Trifunctional reactive diluents for curable compositions

Abstract

The present invention relates to a reactive diluent having formula (1) wherein R1 is a C4-9-alkyl group, a C4-9-alkenyl group, a C4-9-alkynyl group, a C6-14-aryl group, a C3-12-heteroaryl group, a C5-12-cycloalkyl group, a C5-12-cycloalkenyl group or a C4-12-heterocycloalkyl group wherein the C4-9-alkyl group may be substituted by a phenyl group, a C3-8-heteroaryl group, a C5-8-cycloalkyl group, a C4-8-cycloalkenyl group or a C4-8-heterocycloalkyl group; r1 is C6-14-alkyl, C3-12-cycloalkyl, C5-12-cycloalkenyl and C4-12-heterocycloalkyl, and C6-14-aryl, C3-12-heteroaryl, C3-12-cycloalkyl, C5-12-cycloalkenyl, and C4-12-heterocycloalkyl may be substituted by C1-10-alkyl, phenyl, C3-8-heteroaryl, C5-8-cycloalkyl, or C4-8-heterocycloalkyl, R2 is H or methyl, and n is 1.0 to 6.0; and a composition comprising the reactive diluent and at least one oligomer or polymer curable by free radical polymerization; a cured layer formed from the composition; a substrate coated with the cured layer; a method for preparing the reactive diluent; a process for preparing the precursor of the reactive diluent and the use of these compositions as paint or varnish compositions.

Description

[0001] The present invention relates to a reactive diluent, a composition comprising the reactive diluent and at least one curable oligomer or polymer by free radical polymerization, a cured layer formed from these compositions, a substrate coated with the cured layer, a method for preparing the reactive diluent, a method for preparing a precursor of the reactive diluent, and the use of these compositions as paint or varnish compositions.

[0002] Curable compositions have many applications, such as as coating compositions like paint or varnish compositions, as ink compositions, as resist compositions used in photolithography processes, and as reactive compositions used in 3D printing processes.

[0003] A 100% curable composition is a composition that contains virtually no water or organic solvents. 100% curable compositions typically contain an oligomer or polymer that can be cured via free radical polymerization and a free radical initiator.

[0004] Because compositions containing curable oligomers or polymers that can be cured by free radical polymerization and free radical initiators are often too viscous for most applications, 100% curable compositions typically also contain reactive diluents to reduce viscosity, which copolymerize with the oligomers or polymers during light or heat treatment.

[0005] 100% UV-curable coating compositions comprising acrylated or methacrylated oligomers or polymers that can be cured by free radical polymerization, acrylated or methacrylated reactive diluents, and photoinitiators are known in the art.

[0006] R. Schwalm, L. Häussling, W. Reich, E. Beck, P. Enenkel, K. Menzel Progress in Organic Coatings 32, 1997, 191-196 describes UV-curable coating compositions comprising epoxy acrylates, polyester acrylates, polyether acrylates and urethane acrylates (each), a reactive diluent selected from the group consisting of hexanediol diacrylates, oligoether acrylates, di(propylene glycol) diacrylates and tri(propylene glycol) diacrylates, and a photoinitiator.

[0007] DK Chattopadhyay, Siva Sankar Panda, KVSV Raju Progress in Organic Coatings 54, 2005, 10-19 describe UV-curable coating compositions comprising acrylated or methacrylated epoxy resins (5%, 7.5%, and 10% (wt / wt), respectively), 1,1,1-trimethylolpropane triacrylate (TMPTA), and a photoinitiator. The epoxy resins used are epoxy phenolic varnish resins and bisphenol A diglycidyl ether epoxy resins.

[0008] Typically, oligomers or polymers that are curable by free radical polymerization and are present in the composition are selected to obtain a composition that forms a cured layer with the properties desired in the respective application. For example, oligomers or polymers that are curable by free radical polymerization and are present in a coating composition are selected to obtain a coating composition that forms a cured layer with good adhesion to the substrate, high hardness, and / or good chemical resistance.

[0009] However, reactive thinners added to a composition to reduce its viscosity often also affect the properties of the cured layer. This is a drawback because variations in the ratio of free-radical polymers or oligomers that can be cured to the reactive thinner result in compositions with cured layers exhibiting different properties. Therefore, for example, paint or varnish manufacturers have limited flexibility in adjusting the viscosity of their paint or varnish compositions by adding additional reactive thinners without altering the final properties of the paint or varnish.

[0010] The object of the present invention is to provide a reactive diluent that can be used in a curable composition comprising at least one free radical polymer curable oligomer or polymer to reduce the viscosity of the composition to an acceptable viscosity, and simultaneously, the composition comprising the reactive diluent and the free radical polymer curable oligomer or polymer forms a cured layer, wherein the hardness of the cured layer does not change or only changes in a negligible range of ratios of free radical polymer curable oligomer or polymer to reactive diluent.

[0011] This objective is achieved by the reactive diluent as claimed in claim 1, the composition as claimed in claim 6, the layer as claimed in claim 13, the substrate as claimed in claim 14, the method as claimed in claims 15 and 16, and the use as claimed in claim 17.

[0012] The reactive diluent of the present invention is a compound having the following formula.

[0013]

[0014] in

[0015] R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl,

[0016] in

[0017] C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and

[0018] C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution

[0019] R 2 It is H or methyl

[0020] and

[0021] n is between 1.0 and 6.0.

[0022] C 1-10 -alkyl, C 4-9 -alkyl, C 5-8 -alkyl and C 5-6 -Alkyl groups can be branched or unbranched. C 1-10 Examples of -alkyl groups are methyl, ethyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 1,1-dimethyl-3,3-dimethylbutyl, nonyl, and decyl. 4-9 Examples of -alkyl groups are butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, 1,1-dimethyl-3,3-dimethylbutyl, and nonyl. 5-8Examples of -alkyl groups are pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, and 1,1-dimethyl-3,3-dimethylbutyl. C 5-6 Examples of -alkyl groups are pentyl, isopentyl, and hexyl.

[0023] C 5-8 -Alkenyl and C 4-9 -Alkenyl groups can be branched or unbranched. C 5-8 Examples of -alkenyl groups are pent-4-en-1-yl, pent-3-en-1-yl, hex-5-en-1-yl, hex-3-en-1-yl, hep-6-en-1-yl, and oct-7-en-1-yl. 4-9 Examples of -alkenyl groups are but-3-en-1-yl, pent-4-en-1-yl, pent-3-en-1-yl, hex-5-en-1-yl, hex-3-en-1-yl, hep-6-en-1-yl, oct-7-en-1-yl, and non-8-en-1-yl.

