Terminally unsaturated (meth) acrylate cross-linking agent and use thereof

Abstract

The invention relates to a crosslinker mixture for reactive resins. The crosslinker mixture contains a first di (meth) acrylate diester and a second di (meth) acrylate diester. The invention also relates to a reactive resin containing a crosslinker mixture according to the invention, and to a two-component system comprising the reactive resin and a hardener component. The invention also relates to the use of the reactive resin and / or the two-component system, for example for floor coatings and / or road markings.

Description

Technical Field

[0001] The invention relates to a crosslinker mixture for reactive resins. The crosslinker mixture contains a first di(meth)acrylate diester and a second di(meth)acrylate diester. The invention further relates to a reactive resin containing the crosslinker mixture according to the invention, and a 2K (two-component) system comprising the reactive resin and a curing agent component. The invention also relates to the use of the reactive resin and / or the 2K system, for example, for floor coatings and / or road markings. Background Art

[0002] The use of crosslinkers in reactive resins is known in the prior art.

[0003] For example, EP 2 054 453 B1 describes a (meth)acrylate resin which, in addition to various (meth)acrylate monomers and polymers, may also contain a crosslinker. However, this document does not describe mixtures of crosslinkers.

[0004] EP 3 929 245 A1 describes a 2K reactive resin based on (meth)acrylates, which contains monomers and optionally a crosslinker. This document also does not describe mixtures of crosslinkers.

[0005] WO 2020 / 035561 describes the preparation of di(meth)acrylate diesters by reaction of (meth)acrylic anhydride with epoxides in the presence of catalysts and chromium-containing cocatalysts. The document does not describe any crosslinker mixtures or their use in reactive resins.

[0006] The crosslinkers described in the prior art are already suitable as crosslinkers for reactive resins. However, the preparation of the crosslinkers described in the prior art is often laborious and expensive, so that the crosslinkers themselves are also expensive. Summary of the invention

[0007] Purpose

[0008] There is therefore a need for alternative crosslinkers for reactive resins and reactive resins containing these crosslinkers, as well as 2K systems comprising said reactive resins. These alternative crosslinkers should be producible more cheaply than the crosslinkers described in the prior art, and the cured reactive resins produced therefrom should have mechanical properties that are at least comparable to those described in the prior art.

[0009] Achievement of purpose

[0010] The object is achieved by a crosslinker mixture for reactive resins, wherein the crosslinker mixture contains the following components (A) and (B):

[0011] (A) at least one first di(meth)acrylate diester of the general formula (I)

[0012]

[0013] in

[0014] R 1 is H or CH 3 ,

[0015] R 2 is H or CH 3 ,and

[0016] R 3 is H or CH 3 ;

[0017] (B) at least one second di(meth)acrylate diester of the general formula (II)

[0018]

[0019] in

[0020] R 4 is H or CH 3 ,

[0021] R 5 is H or CH 3 ,

[0022] R 6 is H or CH 3 ,and

[0023] n is 2 or 3.

[0024] Furthermore, the object is achieved by a reactive resin comprising:

[0025] 0.1% to 30% by weight of a crosslinker mixture according to any one of claims 1 to 8,

[0026] 20 to 80 wt% of (meth)acrylate monomers,

[0027] 0 to 40% by weight of a prepolymer,

[0028] 0.1 to 10% by weight of initiator or 0.1 to 5% by weight of accelerator, in each case based on the total weight of the reactive resin.

[0029] Furthermore, the object is achieved by a 2K system which comprises the reactive resin according to the invention as first component and a hardener component as second component.

[0030] The invention further provides the use of the reactive resin according to the invention or the 2K system according to the invention for floor coatings, chemical anchors, cable potting compounds and / or road markings.

[0031] It has surprisingly been found that the crosslinking agent mixture of the present invention can be used for reactive resins. The mechanical properties of the reactive resins containing the crosslinking agent mixture of the present invention after curing are similarly good as those of the reactive resins containing the crosslinking agents described in the prior art. In particular, their elongation at break and tensile strength are comparable. At the same time, the crosslinking agent mixture of the present invention can be produced more easily and more cheaply than the crosslinking agents described in the prior art. This makes the reactive resins of the present invention more economically feasible.

[0032] Reactive resins containing the crosslinker mixtures of the invention additionally have good pot lives and curing times.

[0033] It has furthermore surprisingly been found that for the crosslinker mixtures according to the invention the density difference between the monomer and the polymer is found to be smaller than for the crosslinkers described in the prior art, for example ethylene glycol dimethacrylate or 1,4-butanediol dimethacrylate.

