EP2838946A1 - Combinaison à base d'un radical nitroxyle stable et d'un méthide de quinone comme stabilisateur pour des mortiers à base de résine de réaction, à base de composés à réticulation radicalaire - Google Patents

Combinaison à base d'un radical nitroxyle stable et d'un méthide de quinone comme stabilisateur pour des mortiers à base de résine de réaction, à base de composés à réticulation radicalaire

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Publication number
EP2838946A1
EP2838946A1 EP13715966.1A EP13715966A EP2838946A1 EP 2838946 A1 EP2838946 A1 EP 2838946A1 EP 13715966 A EP13715966 A EP 13715966A EP 2838946 A1 EP2838946 A1 EP 2838946A1
Authority
EP
European Patent Office
Prior art keywords
resin
radical
reaction
alkyl
compounds
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.)
Withdrawn
Application number
EP13715966.1A
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German (de)
English (en)
Inventor
Anna KHALYAVINA
Armin Pfeil
Beate GNAß
Michael Leitner
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.)
Hilti AG
Original Assignee
Hilti AG
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Filing date
Publication date
Application filed by Hilti AG filed Critical Hilti AG
Publication of EP2838946A1 publication Critical patent/EP2838946A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/28—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing organic polyacids, e.g. polycarboxylate cements, i.e. ionomeric systems
    • 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
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/16—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00715—Uses not provided for elsewhere in C04B2111/00 for fixing bolts or the like

Definitions

  • the present invention relates to the use of a combination of at least one stable nitroxyl radical and at least one quinone methide as stabilizer for resin mixtures and reaction resin mortar, each based on free-radically curable compounds. Furthermore, the present invention relates to a storage-stable reaction resin mixture and a storage-stable reaction resin mortar in each case based on free-radically curable compounds and their use as binders for chemical fastening technology.
  • the curing reaction ie the polymerization
  • the resin is cured to give duromer.
  • Free-radically curable compounds are frequently used, in particular for chemical fastening technology, vinyl ester resins and unsaturated polyester resins.
  • resin mixtures and reaction resin mortars usually contain stabilizers, such as hydroquinone, substituted hydroquinones, phenothiazine, benzoquinone or tert-butylpyrocatechol, as described, for example, in EP 1935860 A1 or EP 0965619 A1.
  • stabilizers give the reaction resin mortar a storage stability of several months, but usually only in the presence of dissolved in the reaction resin mortar oxygen. If these are stored under Heilausschi uss, begins after a few days, the polymerization. For this reason, so far the reaction resin mortars had to be packed so that they could come into contact with air.
  • the object of the invention is therefore to stabilize resin mixtures based on free-radically curable compounds and reaction resin mortar prepared therefrom against premature polymerization. This object is achieved by the use of a combination of a stable nitroxyl radical and a quinone methide having the features of claim 1 and by the method having the features of claim 11.
  • a further object of the invention is to provide storage-stable resin mixtures and reactive resin mortars containing them which, especially in the case of airtight packaging, have improved storage stability, even in the presence of traces of acid.