[0024] C 5-8 -Alynyl group and C 4-9 -The alkynyl group can be branched or unbranched. C 5-8 Examples of -ynyl groups are pent-4-yn-1-yl, pent-3-yn-1-yl, hex-5-yn-1-yl, hex-3-yn-1-yl, hep-6-yn-1-yl, and oct-7-yn-1-yl. C 4-9 Examples of -ynyl groups are but-3-yn-1-yl, pent-4-yn-1-yl, pent-3-yn-1-yl, hex-5-yn-1-yl, hex-3-yn-1-yl, hept-6-yn-1-yl, oct-7-yn-1-yl, and non-8-yn-1-yl.

[0025] C 6-14 Examples of -aryl groups are phenyl, 1-naphthyl, and 2-naphthyl.

[0026] C 3-8 - Heteroaryl and C 3-12 Examples of heteroaryl groups are

[0027] .

[0028] C 5-8 Examples of cycloalkyl groups are cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. 3-12 Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl.

[0029] C 5-8 Examples of cycloalkenyl groups are cyclopent-3-en-1-yl, cyclohex-2-en-1-yl, cyclohex-3-en-1-yl, cyclohept-3-en-1-yl, and cyclooct-4-en-1-yl. 5-12Examples of cycloalkenyl groups are cyclopent-3-en-1-yl, cyclohex-2-en-1-yl, cyclohex-3-en-1-yl, cyclohept-3-en-1-yl, cyclooct-4-en-1-yl, cyclonon-5-en-1-yl, and cyclodec-5-en-1-yl.

[0030] C 4-8 - Heterocyclic alkyl groups and C 4-12 Examples of heterocyclic alkyl groups are

[0031]

[0032] Where R 10 It is C 1-10 -alkyl.

[0033] A compound having formula (1) can be a single compound or a mixture of compounds. If a compound having formula (1) is a mixture of compounds, then n refers to the average n.

[0034] Instances of n being 1.0 to 6.0 are 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 5.0, and 6.0. Instances of n being 1.0 to 4.0 are 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, and 4.0. Instances of n being 1.0 to 2.0 are 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0. Instances of n being 1.0 to 1.5 are 1.0, 1.1, 1.2, 1.3, 1.4, and 1.5. Instances of n being 1.0 to 1.2 are 1.0, 1.1, and 1.2.

[0035] R 1 Preferably, it is C 5-8 -alkyl, C 5-8 -Alkenyl or C 5-8 -alkynyl group, more preferably C 5-6 -alkyl, with pentyl being the most preferred.

[0036] R 2 H is preferred.

[0037] In the preferred compounds having formula (1), R 1 It is C 5-8 -alkyl and R 2 It is H or methyl.

[0038] In a more preferred compound having formula (1), R 1 It is pentyl and R 2 It is H or methyl.

[0039] In the most preferred compound having formula (1), R 1 It is pentyl and R 2 It is H.

[0040] n is preferably 1.0 to 4.0, more preferably 1.0 to 2.0, even more preferably 1.0 to 1.5, most preferably 1.0 to 1.2, and especially 1.0.

[0041] Another part of the present invention is a method for preparing compounds having the following formula.

[0042]

[0043] in

[0044] R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl,

[0045] in

[0046] C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and

[0047] C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution

[0048] R 2 It is H or methyl

[0049] and

[0050] n is between 1.0 and 6.0.

[0051] The method includes making compounds having the following formula

[0052]

[0053] in

[0054] R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl,

[0055] in

[0056] C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and

[0057] C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution

[0058] and

[0059] n is between 1.0 and 6.0.

[0060] Steps of reacting with compounds having the following formula

[0061]

[0062] Where R 2 It is H or methyl.

[0063] The equivalence ratio of the COOH group of the compound having formula (4) to the OH group of the compound having formula (3) is generally in the range of 0.90 / 1.00 to 1.20 / 1.00, preferably in the range of 1.05 / 1.00 to 1.15 / 1.00.

[0064] The reaction of a compound having formula (3) with a compound having formula (4) can be carried out with or without a solvent. Examples of suitable solvents include hydrocarbons such as n-heptane, cyclohexane, methylcyclohexane, toluene, o-xylene, m-xylene, p-xylene, mixtures of xylene isomers, ethylbenzene, chlorobenzene, o-dichlorobenzene, and m-dichlorobenzene. Also suitable as solvents in the absence of an acidic catalyst are ethers such as dioxane or tetrahydrofuran, and ketones such as methyl ethyl ketone and methyl isobutyl ketone. Preferably, the reaction is carried out in the presence of a solvent. More preferably, the reaction is carried out in the presence of a saturated hydrocarbon such as cyclohexane.

[0065] Preferably, water formed during the reaction is continuously removed during the reaction. Water can be removed by distillation. Water can also be removed by stripping with an inert gas or by reacting in the presence of a dehydrating agent such as MgSO4 and Na2SO4. The described methods can also be combined for water removal. Preferably, water is removed by distillation, or distillation in combination with other dehydration methods.

[0066] Preferably, the reaction is carried out in the presence of at least one catalyst. The catalyst may be selected from the group consisting of acidic inorganic catalysts, acidic organic catalysts, and organometallic catalysts. Preferably, only one catalyst is used.

[0067] Examples of acidic inorganic catalysts include sulfuric acid, metal sulfates such as aluminum sulfate hydrate and alum, metal bisulfates such as sodium bisulfate, as well as acidic silica gel (pH <= 6, especially pH <= 5), acidic alumina, phosphoric acid, phosphonic acid, and diphosphonic acid.

[0068] Examples of acidic organic catalysts are organic compounds containing phosphate ester groups, sulfonic acid groups, sulfate ester groups, or phosphonic acid groups, such as p-toluenesulfonic acid. Further examples of acidic organic catalysts are acidic ion exchangers, such as polystyrene resins crosslinked with divinylbenzene and containing sulfonic acid groups.

[0069] Examples of organometallic catalysts include organoaluminum catalysts such as tris(n-butoxy)aluminum, tris(isopropoxy)aluminum, and tris(2-ethylhexyloxy)aluminum; organotitanium catalysts such as tetra(n-butoxy)titanium(IV), tetra(isopropoxy)titanium(IV), and tetra(2-ethylhexyloxy)titanium(IV); organotin catalysts such as dibutyltin oxide, diphenyltin oxide, dibutyltin dichloride, di(n-octanoic acid)tin(II), di(2-ethylhexanoic acid)tin(II), tin laurate(II), dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, and dioctyltin diacetate; and organozinc catalysts such as zinc acetate.