[0034] The present invention is explained in detail below.

[0035] The crosslinker mixture of the present invention contains components (A) and (B).

[0036] For example, the crosslinker mixture contains component (A) in the range from 50% to 90% by weight, preferably in the range from 60% to 80% by weight, based in each case on the total weight of the crosslinker mixture.

[0037] The crosslinker mixture contains, for example, component (B) in the range from 10 to 50% by weight, preferably in the range from 20 to 40% by weight, based in each case on the total weight of the crosslinker mixture.

[0038] Also preferred is therefore a crosslinker mixture containing

[0039] 50 to 90 wt% of component (A) and

[0040] 10 to 50 wt. % of component (B),

[0041] In each case this is based on the total weight of the crosslinker mixture.

[0042] The weight percentages of components (A) and (B) in the crosslinker mixture preferably add up to 100 weight percent. It is therefore preferred that the crosslinker mixture consists essentially of components (A) and (B).

[0043] Obviously, the weight percentages of components (A) and (B) relate to the weight percentages before the crosslinker mixture reacts with itself or in the reactive resin. It is clear to the person skilled in the art that the composition of the crosslinker mixture may change due to the reaction with itself or in the reactive resin.

[0044] Component (A) is at least one first di(meth)acrylate diester of the general formula (I)

[0045]

[0046] in

[0047] R 1 is H or CH 3 ,

[0048] R 2 is H or CH 3 ,and

[0049] R 3 is H or CH 3 .

[0050] The term "di(meth)acrylate diester" in the present invention refers to both dimethacrylate diester and diacrylate diester. 2 and R 3 is H, then the first di(meth)acrylate diester is the first diacrylate diester. If, for example, R in formula (I) 2 and R 3 Yes CH 3 , then the first di(meth)acrylate diester is the first dimethacrylate diester.

[0051] Component (A) is at least one first di(meth)acrylate diester of the general formula (I). The expression "at least one first di(meth)acrylate diester" in the present invention means exactly one first di(meth)acrylate diester or a mixture of two or more first di(meth)acrylate diesters. Component (A) is preferably a mixture of two or more first di(meth)acrylate diesters.

[0052] When R in the general formula (I) 1 When is H, the first di(meth)acrylate diester is ethylene glycol di(meth)acrylate. Ethylene glycol di(meth)acrylate is also known as 1,2-ethylene glycol di(meth)acrylate.

[0053] When R in the general formula (I) 1 Yes CH 3When the first di(meth)acrylate diester is propylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate is also known as 1,2-propylene glycol di(meth)acrylate.

[0054] As detailed above, component (A) is preferably a mixture of two or more first di(meth)acrylate diesters. Thus, component (A) preferably comprises ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate.

[0055] Preference is therefore also given to crosslinker mixtures in which component (A) comprises ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate.

[0056] For example, component (A) comprises ethylene glycol di(meth)acrylate in the range from 30% to 80% by weight, preferably in the range from 50% to 70% by weight, based in each case on the total weight of component (A).

[0057] For example, component (A) comprises propylene glycol di(meth)acrylate in the range from 20% to 70% by weight, preferably in the range from 30% to 50% by weight, based in each case on the total weight of component (A).

[0058] Preference is therefore also given to a crosslinker mixture in which component (A) comprises

[0059] 30 to 80 wt% of ethylene glycol di(meth)acrylate and

[0060] 20 to 70% by weight of propylene glycol di(meth)acrylate,

[0061] In each case this is based on the total weight of component (A).

[0062] The sum of the weight percentages of ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate in component (A) is preferably 100 weight percent. Component (A) particularly preferably consists of ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate.

[0063] R in formula (I) 2 and R 3 can be the same or different. If R in formula (I) 2 and R 3 Similarly, component (A) is at least one first symmetrical di(meth)acrylate diester. If R in formula (I) 2 and R 3 In contrast, component (A) is at least one first asymmetric di(meth)acrylate diester.

[0064] Component (B) is at least one second di(meth)acrylate diester of the general formula (II)

[0065]

[0066] in

[0067] R 4 is H or CH 3 ,

[0068] R 5 is H or CH 3 ,

[0069] R 6 is H or CH 3 ,and

[0070] n is 2 or 3.

[0071] Component (B) is at least one second di(meth)acrylate diester of the general formula (II). The expression "at least one second di(meth)acrylate diester" in the present invention refers to exactly one second di(meth)acrylate diester or a mixture of two or more second di(meth)acrylate diesters. Component (B) is preferably a mixture of two or more second di(meth)acrylate diesters.

