Terminally unsaturated (METH)acrylate crosslinkers and use thereof

Abstract

The present 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 which contains the claimed crosslinker mixture, and to a two-component system which comprises the reactive resin and a curing 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

[0001] Terminally unsaturated (meth)acrylate crosslinkers and their use

[0002] Description

[0003] Field of the invention

[0004] The present 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. Furthermore, the invention relates to a reactive resin containing the crosslinker mixture according to the invention, as well as to a two-component system comprising the reactive resin and a curing agent component.

[0005] The invention also relates to the use of the reaction resin and / or the 2K system, for example for floor coatings and / or road markings.

[0006] State of the art

[0007] The use of crosslinkers in reactive resins is known from the state of the art.

[0008] For example, EP 2 054 453 B1 describes a (meth)acrylate resin that may contain a crosslinker in addition to various (meth)acrylate monomers and polymers. However, the document does not describe mixtures of crosslinkers.

[0009] EP 3 929245 A1 describes a two-component (meth)acrylate-based reactive resin containing monomers and, optionally, a crosslinker. This document also does not describe mixtures of crosslinkers.

[0010] WO 2020 / 035561 describes the preparation of a di(meth)acrylate diester by reacting a (meth)acrylic anhydride with an epoxide in the presence of a catalyst and a chromium-containing co-catalyst. This document does not describe a mixture of crosslinkers or their use in a reactive resin.

[0011] The crosslinkers described in the prior art are already suitable as crosslinkers for reactive resins. However, the crosslinkers described in the prior art are often complex and costly to produce, making the crosslinkers themselves expensive.

[0012] Task

[0013] There is therefore a need for alternative crosslinkers for use in reactive resins, as well as for reactive resins containing these crosslinkers and two-component systems comprising the reactive resins. These alternative crosslinkers should be more cost-effective to produce than the crosslinkers described in the prior art, and cured reactive resins produced from them should exhibit at least comparable mechanical properties to those described in the prior art.

[0014] Solution

[0015] This task is solved by a crosslinking mixture for reaction resins, whereby the

[0016] Crosslinker mixture containing the following components (A) and (B):

[0017] (A) at least one first di(meth)acrylate diester of the general formula (I) in the

[0018] R 1 H or CH3,

[0019] R 2 H or CH3, and

[0020] R 3 H or CH3;

[0021] (B) at least one second di(meth)acrylate diester of the general formula (II) in the

[0022] R 4 H or CH3,

[0023] R 5 H or CH3,

[0024] R e H or CH3, and n is 2 or 3.

[0025] Furthermore, this task is solved by a reaction resin containing the following components:

[0026] 0.1 to 30 wt.% of the crosslinking mixture according to any one of claims 1 to 8,

[0027] 20 to 80 wt.% of a (meth)acrylate monomer,

[0028] 0 to 40 wt.% prepolymers, either 0.1 to 10 wt.% of an initiator or 0.1 to 5 wt.% of an accelerator, each based on the total weight of the reaction resin.

[0029] Furthermore, this object is achieved by a two-component system comprising the reaction resin according to the invention as the first component and a hardener component as the second component. The present invention further relates to the use of the reaction resin according to the invention or the two-component system according to the invention for floor coatings, chemical anchors, cable casting compounds, and / or road markings.

[0030] It has surprisingly been found that the crosslinker mixture according to the invention can be used in reactive resins. Reactive resins containing the crosslinker mixture according to the invention exhibit similarly good mechanical properties after curing as reactive resins containing crosslinkers described in the prior art. In particular, their elongation at break and tensile strength are comparable. At the same time, the crosslinker mixture according to the invention is easier and more cost-effective to produce than crosslinkers described in the prior art. This makes the reactive resins according to the invention more economical.

[0031] A reaction resin containing the crosslinking mixture according to the invention also has a good pot life and curing time.

[0032] Surprisingly, it was also found that for the crosslinker mixture according to the invention, a smaller density difference between monomer and polymer is found than for crosslinkers described in the prior art, such as, for example, ethylene glycol dimethacrylate or 1,4-butanediol dimethacrylate.

[0033] The invention is explained in more detail below.

[0034] The crosslinking mixture according to the invention contains components (A) and (B).

