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WO2013007602A1 - Système de résine à constituants multiples - Google Patents

Système de résine à constituants multiples Download PDF

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Publication number
WO2013007602A1
WO2013007602A1 PCT/EP2012/063147 EP2012063147W WO2013007602A1 WO 2013007602 A1 WO2013007602 A1 WO 2013007602A1 EP 2012063147 W EP2012063147 W EP 2012063147W WO 2013007602 A1 WO2013007602 A1 WO 2013007602A1
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WO
WIPO (PCT)
Prior art keywords
resin system
reactive diluent
component
resin
alkyl
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/EP2012/063147
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English (en)
Inventor
Johan Franz Gradus Antonius Jansen
Daniel Haveman
Dragos Popescu
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.)
DSM IP Assets BV
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DSM IP Assets BV
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Filing date
Publication date
Application filed by DSM IP Assets BV filed Critical DSM IP Assets BV
Priority to EP12734904.1A priority Critical patent/EP2729517A1/fr
Publication of WO2013007602A1 publication Critical patent/WO2013007602A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
    • 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
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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
    • 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
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/10—Epoxy resins modified by unsaturated compounds

Definitions

  • the present invention relates to a multi-component resin system comprising (a) a vinyl ester resin; (b) reactive diluent; (c) a copper compound; and (d) a peroxide.
  • Curing of resin compositions comprising a vinyl ester resin can be done by a free-radical chain growth crosslinking polymerization between the reactive diluent present in the resin composition and the vinyl ester resin.
  • Peroxides can be used as initiators of free-radical chain growth crosslinking polymerization.
  • an accelerator can be used to accelerate the decomposition of the peroxide.
  • Cobalt naphthenate and cobalt octanoate are the most widely used accelerators, since these cobalt compounds are very effective accelerators for the peroxide decomposition. However, for environmental reasons, the use of cobalt compounds as accelerator for the peroxide decomposition is less preferred.
  • WO-A-2008/003500 for example describes the radical curing of a vinyl ester resin composition in the presence of a copper 2+ salt and an amine compound and/or an ammonium salt.
  • the copper In order to obtain efficient radical curing - as demonstrated by short gel time, short peak time and/or high peak temperature - the copper needs to be present in an amount of at least 50 ppm.
  • a disadvantage of the use of copper in such high amounts is that pre-accelerated resin composition containing such high amounts of copper present a green colour while the cured objects thereof have a green or brownish colour. This can be disadvantageous since in some applications, like for example windmills, flooring and marine applications including boats and the so called gel coats, white colored cured objects are desired. It would therefore be advantageous to being able to use a non-colored or less colored pre- accelerated resin composition, such that the color of the object obtained by curing the pre-accelerated resin composition can be easily tuned by pigmenting the pre- accelerated resin composition.
  • the object of the present invention is therefore being able to obtain a pre-accelerated resin system that, upon curing, may result in a cured object with no or almost no color and at the same time being able to obtain a resin system that can be efficiently cured, i.e. with a short gel time, short peak time and/or high peak temperature.
  • gel time is a very important characteristic of the curing properties.
  • the time from reaching the gel time to reaching peak temperature, and the level of the peak temperature (higher peak temperature generally results in better curing) are important.
  • the multi- component resin system further comprises (e) a bidentate ligand X-R-Y in an amount of at least 10 mmol/(kg resin and reactive diluent), whereby X and Y are independently selected from NH 2 , NHR ⁇ NR 1 R 2 , OH and OR 3 with the proviso that at least one of the groups X and Y is NH 2 or NHR ⁇ R is a C1-C20 alkyl or a C6-C20 aryl; R 1 and R 2 are independently selected from a C1-C20 alkyl and a polymeric residue; R 3 is a
  • the multi-component resin system comprises a compound with the following formula R 4 -Z-C(0)-00-R 5 as peroxide (d), in which Z is not present or is O; R 4 is a
  • R 5 is a C4-C20 alkyl or a C(0)R 6 ; whereby R 6 is a C1-C20 alkyl or a C6-C20 aryl;
  • the acid value of the primary resin system is lower than 12 mg KOH/g primary resin system
  • the amount of copper is at least 0.02 mmol Cu/(kg resin and reactive diluent) and at most 1.5 mmol Cu/(kg resin and reactive diluent);
  • the molar ratio between the bidentate ligand X-R-Y and copper is at least 5; and the molar ratio between the bidentate ligand X-R-Y and the peroxide R 4 -Z-C(0)-00-R 5 is from 0.1 up to and including 10.
  • GB834286 teaches that small amounts of a soluble form of copper in the range 0,25 ppm to 10 ppm of copper improves the inhibiting properties of inter alias aromatic amines, quaternary ammonium salts and amine salts.
