resin composition according to the invention in addition optionally contains a filler in a weight ratio of 0.05: 1 to 20: 1 , preferably in a weight ratio of 0.2: 1 to 3:1 , relative to the total weight of urethane methacrylate resin and the reactive diluent.
  • Thermosetting resin compositions harden by chemical reaction, often generating heat when they are formed, and cannot be melted or readily re-formed once hardened.
  • the resin compositions are liquids at normal temperatures and pressures, so can be used to impregnate reinforcements, for instance fibrous reinforcements, especially glass fibres, and/or fillers may be present in the resin composition, but, when treated with suitable radical forming initiators, the various unsaturated components of the resin composition crosslink with each other via a free radical copolymerization mechanism to produce a hard, thermoset plastic mass (also referred to as cured, structural part).
  • the resin composition according to the invention preferably further comprises one or more inhibitors.
  • the inhibitor of the resin composition of the invention can be any radical inhibitor known to the skilled man, preferably chosen from the group of phenolic compounds, stable radicals like galvinoxyl and N-oxyl based compounds and/or phenothiazines. Suitable examples of inhibitors that can be used in the resin compositions according to the invention are, for instance, 2-methoxyphenol,
  • 1-oxyl-2,2,6,6-tetramethylpiperidine-4-ol (a compound also referred to as TEMPOL), 1-oxyl-2,2,6,6-tetramethylpiperidine-4-one (a compound also referred to as TEMPON), 1-oxyl-2,2,6,6-tetramethyl-4-carboxyl-piperidine (a compound also referred to as 4-carboxy-TEMPO), 1-oxyl-2,2,5,5-tetramethylpyrrolidine, 1-oxyl-2,2,5,5-tetramethyl-3- carboxylpyrrolidine (also called 3-carboxy-PROXYL), aluminium-N-nitrosophenyl hydroxylamine, diethylhydroxylamine, phenothiazine and/or derivatives or combinations of any of these compounds.
  • TEMPOL 1-oxyl-2,2,6,6-tetramethylpiperidine-4-ol
  • TEMPON 1-oxyl-2,2,6,6-tetramethyl-4-carboxyl-piperidine
  • the amount of inhibitor in the resin composition according to the invention is in the range of from 0.00001 to 5 % by weight, preferably from 0.0001 to 2 % by weight, more preferably, from 0.001 to 1 % by weight
  • preferred inhibitors are stable radicals like TEMPOL, TEMPON, 4-carboxy TEMPO, 3-carboxy proxyl and hydroquinones and catechols. In this case for some applications it is even more preferred to employ a combination of a stable radical inhibitor with an
  • hydroquinone or catechol hydroquinone or catechol.
  • a very suitable combination is TEMPOL with catechol or t- butyl catechol.
  • Curing of the resin composition according to the invention is preferably performed by mixing the resin composition with a peroxide selected from the group consisting of hydroperoxides, perketals, peresters, percarbonates and mixtures thereof.
  • the present invention also relates to a process for preparing a radically cured structural part by curing the resin composition according to the invention or obtained with the process according to the invention with a peroxide selected from the group consisting of hydroperoxides, perketals, peresters,
  • the curing is performed by mixing the resin composition with the peroxide.
  • the amount of peroxide relative to the total amount of compounds (a) and (b) is from 0.01 up to and including 10 wt.%, more preferably from 0.05 up to and including 5 wt.% and even more preferably from 0.1 up to and including 3 wt.%.
  • the curing is preferably effected at a temperature in the range of from -20 to +150 °C, more preferably in the range of from -20 to +100 °C and even more preferably in the range of from -20 to + 40 °C.
  • the present invention further also relates to structural parts as are being obtained by mixing the resin composition according to the invention with a peroxide selected from the group consisting of hydroperoxides, perketals, peresters, percarbonates and mixtures thereof as described above and curing at appropriate conditions. These structural parts have excellent mechanical properties.
  • the present invention therefore also relates to the use of the resin composition according to the invention together with the peroxide in adhesive applications, automotive parts, boats, roofing, construction, containers, relining, pipes, tanks, flooring, windmill blades or chemical anchoring.
  • Viscosity was determined analogous to ISO 3219 using a physica MC1 viscometer equipped with a Z2 spindle.
  • Curing was performed using 100 g resin to which 2 g Butanox M50 (a perketal, obtained from AkzoNobel) was added.
  • the curing was monitored by means of standard gel time equipment. This is intended to mean that both the gel time (T ge i or T25->35°c) and peak time (T pea k or T 2 5-> pe ak) were determined by exotherm measurements according to the method of DIN 16945 when curing the resin with the peroxides as indicated in the Examples and Comparative Examples.
  • the equipment used therefore was a Soform gel timer, with a Peakpro software package and National Instruments hardware; the waterbath and thermostat used were respectively Haake W26, and Haake DL30.
  • Example 4 Zr tetra butoxide 63 1083 0.04.g Fe 1 g 2,4-pentadione/1 g potassium