[0035] For example, the crosslinker mixture contains in the range of 50 to 90 wt.% of component (A), preferably in the range of 60 to 80 wt.%, in each case based on the total weight of the crosslinker mixture.

[0036] The crosslinker mixture contains, for example, in the range of 10 to 50 wt.% of component (B), preferably in the range of 20 to 40 wt.%, in each case based on the total weight of the crosslinker mixture.

[0037] Therefore, a crosslinker mixture containing 50 to 90 wt.% of component (A) and 10 to 50 wt.% of component (B), based in each case on the total weight of the crosslinker mixture, is also preferred. The wt.% of components (A) and (B) of the crosslinker mixture preferably add up to 100 wt.%. It is therefore preferred that the crosslinker mixture consists essentially of components (A) and (B).

[0038] It goes without saying that the wt. % of components (A) and (B) refer to the wt. % before the crosslinker mixture has reacted with itself or in a reactive resin. It is clear to those skilled in the art that the composition of the crosslinker mixture may change due to reaction with itself or in a reactive resin.

[0039] Component (A) is at least one first di(meth)acrylate diester of the general formula (I) in the

[0040] R 1 H or CH3,

[0041] R 2H or CH3, and

[0042] R 3 H or CH3.

[0043] For the purposes of the present invention, the term “di(meth)acrylate diester” refers to both dimethacrylate diesters and diacrylate diesters. For example, R 2 and R 3 in formula (I) H, the first di(meth)acrylate diester is a first diacrylate diester. For example, if R 2 and R 3 in formula (I) CH3, the first di(meth)acrylate diester is a first dimethacrylate diester.

[0044] Component (A) is at least one first di(meth)acrylate diester of the general formula (I). The term "at least one first di(meth)acrylate diester" encompasses, within the context of the present invention, both precisely one first di(meth)acrylate diester and 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.

[0045] If in the general formula (I) R 1 H, the first di(meth)acrylate diester is ethyl glycol di(meth)acrylate. Ethylene glycol di(meth)acrylate is also called 1,2-ethanediol di(meth)acrylate.

[0046] If in the general formula (I) R 1 CH3, the first di(meth)acrylate diester is propylene glycol di(meth)acrylate. Propylene glycol di(meth)acrylate is also referred to as 1,2-propanediol di(meth)acrylate. As stated above, component (A) is preferably a mixture of two or more first di(meth)acrylate diesters. Therefore, component (A) preferably comprises ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate.

[0047] Therefore, a crosslinker mixture in which component (A) comprises ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate is also preferred.

[0048] For example, component (A) comprises in the range of 30 to 80 wt.% ethylene glycol di(meth)acrylate, preferably in the range of 50 to 70 wt.%, in each case based on the total weight of component (A).

[0049] For example, component (A) comprises in the range of 20 to 70 wt.% propylene glycol di(meth)acrylate, preferably in the range of 30 to 50 wt.%, in each case based on the total weight of component (A).

[0050] Therefore, a crosslinking mixture is preferred in which component (A)

[0051] 30 to 80 wt.% ethylene glycol di(meth)acrylate and

[0052] 20 to 70 wt.% propylene glycol di(meth)acrylate, each based on the total weight of component (A).

[0053] Preferably, the sum of the wt. % of ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate in component (A) is 100 wt. %. More preferably, component (A) consists of ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate.

[0054] R 2 and R 3 in formula (I) may be the same or different. If R 2 and R 3 in formula (I), component (A) is at least a first symmetrical di(meth)acrylate diester. If R 2 and R 3 in formula (I), component (A) is at least a first asymmetric di(meth)acrylate diester.

[0055] Component (B) is at least one second di(meth)acrylate diester of the general formula (II) ,

[0056] R e H or CH3, and n is 2 or 3.

[0057] Component (B) is at least one second di(meth)acrylate diester of the general formula (II). The term "at least one second di(meth)acrylate diester" within the scope of the present invention encompasses both precisely one second di(meth)acrylate diester and 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.

[0058] If in formula (II) R 4 H, the second di(meth)acrylate diester is usually diethylene glycol di(meth)acrylate and / or triethylene glycol di(meth)acrylate. When in formula (II) R 4 CH3, the second di(meth)acrylate diester is usually dipropylene glycol di(meth)acrylate and / or tripropylene glycol di(meth)acrylate. When in formula (II) R 4CH3, then in the context of the present invention, formula (II) and the terms dipropylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate also include the corresponding isomers.