[0070] Based on the weight of compounds (3) and (4), the amount of all catalysts is generally in the range of 0.1% to 20% by weight, preferably 1% to 10%.

[0071] Preferably, the reaction is carried out in the presence of at least one polymerization inhibitor.

[0072] Examples of polymerization inhibitors include copper(II) chloride, 2,2,6,6-tetramethylpiperidin-1-oxy (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxy (TEMPOL), 4-benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxy, 4-benzyloxy-2,2,6,6-tetramethylpiperidin-1-oxy, 2,2-diphenyl-1-picrylhydrazine (DPPH), tris(p-nitrophenyl)methane, p-phenylenediamines such as N,N'-diphenyl-p-phenylenediamine, phenothiazines, hydroxylamines such as N,N-diethylhydroxylamine (DEHA), quinones such as hydroquinone (HQ), and methylhydroquinone. Quinones, hydroquinone monomethyl ether (MEHQ), 1,4-benzoquinone, tert-butylhydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)-hydroquinone and 2,5-bis(1,1-dimethylbutyl)hydroquinone, p-tert-butylcatechol (TBC), alkoxylated phenols such as 4-methoxyphenol, alkylated phenols such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol and 2,6-di-tert-butyl-4-methylphenol, alkylated and alkoxylated phenols such as 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol.

[0073] The reaction is typically carried out at temperatures ranging from 60°C to 150°C, preferably from 80°C to 120°C.

[0074] The reaction can be monitored by determining the amount of water formed in the reaction. When the target amount of water formed in the reaction is reached, the reaction mixture is typically cooled to room temperature. Preferably, any excess of the compound having formula (4) is removed by water extraction. Then, any solvent present is typically removed by distillation, preferably distillation under reduced pressure, to produce the compound having formula (1), which can be further purified by filtration.

[0075] Compounds having the following formula

[0076]

[0077] in

[0078] R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl,

[0079] in

[0080] C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and

[0081] C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution

[0082] It can be prepared in a method including the following steps:

[0083] (i) Make compounds having the following formula

[0084]

[0085] in

[0086] R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl,

[0087] in

[0088] C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and

[0089] C 6-14 -Aryl, C3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution

[0090] Reacts with formaldehyde to obtain a compound having the following formula

[0091]

[0092] in

[0093] R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl,

[0094] in

[0095] C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and

[0096] C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution

[0097] as well as

[0098] (ii) Reduce the compound having formula (6) to obtain the compound having formula (3”).

[0099] Step (ii) is usually carried out in the presence of a reducing agent. Examples of reducing agents are formaldehyde and hydrogen.

[0100] If formaldehyde is used as a reducing agent in step (ii), steps (i) and (ii) can be carried out in a one-pot process. The molar ratio of formaldehyde to compound (5) is in the range of 2 / 1 to 10 / 1, preferably in the range of 2 / 1 to 8 / 1. Formaldehyde is typically used as an aqueous solution, and optionally one or more polar solvents such as cyclic or acyclic ethers such as tetrahydrofuran, dioxane, or methyl tert-butyl ether, or alcohols such as methanol, ethanol, or 2-ethylhexanol may be present in the reaction mixture. The reaction is typically catalyzed by a base. Examples of bases are tertiary amines such as trimethylamine, triethylamine, or tri(n-propyl)amine, or alkali metal hydroxides such as sodium hydroxide or potassium hydroxide. Preferred bases are alkali metal hydroxides such as potassium hydroxide or sodium hydroxide. The ratio of compound (5) to alkali metal hydroxide is typically in the range of 1.7 / 1 to 2.3 / 1. The reaction is typically carried out at a temperature in the range of 15°C to 80°C. Compound (3”) can be obtained from the reaction mixture by extraction with a suitable solvent (such as methyl tert-butyl ether).

[0101] Weibull, BM, Magnus Acta Chem. Scand. [Scandinavian Chemical Impurities] 1962, 16, 1062 describes the preparation of 1,1,1-tris(hydroxymethyl)alkanes using formaldehyde as a reducing agent.

[0102] If hydrogen is used as a reducing agent in step (ii), steps (i) and (ii) are typically carried out in separate steps. In step (i), the molar ratio of formaldehyde to compound (5) is in the range of 2 / 1 to 6 / 1, preferably in the range of 2 / 1 to 3 / 1. Formaldehyde is typically used as an aqueous solution, and optionally one or more polar solvents such as cyclic or acyclic ethers such as tetrahydrofuran, dioxane, or methyl tert-butyl ether, or alcohols such as methanol, ethanol, or 2-ethylhexanol may be present in the reaction mixture. The reaction is typically catalyzed by a base. Examples of bases are tertiary amines such as trimethylamine, triethylamine, or tri(n-propyl)amine, or alkali metal hydroxides such as sodium hydroxide or potassium hydroxide. A preferred base is a tertiary amine such as trimethylamine. The equivalence ratio of the aldehyde group of compound (5) to the tertiary amine group of the tertiary amine is typically in the range of 5 / 1 to 1000 / 1, preferably in the range of 6 / 1 to 100 / 1. Step (i) is typically carried out at a temperature ranging from 15°C to 80°C. Unreacted formaldehyde, tertiary amines, and / or unreacted compound (5) can be removed by stripping with an inert gas. The resulting mixture containing compound (6) and water can be used in step (ii).

[0103] Step (ii) using hydrogen as a reducing agent is typically carried out in the presence of a metal catalyst such as Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, and Hg. Preferred metal catalysts are Fe, Vo, Ni, Cu, Ru, Pd, and Pt. The most preferred metal catalyst is copper. Copper is typically used on suitable support materials such as titanium oxide, hafnium oxide, silica, or alumina. Step (ii) using hydrogen as a reducing agent is typically carried out in water. Step (ii) using hydrogen as a reducing agent can be carried out continuously or discontinuously. Step (ii) using hydrogen as a reducing agent is typically carried out at a temperature in the range of 50°C to 180°C, preferably in the range of 90°C to 140°C. Step (ii) is typically carried out at a pressure of 10 to 250 bar, preferably at a pressure of 20 to 120 bar, which is adjusted by adding hydrogen. Compound (3”) can be purified by distillation.

[0104] A similar method is described in WO 2012143309 A1. WO 2012143309 A1 describes the preparation of neopentyl glycol by means of: (i) reacting isobutyraldehyde with formaldehyde to obtain hydroxyneopental and (ii) reducing hydroxyneopental with hydrogen to obtain neopentyl glycol.

[0105] Another part of the invention is a method for preparing a compound having formula (3”) as outlined above, wherein the reducing agent is hydrogen.