  • US6329475 furthermore teaches that an amine acts as an inhibitor for catalyst composition containing copper.
  • copper present in small amounts, acts as an inhibitor for the polymerization of ethylenically unsaturated compounds.
  • the multi-component resin system comprises a vinyl ester resin or a mixture of vinyl ester resins.
  • a vinyl ester resin is an oligomer or polymer comprising at least one (meth)acrylate functional end group, also known as (meth)acrylate functional resins.
  • the radical (co)polymerizable resin present in the multi-component resin system according to the present invention is a vinyl ester resin or a mixture of vinyl ester resins.
  • the vinyl ester resin used in the context of the present invention may be any such resin as is known to the person skilled in the art. Examples thereof can be found in a review article of M. Malik et al. in J. M.S. - Rev. Macromol. Chem. Phys., C40 (2&3), p.139-165 (2000). As described by Malik et al., vinyl ester resins having unsaturated sites only in the terminal position are for example introduced by reaction of epoxy oligomers or polymers (e.g.
  • the vinyl ester resin has a number-average molecular weight M n of at least 500 Dalton. As used herein, the number-average molecular weight (M n ) is determined in
  • Preferred vinyl ester resins are oligomers or polymers containing at least one methacrylate functional end group, also known as methacrylate functional resins.
  • Preferred methacrylate functional resins are urethane methacrylate resins and resins obtained by reaction of an epoxy oligomer or polymer with methacrylic acid or methacrylamide, preferably with methacrylic acid.
  • Most preferred vinyl ester resins are resins obtained by reaction of an epoxy oligomer or polymer with methacrylic acid.
  • the amount of vinyl ester resin in the multi-component resin system according to the invention is preferably at least 10 wt. % and at most 90 wt.%, relative to the total amount of vinyl ester resin and reactive diluent.
  • the multi-component resin system according to the present invention comprises a reactive diluent.
  • a reactive diluent is a diluent for the vinyl ester resins present in the composition according to the invention, and is able to copolymerize with the vinyl ester resins present in the composition according to the invention.
  • Suitable reactive diluents are, for instance, alkenyl aromatic monomer, such as for example styrene and divinylbenzene, (meth)acrylates, vinyl ethers and vinyl amides but all other reactive monomers for use in the field of thermosetting resins as are known to the person skilled in the art can be used.
  • Non- limited examples of reactive diluents are styrene, alpha-methyl styrene, chlorostyrene, vinyl toluene, divinyl benzene, methyl methacrylate, n-butyl methacrylate,
  • cyclohexylmethacrylate tert.butyl styrene, tert.butylacrylate, butanediol dimethacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, acetoacetoxyethyl methacrylate and mixtures thereof.
  • Suitable examples of (meth)acrylates reactive diluents are 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, neopentyl glycol di(meth)acrylate, dipropyleneglycol di(meth)acrylate, tripropyleneglycol
  • a (meth)acrylate is used as reactive diluent.
  • Especially preferred reactive diluents are the methacrylate functional reactive diluents like methyl methacrylate, butanediol dimethacrylate and mixtures thereof.
  • a methacrylate functional reactive diluent (also referred to as methacrylate reactive diluent) is a monomer or an oligomer comprising at least one methacrylate group.
  • the methacrylate reactive diluent has a number-average molecular weight M n lower than 500 Dalton.
  • the number-average molecular weight (M n ) is determined in tetrahydrofuran using GPC employing polystyrene standards.
  • Suitable examples of other methacrylate reactive diluents are PEG200 dimethacrylate, 1 ,4-butanediol dimethacrylate, 1 ,3-butanediol dimethacrylate,
  • dimethacrylate trimethylolpropane dimethacrylate, neopentyl glycol dimethacrylate, dipropyleneglycol dimethacrylate, tripropyleneglycol dimethacrylate, PPG250 dimethacrylate, tricyclodecane dimethylol dimethacrylate, 1 ,10-decanediol
  • dimethacrylate tetraethylene glycol dimethacrylate
  • the multi-component resin system comprises a methacrylate reactive diluent.
  • the reactive diluent in the multi-component resin system is a
  • the amount of reactive diluent relative to the total amount of vinyl ester resin and reactive diluent is preferably at least 10 wt.%, more preferably at least 20 wt.%, even more preferably at least 25 wt.% and even more preferably at least 30 wt.%.
  • the amount of reactive diluent relative to the total amount of vinyl ester resin and reactive diluent is preferably at most 90 wt.%, more preferably at most 80 wt.%, even more preferably at most 75 wt.% and even more preferably at most 70 wt.%.
  • the acid value of the primary resin system is determined titrimetrically according to ISO 21 14-2000.
  • the term "primary resin system” is understood to mean the total weight of the multi-component resin system, but excluding peroxide and also any non-soluble compounds, such as fillers, as may be used when applying the resin system for its intended uses.
  • the primary resin system therefore consists of the the vinyl ester resin(s), reactive diluent(s) as well as other solvents as may be present, and any additives soluble in the resin diluted in reactive diluent (such as accelerators, promoters, inhibitors, low-profile agents, colorants (dyes), thixotropic agents, release agents).