[0059] It goes without saying that when n is 2 in formula (II), component (B) typically comprises diethylene glycol di(meth)acrylate and / or dipropylene glycol di(meth)acrylate. When n is 3 in formula (II), component (B) typically comprises triethylene glycol di(meth)acrylate and / or tripropylene glycol di(meth)acrylate.

[0060] R 5 and R e in formula (II) may be the same or different. If R 5 and R e in formula (II) is the same, then component (B) is at least a second symmetrical di(meth)acrylate diester. If R 5 and R e in formula (II), component (B) is at least a second asymmetric di(meth)acrylate diester.

[0061] As stated above, component (B) is preferably a mixture of two or more second di(meth)acrylate diesters. Therefore, component (B) preferably comprises diethylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate.

[0062] Therefore, a crosslinker mixture in which component (B) comprises diethylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate is also preferred.

[0063] Component (B) comprises, for example, 50 to 90 wt.%, preferably in the range of 60 to 80 wt.%, of diethylene glycol di(meth)acrylate, in each case based on the total weight of component (B).

[0064] Component (B) comprises, for example, 10 to 50 wt.%, preferably in the range of 20 to 40 wt.%, of dipropylene glycol di(meth)acrylate, based in each case on the total weight of component (B). Therefore, a crosslinker mixture in which component (B)

[0065] 50 to 90 wt.% diethylene glycol di(meth)acrylate and

[0066] 10 to 50 wt.% dipropylene glycol di(meth)acrylate, in each case based on the total weight of component (B).

[0067] In one embodiment of the present invention, the wt. % of diethylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate in component (B) add up to 100 wt. %. In this embodiment, component (B) consists of diethylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate.

[0068] It is also possible for component (B) to comprise other components. For example, component (B) comprises diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate.

[0069] Therefore, a crosslinker mixture is also preferred in which 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.

[0070] The crosslinking mixture therefore preferably contains

[0071] 25 to 50 wt.% ethylene glycol di(meth)acrylate,

[0072] 10 to 35 wt.% diethylene glycol di(meth)acrylate,

[0073] 0 to 2 wt.% triethylene glycol di(meth)acrylate,

[0074] 20 to 35 wt.% propylene glycol di(meth)acrylate,

[0075] 2 to 15 wt.% dipropylene glycol di(meth)acrylate and

[0076] 0 to 2 wt.% tripropylene glycol di(meth)acrylate, each based on the total weight of the crosslinker mixture.

[0077] Therefore, a crosslinking mixture is preferred which

[0078] 25 to 50 wt.% ethylene glycol di(meth)acrylate,

[0079] 10 to 35 wt.% diethylene glycol di(meth)acrylate,

[0080] 0 to 2 wt.% triethylene glycol di(meth)acrylate,

[0081] 20 to 35 wt.% propylene glycol di(meth)acrylate,

[0082] 2 to 15 wt.% dipropylene glycol di(meth)acrylate and

[0083] 0 to 2 wt.% tripropylene glycol di(meth)acrylate, based in each case on the total weight of the crosslinker mixture. The crosslinker mixture may further contain other components. In particular, the crosslinker mixture may contain in the range of 0.1 to 5 wt.% hydroxyalkyl (meth)acrylate, based on the total weight of the crosslinker mixture. The hydroxyalkyl (meth)acrylate may, for example, originate from the preparation of the crosslinker mixture. Hydroxyalkyl (meth)acrylates originating from the preparation of the crosslinker mixture are, for example, the first hydroxyalkyl (meth)acrylate of the general formula (III) described below and / or the second hydroxyalkyl (meth)acrylate of the general formula (IV) described below.

[0084] The crosslinker mixture according to 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 by esterifying (meth)acrylic acid with glycol and / or propylene glycol and then mixed together.