  • base resin means the pure, curable compound which, by itself or with reaction agents such as hardener, accelerator and the like (not contained in the base resin), hardens by polymerization, the curable compounds may be monomers, dimers, Oligomers and prepolymers; "radically curable compound", that the compound contains functional groups that radically polymerize;
  • Resin Masterbatch the product of the preparation of the base resin after synthesis (without isolation of the base resin), which may contain reactive diluents, stabilizers and catalysts;
  • Resin mixture' means a mixture of the resin masterbatch and accelerators and stabilizers and, where appropriate, other reactive diluents, which term is used to mean the term 'organic binder';
  • Reaction resin mortars a mixture of resin mixture and inorganic and / or organic aggregates; the term “A component” is used to this end;
  • reactive resin composition is a ready-to-use, curing mixture of a reaction resin mortar with the required curing agent or hardener; this term is synonymous with the term “mortar mass”used;
  • “Curing agent” means substances which cause the polymerization (hardening) of the base resin
  • Hardener means a mixture of hardener and optionally phlegmatizer, solvent (s) and, optionally, inorganic and / or organic additives, this term being used synonymously with the term "B component";
  • Reactive diluents liquid or low viscosity base resins which dilute other base resins, the resin masterbatch or the resin mixture and thereby impart the viscosity necessary for their application contain functional groups capable of reacting with the base resin and in the polymerization (hardening) component for the most part of hardened material (mortar);
  • “Accelerator” means a compound capable of accelerating the polymerization reaction (cure) and serving to accelerate the formation of the radical initiator;
  • Stabilizer means a compound capable of inhibiting the polymerization reaction (curing) and serving to avoid the polymerization reaction and thus unwanted premature polymerization of the radically polymerizable compound during storage, these compounds are usually used in such small amounts that the gel time is not being affected;
  • “Inhibitor” also means a compound capable of inhibiting the polymerization reaction (curing) which serves to retard the polymerization reaction immediately after the addition of the curing agent, these compounds are usually used in amounts such that the gel time is affected;
  • “Storage stability” means that a resin mixture or a reaction resin mortar (without addition of a curing agent or a hardener) during storage neither shows an increase in viscosity nor a gelation;
  • pot life also means the maximum time within which a multi-component system should be processed after mixing, more precisely, the time within which the temperature of the reaction resin mass after its preparation is from + 25 ° C to + Increased to 35 ° C;
  • Gel time (for a certain selected period of time, for example 30 or 60 days) refers to the phenomenon that when the cure is at a time other than the reference standard time of cure, for example, 24 hours after preparation of the reaction resin, or the reaction resin mass, the observed gel time deviates from the time of reference.
  • the inventors have found that it is possible to provide resin blends and reaction resin mortars made therefrom, especially those having traces of acid and / or inorganic aggregates, with increased storage stability without requiring expensive and costly purification of the respective components, such as precursor compounds, e.g. the polymeric methylene diphenyl diisocyanate (pMDl), or the reactive diluent must be made.
  • precursor compounds e.g. the polymeric methylene diphenyl diisocyanate (pMDl)
  • pMDl polymeric methylene diphenyl diisocyanate
  • Reaction resin mortars are usually prepared by the required for the preparation of the base resin starting compounds optionally together with catalysts and solvents, in particular reactive diluents, placed in a reactor and reacted with each other. After completion of the reaction and optionally already at the beginning of the reaction, inhibitors for storage stability, also called stabilizers, are added to the reaction mixture, whereby the so-called resin masterbatch is obtained.
  • inhibitors for storage stability also called stabilizers
  • This resin mixture is used to adjust various properties, such as rheology and the concentration of the base resin, added with inorganic additives, whereby the reaction resin mortar, the A component, is obtained.
  • the reaction resin mortar is filled for storage, depending on the intended application, in glass cartridges, cartridges or in foil bags, which may be airtight.
  • a resin mixture contains at least one free-radically curable compound, reactive diluents, accelerators, stabilizers and optionally further inhibitors and a reaction resin mortar in addition to the resin mixture just described organic and / or inorganic additives, with inorganic additives are particularly preferred, as described in more detail below.
  • reaction resin mortars in particular those which contain acid traces due to their production, can be markedly improved.
  • the inventors have been able to show that this is possible by using a combination of (i) at least one stable nitroxyl radical and (ii) at least one quinone methide, as stabilizer, and as a result resin mixtures and reaction resin mortars based on free-radically curable compounds can be produced, whose storage stability is markedly improved versus those stabilized with Tempol or a quinone methide alone.
  • stabilized reaction resin mortars according to the invention have a storage stability which is greater by a factor of five to six than that of the corresponding resin mixtures.
  • a particular advantage of the combination used is that, contrary to expectations, it has been shown that the gel times of the resin mixtures and reaction resin mortars made stable on storage with the stabilizers according to the invention are not influenced despite the high storage stability.