  • the primary resin system consists of the vinyl ester resins present in the multi-component resin system, any solvent present in the multi- component resin system and any additive present in the multi-component resin system that is soluble in the resin diluted in reactive diluent.
  • the amount of additives soluble in the resin diluted in reactive diluent usually may be as from 1 to 25 wt.% of the primary resin system.
  • the primary resin system explicitly does not include compounds not being soluble (at room temperature) in the resin diluted in reactive diluent, such as fillers (e.g. glass or carbon fibers), talc, clay, solid pigments (such as, for instance, titanium dioxide (titanium white)), flame retardants, e.g. aluminum oxide hydrates, etc.
  • the multi-component resin system comprises a copper compound (b), preferably a copper 2+ compound.
  • the copper ⁇ compound is preferably a copper salt or complex. Even more preferably, the copper compound is a copper 2+ salt.
  • the copper compound is preferably an organo soluble copper compound like for instance copper carboxylates, copper acetoacetates and/or copper chlorides. It will be clear that, instead of a single copper compound also a mixture of copper compounds can be used.
  • the multi- component resin system preferably comprises a copper carboxylate, more preferably a C C 3 o carboxylate and even more preferably a C Ci 6 carboxylate.
  • the amount of copper compound in the multi-component resin system is such that the amount of copper in the multi-component resin system is at least 0.02 mmol Cu/(kg resin and reactive diluent) and at most 1 .5 mmol Cu/(kg resin and reactive diluent).
  • the amount of copper ⁇ in the multi- component resin system is at least 0.02 mmol Cu 2 7(kg resin and reactive diluent) and at most 1 .5 mmol Cu 2 7(kg resin and reactive diluent).
  • per kg resin and reactive diluent is meant to be per kg vinyl ester resins and reactive diluents.
  • the multi-component resin system according to the invention comprises (e) a bidentate ligand X-R-Y, whereby X and Y are independently selected from NH 2 , NHR ⁇ NR 1 R 2 , OH and OR 3 with the proviso that at least one of the groups X and Y is NH 2 or NHR ⁇ R is a C1 -C20 alkyl or a C6-C20 aryl; R 1 and R 2 are
  • R 3 is a
  • Ri and R 2 are independently selected from a C1 -C20 alkyl.
  • X is NH 2 and Y is NH 2 , NHR 1 or OH. More preferably, X is NH 2 and Y is NH 2 .
  • R is a C1 -C20 alkyl, more preferably a C2-C8 alkyl.
  • the amount of bidentate ligand X-R-Y in the multi-component resin system is at least 10 mmol/(kg resin and reactive diluent), preferably at least
  • the amount of bidentate ligand X-R-Y in the multi-component resin system is preferably at most 1000 mmol/(kg resin and reactive diluent), more preferably at most 500 mmol/(kg resin and reactive diluent), even more preferably at most 250 mmol/(kg resin and reactive diluent) and even more preferably at most
  • the amount of bidentate ligand X-R-Y in the multi-component resin system is preferably ranging from 20 mmol/(kg resin and reactive diluent) up to and including 500 mmol/(kg resin and reactive diluent) and even more preferably ranging from 100 mmol/(kg resin and reactive diluent) up to and including 200 mmol/(kg resin and reactive diluent).
  • the molar ratio between the bidentate ligand X-R-Y and the copper in the multi-component resin system is at least 10, more preferably at least 50 and even more preferably at least 100.
  • the multi-component resin system according to the invention comprises a compound with the following formula R 4 -Z-C(0)-00-R 5 as peroxide, in which Z is not present or is O; R 4 is a C1 -C20 alkyl or a C6-C20 aryl; R 5 is a C4-C20 alkyl or a C(0)R 6 ; whereby R 6 is a C1-C20 alkyl or a C6-C20 aryl.
  • the multi-component resin system according to the invention comprises a compound with the following formula R 4 -Z-C(0)-00-R 5 as peroxide, in which Z is not present, R 4 is C6 aryl and R 5 is tertiar butyl. It will be clear that, instead of a single peroxide compound with formula R 4 -Z-C(0)-00-R 5 also a mixture of peroxide compounds with formula R 4 -Z-C(0)-00-R 5 can be used.
  • the molar ratio between the bidentate ligand X-R-Y and the peroxide R -Z-C(0)-00-R 5 in the multi-component resin system is preferably from 0.2 up to and including 8, preferably from 0.5 up to and including 5.
  • the multi-component resin system according to the invention is preferably essentially free of cobalt.
  • Essentially free of cobalt means that the cobalt concentration is lower than 0,1 mmol Co per kg vinyl ester resin and reactive diluent, preferably lower than 0,01 mmol Co per kg vinyl ester resin and reactive diluent.
  • Most preferably the multi-component resin system is free of cobalt.
  • the multi-component resin system according to the invention is preferably essentially free of vanadium.
  • Essentially free of vanadium means that the vanadium concentration is lower than 0,1 mmol V per kg vinyl ester resin and reactive diluent, preferably lower than 0,01 mmol V per kg vinyl ester resin and reactive diluent.
  • Most preferably the multi-component resin system is free of vanadium.
  • the multi-component resin system preferably further comprises a radical inhibitor.
  • radical inhibitors are preferably chosen from the group of phenolic compounds, benzoquinones, hydroquinones, catechols, stable radicals and/or phenothiazines.
  • Suitable examples of radical inhibitors that can be used in the 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