[0085] Preferably, the crosslinker mixture is prepared by a process comprising the following steps a) to d): a) reacting (meth)acrylic acid with at least one epoxide selected from the group consisting of 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 the first catalyst:

[0086] (C) at least one first hydroxyalkyl (meth)acrylate of the general formula (III) (St.), in the

[0087] R 1 H or CH3, and

[0088] R 2 H or CH3;

[0089] (D) at least one second hydroxyalkyl (meth)acrylate of the general formula (IV) in the

[0090] R 4 H or CH3, R 5H or CH3, and n is 2 or 3; 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 residues of component (C) and also the first catalyst, c) reacting the first bottom stream obtained in step b) with (meth)acrylic acid and / or a Ci-C4-alkyl (meth)acrylate in the presence of a second catalyst to obtain a mixture containing the crosslinker mixture and the first catalyst and the second catalyst, d) distilling the mixture obtained in step c) to obtain a second top stream containing the crosslinker mixture and a second bottom stream containing the first catalyst and the second catalyst.

[0091] The first catalyst in step a) is preferably selected from the group consisting of metal salts and organic compounds, each of which is selected from the group consisting of chromium and iron, and mixtures thereof. Such first catalysts are known per se.

[0092] The second catalyst in step c) is preferably selected from the group consisting of Brönsted acids and metal salts and organic compounds, each of metals selected from the group consisting of tin, titanium, zirconium, alkali metals and

[0093] Alkaline earth metals and mixtures thereof. Such second catalysts are known as such.

[0094] The process comprising steps a) to d) for preparing the crosslinker mixture is particularly advantageous because the distillation residue (the first bottom stream) obtained during the production of hydroxyalkyl (meth)acrylates can be reused. This avoids purely thermal disposal of the distillation residue.

[0095] The crosslinker mixture according to the invention can be used as a crosslinker. For example, the crosslinker mixture can be used as a crosslinker in a reactive resin.

[0096] The present invention therefore also relates to a reaction resin containing the following components

[0097] 0.1 to 30 wt.% of the crosslinking mixture according to the invention,

[0098] 20 to 80 wt.% of a (meth)acrylate monomer,

[0099] 0 to 40 wt.% prepolymers, either 0.1 to 10 wt.% of an initiator or 0.1 to 5 wt.% of an accelerator, each based on the total weight of the reaction resin.

[0100] The previously described explanations and preferences for the crosslinker mixture according to the invention apply accordingly to the crosslinker mixture contained in the reactive resin. The reactive resin contains a (meth)acrylate monomer. In the context of the present invention, "a (meth)acrylate monomer" is understood to mean both precisely one (meth)acrylate monomer and a mixture of two or more different (meth)acrylate monomers.

[0101] For the purposes of the present invention, "(meth)acrylate monomers" are understood to mean acrylate monomers, methacrylate monomers, and monomers copolymerizable with these, such as 1-alkenes and styrene. Furthermore, the term "(meth)acrylate monomers" also includes (meth)acrylic acid.

[0102] The (meth)acrylate monomer is therefore preferably selected from the group consisting of alkyl (meth)acrylates, (meth)acrylic acid, 1-alkenes, styrene and mixtures thereof.

[0103] If the (meth)acrylate monomer comprises a monomer copolymerizable with acrylate monomers or methacrylate monomers, it is preferred that the (meth)acrylate monomer then comprises a mixture of the copolymerizable monomer and an acrylate monomer or methacrylate monomer.

[0104] Therefore, a reaction resin in which the (meth)acrylate monomer is selected from the group consisting of alkyl (meth)acrylates, (meth)acrylic acid, 1-alkenes, styrene and mixtures thereof is also preferred.

[0105] For the purposes of the present invention, "alkyl (meth)acrylates" refers to both alkyl acrylates and alkyl methacrylates. C1-C18 alkyl (meth)acrylates are preferred. C1-C18 alkyl (meth)acrylates are understood to mean alkyl esters of (meth)acrylic acid which have 1 to 18 carbon atoms in the alkyl radical. The alkyl radical can be linear, cyclic, and / or branched. In addition, it can contain aromatic radicals. For example, alkyl (meth)acrylates according to the invention are selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isopentyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, and lauryl (meth)acrylate.

[0106] In the context of the present invention, the term “(meth)acrylic acid” encompasses both acrylic acid and methacrylic acid.

[0107] 1-Alkenes that can copolymerize with methacrylate monomers and / or acrylate monomers are known as such and include, for example, 1-hexene, 1-heptene, vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, and 4-methylpentene-1. In the context of the present invention, the term "styrene" refers not only to styrene as such, but also to substituted styrenes such as, for example, a-methylstyrene, a-ethylstyrene, vinyltoluene, p-methylstyrene, monochlorostyrenes, dichlorostyrenes, and tribromostyrenes.