  • inorganic additives are frequently used which react strongly basicly, eg cement. Further, the radically curable compounds are not worked up, ie, isolated, but the resin masterbatch is used to prepare the resin mixtures and the reaction resin mortars.
  • suitable quinone methide compounds are compounds of the general formula (I) in which R 1 and R 2 are independently a CRCI 8 alkyl, C 5 -C 2 cycloalkyl, C 7 -C 5 phenylalkyl or an optionally substituted C 6 -C mean 0 aryl; R 3 and R 4 are independently an optionally substituted alkyl group having a dC 8 C 6 -C 0 aryl, 2-, 3- or 4-pyridyl, 2- or 3-furyl, 2- or 3-thienyl -, 2- or 3-pyrryl, -COOH, -COOR 10 , -CONH 2 , -CONR 10 2 , -CN, -COR 10 , - OCOR 10 , -OPO (OR 10 ) 2 , mean, or one of R 3 or R 4 is hydrogen; R 10 is a C 1 -C 8 alkyl or phenyl radical; selected.
  • R 1 and R 2 are each independently a Ci-C 8 alkyl
  • R 3 is optionally substituted with one -C 8 alkyl-substituted C 6 -C 0 aryl, 2-, 3- or 4-pyridyl, 2- or 3-furyl, 2- or 3-thienyl, 2- or 3-pyrryl and R 4 is hydrogen.
  • R 1 and R 2 represent a butyl group in particular tert-butyl radical and R 4 is hydrogen and R 3 is an unsubstituted C 6 -C 0 aryl, in particular phenyl.
  • E 1 and E 3 independently of one another denote a C 1 -C 5 -alkyl or phenyl radical
  • E 2 and E 4 independently of one another denote a C 1 -C 5 -alkyl radical
  • T denotes a divalent group which together with the nitrogen atom and the two quaternary radicals Carbon atoms form a five- or six-membered ring, where the group T may optionally be substituted, the point means an unpaired electron.
  • piperidinyl-N-oxyl or tetrahydropyrrole N-oxyl compounds are preferred. Such compounds are known, for example, from DE 19531649 A1, the content of which is hereby incorporated into this application.
  • Particularly preferred stabilizer is a combination of (i) 4-hydroxy-2, 2,6,6-tetramethylpiperidine-1-oxyl and (ii) 2,6-di-tert-butyl-4-benzylidene-cyclohexa-2, 5-dien-1 - on.
  • the storage stability of free-radically curable reaction resins can be significantly increased.
  • a maximum increase in stability is achieved, so that at 1:> 9, no further effect is observed by adding a quinone methide to a stable nitroxyl radical.
  • a further subject of the invention is therefore a resin mixture prepared using the above-described combination of a stable nitroxyl radical and a quinone methide as stabilizer.
  • a resin composition has an increased storage stability as compared with a resin mixture containing a stable nitroxyl radical or a quinone methide as the sole stabilizer.
  • the stabilizer ie the combination of stable nitroxyl radical and quinone methide, is used in an amount of 0.02 to 1 wt .-%, preferably 0.025 to 0.3 wt .-% and particularly preferably 0.03 to 0.06 wt. %, based on the resin mixture used.
  • the resin mixture for adjusting the gel time and the reactivity may additionally comprise 0.005 to 3% by weight, preferably 0.05 to 1% by weight, based on the resin mixture, of a conventional inhibitor, in particular a phenolic inhibitor, such as phenols, Quinones or phenothiazines, e.g. B. 2,6-di-tert-butyl-p-cresol, but also stable nitroxyl radicals, such as Tempol, and catechols, such as pyrocatechol and derivatives thereof (see, EP 1 935 860 A1) included.