  • galvinoxyl aluminium-N-nitrosophenyl hydroxylamine, diethylhydroxylamine, phenothiazine and/or derivatives or combinations of any of these compounds.
  • the amount of radical inhibitor in the multi-component resin system (relative to the total amount of compounds (a) and (b)) is in the range of from 0.0001 to 10 % by weight. More preferably, the amount of inhibitor in the multi-component resin system is in the range of from 0.001 to 1 % by weight.
  • the multi-component resin system according to the invention may further comprise (in)organic filler.
  • the amount of (in)organic filler relative to the total amount of compounds (a) and (b) is preferably from 10 to 90 wt.%.
  • the multi-component resin system comprises fibre as filler. Suitable fillers are aluminium trihydrate, calcium carbonate, mica, glass, microcrystalline silica, quartz, barite and/or talc. These fillers may be present in the form of sands, flours or molded objects, especially in the form of fibers or spheres. Examples of fibres are glass fibres and carbon fibres.
  • multi-component resin system requires mixing of the compounds (a), (b), (c) and (e) together with a hardener, in particular compound (d) to obtain a cured resin network.
  • multi-component systems means a system with at least two spatially separated components whereby the peroxide is present in one component that does not comprise radical copolymerizable compounds including compound (a) and reactive diluent (b) in order to prevent premature radical copolymerization of the compounds (a) and reactive diluents (b) prior to the use of the multi-component system to obtain the cured network.
  • the multi-component system according to the invention comprises at least two components.
  • the multi-component resin system comprises at least two components A and B, whereby component A comprises resin (a), reactive diluent (b), copper compound (c) and bidentate ligand (e) and component B comprises peroxide (d), whereby compounds (a), (b), (c), (d) and (e) are as defined above.
  • the multi-component resin system is a two component system consisting of a first component A and a second component B, whereby component A comprises vinyl ester resin (a), reactive diluent (b), copper compound (c) and bidentate ligand (e) and component B comprises peroxide (d), whereby compounds (a), (b), (c), (d) and (e) are as defined above.
  • component A comprises vinyl ester resin (a), reactive diluent (b), copper compound (c) and bidentate ligand (e)
  • component B comprises peroxide (d), whereby compounds (a), (b), (c), (d) and (e) are as defined above.
  • the use of the two component resin system according to the invention requires mixing of the components A and B to obtain a cured resin network.
  • the present invention further relates to a process for radically curing a resin composition
  • a resin composition comprising (a) a vinyl ester resin and (b) reactive diluent in the presence of a copper compound (c) and a peroxide (d), whereby the radical curing is effected in the presence of a compound with the following formula R 4 -Z-C(0)-00-R 5 as peroxide (d), in which Z is not present or is O;
  • R 4 is a C1-C20 alkyl or a C6-C20 aryl;
  • R 5 is a C4-C20 alkyl or a C(0)R 6 ; whereby R 6 is a C1-C20 alkyl or a C6-C20 aryl;
  • the radical curing is effected in the further presence of a bidentate ligand X-R-Y (e) in an amount of at least 10 mmol/(kg resin and reactive diluent), whereby X and Y are independently selected from NH 2 , NHRi , NRiR 2 , OH and OR 3 with the proviso that at least one of the groups X and Y is NH 2 or NHR ⁇ R is a C1-C20 alkyl or a C6-C20 aryl; Ri and R 2 are independently selected from a C1-C20 alkyl and a polymeric residue; R 3 is a C1-C20 alkyl;
  • the acid value of the primary resin system is lower than 12 mg KOH/g primary resin system
  • the amount of copper is at least 0.02 mmol Cu/(kg resin and reactive diluent) and at most 1.5 mmol Cu/(kg resin and reactive diluent);
  • the molar ratio between the bidentate ligand X-R-Y and the copper is at least 5; and the molar ratio between the bidentate ligand X-R-Y and the peroxide R 4 -Z-C(0)-00-R 5 is from 0.1 up to and including 10.
  • the process according to the invention 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 process according to the invention is preferably effected in the substantial absence of cobalt.
  • Substantial absence of cobalt means that the cobalt concentration is lower than 0,1 mmol Co per kg vinyl ester resin and reactive diluent, preferably lower than 0,01 mmol Co per kg vinyl ester resin and reactive diluent.
  • Most preferably the process according to the invention is effected in the absence of cobalt.
  • the process according to the invention is preferably effected also in the substantial absence of vanadium.
  • Substantial absence of vanadium means that the vanadium concentration is lower than 0,1 mmol V per kg vinyl ester resin and reactive diluent, preferably lower than 0,01 mmol V per kg vinyl ester resin and reactive diluent.
  • Most preferably the process according to the invention is effected in the absence of vanadium.
  • the present invention further relates to cured structural objects obtained by mixing the compounds of the multi-component system as described above or by mixing components (A) and (B) of the two-component resin system as described above or obtained with the process for radical curing as described above.
  • the present invention further relates to the use of the cured objects in anyone of the areas of automotive parts, boats, chemical anchoring, roofing, construction, containers, relining, pipes, tanks, flooring or windmill blades