[0072] When R in formula (II) 4 When R in formula (II) is H, the second di(meth)acrylate diester is usually diethylene glycol di(meth)acrylate and / or triethylene glycol di(meth)acrylate. 4 Yes CH 3 When the second di(meth)acrylate diester is usually dipropylene glycol di(meth)acrylate and / or tripropylene glycol di(meth)acrylate. 4 Yes CH 3 In the present invention, formula (II) and the terms "dipropylene glycol di(meth)acrylate" and "tripropylene glycol di(meth)acrylate" also include the corresponding isomers.

[0073] Obviously, when n in formula (II) is 2, component (B) generally comprises diethylene glycol di(meth)acrylate and / or dipropylene glycol di(meth)acrylate. When n in formula (II) is 3, component (B) generally comprises triethylene glycol di(meth)acrylate and / or tripropylene glycol di(meth)acrylate.

[0074] R in formula (II) 5 and R 6 can be the same or different. If R in formula (II) 5 and R 6Similarly, component (B) is at least one second symmetrical di(meth)acrylate diester. If R in formula (II) 5 and R 6 In contrast, component (B) is at least one second asymmetric di(meth)acrylate diester.

[0075] As detailed above, component (B) is preferably a mixture of two or more second di(meth)acrylate diesters. Thus, component (B) preferably comprises diethylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate.

[0076] Preference is therefore also given to crosslinker mixtures in which component (B) comprises diethylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate.

[0077] Component (B) comprises, for example, in the range from 50% to 90% by weight, preferably in the range from 60% to 80% by weight, based in each case on the total weight of component (B), of diethylene glycol di(meth)acrylate.

[0078] Component (B) comprises, for example, from 10 to 50% by weight, preferably in the range from 20 to 40% by weight, of dipropylene glycol di(meth)acrylate, based in each case on the total weight of component (B).

[0079] Preference is therefore also given to a crosslinker mixture in which component (B) comprises

[0080] 50 to 90 wt % of diethylene glycol di(meth)acrylate and

[0081] 10 to 50% by weight of dipropylene glycol di(meth)acrylate,

[0082] In each case this is based on the total weight of component (B).

[0083] In one embodiment of the present invention, the weight percentage of diethylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate in component (B) is 100 wt %. In this embodiment, component (B) consists of diethylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate.

[0084] It is also possible that component (B) contains additional components. For example, component (B) contains diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate.

[0085] Preference is therefore also given to a crosslinker mixture, wherein the crosslinker mixture contains the following components: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate.

[0086] The crosslinker mixture therefore preferably contains

[0087] 25 to 50% by weight of ethylene glycol di(meth)acrylate,

[0088] 10 to 35% by weight of diethylene glycol di(meth)acrylate,

[0089] 0 to 2% by weight of triethylene glycol di(meth)acrylate,

[0090] 20 to 35% by weight of propylene glycol di(meth)acrylate,

[0091] 2 to 15 wt % of dipropylene glycol di(meth)acrylate and

[0092] 0 to 2% by weight of tripropylene glycol di(meth)acrylate,

[0093] In each case this is based on the total weight of the crosslinker mixture.

[0094] Also preferred is therefore a crosslinker mixture containing

[0095] 25 to 50% by weight of ethylene glycol di(meth)acrylate,

[0096] 10 to 35% by weight of diethylene glycol di(meth)acrylate,

[0097] 0 to 2% by weight of triethylene glycol di(meth)acrylate,

[0098] 20 to 35% by weight of propylene glycol di(meth)acrylate,

[0099] 2 to 15 wt % of dipropylene glycol di(meth)acrylate and

[0100] 0 to 2% by weight of tripropylene glycol di(meth)acrylate,

[0101] In each case this is based on the total weight of the crosslinker mixture.

[0102] The crosslinker mixture may additionally contain additional components. In particular, the crosslinker mixture may contain hydroxyalkyl (meth)acrylates in an amount of 0.1% to 5% by weight based on the total weight of the crosslinker mixture. The hydroxyalkyl (meth)acrylates may, for example, be derived from the preparation of the crosslinker mixture. The hydroxyalkyl (meth)acrylates derived from the preparation of the crosslinker mixture are, for example, the first hydroxyalkyl (meth)acrylate of the general formula (III) described further below and / or the second hydroxyalkyl (meth)acrylate of the general formula (IV) described further below.

[0103] The crosslinker mixture of the invention can be prepared by methods known to those skilled in the art. For example, the individual components of the crosslinker mixture are prepared separately from one another by esterification of (meth)acrylic acid with diols and / or propylene glycol and then mixed together.