  • a conventional inhibitor in particular a phenolic inhibitor, such as phenols, Quinones or phenothiazines, e.g. B. 2,6-di-tert-butyl-p-cresol, but also stable nitroxyl radicals, such as Tempol, and catechols, such as pyrocatechol and derivatives thereof (see, EP 1 935 860 A1) included.
  • Suitable free-radically curable compounds according to the invention are ethylenically unsaturated compounds, cyclic monomers, compounds having carbon-carbon triple bonds and thiol-Yn / En resins, as known to the person skilled in the art.
  • ethylenically unsaturated compounds comprising styrene and derivatives thereof, (meth) acrylates, vinyl esters, unsaturated polyesters, vinyl ethers, allyl ethers, itaconates, dicyclopentadiene compounds and unsaturated fats, of which in particular unsaturated polyester resins and vinyl ester resins are suitable and
  • unsaturated polyester resins and vinyl ester resins are suitable and
  • vinyl ester resins are most preferred because of their hydrolytic resistance and excellent mechanical properties.
  • suitable unsaturated polyesters which may be used in the resin composition of the present invention are classified into the following categories as described by M. Malik et al. in JMS - Rev. Macromol. Chem. Phys., C40 (2 and 3), p.139-165 (2000):
  • Ortho resins These are based on phthalic anhydride, maleic anhydride or fumaric acid, and glycols such as 1,2-propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol or hydrogenated bisphenol-A;
  • Iso resins These are prepared from isophthalic acid, maleic anhydride or fumaric acid and glycols. These resins may contain higher levels of reactive diluents than the ortho resins; (3) bisphenol A fumarates: these are based on ethoxylated bisphenol-A and fumaric acid;
  • HET acid resins hexachloro-endo-methylene-tetrahydrophthalic acid resins: resins obtained from chlorine-bromine-containing anhydrides or phenols in the production of unsaturated polyester resins.
  • DCPD resins can be distinguished as unsaturated polyester resins.
  • the class of DCPD resins is obtained either by modification of one of the above resin types by Diels-Alder reaction with cyclopentadiene, or alternatively by a first reaction of a dicarboxylic acid, e.g. Maleic acid with dicyclopentadienyl and then by a second reaction, the usual preparation of an unsaturated polyester resin, the latter being referred to as a DCPD maleate resin.
  • a dicarboxylic acid e.g. Maleic acid with dicyclopentadienyl
  • the unsaturated polyester resin preferably has a molecular weight Mn in the range of 500 to 10,000 daltons, more preferably in the range of 500 to 5000, and even more preferably in the range of 750 to 4000 (according to ISO 13885-1).
  • the unsaturated polyester resin has an acid value in the range of 0 to 80 mg KOH / g resin, preferably in the range of 5 to 70 mg KOH / g resin (according to ISO 21 14-2000).
  • the acid value is preferably 0 to 50 mg KOH / g resin.
  • vinyl ester resins are monomers, oligomers, prepolymers or polymers having at least one (meth) acrylate end group, so-called (meth) acrylate groups.
  • functionalized resins which include urethane (meth) acrylate resins and epoxy (meth) acrylates.
  • Vinyl ester resins which have unsaturated groups only in the terminal position are obtained, for example, by reaction of epoxide oligomers or polymers (eg bisphenol A digylcidyl ether, epoxides of the phenol novolak type or epoxide oligomers based on tetrabromobisphenol A) with, for example (Meth) acrylic acid or (meth) acrylamide.
  • epoxide oligomers or polymers eg bisphenol A digylcidyl ether, epoxides of the phenol novolak type or epoxide oligomers based on tetrabromobisphenol A
  • Preferred vinyl ester resins are (meth) acrylate-functionalized resins and resins obtained by reacting an epoxy oligomer or polymer with methacrylic acid or methacrylamide, preferably with methacrylic acid.
  • vinyl ester resin examples include (meth) acrylate-functionalized resins, e.g. by reaction of di- and / or higher-functional isocyanates with suitable acrylic compounds, optionally with the participation of hydroxy compounds which contain at least two hydroxyl groups, as described, for example, in DE 3940309 A1.