[0108] According to the invention, the reaction resin contains 20 to 80% by weight, preferably 45 to 75% by weight, of the (meth)acrylate monomer, in each case based on the total weight of the reaction resin.

[0109] The term “prepolymers” refers to both one prepolymer and a mixture of two or more prepolymers.

[0110] A “prepolymer” in the sense of the present invention has a weight-average molecular weight in the range from 1,000 g / mol to 80,000 g / mol, preferably in the range from 25,000 g / mol to 70,000 g / mol, determined by GPC with PMMA as standard.

[0111] Suitable prepolymers are, for example, selected from the group consisting of polyalkyl (meth)acrylates, polyesters, polyurethane (meth)acrylates and mixtures thereof.

[0112] Therefore, a reaction resin in which the prepolymers are selected from the group consisting of polyalkyl (meth)acrylates, polyesters, polyurethane (meth)acrylates and mixtures thereof is also preferred.

[0113] For the purposes of the present invention, “polyalkyl(meth)acrylates” are understood to mean polymers and copolymers of alkyl(meth)acrylates as described above.

[0114] Suitable polyesters are known as such and are preferably available via polycondensation or ring-opening polymerization.

[0115] For the purposes of the present invention, "polyurethane (meth)acrylates" are (meth)acrylates linked to one another via urethane groups. They are obtainable by reacting hydroxyalkyl (meth)acrylates with polyisocyanates and polyoxyalkylenes containing at least two hydroxy functionalities. Instead of hydroxyalkyl (meth)acrylates, esters of (meth)acrylic acid with oxiranes, such as ethylene oxide or propylene oxide, or corresponding oligooxiranes or polyoxiranes can also be used. Suitable polyurethane (meth)acrylates are known per se.

[0116] The reaction resin contains 0 to 40 wt.%, preferably 5 to 30 wt.% prepolymers, based on the total weight of the reaction resin.

[0117] The reaction resin according to the invention contains either an initiator or an accelerator.

[0118] In the context of the present invention, “either an initiator or an accelerator” means that preferably the reaction resin contains only the initiator and no accelerator or the reaction resin contains only an accelerator and no initiator.

[0119] Preferably, the reaction resin contains only the accelerator. It is therefore preferable that the reaction resin does not contain an initiator.

[0120] In the context of the present invention, "one initiator" means both exactly one initiator and a mixture of two or more different initiators. Exactly one initiator is preferred according to the invention.

[0121] Suitable initiators include all compounds known to the person skilled in the art that can initiate radical polymerization of the (meth)acrylate monomer. For example, the at least one initiator is selected from the group consisting of peroxides, azo compounds, and persulfates. Preferably, the initiator is selected from the group consisting of peroxides and azo compounds.

[0122] Therefore, a reaction resin in which the initiator is selected from the group consisting of peroxides and azo compounds is also preferred.

[0123] Suitable peroxides are, for example, selected from the group consisting of hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxodicarbonate, dilauryl peroxide, methyl ethyl ketone peroxide, acetylacetone peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroctanoate, tert-butyl per-2-ethylhexanoate, tert-butyl perneodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perbenzoate, di(tert-amyl)peroxide (DTAP), tert-butylperoxy-(2-ethylhexyl)carbonate (TBPEHC), dicumyl peroxide, diisopropyl peroxydicarbonate and bis(4-t-butylcyclohexyl)peroxydicarbonate.

[0124] Suitable azo compounds are, for example, selected from the group consisting of 2,2-azobisiso-2,4-dimethylvaleronitrile, 2,2-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2-(carbamoylazo)isobutyronitrile and 4,4'-azobis(cyanovaleric acid).

[0125] Suitable persulfates are, for example, selected from the group consisting of lithium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate and ammonium peroxodisulfate.

[0126] For example, the reaction resin contains 0.1 to 10 wt.%, preferably 1 to 5 wt.%, of the initiator, based on the total weight of the reaction resin.

[0127] As stated above, in a preferred embodiment of the present invention, the reactive resin does not contain an initiator. "An accelerator" in the context of the present invention means both precisely one accelerator and a mixture of two or more different accelerators. Precisely one accelerator is preferred.