[0104] The crosslinker mixture is preferably prepared by a process comprising the following steps a) to d):

[0105] a) reacting (meth)acrylic acid with at least one epoxide selected from ethylene oxide and propylene oxide in the presence of a first catalyst to obtain a hydroxyalkyl (meth)acrylate mixture, wherein the hydroxyalkyl (meth)acrylate mixture contains the following components (C) and (D) and a first catalyst:

[0106] (C) at least one first hydroxyalkyl (meth)acrylate of the general formula (III)

[0107]

[0108] in

[0109] R 1 is H or CH 3 ,and

[0110] R 2 is H or CH 3 ;

[0111] (D) at least one second hydroxyalkyl (meth)acrylate of the general formula (IV)

[0112]

[0113] in

[0114] R 4 is H or CH 3 ,

[0115] R 5 is H or CH 3 ,and

[0116] n is 2 or 3;

[0117] b) distilling the hydroxyalkyl (meth)acrylate mixture obtained in step a) to obtain a first top stream containing component (C) and a first bottom stream containing component (D) and residual component (C) and the first catalyst,

[0118] c) reacting the first bottom stream obtained in step b) with (meth)acrylic acid and / or (meth)acrylic acid C 1 -C 4 - reacting the alkyl ester in the presence of a second catalyst to obtain a mixture containing a crosslinking agent mixture and a first catalyst and a second catalyst,

[0119] d) distilling the mixture obtained in step c) to obtain a second top stream comprising the crosslinker mixture, and a second bottom stream comprising the first catalyst and the second catalyst.

[0120] The first catalyst in step a) is preferably selected from metal salts and organic compounds, the metals being each selected from chromium and iron and mixtures thereof. Such first catalysts are known per se.

[0121] The second catalyst in step c) is preferably selected from Bronsted acids and metal salts and organic compounds, the metals being each selected from tin, titanium, zirconium, alkali metals and alkaline earth metals, and mixtures thereof. Such second catalysts are known per se.

[0122] The process for producing a crosslinker mixture comprising steps a) to d) is particularly advantageous because the distillation residues obtained in the preparation of hydroxyalkyl (meth)acrylates (first bottom stream) can be further utilized. Purely thermal disposal of the distillation residues can thus be avoided.

[0123] The crosslinker mixture of the present invention can be used as a crosslinker. For example, the crosslinker mixture can be used as a crosslinker in a reactive resin.

[0124] The present invention therefore also provides a reactive resin comprising the following components

[0125] 0.1% to 30% by weight of the crosslinker mixture of the invention,

[0126] 20 to 80 wt% of (meth)acrylate monomers,

[0127] 0 to 40% by weight of a prepolymer,

[0128] 0.1 to 10% by weight of initiator or 0.1 to 5% by weight of accelerator, in each case based on the total weight of the reactive resin.

[0129] The crosslinker mixture present in the reactive resin applies correspondingly to the embodiments and preferences described above for the crosslinker mixture of the invention.

[0130] The reactive resin contains (meth)acrylate monomers. In the present invention, "(meth)acrylate monomers" refers to both exactly one (meth)acrylate monomer and a mixture of two or more different (meth)acrylate monomers.

[0131] The "(meth)acrylate monomer" in the present invention refers to acrylate monomers, methacrylate monomers and monomers copolymerizable therewith, such as 1-olefins and styrene. In addition, the term "(meth)acrylate monomer" also includes (meth)acrylic acid.

[0132] The (meth)acrylate monomer is therefore preferably selected from alkyl (meth)acrylates, (meth)acrylic acid, 1-olefins, styrene and mixtures thereof.

[0133] If the (meth)acrylate monomer contains a monomer copolymerizable with an acrylate monomer or a methacrylate monomer, it is preferred that the (meth)acrylate monomer contains a mixture of a copolymerizable monomer and an acrylate monomer or a methacrylate monomer.

[0134] Preference is therefore also given to reactive resins in which the (meth)acrylate monomer is selected from the group consisting of alkyl (meth)acrylates, (meth)acrylic acid, 1-olefins, styrenes and mixtures thereof.

[0135] "(Meth) acrylate alkyl ester" in the present invention refers to both acrylate alkyl ester and methacrylate alkyl ester. 1 -C 18 -alkyl ester. "(Meth)acrylic acid C 1 -C 18 "-alkyl ester" refers to an alkyl ester of (meth)acrylic acid having 1 to 18 carbon atoms in the alkyl group. The alkyl group may be linear, cyclic and / or branched. In addition, it may contain an aromatic group. For example, the alkyl (meth)acrylate of the present invention is selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isopentyl (meth)acrylate, octadecyl (meth)acrylate, benzyl (meth)acrylate and dodecyl (meth)acrylate.