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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)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne un système de résine à constituants multiples comprenant a) une résine d'ester vinylique; b) un diluant réactif; c) un composé de cuivre; et d) un peroxyde. Le système de résine à constituants multiples comprend en outre e) un ligand bidenté X-R-Y en une quantité d'au moins 10 mmol/(kg de résine et de diluant réactif). Dans ladite formule, X et Y sont indépendamment choisis parmi NH2, NHR1 NR1R2, OH et OR3, à condition qu'au moins l'un des groupes X et Y soit NH2 ou NHR1; R est alkyle C1-C20 ou aryle C6-C20; R1 et R2 sont indépendamment choisis parmi alkyle C1-C20 et un résidu polymérique; R3 est alkyle C1-C20. Le système de résine à constituants multiples comprend un composé de la formule suivante R4-Z-C(O)-OO-R5 représentant le peroxyde du point d). Dans ladite formule, Z est absent ou représente O; R4 est alkyle C1-C20 ou aryle C6-C20; R5 est alkyle C4-C20 ou un C(O)R6, R6 étant alkyle C1-C20 ou aryle C6-C20. L'indice d'acidité du système de résine primaire est inférieure à 12 mg de KOH/g du système de résine primaire. La quantité de cuivre est d'au moins 0,02 mmol de Cu/(kg de résine et de diluant réactif) et d'au plus 1,5 mmol Cu/(kg de résine et de diluant réactif). Le rapport molaire entre le ligand bidenté X-R-Y et le cuivre est d'au moins 5; et le rapport molaire entre la ligand bidenté X-R-Y et le peroxyde R4-ZC (O)-OO-R 5 est compris entre 0,1 et 10 inclus.
PCT/EP2012/063147 2011-07-08 2012-07-05 Système de résine à constituants multiples Ceased WO2013007602A1 (fr)

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EP12734904.1A EP2729517A1 (fr) 2011-07-08 2012-07-05 Système de résine à constituants multiples

Applications Claiming Priority (2)

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EP11173226 2011-07-08
EP11173226.9 2011-07-08

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WO2013007602A1 true WO2013007602A1 (fr) 2013-01-17

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB834286A (en) 1956-05-07 1960-05-04 Us Rubber Co Improvements in polyester resin compositions
US4524177A (en) 1982-12-03 1985-06-18 Bayer Aktiengesellschaft Use of 1,4-dihydroxynaphthalene in the hardening of ethylenically unsaturated compounds
WO1990012824A1 (fr) * 1989-04-26 1990-11-01 Akzo N.V. Cocatalyseurs de polymerisation contenant de l'azote organique
US6329475B1 (en) 1992-08-12 2001-12-11 The Dow Chemical Company Curable epoxy vinylester composition having a low peak exotherm during cure
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