WO2011098564A1

WO2011098564A1 - Multicomponent resin system

Info

Publication number: WO2011098564A1
Application number: PCT/EP2011/052042
Authority: WO
Inventors: Arie Boer Den; Johan Franz Gradus Antonius Jansen; Daniel Raimann; Erik Reuther
Original assignee: DSM IP Assets BV
Current assignee: DSM IP Assets BV
Priority date: 2010-02-11
Filing date: 2011-02-11
Publication date: 2011-08-18
Anticipated expiration: 2012-08-11
Also published as: EP2534185A1; JP5875008B2; CN102770472A; WO2011098566A1; CN102770472B; EP2534185B1; US20130190452A1; ES2453093T3; WO2011098562A1; US9115281B2; JP2013519747A

Abstract

The present invention relates to a multicomponent resin system comprising: a. a radical curable resin selected from the group consisting of unsaturated polyester resins, vinyl ester resins, vinyl ester urethane resins and mixtures thereof, b. an epoxide functional resin, c. a primary and/or secondary aliphatic amine, and wherein the resin system further comprises d. a bridging compound containing at least two reactive functionalities, of which one functionality is capable of radical copolymerization with the unsaturated polyester resin, vinyl ester resin or vinyl ester urethane resin and at least one functionality is capable of reacting with the aliphatic amine, and wherein the bridging compound has a number-average molecular weight M_n lower than 400 Dalton.

Description

MULTICOMPONENT RESIN SYSTEM

The present invention relates to a multicomponent resin system suitable for obtaining a composite material comprising (a) a radical curable resin selected from the group consisting of unsaturated polyester resins, vinyl ester resins, vinyl ester urethane resins and mixtures thereof and (b) an epoxide functional resin. By curing such a resin system with a peroxide and a primary and/or secondary aliphatic amine, a hybrid cured resin network can be obtained. Hybrid curing refers to curing effected by at least two different reaction mechanisms.

Such multicomponent resin system is used for obtaining an

Interpenetrating Polymer Network (IPN). As used herein, an Interpenetrating Polymer Network is a composition of at least two chemically distinct polymer networks that are at least partially interlaced on a molecular scale and that are optionally covalently bonded to each other. Besides true IPNs in which no covalent binding exists between the polymer networks, also semi IPNs can be formed. In a semi IPN, the two networks are covalently linked via a linking component which can react with the amine as well as can undergo a radical polymerisation. In case covalent binding is present between the polymer networks, the IPN is referred to as a semi IPN. In an IPN each network may retain its individual properties. As a result an improvement in properties can be attained as in an IPN the individual properties of at least two networks are combined.

In the article "Curing behaviour of IPNs formed from model VERs and epoxy systems I amine cured epoxy", K. Dean, W.D. Cook, M.D. Zipper, P. Burchill, Polymer 42 (2001 ), 1345-1359, it is described that one thermoset polymer network is formed by radical copolymerization of vinyl ester resin dissolved in styrene with a radical initiator such as a peroxide. The other thermoset polymer network is formed by step growth copolymerization of an epoxy compound with an amine. The primary amine initially reacts with the epoxy group followed by the reaction of the secondary amine. It is also stated that there is also reaction between the amines and the methacrylate groups, that are present in vinyl ester resins, by Michael addition. Thus, a semi-IPN is formed.