[0136] The term "(meth)acrylic acid" in the present invention includes acrylic acid and methacrylic acid.

[0137] 1-Olefins copolymerizable with methacrylate monomers and / or acrylate monomers are known per se and are, for example, 1-hexene, 1-heptene, vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene and 4-methyl-1-pentene.

[0138] The term "styrenes" in the present invention refers not only to styrene itself but also to substituted styrenes such as α-methylstyrene, α-ethylstyrene, vinyltoluene, p-methylstyrene, monochlorostyrene, dichlorostyrene and tribromostyrene.

[0139] According to the invention, the reactive resin contains 20% to 80% by weight, preferably 45% to 75% by weight, of (meth)acrylate monomers, based in each case on the total weight of the reactive resin.

[0140] The term "prepolymer" refers to exactly one prepolymer or a mixture of two or more prepolymers.

[0141] The “prepolymer” in the present invention has a weight average molecular weight in the range of 1000 to 80 000 g / mol, preferably in the range of 25 000 to 70 000 g / mol, as determined by GPC using PMMA as a standard.

[0142] Suitable prepolymers are selected, for example, from polyalkyl (meth)acrylates, polyesters, polyurethane (meth)acrylates and mixtures thereof.

[0143] Preference is therefore also given to reactive resins in which the prepolymer is selected from polyalkyl(meth)acrylates, polyesters, polyurethane(meth)acrylates and mixtures thereof.

[0144] "Polyalkyl (meth)acrylate" in the present invention refers to polymers and copolymers of alkyl (meth)acrylate as described above.

[0145] Suitable polyesters are known per se and are preferably obtainable by polycondensation or ring-opening polymerization.

[0146] "Polyurethane (meth)acrylates" in the context of the present invention are (meth)acrylates which are linked to one another via urethane groups. They can be obtained by reacting hydroxyalkyl (meth)acrylates with polyisocyanates and polyoxyalkylenes having at least two hydroxyl functions. Instead of hydroxyalkyl (meth)acrylates, it is also possible to use esters of (meth)acrylic acid with alkylene oxides, for example ethylene oxide or propylene oxide, or the corresponding oligomeric or polyalkylene oxides. Suitable polyurethane (meth)acrylates are known per se.

[0147] The reactive resin contains 0% to 40% by weight, preferably 5% to 30% by weight, of prepolymer, based on the total weight of the reactive resin.

[0148] The reactive resin of the present invention contains an initiator or an accelerator. In the present invention, "initiator or accelerator" means that the reactive resin preferably contains only an initiator without an accelerator, or that the reactive resin contains only an accelerator without an initiator.

[0149] The reactive resin preferably contains only accelerators. It is therefore preferred that the reactive resin does not contain any initiators.

[0150] "Initiator" in the context of the present invention means exactly one initiator or a mixture of two or more different initiators. According to the present invention, exactly one initiator is preferred.

[0151] Suitable initiators are all compounds known to the person skilled in the art that are capable of initiating free radical polymerization of (meth)acrylate monomers. For example, the at least one initiator is selected from peroxides, azo compounds and persulfates. The initiator is preferably selected from peroxides and azo compounds.

[0152] Preference is therefore also given to reactive resins in which the initiator is selected from peroxides and azo compounds.

[0153] Suitable peroxides are, for example, selected from hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, acetylacetone peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroctoate, tert-butyl per-2-ethylhexanoate, tert-butyl perneodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perbenzoate, di(tert-amyl) peroxide (DTAP), tert-butyl peroxy(2-ethylhexyl)carbonate (TBPEHC), diisopropyl peroxydicarbonate and bis(4-tert-butylcyclohexyl) peroxydicarbonate.

[0154] Suitable azo compounds are selected, for example, from 2,2-azobisiso-2,4-dimethylvaleronitrile, 2,2-azobisisobutyronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2-(carbamoylazo)isobutyronitrile and 4,4′-azobis(cyanovaleric acid).

[0155] Suitable persulfates are, for example, selected from lithium peroxodisulphate, sodium peroxodisulphate, potassium peroxodisulphate and ammonium peroxodisulphate.

[0156] For example, the reactive resin contains 0.1% to 10% by weight, preferably 1% to 5% by weight, of initiator, based on the total weight of the reactive resin.

[0157] As mentioned above, in a preferred embodiment of the present invention, the reactive resin does not contain any initiator.