  • isocyanates it is possible to use aliphatic (cyclic or linear) and / or aromatic di or higher-functional isocyanates or prepolymers thereof.
  • the use of such compounds serves to increase the wettability and thus the improvement of the adhesion properties.
  • Preference is given to aromatic di- or higher-functional isocyanates or prepolymers thereof, particular preference being given to aromatic di or higher-functional prepolymers.
  • tolylene diisocyanate (TDI), diisocyanatodiphenylmethane (MDI) and polymeric diisocyanatodiphenylmethane (pMDl) may be mentioned to increase chain stiffening and hexane diisocyanate (HDI) and isophorone diisocyanate (IPDI) which improve flexibility, of which polymeric diisocyanatodiphenylmethane (pMDl) is most preferred
  • acyl compounds are acrylic acid and acrylic acid substituted on the hydrocarbon radical, such as (meth) acrylic acid, hydroxyl-containing esters of (meth) acrylic acid with polyhydric alcohols, pentaerythritol tri (meth) acrylate, glycerol di (meth) acrylate, such as Trimethylolpropandi (meth) acrylate, neopentyl glycol mono (meth) acrylate suitable.
  • (meth) acrylic acid hydroxyalkyl esters such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, especially since such compounds serve steric hindrance of the saponification reaction.
  • hydroxy compounds are suitable dihydric or higher alcohols, such as derivatives of ethylene or propylene oxide, such as ethanediol, di- or triethylene glycol, propanediol, dipropylene glycol, other diols, such as 1, 4-butanediol, 1, 6-hexanediol, Neopentylglycol, diethanolamine, bisphenol A or -F or their Oxethyl michs- and / or hydrogenation or halogenation products, higher alcohols such as glycerol, trimethylolpropane, hexanetriol and pentaerythritol, hydroxyl-containing polyethers, for example, oligomers of aliphatic or aromatic oxiranes and / or higher cyclic ethers, such as ethylene oxide, propylene oxide, styrene oxide and furan, polyethers which contain aromatic structural units in the main chain, such as those of bisphenol A or F, hydroxy
  • hydroxy compounds having aromatic structural units for chain-stiffening the resin hydroxy compounds containing unsaturated structural units, such as fumaric acid, for increasing the crosslinking density
  • hydroxy compounds containing unsaturated structural units such as fumaric acid
  • branched or star-shaped hydroxy compounds in particular trihydric or higher alcohols and / or polyethers or polyesters, and the like
  • Structural units containing, branched or star-shaped urethane (meth) acrylates to achieve lower viscosity of the resins or their solutions in reactive diluents and higher reactivity and crosslinking density.
  • the vinyl ester resin preferably has a molecular weight Mn in the range of 500 to 3000 daltons, more preferably 500 to 1500 daltons (according to ISO 13885-1).
  • the vinyl ester resin has an acid value in the range of 0 to 50 mg KOH / g resin, preferably in the range of 0 to 30 mg KOH / g resin (according to ISO 2114-2000).
  • resins which can be used in accordance with the invention can be modified according to methods known to those skilled in the art, for example by reducing them Acid numbers, hydroxide numbers or anhydride numbers or made more flexible by the introduction of flexible units in the backbone, and the like.
  • the resin may contain other reactive groups that can be polymerized with a free-radical initiator, such as peroxides, for example, reactive groups derived from itaconic acid, citraconic acid and allylic groups, and the like.
  • Particularly useful is the use of the combination of a stable nitroxyl radical and a quinone methide in a resin mixture whose curable component contains traces of acid such as mineral acid or carboxylic acid which are formed, for example, in the preparation of the radically curable compound or a precursor compound thereof.
  • the base resins are used in an amount of 20 to 100 wt .-%, preferably 40 to 65 wt .-%, based on the resin mixture.