The present invention relates to multicomponent thermosetting resin systems. Thermosetting resins are generally used to produce a composite material for obtaining a structural object. As meant herein, structural objects are considered to have a thickness of at least 0.5 mm and appropriate (depending on the ultimate application of the structural object) mechanical properties. One of the more demanding structural applications is the chemical anchoring application, as in this application the mechanical strength of the cured resin, the adhesion of the cured resin to concrete and the adhesion of the cured resin to steel must be very good. Chemical anchoring refers to chemical fastening of anchoring elements such as tie bars, dowels, rock bolts, screws, anchor rods in boreholes of any kind of substrate such as for example concrete, bricks, natural and artificial rocks. A test for evaluating the mechanical strength of the cured resin, the adhesion of the cured resin to concrete and the adhesion of the cured resin to steel is the pull-out test. A low pull-out value represents a low tensile strength of the cured resin, low adhesion of the cured resin to metal and/or to concrete. In chemical anchoring applications, the pull-out values are preferably high under different circumstances, including under severe conditions such as low temperature (at temperature of 0 °C or lower) circumstances (wintertime and/or high latitudes) and high temperature (higher than room temperature) circumstances (summertime and/or low latitudes).

It has furthermore been found that the performance at lower temperature (at room temperature or lower) of hybrid cured resin networks obtained upon curing of hybrid resin systems comprising (a) a radical curable resin selected from the group consisting of unsaturated polyester resins, vinyl ester resins, vinyl ester urethane resins and mixtures thereof and (b) an epoxide functional resin, with a peroxide and a primary and/or secondary aliphatic amine, is relatively poor.

The object of the invention is to improve the performance at such lower temperature of such hybrid cured resin networks.

It has been found that this can be achieved in that the multicomponent resin system further contains a bridging compound (d) containing at least two reactive functionalities, of which one functionality is capable of radical copolymerization with the radical curable resin and at least one functionality is capable of reacting with the aliphatic amine, and wherein the bridging compound (d) has a number-average molecular weight M_n lower than 400 Dalton.

WO2010/007148 describes the use of a system comprising a radically polymerisable monomer, a radical former, an epoxide resin and a tertiary amine. In the prior art description part of this patent publication it is said that aliphatic amines, which are known to be able to harden epoxide resins, are not applicable in hybrid systems of (meth)acrylates and epoxide resins as aliphatic amines retard the radical polymerization of (meth)acrylates. In the light thereof, this patent publication teaches to apply a tertiary aliphatic amine as catalyst for the hydroxyl-epoxy addition reaction.

End segments where the resin systems according to the present invention can be applied are chemical anchoring, but can also be used to obtain for example automotive parts, boats, roofing, construction, containers, relining, pipes, tanks, flooring, windmill blades.

The multicomponent resin system according to the invention comprises

a. a radical curable resin selected from the group consisting of unsaturated

polyester resins, vinyl ester resins, vinyl ester urethane resins and mixtures thereof, which resin preferably do not contain epoxide functionalities, b. an epoxide functional resin, preferably not having radical curable functionalities, c. a primary and/or secondary aliphatic amine, and

d. a bridging compound containing at least two reactive functionalities, of which one functionality is capable of radical copolymerization with the unsaturated polyester resin, vinyl ester resin or vinyl ester urethane resin and at least one functionality is capable of reacting with the aliphatic amine, and wherein the bridging compound has a number-average molecular weight M_n lower than 400 Dalton,

which resin system can be cured with a peroxide.

As used herein, number-average molecular weight (M_n) is determined in tetrahydrofuran using GPC employing polystyrene standards.

The use of the multicomponent resin system according to the invention requires mixing of the compounds (a), (b), (c) and (d) together with a hardener, in particular a peroxide to obtain a hybrid cured resin network. As used herein, multicomponent resin systems means that the different compounds of the system are present in at least two spatially separated components in order to prevent premature polymerization of the compounds prior to the use of the multicomponent resin system to obtain the hybrid cured resin network. The multicomponent resin system according to the invention comprises at least two components. In one embodiment, the multicomponent resin system is a three component system consisting of three components A, B and C, wherein component A consists of a resin composition comprising compounds (a), (b) and (d) as described above; component B consists of a composition comprising a peroxide and component C consists of a composition comprising a primary and/or secondary aliphatic amine (c). The use of the three component resin system according to the invention requires mixing of the components A, B and C to obtain a hybrid cured resin network. Mixing of components A, B and C can be done in various ways. A preferred way is first mixing component A with component C and then adding component B. In another embodiment, the

multicomponent resin system is a two component system consisting of two

components A and B, wherein component A consists of a resin composition comprising compounds (a), (b) and (d) as described above and component B consists of a composition comprising a peroxide and a primary and/or secondary aliphatic amine (c). The use of the two component resin system according to the invention requires mixing of the components A and B to obtain a hybrid cured resin network. The peroxide is preferably a perester or a monopercarbonate.