[0158] "Accelerator" in the context of the present invention means exactly one accelerator or a mixture of two or more different accelerators. Exactly one accelerator is preferred.

[0159] The accelerators used may be compounds known to the person skilled in the art which accelerate the curing of reactive resins. Suitable accelerators are, for example, symmetrical tertiary aromatic amines, unsymmetrical tertiary aromatic amines and / or phosphites.

[0160] Suitable symmetrical tertiary aromatic amines are, for example, selected from N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine and N,N-bis(2-hydroxypropyl)-p-toluidine.

[0161] Suitable asymmetric amines are, for example, selected from N-methyl-N-(hydroxyethyl)-p-toluidine, N-methyl-N-(hydroxyethyl)-m-toluidine, N-methyl-N-(hydroxypropyl)-p-toluidine, N-methyl-N-(hydroxyethyl)xylidine, N-methyl-N-(hydroxypropyl)xylidine, N-methyl-N-(hydroxyethyl)aniline and N-methyl-N-(hydroxypropyl)aniline.

[0162] Suitable phosphites are, for example, selected from the group consisting of tri-2-ethylhexyl phosphite, tri-2-ethylhexyl trithiophosphite, tri-isooctyl phosphite, tri-isooctyl trithiophosphite, tridecyl phosphite, tridecyl trithiophosphite, trilauryl phosphite, trilauryl trithiophosphite, trioctadecyl phosphite, trioctadecyl trithiophosphite, phenyl didecyl phosphite, phenyl didecyl trithiophosphite, phenyl dilauryl phosphite, phenyl distearyl phosphite, phenyl distearyl trithiophosphite, diphenyl decyl phosphite, diphenyl lauryl phosphite, diphenyl stearyl phosphite, diphenyl stearyl trithiophosphite, trimetyl ... Ester, triethoxyethyl phosphite, tributoxyethyl phosphite, tritetrahydrofurfuryl phosphite, tritetrahydrofurfuryl trithiophosphite, triphenylethyl phosphite, S-phenyl dilauryl monothiophosphite, S-phenyl didecyl monothiophosphite, SS-diphenyllauryl dithiophosphite, SS-diphenyldecyl dithiophosphite, tri-o-naphthyl phosphite, SS-diphenyldecyl dithiophosphite, phenyl dilauryl trithiophosphite, tridodecylphenyl phosphite, trichlorophenyl phosphite, diphenyllauryl trithiophosphite, S-lauryl diphenyl monothiophosphite, tri-p-methoxyphenyl phosphite, SO-diphenyl S-lauryl dithiophosphite, tri-o-methoxyphenyl dithiophosphite, SS-dilaurylphenyl dithiophosphite and SO-dilauryl S-phenyl dithiophosphite.

[0163] For example, the reactive resin contains 0.1% to 5% by weight, preferably 0.5% to 3% by weight, of accelerator, in each case based on the total weight of the reactive resin.

[0164] The reactive resins according to the invention can be used, for example, in 2K systems.

[0165] The present invention therefore also provides a 2K system which comprises the reactive resin according to the invention as a first component and a hardener component as a second component.

[0166] The first component (the reactive resin of the invention) is applicable to the embodiments and preferences described above.

[0167] The second component (curing agent component) initiates and / or accelerates the polymerization of at least the (meth)acrylate monomers present in the reactive resin when mixed with the first component (reactive resin).

[0168] The curing agent component thus contains an accelerator or an initiator. Typically, the curing agent component contains an accelerator when the reactive resin contains an initiator. When the reactive resin contains an accelerator, the curing agent component contains an initiator.

[0169] The embodiments and preferences described above for the initiators present in the reactive resin apply correspondingly to the initiators present in the hardener component.

[0170] For example, the hardener component contains 0.1% to 10% by weight, preferably 1% to 5% by weight, of initiator, based on the total weight of the reactive resins present in the 2K system.

[0171] The embodiments and preferences described above for the accelerators present in the reactive resin apply correspondingly to the accelerators present in the hardener component.

[0172] For example, the hardener component contains 0.1% to 5% by weight, preferably 0.5% to 3% by weight, of accelerator, based in each case on the total weight of the reactive resins present in the 2K system.

[0173] The curing agent component may consist of an initiator or an accelerator. In this case, the reactive resin preferably does not contain the components constituting the curing agent component.

[0174] It is further possible that, in addition to initiators or accelerators, the curing agent component may also contain additional components, such as colorants and / or fillers and / or auxiliaries and additives mentioned further below. It is preferred according to the invention that the curing agent component is substantially free of (meth)acrylate monomers.