  • the resin mixture contains at least one reactive diluent for the curable component (a), wherein the reactive diluent in an amount of 0 to 80 wt .-%, preferably 30 to 60 wt .-%, based on the resin mixture added can be.
  • Suitable reactive diluents are described in EP 1 935 860 A1 and DE 195 31 649 A1.
  • the resin mixture is inticianministerter form, that is, it contains at least one accelerator for the curing agent.
  • Preferred accelerators for the curing agent are aromatic amines and / or salts of cobalt, manganese, tin, vanadium or cerium.
  • N, N-dimethylaniline, ⁇ , ⁇ -diethylaniline, N, N-di-isopropanol-p-toluidine, N, N-diisopropylidene-p have particularly advantageously been used as accelerators.
  • toluidine N, N-dimethyl-p-toluidine, N, N-diethylol-p-toluidine, N, N-diisopropylol-m-toluidine, N, N-bis (2-hydroxyethyl) toluidine, N, N-bis ( 2-hydroxyethyl) xylidine, N-methyl-N-hydroxyethyl-p-toluidine, cobalt octoate, cobalt naphthenate, vanadium (IV) acetylacetonate, and vanadium (V) acetylacetonate.
  • the accelerator or the accelerator mixture is used according to the invention in an amount of 0.05 to 5 wt .-%, preferably 1, 3 to 3 wt .-%, based on the resin mixture.
  • the novel resin mixtures can be used for the production of reactive resin mortars for chemical fastening technology.
  • the reaction resin mortars prepared according to the invention are characterized by a particularly good storage stability, even in the absence of atmospheric oxygen.
  • Another object of the invention is therefore a reaction resin mortar containing in addition to the resin mixture of conventional inorganic additives such as fillers, thickeners, thixotropic agents, non-reactive solvents, flowability improvers and / or wetting agents.
  • the fillers are preferably made of particles of quartz, fused silica, corundum, calcium carbonate, calcium sulfate, glass and / or organic polymers of various sizes and shapes, for example as sand or flour, in the form of spheres or hollow spheres, but also in the form of fibers of organic polymers , such as polymethyl methacrylate, polyester, polyamide or in the form of microspheres of polymers (perpolymers).
  • the globular, inert substances (spherical form) have a preferential and more pronounced strengthening effect.
  • Preferred thickeners or thixotropic agents are those based on silicates, bentonite, laponite, fumed silica, polyacrylates and / or polyurethanes.
  • Another object of the invention is a multi-component mortar system comprising at least two (spatially) separate components A and B.
  • the multi-component mortar system comprises two or more separate, interconnected and / or nested containers, one containing component A, the reaction resin mortar and the other component B, the Hardener, which may optionally be filled with inorganic and / or organic additives, includes.
  • the multi-component mortar system may be in the form of a cartridge, a cartridge or a foil bag.
  • component A and component B are pressed out of the cartridges, cartridges or foil bags under the action of mechanical forces or gas pressure, mixed together, preferably with the aid of a static mixer through which the components are passed, and in introduced the borehole, after which the devices to be fastened, such as anchoring threaded rods and the like are introduced into the borehole fed with the curing reaction resin and adjusted accordingly.
  • Preferred hardeners are storage-stable organic peroxides.
  • dibenzoyl peroxide and methyl ethyl ketone peroxide are particularly suitable, furthermore terf-butyl perbenzoate, cyclohexanone peroxide, lauryl peroxide and cumene hydroperoxide, as well as te / f-butyl peroxy-2-ethylhexanoate.
  • the peroxides are used in amounts of 0.3 to 15 wt .-%, preferably from 1 to 5 wt .-%, based on the reaction resin mortar.
  • the hardeners are suitably phlegmatized by inert fillers, quartz sands being preferred.
  • the A component in addition to the curable component (a) additionally contains a hydraulically setting or polycondensable inorganic compound, in particular cement, and the B component in addition to the curing agent still water.
  • a hydraulically setting or polycondensable inorganic compound in particular cement
  • the B component in addition to the curing agent still water.