[0106] Compounds having the following formula

[0107]

[0108] in

[0109] R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl,

[0110] in

[0111] C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and

[0112] C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution

[0113] and

[0114] n is greater than 1.0 to 6.0.

[0115] It can be obtained as a byproduct in the methods described above for preparing compounds having formula (3”).

[0116] Examples of n greater than 1.0 to 6.0 are 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 5.0, and 6.0. Preferably, it has equation (3) In compounds of ), n ranges from 1.1 to 6.0. Examples of n ranging from 1.1 to 6.0 are 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 5.0, and 6.0.

[0117] Compounds having the following formula

[0118]

[0119] in

[0120] R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl,

[0121] in

[0122] C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8-cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and

[0123] C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution

[0124] and

[0125] n is greater than 1.0 and can be between 1.0 and 6.0.

[0126] It can also be prepared in a method that includes the step of oligomerizing a compound having the following formula.

[0127]

[0128] in

[0129] R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl,

[0130] in

[0131] C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and

[0132] C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution.

[0133] Oligopolymerization is typically carried out in the presence of an acidic catalyst, preferably sulfuric acid. The amount of acid catalyst is typically from 0.01% to 8.0% by weight, and preferably from 0.01% to 3.0%, based on the weight of compound (3”).

[0134] Oligopolymerization is typically carried out at elevated temperatures, usually in the range of 80°C to 220°C, preferably in the range of 120°C to 220°C.

[0135] Preferably, water formed during the reaction is removed continuously. Water can be removed by distillation. Distillation is typically carried out under reduced pressure, such as in the range of 0.1 to 200 mbar, preferably in the range of 0.1 to 50 mbar. Water can also be removed by stripping with an inert gas or by reacting it in the presence of a dehydrating agent (such as MgSO4 and Na2SO4). The described methods can also be combined for water removal. Preferably, water is removed by distillation, optionally in combination with other dehydration methods.

[0136] Oligopolymerization of compounds having formula (3) can be carried out with or without a solvent. Examples of suitable solvents include hydrocarbons such as n-heptane, cyclohexane, methylcyclohexane, toluene, o-xylene, m-xylene, p-xylene, mixtures of xylene isomers, ethylbenzene, chlorobenzene, o-dichlorobenzene, and m-dichlorobenzene. Preferred solvents form azeotropic mixtures with water.

[0137] The reaction can be monitored by determining the amount of water formed in the reaction. When the target amount of water formed in the reaction is reached, the reaction mixture is typically cooled to a temperature below 120°C, preferably below 100°C. The reaction mixture can be neutralized by adding an aqueous solution of sodium hydroxide. Then, any solvent and water present are typically removed by distillation, preferably distillation under reduced pressure, to produce a product having the formula (3). ) compounds.

[0138] Another part of the invention is a composition comprising at least one compound having formula (1), at least one oligomer or polymer (P) different from the compound having formula (1), and optionally at least one free radical initiator (I), the oligomer or polymer (P) being curable by free radical polymerization.

[0139] The oligomer or polymer (P) can be any oligomer or polymer that is different from a compound having formula (1) and can be cured by free radical polymerization.

[0140] The weight-average molecular weight and number-average molecular weight of the oligomer or polymer (P) are preferably in the range of 450 to 500,000 g / mol, more preferably in the range of 450 to 50,000 g / mol, even more preferably in the range of 500 to 20,000 g / mol, and most preferably in the range of 500 to 8,000 g / mol. The weight-average molecular weight and number-average molecular weight can be determined using gel permeation chromatography calibrated with polystyrene standards.

[0141] The oligomer or polymer (P) is preferably an oligomer or polymer that can be cured by free radical polymerization and carries or contains at least one group, preferably two groups, selected from the group consisting of.

[0142] ,

[0143]

[0144] Where R 3 R 4 and R 5 Each is independently H or methyl, preferably H, and R 6 Is it H or C? 1-20 -alkyl.

[0145] Examples of oligomers or polymers (P) are polyurethanes, acrylic resins, mixtures of polyurethanes and acrylic resins, polyesters, polyamides, polyureas, polysiloxanes, polyethers, polycarbonates, epoxy resins, resins derived from epoxy resins, alkyd resins, polyolefins, and polyvinyl acetate, which can be cured by free radical polymerization and carry or contain at least one group, preferably two groups, selected from the group consisting of.

[0146] ,

[0147]

[0148] Where R 3 R 4 and R 5 Each is independently H or methyl, preferably H, and R 6 Is it H or C? 1-20 -alkyl.

[0149] Polyurethane is an oligomer or polymer containing urethane linking groups. Polyurethane is typically obtained by reacting a diol with a diisocyanate. The diol can be a polyester glycol, acrylic polymer glycol, polycarbonate glycol, or polyether glycol. Polyurethane may contain additional linking groups, such as ester, ether, thioether, or urethane linking groups, in the main chain in numbers fewer than the number of urethane groups.

[0150] Acrylic resins are oligomers or polymers that can be obtained by free radical polymerization of polymerizable unsaturated monomers comprising acrylates or methacrylates and optionally other polymerizable unsaturated monomers by methods known in the art, such as emulsion polymerization. Examples of other polymerizable unsaturated monomers are polymerizable unsaturated monomers carrying OH groups, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)allyl alcohol, and polymerizable unsaturated monomers carrying acidic groups, such as acrylic acid, methacrylic acid, maleic acid, citracic acid, itaconic acid, maleic anhydride, citracic anhydride, and itaconic anhydride.

[0151] For example, acrylic resin can be prepared as described above, but in the presence of polyurethane, a mixture of polyurethane and acrylic resin can be obtained.

[0152] Polyesters are oligomers or polymers containing monomers linked via ester linkages. Polyesters are typically obtained through esterification or transesterification of a component carrying two acidic groups and a diol. Polyesters may contain fewer additional linking groups in the main chain than ester groups, such as amide, urea, carbonate, ether, thioether, or urethane linking groups.

[0153] Polyamides are oligomers or polymers containing monomers linked via amide linkages. Polyamides are typically obtained by the condensation reaction of a component carrying two acidic groups with a diamine. Polyamides may contain additional linking groups in the main chain, fewer in number than amide groups, such as ester, urea, carbonate, ether, thioether, or urethane linking groups.

[0154] Polyurea is an oligomer or polymer containing monomers linked via urea linkages. Polyurea is typically obtained by reacting a diamine with a diisocyanate. Polyurea may contain fewer additional linking groups in its main chain than the number of urea groups, such as ester, amide, carbonate, ether, thioether, or urethane linking groups.