[0128] Compounds known to those skilled in the art that accelerate the curing of the reactive resin can be used as accelerators. Suitable accelerators include, for example, symmetrical tertiary aromatic amines, asymmetrical tertiary aromatic amines, and / or phosphites.

[0129] Suitable symmetrical tertiary aromatic amines are, for example, selected from the group consisting of N,N-dimethyl-p-toluidine, N,N-bis-(2-hydroxyethyl)-p-toluidine and N,N-bis-(2-hydroxypropyl)-p-toluidine.

[0130] Suitable asymmetric amines are, for example, selected from the group consisting of N-methyl-N-(hydroxyethyl)-p-toluidine, N-methyl-N-(hydroxyethyl)-m-toluidine, N-methyl-N-(hydroxypropyl)-p-toluidine, an N-methyl-N-(hydroxyethyl)-xylidine, an N-methyl-N-(hydroxypropyl)-xylidine, N-methyl-N-(hydroxyethyl)-aniline and N-methyl-N-(hydroxypropyl)-aniline.

[0131] Geeignete Phosphite sind beispielsweise ausgewählt aus der Gruppe bestehend aus Tri-2- ethylhexylphosphit, Tri-2-ethylhexyltrithiophosphit, Triisooctylphosphit, Triisooctyltrithiophosphit, Tridecylphosphit, Tridecyltrithiophosphit, Trilaurylphosphit, Trilauryltrithiophosphit, Trioctadecylphosphit, Trioctadecyltrithiophosphit, Phenyldidecylphosphit, Phenyldidecyltrithiophosphit, Phenyldilaurylphosphit, Phenyldistearylphosphit, Phenyldistearyltrithiophosphite, Diphenyldecylphosphit, Diphenyllaurylphosphit, Diphenylstearylphosphit, Diphenylstearyltrithiophosphit, Tri-para-kresylphosphit, Tri-meta- kresylphosphit, Tri-ortho-kresylphosphite, Tri-para-Kresyldithiophosphit, Tri-para- octylphenyltrithiophosphit, Tri-ortho-octylphenylphosphit, Tris(dipropyleneglykol)phosphit, Triethoxyethylphosphit, Tributoxyethylphosphit, Tritetrahydrofurfurylphosphit, Tritetrahydrofurfuryltrithiophosphit, Triphenylethylphosphit, S-Phenyldilaurylmonothiophosphit, S- Phenyldidecylmonothiophosphit,SS-Diphenyllauryldithiophosphite, SS-Diphenyldecyldithiophosphite, Tri-ortho-naphthylphosphite, SS-diphenyldecyldithiophosphite, Phenyldilauryltrithiophosphite, Tridodecylphenylphosphite, Triochlorophenylphosphite, Diphenyllauryltrithiophosphite, S-lauryldiphenylmonothiophosphite, Tri-p-methoxyphenyl phosphite, SO-diphenyl-S-lauryldithiophosphite, tri-o-methoxyphenyldithiophosphite, SS-dilaurylphenyldithiophosphite and SO-dilauryl-S-phenyldithiophosphite.,

[0132] For example, the reactive resin contains 0.1 to 5 wt.%, preferably 0.5 to 3 wt.%, of the accelerator, based in each case on the total weight of the reactive resin. The reactive resin according to the invention can be used, for example, in a 2K system.

[0133] The present invention therefore also relates to a 2K system which comprises the reaction resin according to the invention as the first component and a hardener component as the second component.

[0134] The previously described statements and preferences apply to the first component, the reaction resin according to the invention.

[0135] The second component, the hardener component, initiates and / or accelerates the polymerization of at least the (meth)acrylate monomer contained in the reaction resin when mixed with the first component, the reaction resin.

[0136] The hardener component therefore contains either the accelerator or the initiator. Typically, the hardener component contains the accelerator if the reactive resin contains the initiator. The hardener component contains the initiator if the reactive resin contains the accelerator.

[0137] The explanations and preferences previously described for the initiator contained in the reaction resin apply accordingly to the initiator contained in the hardener component.

[0138] For example, the hardener component contains 0.1 to 10 wt.%, preferably 1 to 5 wt.%, of the initiator, based on the total weight of the reaction resin contained in the 2K system

[0139] The statements and preferences previously described for the accelerator contained in the reactive resin apply accordingly to the accelerator contained in the hardener component.