The multicomponent resin system comprises a radical curable resin (compound (a)) selected from the group consisting of unsaturated polyester resins, vinyl ester resins, vinyl ester urethane resins and mixtures thereof. The unsaturated polyester resin, vinyl ester resin or vinyl ester urethane 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 of suitable unsaturated polyester resins and vinyl ester resins 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). The authors describe a classification of such resins - on the basis of their structure - in five groups:

(1 ) 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.

(2) Iso-resins: these are prepared from isophthalic acid, maleic anhydride or

fumaric acid, and glycols.

(3) Bisphenol-A-fumarates: these are based on ethoxylated bisphenol-A and

fumaric acid.

(4) Chlorendics: are resins prepared from chlorine/bromine containing anhydrides or phenols in the preparation of the UP resins.

(5) Vinyl ester resins: these are resins, which are mostly used because of their hydrolytic resistance and excellent mechanical properties. They have unsaturated sites only in the terminal position, for example introduced by reaction of epoxy resins (e.g. diglycidyl ether of bisphenol-A, epoxies of the phenol-novolac type, or epoxies based on tetrabromobisphenol-A) with (meth)acrylic acid. Instead of (meth)acrylic acid also (meth)acrylamide may be used.

Besides the vinyl ester resins as described in Malik et al., also the class of vinyl ester urethane resins (also referred to urethane (meth)acylate resins) can be used in the present invention. As used herein, a vinyl ester resin or vinyl ester urethane resin is an oligomer or polymer containing at least one (meth)acrylate functional end group, also known as (meth)acrylate functional resins. Preferred vinyl ester (urethane) resins are methacrylate functional resins. Preferred methacrylate functional resins are resins obtained by reaction of an epoxy oligomer or polymer with methacrylic acid or methacrylamide, preferably with methacrylic acid or resins obtained by reaction of a hydroxyl functional methacrylate with an isocyanate.

Preferably, the resin system according to the invention comprises an unsaturated polyester resin, a vinyl ester resin or a vinyl ester urethane resin as radical curable resin (a). More preferably, the resin system according to the invention comprises a vinyl ester resin or a vinyl ester urethane resin as radical curable resin (a). In a preferred embodiment, the radical curable resin (a) is a vinyl ester resin or a vinyl ester urethane resin.

Preferably, the radical curable resin (a) has a number-average molecular weight M_n higher than 350 Dalton, preferably higher than 500 Dalton and preferably lower than 10.000 Dalton, preferably lower than 7000 Dalton and more preferably lower than 5000 Dalton.

The radical curable resin (a) preferably has an acid value as low as possible in order to prevent salt formation of the radical polymerisable compound with the amine. The radical curable resin (a) preferably has an acid value of at most 60 mg KOH/g (determined according to ISO 21 14-2000), more preferably of at most 40 mg KOH/g, more preferably of at most 10 mg KOH/g, even more preferably of at most 5 mg KOH/g and even more preferably 0 mg KOH/g. In view of this, a vinyl ester resin is preferably applied as radical curable resin (a).

Preferably, the resin system further comprises a reactive diluent. The diluent, for instance, will be applied for adjustment of the viscosity of the resin system in order to make handling thereof more easy. Preferably, at least part of the reactive diluent is capable of undergoing radical copolymerization. More preferably, at least part of the reactive diluent is a methacrylate containing compound and even more preferably, the reactive diluent is a methacrylate containing compound or a mixture of methacrylate containing compounds. Suitable examples of (meth)acrylates reactive diluents are 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, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, 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 di(meth)acrylate, PEG200 di(meth)acrylate, PPG250 di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, 1 ,10-decanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate and

trimethylolpropanetri(meth)acrylate.