[0155] Polyethers are oligomers or polymers containing ether linkage groups. Polyethers are typically prepared by acid-catalyzed polymerization of ethers (such as ethylene oxide, propylene oxide, butane oxide, or tetrahydrofuran) using alcohols. Examples of polyethers are polyoxyethylene polyether, polyoxypropylene polyether, polyoxybutylene polyether, and polytetrahydrofuran. Polyethers may contain fewer additional linking groups in their main chain than the number of ether groups, such as ester, amide, urea, carbonate, thioether, or urethane linking groups.

[0156] Polycarbonate is an oligomer or polymer containing carbonate linking groups. Polycarbonate is usually obtained by reacting carbonate with diol. Polycarbonate may contain fewer additional linking groups in its main chain than carbonate groups, such as ester, amide, urea, ether, thioether, or urethane linking groups.

[0157] Epoxy resins are oligomers or polymers carrying at least one, preferably at least two, epoxy groups. An example of an epoxy resin is bisphenol A diglycidyl ether resin, which can be obtained by first reacting bisphenol A with epichlorohydrin, followed by dehydrohalogenation to obtain a bisphenol A diglycidyl ether monomer, and then polymerizing the bisphenol A diglycidyl ether monomer with bisphenol A. Another example of an epoxy resin is the product of phenolic varnish resin (a polymer formed by the reaction of phenol and formaldehyde) and epichlorohydrin.

[0158] Resins derived from epoxy resins are oligomers or polymers obtained by reacting the epoxy groups of epoxy resins with another compound such as acrylic acid or methacrylic acid.

[0159] Alkyd resins are polyesters carrying fatty acid-derived groups. They are typically obtained through esterification or transesterification of a component carrying two acidic groups, a polyol, and a glycerol fatty acid triester. Examples of components carrying two acidic groups are phthalic anhydride and maleic anhydride. Examples of polyols are trimethylolpropane, glycerol, and pentaerythritol. Examples of glycerol fatty acid triesters are soybean oil, flaxseed oil, and coconut oil.

[0160] Polyolefins are oligomers or polymers obtained by polymerization of at least one olefin monomer, optionally in the presence of at least one polymerizable unsaturated monomer that is not an olefin monomer, by methods known in the art, such as emulsion polymerization. An olefin monomer is a monomer containing only H and C atoms. Examples of olefin monomers are ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-decene, and 1-dodecene; conjugated dienes and non-conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, and 1,5-hexadiene, as well as styrene. Examples of polymerizable unsaturated monomers that are not olefin monomers are vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, and itaconic anhydride.

[0161] The oligomer or polymer (P) is commercially available or can be prepared by methods known in the art.

[0162] For example, oligomers or polymers (P) carrying at least one group having the following formula.

[0163]

[0164] Where R 3 It is H or methyl, and R 4 and R 5 It's H.

[0165] It can be prepared by esterifying at least one OH group of the polymer precursor with acrylic acid or methacrylic acid, by ring-opening the epoxy group of the epoxy polymer with acrylic acid or methacrylic acid, or by using a monomer that already carries a group having formula (10) to prepare an oligomer or polymer (P).

[0166] The oligomer or polymer (P) is more preferably an oligomer or polymer that can be cured by free radical polymerization and carries at least one group having the following formula, preferably at least two groups having the following formula.

[0167]

[0168] Where R 3 It is H or methyl, preferably H.

[0169] Oligomers or polymers (P), and even more preferably oligomers or polymers, carrying at least one group having the following formula, preferably at least two groups having the following formula.

[0170]

[0171] Where R 3 It is H or methyl, preferably H.

[0172] The oligomer or polymer (P) is most preferably at least one oligomer or polymer selected from the group consisting of the following:

[0173] ,

[0174]

[0175] as well as

[0176]

[0177] Where L 1 It is an organic residue.

[0178] R 3 It is H or methyl, and

[0179] m is between 0 and 16.0.

[0180] Having equations (2#), (2”) and (2) The oligomers or polymers of ) can be single oligomers or polymers or mixtures of oligomers or polymers. If they have formulas (2#), (2”) and (2”), then... If the oligomers or polymers are mixtures of oligomers or polymers, then m refers to the average m.

[0181] Examples of m ranging from 0 to 16.0 are 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 8.0, 10.0, 12.0, 14.0, and 16.0. Examples of m ranging from 0.1 to 16.0 are 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 8.0, 10.0, 12.0, 14.0, and 16.0. Examples of m ranging from 0.2 to 10.0 are 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 8.0, and 10.0. Examples of m ranging from 0.3 to 5.0 are 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.5, and 5.0. Examples of m ranging from 0.4 to 3.0 are 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.4, 2.6, 2.8, and 3.0. Examples of n ranging from 0.5 to 1.5 are 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, and 1.5.

[0182] R 3 H is preferred.

[0183] m is preferably 0.1 to 16.0, more preferably 0.2 to 10.0, even more preferably 0.3 to 5.0, most preferably 0.4 to 3.0, and especially 0.8 to 1.5.

[0184] L1 It can be any organic residue. L 1 Preferably, the following groups are selected.

[0185]

[0186]

[0187]

[0188]

[0189]

[0190] .

[0191] More preferably, L 1 yes

[0192] .

[0193] In preferred oligomers or polymers having formula (2),

[0194] R 3 It's H.

[0195] m is 0.1 to 16.0, preferably 0.2 to 10.0, even more preferably 0.3 to 5.0, most preferably 0.4 to 3.0, and particularly 0.8 to 1.5.

[0196] L 1 yes

[0197] .

[0198] They respectively have equations (2#), (2”) and (2) oligomers or polymers of (2#), (2”) and (2”) selected from (2#), (2”) and (2”) A mixture of at least two oligomers or polymers in a group consisting of (2) is also called an oligomer or polymer having formula (2).

[0199] In oligomer (2a) of Example 4, R 3 It's H, L 1 It is a group having formula (12) and m is 1.1.

[0200] oligomers or polymers that are at least one selected from the group consisting of

[0201] ,

[0202] ,

[0203] as well as

[0204]

[0205] in

[0206] R 3 It is H or methyl.

[0207] L 1 It is an organic residue, and

[0208] m is between 0 and 16.0

[0209] It can be obtained by making oligomers or polymers having the following formula.

[0210]

[0211] in

[0212] L 1 It is an organic residue, and

[0213] m is between 0 and 16.0

[0214] Reaction with compounds having the following formula

[0215]

[0216] Where R 3 It is H or methyl.

[0217] This reaction is typically carried out in the presence of a catalyst. Examples of catalysts include tertiary amines, quaternary ammonium salts, trialkylphosphines, triarylphosphines, dialkylarylphosphines, diarylalkylphosphines, and heteroaromatic compounds containing at least one nitrogen atom.