[0175] For example, the 2K system comprises 50 wt % to 99.9 wt % of the first component and 0.1 wt % to 50 wt % of the second component.

[0176] According to the invention, the first component in the 2K system, i.e. the reactive resin, contains an accelerator. In this case, the second component, i.e. the curing agent component, contains an initiator. In this embodiment, the reactive resin preferably does not contain any initiator. In this case, the curing agent component preferably does not contain any accelerator.

[0177] Preference is therefore also given to 2K systems in which the reactive resin comprises an accelerator and the hardener component comprises an initiator.

[0178] The 2K system may also contain colorants and / or fillers. For example, based on the total weight of the 2K system, the 2K system contains colorants and / or fillers in the range of 0 wt % to 90 wt %, preferably in the range of 5 wt % to 50 wt %.

[0179] Particularly suitable colorants are, for example, white, red, blue, green and / or yellow inorganic pigments. Particularly preferred are white inorganic pigments such as titanium dioxide.

[0180] The filler is in particular a mineral filler. The mineral filler is preferably selected from the group consisting of calcium carbonate, barium sulfate, quartz, quartz powder, precipitated silica, fumed silica, corundum, glass beads and cristobalite.

[0181] The 2K system may additionally contain auxiliaries and additives. For example, the 2K system contains auxiliaries and additives in the range of 0.1% to 5% by weight, based on the total weight of the 2K system. The auxiliaries and additives for 2K systems are known per se and are selected, for example, from chain transfer agents, plasticizers, paraffins, stabilizers, inhibitors, waxes and oils.

[0182] For example, paraffin wax is added to prevent oxygen from the air from inhibiting polymerization. It is possible to use two or more paraffin waxes with different melting points in different concentrations for this purpose.

[0183] The chain transfer agent used may be any compound known in free-radical polymerization. Preference is given to using mercaptans such as n-dodecyl mercaptan, and polyfunctional mercapto compounds such as pentaerythritol tetrathioglycolate.

[0184] Plasticizers used are preferably esters, polyols, oils, low molecular weight polyethers or phthalates.

[0185] Useful stabilizers are in particular UV stabilizers. The UV stabilizers are preferably selected from benzophenone derivatives, benzotriazole derivatives, thioxanthonate derivatives, piperidinol carboxylate derivatives and cinnamate derivatives.

[0186] Among the inhibitors, preference is given to using substituted phenols, hydroquinone derivatives, phosphines and phosphites.

[0187] In order to use a 2K system, a first component (reactive resin) and a second component (curing agent component) are mixed with one another. After the first component has been mixed with the second component, the 2K system generally has only a limited open time, for example 2 to 40 minutes, available for use, for example for application, pouring, coating or filling. Thereafter, the 2K system is generally cured. The term "open time" therefore refers according to the invention to the time period between the mixing of the first component with the second component and the curing of the 2K system. The open time therefore corresponds to the time during which the 2K system can be processed. The open time is also referred to as the pot life.

[0188] The 2K systems of the invention and / or the reactive resins of the invention can be used, for example, in floor coatings, chemical anchors, cable potting compounds and / or road markings.

[0189] The present invention is explained in detail below by way of examples, but the present invention is not limited thereto. DETAILED DESCRIPTION

[0190] Example

[0191] Curing experiments using different crosslinkers

[0192] For curing, 2% by weight of a curing agent component (50% dibenzoyl peroxide (BPO) in dicyclohexyl phthalate) were admixed to a reactive resin containing the components specified in Table 1 and 5% by weight of a crosslinker specified in Table 2, stirred for 2 minutes and then applied to a metal surface in a layer thickness of approximately 2 mm or poured into the test cup described below.

[0193] Table 1:

[0194]

[0195] Table 2:

[0196]

[0197] Table 3:

[0198] Composition of the crosslinking agent mixture of the present invention [GC area %] Ethylene glycol dimethacrylate 32.82 Diethylene glycol dimethacrylate 26.93 Triethylene glycol dimethacrylate 0.52 1,2-Propanediol dimethacrylate 28.11 Dipropylene glycol dimethacrylate, sum of isomers 8.69 Tripropylene glycol dimethacrylate, sum of isomers 0.13 Other ingredients 2.80

[0199] To determine the pot life (TZ), the time required for the resulting 2K system to warm from room temperature (20-22° C.) to 32° C. by itself after stirring in the hardener component is measured. For this purpose, 20 g of the 2K system described above are prepared in a plastic container.