  • the A component preferably contains, as a hydraulically setting or polycondensable inorganic compound, cement, for example Portland cement or aluminate cement, with iron oxide-free or low-iron cements being particularly preferred.
  • hydraulically setting inorganic compound may also be used gypsum as such or in admixture with the cement.
  • the A component may comprise as polycondensable inorganic compound also silicate, polycondensable compounds, in particular soluble, dissolved and / or amorphous silica containing substances.
  • the great advantage of the invention is that testing of the components of the resin composition, such as the curable component (a) or its precursor (s) on acid traces, such as mineral acid, and their possibly expensive and costly cleaning is no longer required.
  • acid traces such as mineral acid
  • thermostability To simulate a longer shelf life, the samples were subjected to a thermal stability test at elevated temperature. Each 20 mL of the resin sample (resin mixture) is sealed in an oxygen-tight film (11x17 cm) and annealed at 80 ° C. It is observed if gelation occurs during storage. The noticeable increase in viscosity (consistency in gelation: similar to liquid honey to gummy-bearish (gel-like)) provides the information on thermostability.
  • the resin mixtures prepared under Comparative Examples 1 and 2 serve as a comparison, the Tempol-stabilized resin mixture (Comparative Example 1) being stable for at least 31 hours but gelled after 47 hours at the latest, and those in the case of 2,6-Bis (1, 1-dimethylethyl) -4- (phenylenemethylene) cyclohexa-2,5-diene-1-one stabilized resin mixture was stable for at least 127 hours. In each case two independent double determinations were carried out. As a result, the maximum time t at which the sample has not yet gelled was obtained. The results are listed in Table 2.
  • the resin mixtures prepared as described above are mixed with 30 to 45 wt .-% quartz sand, 15 to 25 wt .-% cement and 1 to 5 wt .-% fumed silica in a dissolver to a homogeneous mortar composition, the reaction resin mortars.
  • the stability of both the resin mixture and the reaction resin mortar increases, the increase in the resin mixture being less pronounced than in the reaction resin mixture, which is already at a molar ratio of tolol: 2,6-bis (1,1-dimethylethyl) -4- (phenylenemethylene ) cyclohexa-2,5-diene-1 -one of about 3: 1, the gelling time of the reaction resin mortar by a factor of 5.5 higher than that of the reaction resin mortar underlying resin mixture.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
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Abstract

L'invention concerne l'utilisation d'une combinaison comprenant au moins un radical nitroxyle stable et au moins un méthide de quinone comme stabilisateur pour des mélanges de résines et des mortiers à base de résine de réaction, respectivement à base de composés à réticulation radicalaire. Des mélanges de résines et notamment des mortiers à base de résine de réaction peuvent, de manière très efficace, devenir stables au stockage au moyen d'une combinaison d'au moins un radical nitroxyle stable et d'au moins un méthide de quinone.
EP13715966.1A 2012-04-20 2013-04-10 Combinaison à base d'un radical nitroxyle stable et d'un méthide de quinone comme stabilisateur pour des mortiers à base de résine de réaction, à base de composés à réticulation radicalaire Withdrawn EP2838946A1 (fr)

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PCT/EP2013/057439 WO2013156360A1 (fr) 2012-04-20 2013-04-10 Combinaison à base d'un radical nitroxyle stable et d'un méthide de quinone comme stabilisateur pour des mortiers à base de résine de réaction, à base de composés à réticulation radicalaire

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EP3424971A1 (fr) * 2017-07-03 2019-01-09 HILTI Aktiengesellschaft Composés de méthacrylate d'uréthane comprenant une résine de réaction, composants de résine de réaction et système de résine de réaction et son utilisation
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US11180578B2 (en) 2018-07-13 2021-11-23 Ecolab Usa Inc. Polymerization inhibitor and retarder compositions with amine stabilizer
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WO2013156360A1 (fr) 2013-10-24

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