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une composition de résine uréthane-méthacrylate qui comprend (a) une résine uréthane-méthacrylate, (b) un diluant réactif et (c) un composé à base de métal de transition en tant qu'accélérateur, la méthode comprenant (1) la préparation d'une résine uréthane-méthacrylate par réaction d'au moins un méthacrylate fonctionnalisé par hydroxy et d'un isocyanate et éventuellement d'autres alcools en présence d'un catalyseur de réaction, dans laquelle un méthacrylate d'hydroxyalkyle secondaire est utilisé en tant que méthacrylate, et l'isocyanate est un di ou tri-isocyanate aromatique et/ou aliphatique ; (2) l'ajout d'un diluant réactif à la résine uréthane-méthacrylate pendant et/ou après sa préparation, et (3) l'ajout d'au moins un composé à base de métal de transition à la résine uréthane-méthacrylate, dans lequel un alkoxyde de zirconium et/ou un carboxylate de zirconium est utilisé en tant que catalyseur de réaction et un composé à base de Co, Cu, Mn et/ou Fe est utilisé en tant que composé à base de métal de transition.
PCT/EP2011/072307 2010-12-09 2011-12-09 Procédé de préparation de résine uréthane-méthacrylate WO2012076686A2 (fr)

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Application Number Priority Date Filing Date Title
EP10194342 2010-12-09
EP10194342.1 2010-12-09

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WO2012076686A3 WO2012076686A3 (fr) 2013-06-27

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PCT/EP2011/072307 WO2012076686A2 (fr) 2010-12-09 2011-12-09 Procédé de préparation de résine uréthane-méthacrylate

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012219477A1 (de) 2012-10-24 2014-04-24 Hilti Aktiengesellschaft Verfahren zur Herstellung von Vinylesterurethanharzen auf Basis von Dianhydrohexitol-Verbindungen und ihre Verwendung
JP2015508389A (ja) * 2011-12-12 2015-03-19 ジーカ テクノロジー アクチェンゲゼルシャフト ポリウレタン組成物のための触媒としての鉄（ｉｉｉ）錯体
EP2862847A1 (fr) 2013-10-21 2015-04-22 HILTI Aktiengesellschaft Procédé de fabrication d'un mélange de résine à base de résines de vinylesteruréthane, mortier de résine réactive contenant celui-ci et son utilisation
EP3428208A1 (fr) 2017-07-10 2019-01-16 HILTI Aktiengesellschaft Procédé de préparation d'une composition d'une résine uréthane stable au stockage contenant de tempol
EP3423508B1 (fr) 2016-03-04 2022-04-27 Dow Global Technologies Llc Composition d'uréthane acrylate durcissable

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5632146B2 (ja) * 2009-09-02 2014-11-26 太陽ホールディングス株式会社 硬化性樹脂組成物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2217722A (en) 1988-04-29 1989-11-01 Scott Bader Co Vinyl terminated urethane containing resins
WO2003074579A1 (fr) 2002-03-04 2003-09-12 Dsm N.V. Composition de resine liquide durcissante

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2217722A (en) 1988-04-29 1989-11-01 Scott Bader Co Vinyl terminated urethane containing resins
WO2003074579A1 (fr) 2002-03-04 2003-09-12 Dsm N.V. Composition de resine liquide durcissante

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015508389A (ja) * 2011-12-12 2015-03-19 ジーカ テクノロジー アクチェンゲゼルシャフト ポリウレタン組成物のための触媒としての鉄（ｉｉｉ）錯体
DE102012219477A1 (de) 2012-10-24 2014-04-24 Hilti Aktiengesellschaft Verfahren zur Herstellung von Vinylesterurethanharzen auf Basis von Dianhydrohexitol-Verbindungen und ihre Verwendung
US9550852B2 (en) 2012-10-24 2017-01-24 Hilti Aktiengesellschaft Method for producing vinyl ester urethane resins based on dianhydrohexitol compounds and use thereof
EP2862847A1 (fr) 2013-10-21 2015-04-22 HILTI Aktiengesellschaft Procédé de fabrication d'un mélange de résine à base de résines de vinylesteruréthane, mortier de résine réactive contenant celui-ci et son utilisation
EP3423508B1 (fr) 2016-03-04 2022-04-27 Dow Global Technologies Llc Composition d'uréthane acrylate durcissable
EP3428208A1 (fr) 2017-07-10 2019-01-16 HILTI Aktiengesellschaft Procédé de préparation d'une composition d'une résine uréthane stable au stockage contenant de tempol
WO2019011684A1 (fr) 2017-07-10 2019-01-17 Hilti Aktiengesellschaft Procédé de préparation d'une composition de résine uréthane contenant du tempol, qui possède une meilleure stabilité au stockage

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