[0140] For example, the hardener component contains 0.1 to 5 wt.%, preferably 0.5 to 3 wt.%, of the accelerator, in each case based on the total weight of the reaction resin contained in the 2K system.

[0141] The hardener component can consist of either the initiator or the accelerator. In this case, the reactive resin preferably does not contain the component that makes up the hardener component.

[0142] It is also possible for the hardener component to contain other components in addition to either the initiator or the accelerator, such as the dyes and / or fillers and / or auxiliaries and additives mentioned below. According to the invention, it is preferred that the hardener component be substantially free of (meth)acrylate monomers. For example, the 2K system comprises 50 to 99.9 wt.% of the first component and 0.1 to 50 wt.% of the second component.

[0143] According to the invention, in the 2K system, the first component, the reactive resin, preferably contains the accelerator. The second component, the hardener component, then contains the initiator. In this embodiment, the reactive resin preferably does not contain an initiator. The hardener component then preferably does not contain an accelerator.

[0144] A 2K system is therefore preferred, in which the reaction resin contains the accelerator and the hardener component contains the initiator.

[0145] The two-component system may also contain dyes and / or fillers. For example, the two-component system contains dyes and / or fillers in the range of 0 to 90 wt.%, preferably in the range of 5 to 50 wt.%, based on the total weight of the two-component system.

[0146] Particularly suitable dyes include white, red, blue, green, and / or yellow inorganic pigments. White inorganic pigments such as titanium dioxide are particularly preferred.

[0147] Fillers are, in particular, mineral fillers. Mineral fillers are preferably selected from the group consisting of calcium carbonate, barium sulfate, quartz, quartz powder, precipitated silicas, pyrogenic silicas, corundum, glass beads, and cristobalites.

[0148] The two-component system may also contain auxiliaries and additives. For example, the two-component system contains auxiliaries and additives in the range of 0.1 to 5% by weight, based on the total weight of the two-component system. Auxiliaries and additives for two-component systems are known as such and are selected, for example, from the group consisting of regulators, plasticizers, paraffins, stabilizers, inhibitors, waxes, and oils.

[0149] For example, paraffins are added to prevent inhibition of polymerization by oxygen in the air. For this purpose, several paraffins with different melting points can be used in different concentrations.

[0150] All compounds known from radical polymerization can be used as regulators. Mercaptans such as n-dodecyl mercaptan, but polyvalent mercapto compounds such as pentaerythritol tetrathioglycolate, are preferred.

[0151] Esters, polyols, oils, low-molecular-weight polyethers, or phthalates are preferred as plasticizers. UV stabilizers are particularly suitable as stabilizers. The UV stabilizers are preferably selected from the group consisting of benzophenone derivatives, benzotriazole derivatives, thioxanthonate derivatives, piperidinolcarboxylic acid ester derivatives, and cinnamic acid ester derivatives.

[0152] From the group of inhibitors, substituted phenols, hydroquinone derivatives, phosphines and phosphites are preferably used.

[0153] To use the 2K system, the first component, the reactive resin, and the second component, the hardener, are mixed together. After mixing the first component with the second component, the 2K system usually only has a limited open time of, for example, 2 to 40 minutes, which remains for use in applications such as applying, pouring, coating or filling. The 2K system then usually cures. For the purposes of the invention, the term "open time" refers to the period between mixing 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 pot life.

[0154] The 2K system according to the invention and / or the reaction resin according to the invention can be used, for example, for floor coatings, chemical anchors, cable casting compounds and / or road markings.

[0155] The invention is explained in more detail below using examples without being limited thereto.

[0156] Examples

[0157] Curing tests with different crosslinkers

[0158] To cure, 2 wt. % of a hardener component (50% dibenzoyl peroxide (BPO) in dicyclohexyl phthalate) is added to a reaction resin containing the components listed in Table 1 and 5 wt. % of the crosslinker listed in Table 2. The mixture is stirred for two minutes and then applied to a metal surface in a layer thickness of approximately 2 mm or poured into the test cups described below. Table 1:

[0159] Table 2:

[0160] Table 3:

[0161] To determine the pot life (TW), the time required by the resulting 2K system to warm itself from room temperature (20 to 22 °C) to 32 °C after stirring in the hardener component is determined. For this purpose, 20 g of the 2K system are prepared in a plastic container as described above.