The system according to the invention comprises an epoxide functional resin (b), i.e. a resin containing at least one epoxide group. Preferably, the resin system according to the invention comprises a bisepoxide (containing two epoxide groups) as epoxide functional resin (b). In a preferred embodiment, the epoxide functional resin (b) is a bisepoxide.

Preferably, the epoxide functional resin (b) comprises a glycidylether as epoxide function. In a preferred embodiment, the resin system according to the invention comprises a glycidylether as epoxide functional resin (b). In a more preferred embodiment, the epoxide functional resin (b) is a glycidylether.

Preferably, the epoxide functional resin (b) has a number-average molecular weight M_n of at least 300 Dalton, more preferably of at least 500 Dalton and even more preferably of at least 750 Dalton. Preferably, the epoxide functional resin (b) has a number-average molecular weight M_n of at most 10.000 Dalton, more preferably of at most 5000 Dalton and more preferably of at most 3000 Dalton.

The resin system of the present invention comprises compound (a) and compound (b) as two separate compounds and further comprises a bridging compound (d) having at least two reactive functionalities, of which one functionality is capable of undergoing a radical copolymerization and one functionality is capable of reacting with the aliphatic amine.

Preferably, the bridging compound (d) contains a radical curable functionality, i.e. a functionality capable of undergoing a radical copolymerization, selected from the group consisting of acrylate, methacrylate, vinyl ether, vinyl ester and allyl ether, more preferably being a methacrylate or acrylate and even more preferably being a methacrylate. More preferably, the radical curable functionality of the bridging compound (d) is selected from acrylate, methacrylate, vinyl ether, vinyl ester and allyl ether, more preferably is a methacrylate or acrylate and even more preferably is a methacrylate.

Preferably, the bridging compound (d) contains an isocyanate, an epoxide, an acetoacetoxy, an oxalic-amide or a cyclic carbonate as functionality capable of reacting with the aliphatic amine, more preferably an epoxide and even more preferably a glycidyl ether. More preferably, the functionality of the bridging component capable of reacting with the aliphatic amine is selected from the group consisting of an isocyanate, an epoxide and a cyclic carbonate, more preferably is an epoxide and even more preferably is a glycidyl ether. In a preferred embodiment, the radical copolymerizable functionality of the bridging compound (d) is a methacrylate and the amine reactive functionality is an epoxide functionality.

In a preferred embodiment, the resin system comprises

glycidylmethacrylate as bridging compound (d). In a more preferred embodiment, the bridging compound (d) is glycidylmethacrylate.

Preferably, the number-average molecular weight M_n of the bridging compound (d) is less than 300 Dalton, preferably less than 250 Dalton, as this results in that the low temperature performance of the hybrid cured resin network is even more improved.

The resin system preferably comprises the bridging compound (d) with a number-average molecular weight M_n lower than 400 Dalton in an amount of less than 50 wt.%, more preferably less than 40 wt.% and preferably more than 5 wt.%, more preferably more than 7.5 wt.%, wherein the sum of the amounts of (a) + (b) + (d) is 100wt.%.

The resin system may further comprise a bridging compound (d) containing at least one functionality capable of radical copolymerization with the unsaturated polyester resin, vinyl ester resin or vinyl ester urethane resin and at least one functionality capable of reacting with an aliphatic amine, and wherein the bridging compound (d) has a number-average molecular weight M_n higher than or equal to 400 Dalton.