[0218] Examples of tertiary amines are tributylamine, 1,4-diazabicyclo-[2.2.2]octane, N-methylmorpholine, N-ethylmorpholine, bis[2-(N,N-dimethylamino)ethyl] ether, 2,2'-dimorpholino-diethyl ether, N,N,N',N'-tetramethylethylenediamine, N,N-dimethylcyclohexylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, 1,1,3,3-tetramethylguanidine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0219] Examples of quaternary ammonium salts are tetraethylammonium bromide, tetrabutylammonium bromide, and N,N,N-trimethylbenzylammonium bromide.

[0220] An example of triarylphosphine is triphenylphosphine.

[0221] Examples of heteroaromatic compounds containing at least one N as a heteroatom are pyridine, quinoline, isoquinoline, 2-ethylimidazole, N-methylimidazole and N-butylimidazole.

[0222] The weight ratio of the amine catalyst to the oligomer (7) and compound (4) is preferably 1% to 20%, more preferably 2% to 10%.

[0223] The reaction can be carried out with or without a solvent. Preferably, the reaction is carried out in the absence of a solvent.

[0224] The reaction is typically carried out at temperatures ranging from 50°C to 150°C, preferably from 80°C to 120°C.

[0225] This reaction is usually carried out in the presence of a polymerization inhibitor.

[0226] Examples of polymerization inhibitors include copper(II) chloride, 2,2,6,6-tetramethylpiperidin-1-oxy (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxy (TEMPOL), 4-benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxy, 4-benzyloxy-2,2,6,6-tetramethylpiperidin-1-oxy, 2,2-diphenyl-1-picrylhydrazine (DPPH), tris(p-nitrophenyl)methane, p-phenylenediamines such as N,N'-diphenyl-p-phenylenediamine, phenothiazines, hydroxylamines such as N,N-diethylhydroxylamine (DEHA), quinones such as hydroquinone (HQ), and methylhydroquinone. Quinones, hydroquinone monomethyl ether (MEHQ), 1,4-benzoquinone, tert-butylhydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)-hydroquinone and 2,5-bis(1,1-dimethylbutyl)-hydroquinone, p-tert-butylcatechol (TBC), alkoxylated phenols such as 4-methoxyphenol, alkylated phenols such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol and 2,6-di-tert-butyl-4-methylphenol, alkylated and alkoxylated phenols such as 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol.

[0227] The reaction can be monitored by determining the acid value of the reaction mixture.

[0228] oligomers or polymers having the following formula

[0229]

[0230] in

[0231] L 1 It is an organic residue, and

[0232] m is between 0 and 16.0

[0233] It is commercially available or can be prepared by methods known in the art, for example by a compound having the following formula.

[0234]

[0235] in

[0236] L 1 It is an organic residue.

[0237] Polymerization with compounds having the following formula

[0238]

[0239] in

[0240] L 1 It is an organic residue.

[0241] The free radical initiator (I) can be any compound that forms free radicals during heat treatment (thermal free radical initiator) or radiation (photoinitiator).

[0242] Examples of thermal free radical initiators are peroxides such as potassium persulfate, benzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, acetylcyclohexylsulfonyl peroxide, diisopropyl percarbonate, tert-butyl peroctanoate, cumene hydroperoxide, dicumyl peroxide, as well as tert-butyl perbenzoate, azobisisobutyronitrile, and benzinol.

[0243] Examples of photoinitiators include acetophenone, 2,2-dimethoxy-2-phenylacetophenone (benzoylayl dimethyl ketal), 2,2-diethoxyacetophenone, 4-dimethylaminoacetophenone, benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 2-chlorobenzophenone, 4,4'-bis(diethylamino)-benzophenone, thioxanone, isopropyl-9H-thioxan-9-one, methyl phenylglyoxylate, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin dimethyl ketal, cyclohexylphenyl ketone, 1-hydroxy-cyclohexylphenyl ketone, p-isopropyl-2-hydroxyisobutyrylphenyl, 2-hydroxy-2-methyl-1-phenyl- 1-Propane, oligomeric [2-hydroxy-2-methyl-1-[4-(1-methyl-vinyl)phenyl]propanone], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-methyl-1-(4-methylthiophene)-2-morpholinoprop-1-one, 4-(2-hydroxyethoxy)phenyl-2-hydroxy-2-propanone, acylphosphine oxides (such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide), methyl-2-benzoylbenzoate and ethylphenyl(2,4,6-trimethylbenzoyl)phosphine ester.

[0244] Mixtures of initiators may also be used. Examples of mixtures of initiators include mixtures of at least two photoinitiators, mixtures of at least one photoinitiator and at least one thermal radical initiator, and mixtures of at least two thermal radical initiators.

[0245] Common mixtures of photoinitiators include mixtures of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-propanone, mixtures of 1-hydroxycyclohexylphenyl ketone and benzophenone, mixtures of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 1-hydroxy-cyclohexylphenyl ketone, mixtures of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-propanone, mixtures of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone, and mixtures of 4-methylbenzophenone and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

[0246] The at least one initiator is preferably a photoinitiator, more preferably a UV photoinitiator. A UV photoinitiator is an initiator that forms free radicals upon UV radiation treatment. Preferred initiators are selected from the group consisting of: diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethylphenyl(2,4,6-trimethylbenzoyl)phosphine ester, benzophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2,2-dimethoxy-2-phenylacetophenone (benzoyladium dimethyl ketal).

[0247] The composition may also contain additional additives, such as reactive diluents (R) other than compounds and oligomers or polymers (P) having formula (1), polymerization inhibitors, thickeners, ultraviolet absorbers, light stabilizers, surfactants, photosensitizers, curing catalysts, defoamers, plasticizers, fillers, pigments, dyes, flow control agents, antioxidants, flame retardants, antistatic agents, thixotropic agents, leveling agents, tackifiers, chelating agents, matting agents, and compatibilizers.