[0162] To determine the temperature maxima (Tmax), the time required for 20 g of the resulting 2K system to reach the maximum temperature during curing in a 45 mm diameter PE cup was determined. The time required to pass the surface test (O-test) is determined as the time at which the surface of the 2 mm poured layer has cured to a tack-free level. The time is started by stirring the hardener component into the reaction resin and is stopped when the poured layer no longer sticks to the touch of a gloved finger.

[0163] The mechanical properties (tensile modulus, tensile strength, stress at break, elongation at break) were determined at 23 °C according to DIN EN ISO 527:2019 by casting the corresponding reactive resin into test specimens. The results are presented in Table 4.

[0164] Table 4:

[0165] The crosslinker mixture according to the invention achieves mechanical properties comparable to those of 1,4-BDDMA. Compared to EGDMA, even improved mechanical properties are achieved. In particular, the tensile modulus is particularly high in the crosslinking tests.

[0166] By using the crosslinker mixture according to the invention, not only are comparable mechanical properties achieved, but the crosslinker mixture according to the invention is also more cost-effective to produce than, for example, 1,4-BDDMA and EGDMA.

Claims

Claims Crosslinking mixture for reaction resins, wherein the crosslinking mixture comprises the following Components (A) and (B) contain: (A) at least one first di(meth)acrylate diester of general formula (I) in the R 1 H or CH3 is R 2 H or CH3 is, and R 3 H or CH3 is; (B) at least one second di(meth)acrylate diester of general formula (II) in the R 4 H or CH3 is R 5 H or CH3 is R e H or CH3, and n is 2 or 3. Crosslinking mixture according to claim 1, characterized in that the crosslinking mixture 50 to 90 wt.% of component (A) and Contains 10 to 50 wt.% of component (B), in each case based on the total weight of the crosslinking mixture. Crosslinking mixture according to claim 1 or 2, characterized in that component (A) comprises ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate. Crosslinking mixture according to claim 3, characterized in that component (A) 30 to 80 wt% ethylene glycol di(meth)acrylate and comprising 20 to 70 wt.% propylene glycol di(meth)acrylate, in each case based on the total weight of component (A). Crosslinking 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. Crosslinking mixture according to claim 5, characterized in that component (B) 50 to 90 wt% diethylene glycol di(meth)acrylate and comprising 10 to 50 wt.% dipropylene glycol di(meth)acrylate, in each case based on the total weight of component (B). Crosslinking mixture according to any one of claims 1 to 6, characterized in that the crosslinking 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. Crosslinking mixture according to claim 7, characterized in that the crosslinking mixture contains 25 to 50 wt.% ethylene glycol di(meth)acrylate, 10 to 35 wt% diethylene glycol di(meth)acrylate, 0 to 2 wt% triethylene glycol di(meth)acrylate, 20 to 35 wt% propylene glycol di(meth)acrylate, 2 to 15 wt% dipropylene glycol di(meth)acrylate and Contains 0 to 2 wt% tripropylene glycol di(meth)acrylate, based on the total weight of the crosslinking mixture. Reaction resin containing the following components: 0.1 to 30 wt.% of the crosslinking mixture according to any one of claims 1 to 8, 20 to 80 wt% of a (meth)acrylate monomer, 0 to 40 wt.% prepolymers, either 0.1 to 10 wt.% of an initiator or 0.1 to 5 wt.% of an accelerator, each based on the total weight of the reaction resin. Reaction resin according to claim 9, characterized in that the prepolymers are selected from the group consisting of polyalkyl(meth)acrylates, polyesters, polyurethane(meth)acrylates, and mixtures thereof. Reaction 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-alkenes, styrene, and mixtures thereof. 2K system comprising as the first component the reaction resin according to any one of claims 9 to 10. 11 and, as a second component, a hardener component.

13. 2K system according to claim 12, characterized in that the reaction resin contains the accelerator and that the hardener component contains the initiator.

14. Use of the reaction resin according to any one of claims 9 to 11 or of the 2K Systems according to claim 12 or 13 for floor coatings, chemical anchors, cable potting compounds and / or road markings.

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