The molar ratio of radical polymerizable functionalities and the funtionalities capable of reacting with the aliphatic amine in the resin system is preferably from 10:1 to 1 : 10, more preferably from 5:1 to 1 :5 and even more preferably from 3:1 to 1 :3. As used herein, for all upper and/or lower boundaries of any range given, the boundary value is included in the range. The molar ratio of epoxide functionalities and amine -NH- functionalities in the resin system according to the invention is preferably from 5:1 to 1 : 5, more preferably from 3:1 to 1 :3, even more preferably from 2:1 to 1 :2, even more preferably from 1.5:1 to 1 :1.5 and most preferably 1 :1. For clarity, a primary amine has two NH functionalities and a secondary amine has one NH functionality.

The resin system preferably further comprises a transition metal salt or complex. The presence of such transition metal compound is beneficial as it accelerates the decomposition of the peroxide and therefore accelerates the radical polymerisation. Preferably, the resin system further comprises a salt or complex of transition metal with an atomic number in the range from 22 to 29 or with an atomic number in the range from 38 to 49 or with an atomic number in the range from 57 to 79. More preferably, the transition metal salt or complex is a salt or complex of Mn, Fe, Cu, V and Co. Even more preferably, the transition metal salt or complex is a salt or complex of Mn, Fe and Cu. Even more preferably, the transition metal salt or complex is a salt or complex of Mn and Cu as the low temperature performance of the hybrid cured resin network can be even further improved. The Mn, Fe, Cu, V or Co compound is preferably a Mn, Fe, Cu, V or Co carboxylate, more preferably a Mn, Fe, Cu, V or Co C C₃o carboxylate and even more preferably a Mn, Fe, Cu, V or Co C Ci₆

carboxylate.

A skilled person will be able to determine a suitable amount of transition metal compound. The amount of transition metal compound present in the resin system according to the invention is preferably such that at least 0,0001 mmol transition metal per kg of curable compounds is present, more preferably at least 0,0025 mmol transition metal per kg of curable compounds and even more preferably at least 0,025 mmol transition metal per kg of curable compounds. The upper limit of transition metal content is not very critical, although for reasons of cost efficiency of course no extremely high concentrations will be applied. Generally the concentration of transition metal in the resin system will be lower than 50 mmol transition metal per kg of curable compounds, preferably lower than 20 mmol transition metal per kg of curable compounds.

The resin system preferably further comprises a storage stabilizer in order to further improve its storage stability. Preferably, the storage stabilizer is selected from the group of stable radicals, phenolic compounds, hydroquinones, catechols, phenothiazines and mixtures thereof. Suitable examples of storage stabilizers that can be used for improving the storage stability of the resin systems according to the invention are, for instance, 2-methoxyphenol, 4-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, 2,4,6-trimethyl-phenol,

2,4,6-tris-dimethylaminomethyl phenol, 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-isopropylidene diphenol, 2,4-di-t-butylphenol, 6,6'-di-t-butyl-2,2'-methylene di-p-cresol, hydroquinone, 2-methylhydroquinone, 2-t-butylhydroquinone,

2.5- di-t-butylhydroquinone, 2,6-di-t-butylhydroquinone, 2,6-dimethylhydroquinone , 2,3,5-trimethylhydroquinone, catechol, 4-t-butylcatechol, 4,6-di-t-butylcatechol, benzoquinone, 2,3,5,6-tetrachloro-1 ,4-benzoquinone, methylbenzoquinone,

2.6- dimethylbenzoquinone, napthoquinone, 1 -oxyl-2,2,6,6-tetramethylpiperidine, 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.

Preferably, at least a primary aliphatic amine is used to cure compound (b). More preferably, a primary aliphatic amine as well a secondary aliphatic amine is used to cure compound (b). Examples of suitable aliphatic amines are: 1 ,2- diaminoethane; 1 ,2-diaminopropane; 1 ,3-diaminopropane; 1 ,4-diaminobutane; as well as 2-methyl-1 ,5-diaminopentane; 1 ,3-diaminopentane; 2,2,4-trimethyl-1 ,6- diaminohexane; 2,4,4-trimethyl-1 ,6-diaminohexane; 1-amino-3-aminomethyl-3,5,5- trimethylcyclohexane; 2,2-dimethyl-l, 1 ,3-diaminopropane; 1 ,3- bis(aminomethyl)cyclohexane; 1 ,2-diaminocyclohexane and 1 ,3- bis(aminomethyl)benzene.