[0200] The temperature maximum (Tmax) was determined by measuring the time required for 20 g of the resulting 2K system to reach the temperature maximum during the curing process in a PE beaker with a diameter of 45 mm.

[0201] The time taken until the surface test (O-test) is passed is determined as the time at which the surface of the layer cast with a thickness of 2 mm has cured and is no longer tacky. The time begins with the stirring addition of the hardener component to the reactive resin; it is stopped as soon as the cast layer is no longer tacky when in contact with a gloved finger.

[0202] The mechanical properties (tensile modulus, tensile strength, stress at break, elongation at break) were determined in accordance with DIN EN ISO 527:2019 at 23° C. by casting the corresponding reactive resins into test specimens. The results are shown in Table 4.

[0203] Table 4:

[0204]

[0205] Mechanical properties comparable to those of 1,4-BDDMA are achieved by the crosslinker mixture according to the invention. Compared to EGDMA, even improved mechanical properties are achieved. In particular, the tensile modulus was found to be particularly high in a comparison of the crosslinking experiments.

[0206] The use of the crosslinker mixture according to the invention not only achieves comparable mechanical properties, but the crosslinker mixture according to the invention is also cheaper in its production than, for example, 1,4-BDDMA and EGDMA.

Claims

1. A crosslinker mixture for reactive resins, wherein the crosslinker mixture contains the following components (A) and (B): (A) at least one first di(meth)acrylate diester of the general formula (I) in R 1 is H or CH3, R 2 is H or CH3, and R 3 is H or CH3; (B) at least one second di(meth)acrylate diester of the general formula (II) in R 4 is H or CH3, R 5 is H or CH3, R 6 is H or CH3, and n is 2 or 3.

2. The crosslinking agent mixture according to claim 1, characterized in that The crosslinking agent mixture contains 50 to 90 wt% of component (A) and 10 to 50 wt. % of component (B), In each case this is based on the total weight of the crosslinker mixture.

3. The crosslinking agent mixture according to claim 1 or 2, characterized in that Component (A) comprises ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate.

4. The crosslinking agent mixture according to claim 3, characterized in that Component (A) comprises 30 to 80 wt% of ethylene glycol di(meth)acrylate and 20 to 70% by weight of propylene glycol di(meth)acrylate, In each case this is based on the total weight of component (A).

5. The crosslinking agent mixture according to any one of claims 1 to 4, characterized in that Component (B) comprises diethylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate.

6. The crosslinking agent mixture according to claim 5, characterized in that Component (B) comprises 50 to 90 wt % of diethylene glycol di(meth)acrylate and 10 to 50% by weight of dipropylene glycol di(meth)acrylate, In each case this is based on the total weight of component (B).

7. The crosslinker mixture according to any one of claims 1 to 6, characterized in that The crosslinking agent mixture contains the following components: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate.

8. The crosslinking agent mixture according to claim 7, characterized in that The crosslinking agent mixture contains 25 to 50% by weight of ethylene glycol di(meth)acrylate, 10 to 35% by weight of diethylene glycol di(meth)acrylate, 0 to 2% by weight of triethylene glycol di(meth)acrylate, 20 to 35% by weight of propylene glycol di(meth)acrylate, 2 to 15 wt % of dipropylene glycol di(meth)acrylate and 0 to 2% by weight of tripropylene glycol di(meth)acrylate, In each case this is based on the total weight of the crosslinker mixture.

9. A reactive resin comprising the following components: 0.1% to 30% by weight of a crosslinker mixture according to any one of claims 1 to 8, 20 to 80% by weight of (meth)acrylate monomers, 0 to 40% by weight of a prepolymer, 0.1 to 10% by weight of initiator or 0.1 to 5% by weight of accelerator, in each case based on the total weight of the reactive resin.

10. The reactive resin according to claim 9, characterized in that The prepolymer is selected from the group consisting of polyalkyl (meth)acrylates, polyesters, polyurethane (meth)acrylates and mixtures thereof.

11. The reactive resin according to claim 9 or 10, characterized in that The (meth)acrylate monomer is selected from the group consisting of alkyl (meth)acrylates, (meth)acrylic acid, 1-olefins, styrenes, and mixtures thereof. 12 . A two-component system comprising the reactive resin according to claim 9 as a first component and a curing agent component as a second component.

13. The two-component system according to claim 12, characterized in that The reactive resin contains an accelerator, and the curing agent component contains an initiator.

14. Use of the reactive resin according to any one of claims 9 to 11 or the two-component system according to claim 12 or 13 for floor coatings, chemical anchors, cable potting compounds and / or road markings.

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