[0248] Examples of reactive diluents (R) that differ from compounds and oligomers or polymers (P) having formula (1) include styrene, p-tert-butylstyrene, p-methylstyrene, o-methylstyrene, 2-vinyl-naphthalene, divinylstyrene, butadiene, isoprene, chloroprene, ethylene, propylene, 1-butene, 2-butene, isobutene, cyclopentene, cyclohexene, cyclododecene, vinyl acetate, vinyl propionate, vinyl chloride and vinylidene chloride, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, etc. Divinyl glycol ether, di(ethylene glycol) divinyl ether, tri(ethylene glycol) divinyl ether, trimethylolpropane trivinyl ether, 1,4-cyclohexanediethanol divinyl ether, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, tert-amyl vinyl ether, dodecyl vinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, cyclohexyl vinyl ether, allyl acetate, diallyl phthalate, triallyl cyanurate, trimethylolpropane triallyl ether, α,β-unsaturated C 4-10 -Dicarboxylic acids (such as maleic acid, fumaric acid, itaconic acid, citraconic acid, medoconic acid, and 2-methylglutaric acid and their salts), α,β-unsaturated C 4-10- Dicarboxylic acid esters (such as dimethyl maleate, ethyl methyl maleate, diethyl maleate, dimethyl fumarate, ethyl methyl fumarate and diethyl fumarate), α,β unsaturated nitriles such as (meth)acrylonitrile, and α,β unsaturated aldehydes (such as (meth)acrylonitrile), and α,β unsaturated amides (such as (meth)acrylamide), α,β unsaturated C3-8-carboxylic acids (such as acrylic acid, methacrylic acid and 3,3-dimethacrylic acid and their salts).

[0249] Another example of a reactive diluent (R) that differs from compounds and oligomers or polymers (P) having formula (1) is (meth)acrylic acid C. 1-20 alkyl esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, 2-methylbutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, and methyl propylene. Heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, 2-propylheptamethacrylate, nonyl methacrylate, decyl methacrylate, isodecyl methacrylate, undecyl methacrylate and dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecanyl methacrylate, octadecyl methacrylate and nonadecanyl methacrylate, C(meth)acrylate 5-12 -Cycloalkyl esters such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and cycloheptyl (meth)acrylate, acetylacetoxy (C 2-6 -alkyl) esters such as acetylacetoxyethyl (meth)acrylate, acetylacetoxypropyl (meth)acrylate, and acetylacetoxybutyl (meth)acrylate, (meth)acrylate [C 1-10 -alkoxy (C 1-10 -alkoxy) 0-5 C 1-10-Alkyl esters such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 2-(2'-methoxyethoxy)ethyl (meth)acrylate and 2-(2'-ethoxy-ethoxy)ethyl (meth)acrylate, 2-norbornyl (meth)acrylate, dihydrodicyclopentadienyl (meth)acrylate, 4-tetrahydropyranyl (meth)acrylate, 2-tetrahydropyranyl (meth)acrylate, tetrahydrofuranyl (meth)acrylate, C 1-20 Diesters of diols and (meth)acrylic acid, such as 1,2-ethylene glycol di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,2-butanediol di(meth)acrylate, 1,3-butanediol-di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-bis(hydroxymethyl)-cyclohexane di(meth)acrylate, 1,4-bis(hydroxymethyl)-cyclohexane di(meth)acrylate, and cyclohexane-1,4-diol di(meth)acrylate, ethoxylated and / or propoxylated C 1-20- Diesters of diols and (meth)acrylic acid such as ethoxylated and / or propoxylated 1,2-butanediol di(meth)acrylate, ethoxylated and / or propoxylated 1,4-butanediol di(meth)acrylate, ethoxylated and / or propoxylated neopentyl glycol di(meth)acrylate, ethoxylated and / or propoxylated 1,4-bis(hydroxymethyl)-cyclohexane di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol-polypropylene glycol di(meth)acrylate—the sequence of ethylene oxide or propylene oxide units is block or random, polytetramethylene glycol di(meth)acrylate. Acrylic esters, polytetrahydrofuran di(meth)acrylates, and ethoxylated or propoxylated bisphenol A di(meth)acrylates, glycerol tri(meth)acrylates, 1,1,1-trimethylolpropane tri(meth)acrylates, 1,1,1-trimethylolethane tri(meth)acrylates, pentaerythritol tetra(meth)acrylates, di(1,1,1-trimethylolpropane)tetra(meth)acrylates and dipentaerythritol hexa(meth)acrylates, ethoxylated and / or propoxylated glycerol tri(meth)acrylates, ethoxylated and / or propoxylated 1,1,1-trimethylolpropane tri(meth)acrylates, ethoxylated and / or propoxylated pentaerythritol tetra(meth)acrylates, ethoxylated and / or propoxylated di(1,1,1-trimethylolpropane)tetra(meth)acrylates and ethoxylated and / or propoxylated dipentaerythritol hexa(meth)acrylates.

[0250] The term "(meth)acryloyl" includes acryloyl and methacryloyl.

[0251] The reactive diluent (R), unlike compounds and oligomers or polymers (P) having formula (1), preferably has a weight-average molecular weight of less than 1000 g / mol and a number-average molecular weight of less than 750 g / mol. The weight-average molecular weight and number-average molecular weight can be determined using gel permeation chromatography calibrated with polystyrene standards.

[0252] Examples of polymerization inhibitors include copper(II) chloride, 2,2,6,6-tetramethylpiperidin-1-oxy (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxy (TEMPOL), 4-benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxy, 4-benzyloxy-2,2,6,6-tetramethylpiperidin-1-oxy, 2,2-diphenyl-1-picrylhydrazine (DPPH), tris(p-nitrophenyl)methane, p-phenylenediamines such as N,N'-diphenyl-p-phenylenediamine, phenothiazines, hydroxylamines such as N,N-diethylhydroxylamine (DEHA), quinones such as hydroquinone (HQ), and methylhydroquinone. Quinones, hydroquinone monomethyl ether (MEHQ), 1,4-benzoquinone, tert-butylhydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)-hydroquinone and 2,5-bis(1,1-dimethylbutyl)hydroquinone, p-tert-butylcatechol (TBC), alkoxylated phenols such as 4-methoxyphenol, alkylated phenols such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol and 2,6-di-tert-butyl-4-methylphenol, alkylated and alkoxylated phenols such as 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol.

[0253] Examples of thickeners are hydroxymethyl cellulose and bentonite. Examples of UV absorbers are benzotriazoles such as 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzo-triazole, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol and 2-(2H-benzotriazol-2-yl)-p-cresol, triazines such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)5-((hexyl)oxy)phenol, cyanoacrylates and benzophenone. Examples of light stabilizers are hindered amine light stabilizers (HALS) such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine and bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate. Examples of fillers include talc, diatomaceous earth, clay, aluminum silicate, magnesium silicate, calcium carbonate, calcium sulfate, barium sulfate, aluminum hydroxide, alumina, and organic fillers such as polyacrylic acid and cellulose. Examples of chelating agents are ethylenediaminetetraacetic acid and β-diketone.

[0254] The compositions of the present invention typically contain

[0255] 10.0% to 98.0% by weight of compounds having formula (1) and

[0256] 2.0% to 90.0% by weight of oligomers or polymers (P)

[0257] Based on the weight of the composition.