In the resin system according to the invention also fillers and/or fibres can be present. A wide variety of fillers can be applied like for instance, without being limited thereto, silica, sand, cement, pigments. A wide variety of fibres can be applied like for instance, without being limited thereto, glass and carbon fibres.

The present invention also relates to a process for curing the multicomponent resin system according to the invention by mixing the compounds of the multicomponent resin system together with a peroxide. The curing is preferably effected at a temperature in the range of from -20 to +200 °C, preferably in the range of from -20 to +100 °C, and most preferably in the range of from -10 to +60 °C (so-called cold curing). In case the peroxide and the primary and/or secondary aliphatic amine are separately mixed into the resin composition, in which embodiment use is preferably made of a three component resin system as described above, the aliphatic amine is preferably first added to the resin composition, followed by adding the peroxide. In another embodiment, the primary and/or secondary aliphatic amine and the peroxide are first mixed and the resulting mixture is mixed into the resin composition according to the invention. In this embodiment, use is preferably made of a two component system as described above.

The peroxide used for the initiation of the radical copolymerization can be any peroxide known to the person skilled in the art for being used in curing of unsaturated polyester resins, vinyl ester resins and vinyl ester urethane resins. Such peroxides include organic and inorganic peroxides, whether solid or liquid; also hydrogen peroxide may be applied. The peroxide is preferably an organic peroxide. Examples of suitable peroxides are, for instance, peresters, monopercarbonates, perketals, peranhydrides, hydroperoxides and perethers. The required amount of peroxide can be easily determined by a person skilled in the art and the amount can be varied within wide ranges, in general higher than 0,0001 wt.% and less than 20 wt.%, preferably less than 10 wt.% and more preferably less than 5 wt.% (wherein the amount of peroxide is relative to the total amount of curable compounds). The peroxide is preferably a perester and/or a monopercarbonate as the low temperature performance of the hybrid cured resin system can further be improved. More preferably, the peroxide is a perester or a monopercarbonate. Even more preferably, the peroxide is a perester.

The present invention further also relates to cured objects, in particular structural objects, as are being obtained when curing the multicomponent resin system according to the invention by mixing the compounds together with a peroxide or obtained with the process for 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, windmill blades.

The invention is now demonstrated by means of a series of examples and comparative examples. All examples are supportive of the scope of claims. The invention, however, is not restricted to the specific embodiments as shown in the examples. Examples and Comparative Experiments

Synthesis resins (compound (a)):

Resin A: bisphenol A glycerolate dimethacrylate (Aldrich) (vinyl ester resin). Resin B (vinyl ester resin): A reaction vessel was charged with 424.8g bisphenol A diglycidyl ether and 82g bisphenol A followed by heating to 160°C. The reaction mixture was kept at this temperature until all the bisphenol A has reacted ( at least 2 hrs) followed by cooling to 1 10°C at which temperature 126.2 g methacrylic acid was added slowly during at least 1 hr and stirred at this temperature for another hour after which the reaction mixture was cooled to room temperature and resin B was obtained.

Resin C (vinyl ester urethane resin???): A reaction vessel was charged with 367.1 g bisphenol A diglycidyl ether. Heated to 100°C and adding slowly 161.6 g methacrylic acid at such a rate that the temperature does not exceed 1 10°C. The reaction mixture was kept at 100°C for an additional hour after which 15.9 g maleic anhydride was added followed by stirring for an additional 3 hrs before cooling to 85°C after which 46.6g toluenediisocyante was added. Stirring at 85°C was maintained until all the isocyanate has reacted after which the reaction was cooled down to room temperature yielding resin C.

Resin D (vinyl ester urethane resin): To a strirred reactor, charged with 575 g methylene-1 ,1 '-diphenyl-diisocyanate MDI and 0.3 g dibutyltin dilaurate, was added 71 g dipropyleneglycol at such a rate that the temperature did not exceed 60°C. After stirring for 30 min at 60°C, 792 g hydroxypropylmethacryalte (HPMA) was added and the temperature rose to 90°C. After stirring for 2 hr at 90°C, the mixture was cooled to room temperature after which resin D was obtained.

Resin E (unsaturated polyester resin): A reaction vessel was charged with 402.6g propylene glycol, 492.7g ethylene glycol, 908.6 g maleic anhydride and 196g phtalic anhydride. The reaction vessel was slowly heated to 140°C, kept at this temperature for 2 hrs and subsequently heated to 210°C. After 3 hrs at 210°C, vacuum was applied and the reaction was continued till an acid value of 10 mg KOH/g resin was obtained after which the reaction was cooled to room temperature and unsaturated polyester resin E was obtained. Resin F: Palatal AE-100; methacrylate functional resin diluted in BDDMA (1 ,4- butanediol dimethacrylate).

Synthesis bridge number-average molecular weight M 450

To 340 g bisphenol A diglycidyl ether (1 Mol) and 0,1 g hydroquinone in 100 ml toluene was added, under stirring at 90°C, 86 g methacrylic (1 mol) acid in a dropwise fashion. After completion of the addition, stirring at 90°C was continued until the acid value was below 2 mg KOH/g resin. Next the toluene was evaporated after which a resin containing both a methacrylate as well as an epoxide functionality with a number-average molecular weight M_n around 450.

Pull out experiments

The mechanical strength of the cured system was assessed analogous to a pull out test from concrete using as standard a 14 mm drill hole and a M12 12.9 steel anchor with a setting depth of 72 mm using a confined setting for pulling.

In this test the unfilled resin formulations were used. The cited values (kNewton) are an average of 6 measurements. Examples 1-2 and comparative experiments A-D

Formulations were prepared as listed in table 1 (amounts are in g). The formulations were cured using Dytek A (1 ,5-diamino-2-methylpentane, Aldrich) and Trigonox C (t-butylperbezoate, Akzo).

Table 1

the anchor can be removed manually This table clearly shows that when resin systems according to the invention are used, good mechanical properties and adhesion under various conditions as indicated by the pull out values under several conditions can be obtained.

Comparing example 1 and 2 with experiment A-C show that higher values are obtained both in the half cleaned wet holes at well as in the holes at -5C. Especially in the holes at -5C employing no bridging component or only using a bridging component with a M_n > 400 i.e. 450 results in a dramatic reduction of the pullout value.

Furthermore experiment D demonstrates that having only the bridging compound as resin results in a poor performance of the hybrid cured resin network.

Examples 3-10

Several formulations were prepared according to table 2 (amounts in g) and cured with Dytek A and Trigonox C (t-butylperbezoate, Akzo).

Table 2

These examples clearly demonstrate that various resins can be used according to the invention. Examples 1 1-15

Formulations were made from 192g resin A, 128g reactive diluents, 161 g GMA, 514g bisphenol A diglycidylether and 4g Cu naftenate solution (8 wt% Cu). Curing was performed by adding 124g Dytek A immediately followed by 16g Trigonox C.The results of the pull out test are shown in the next table.

Table 3

The examples clearly demonstrate that various reactive diluents can be used. Examples 16-18

Formulations were made from 192g resin A, 128g butane diol dimethacrylate, 161 g GMA, 514g bisphenol A diglycidylether and 4g transition metal (8 wt%) solution. Curing was performed by adding 124g Dytek A immediately followed by 16g Trigonox C.

The Commercial Nuodex Mn-10 (10 wt% Mn in spirits) was diluted with spirits to 8 wt%. The Commercial Nuodex Fe-12 (12 wt% Fe in spirits) was diluted with spirits to 8 wt%.

The results of the pull out test are shown in the next table.

Table 4

These examples clearly show that various transition metal salts and complexes can be used according to the invention. Examples 19-21

Formulations were made from 192g resin A, 128g butane diol dimethacrylate, 161 g GMA, 514g bisphenol A diglycidylether and 4g Cu naphtenate. Curing was performed by adding 124g of a diamine immediately followed by 16g Trigonox C.

The results of the pull out test are shown in the next table.

Table 5

These examples clearly show that various amines can be used according to the invention.

Examples 22-26

Resin A was diluted with 40% BDDMA. With this diluted resin, various formulations were prepared (see table 6, amounts are in g) and tested in the pullout test.

Table 6

These examples clearly show that various amounts can be employed according to the invention.

Claims

Multicomponent resin system comprising:

a. a radical curable resin selected from the group consisting of unsaturated polyester resins, vinyl ester resins, vinyl ester urethane resins and mixtures thereof,

b. an epoxide functional resin,

c. a primary and/or secondary aliphatic amine, and

characterized in that the resin system further comprises

d. a bridging compound containing at least two reactive functionalities, of which one functionality is capable of radical copolymerization with the unsaturated polyester resin, vinyl ester resin or vinyl ester urethane resin and at least one functionality is capable of reacting with the aliphatic amine, and wherein the bridging compound has a number-average molecular weight M_n lower than 400 Dalton.

Multicomponent resin system according to claim 1 , characterized in that the system comprises an unsaturated polyester resin, a vinyl ester resin or a vinyl ester urethane resin as radical curable resin (a).

Multicomponent resin system according to claim 1 , characterized in that the system comprises a vinyl ester resin or a vinyl ester urethane resin as radical curable resin (a).

Multicomponent resin system according to any of the claims 1-3, characterized in that the resin system further comprises a reactive diluent and that the reactive diluent is a methacrylate containing compound.

Multicomponent resin system according to any of the claims 1-4, characterized in that the resin system comprises a bisepoxide as epoxide functional resin

(b).

Multicomponent resin system according to any of the claims 1-5, characterized in that the resin system comprises a glycidylether as epoxide functional resin (b).

Multicomponent resin system according to anyone of the preceding claims, characterized in that the radical curable functionality of the bridging compound (d) is a methacrylate. Multicomponent resin system according to anyone of the preceding claims, characterized in that the functionality of the bridging compound (d) capable of reacting with the aliphatic amine is a glycidylether.

Multicomponent resin system according to anyone of the preceding claims, characterized in that the M_n of the bridging compound (d) is less than 300 Dalton.

Multicomponent resin system according to anyone of the preceding claims, characterized in that the resin system comprises glycidylmethacrylate as bridging compound (d).

Multicomponent resin system according to any of the preceding claims, characterized in that the molar ratio of radical polymerizable functionalities and the functionalities capable of reacting with the aliphatic amine is from 10: 1 to 1 : 10, preferably from 5:1 to 1 :5 more preferably from 3:1 to 1 :3.

Multicomponent resin system according to any of the preceding claims, characterized in that the system further comprises a salt or complex of manganese or copper.

Multicomponent resin system according to any of the preceding claims, characterized in that the system further comprises a peroxide, preferably a perester and/or a monopercarbonate.

Process for curing a multicomponent resin system according to claim 13, characterized in that the process comprises mixing the compounds of the resin system.

Process according to claim 14, characterized in that a monopercarbonate or a perester is used as peroxide.

Cured structural objects obtained by curing a multicomponent resin system according to anyone of claims 1-12 with a peroxide or obtained with the process according to claim 14 or 15.