[0258] The composition of the present invention preferably contains

[0259] 25.0% to 96.0% by weight of compounds having formula (1) and

[0260] 4.0% to 75.0% by weight of oligomers or polymers (P)

[0261] Based on the weight of the composition.

[0262] The composition of the present invention more preferably contains

[0263] 40.0% to 95.0% by weight of compounds having formula (1) and

[0264] 5.0% to 60.0% by weight of oligomers or polymers (P)

[0265] Based on the weight of the composition.

[0266] The compositions of the present invention typically contain

[0267] The free radical initiator (I) is 0% to 20.0% by weight of the compound having formula (1) and the oligomer or polymer (P).

[0268] The compositions of the present invention preferably contain 0.1% to 15.0% by weight of a free radical initiator (I) based on the weight of the compound having formula (1) and the oligomer or polymer (P).

[0269] The compositions of the present invention more preferably contain 1.0% to 10.0% by weight of a free radical initiator (I) based on the weight of the compound having formula (1) and the oligomer or polymer (P).

[0270] The composition preferably contains less than 5% by weight, more preferably less than 2% by weight, and most preferably less than 1% water based on the weight of the composition.

[0271] The composition preferably contains less than 10% by weight, more preferably less than 5% by weight, even more preferably less than 2% by weight, and most preferably less than 1% of an organic solvent based on the weight of the composition.

[0272] The compositions of the present invention can be prepared by mixing a compound having formula (1) with an oligomer or polymer (P), a free radical initiator (if present), and an additive (if present) in any order.

[0273] Another part of the invention is a cured layer formed from the composition of the invention.

[0274] The cured layer can be obtained by a method comprising the following steps: (i) applying the composition of the present invention to a substrate to form a layer, and (ii) treating the layer of step (i) with heat, radiation or an electron beam to form a cured layer.

[0275] The compositions of the present invention can be applied to a substrate by any method known in the art, such as by doctor blade, spraying, smearing, doctor blade coating, brushing, rolling, roller coating, flow coating and lamination, doctor blade, various printing processes such as gravure printing, transfer printing, offset printing and inkjet printing, and by using a stick.

[0276] The layer obtained directly after the composition is applied to the substrate preferably has a thickness in the range of 20 to 500 micrometers, more preferably in the range of 40 to 300 micrometers, most preferably in the range of 60 to 240 micrometers, and particularly in the range of 60 to 200 micrometers.

[0277] In step (ii), the layer of step (i) is treated with an electron beam, heat, or radiation to form a crosslinked layer. Heat can be applied by any suitable heat source, including near-infrared (NIR) radiation, such as radiation with wavelengths in the range of 760 nm to 2500 nm. Preferably, the layer of step (i) is treated with ultraviolet radiation, sunlight, or an electron beam. More preferably, the layer of step (i) is treated with radiation with wavelengths in the range of 200 to 700 nm, even more preferably in the range of 200 to 500 nm, and most preferably in the range of 250 to 400 nm.

[0278] Examples of radiation sources include low-pressure mercury vapor lamps, medium-pressure mercury vapor lamps, high-pressure mercury vapor lamps, lasers, pulsed lamps (flash lamps), halogen lamps, excimer lamps, and LED lamps (including UV-A LEDs, UV-B LEDs, and UV-C LEDs). A radiation dose sufficient for curing is typically selected. In the case of UV radiation, 80 to 3000 mJ / cm² is commonly used. 2 Preferred concentration: 100 to 2000 mJ / cm 2 The radiation dose. Combinations of different radiation sources can also be used.

[0279] Step (ii) can be performed in the presence of oxygen or in the absence of oxygen (e.g., in an inert gas atmosphere). Suitable inert gases are nitrogen, argon, and carbon dioxide. The layer of step (i) can also be covered with a transparent medium such as a transparent polymer film, glass, or water, and irradiated through this transparent medium. Irradiation can also be performed by passing the substrate coated with the layer of step (i) through a radiation source at a constant speed.

[0280] The substrate can be any suitable substrate. Preferably, the substrate is selected from the group consisting of: wood substrates, engineered wood substrates, engineered bamboo substrates, engineered cellulose substrates other than engineered wood or engineered bamboo substrates, fiber-reinforced composite (FRC) substrates, wood-plastic composite (WPC) substrates, plastic substrates (such as melamine-formaldehyde substrates), paper substrates, recycled paper substrates, cardboard (also known as hardboard) substrates, recycled cardboard (also known as recycled hardboard) substrates, metal substrates, stone substrates, glass substrates, textile substrates, leather substrates, ceramic substrates, and mineral building material substrates (such as molded cement blocks and fiber-cement boards). The substrate may also be pre-coated with a coating composition different from the coating composition of the present invention.

[0281] Examples of wood substrates include oak, beech, maple, alder, ash, pine, fir, spruce, chestnut, locust, birch, elm, teak, walnut, and softwood.

[0282] Timber can take the form of, for example, sawn timber (also called lumber), planks for flooring (such as parquet flooring), fixtures for building construction or domestic applications, or solid wood furniture. Softwood can take the form of, for example, tiles for flooring or fixtures for domestic applications.

[0283] Engineered wood substrates are derivative wood substrates manufactured by bonding or fixing strips, particles, fibers, veneers, or boards of wood with adhesives or other fixing methods to form composite materials. Examples of adhesives are urea-formaldehyde resin, phenolic resin, melamine-formaldehyde resin, polymethylene diphenyl diisocyanate, polyvinyl acetate, and polyurethane. Examples of engineered wood substrates are glued laminated timber, cross-laminated timber (CLT), parallel strip lumber (PSL), laminated veneer lumber (LSL), laminated veneer lumber (LVL), plywood, oriented strand board (OSB), composite boards, particleboard (also known as chipboard or wood chip laminate), fiberboard such as hardboard (also known as high-density fiberboard, HDF), and medium-density fiberboard (MDF).

[0284] Engineered wood substrates can take the form of sheets used for engineered wood flooring (such as laminate flooring), devices used for building construction or home applications, and furniture (such as flat-panel furniture).

[0285] Engineered bamboo substrates are derivative bamboo substrates manufactured by bonding or fixing bamboo portions together with adhesives or other fixing methods to form a composite material. An example of engineered bamboo substrates is laminated bamboo.

[0286] Engineered cellulose substrates, other than engineered wood and engineered bamboo substrates, are products derived from lignin-containing materials other than wood and bamboo (such as rye straw, wheat straw, rice straw, hemp stalks, flax stalks, and bagasse), which are manufactured by bonding or fixing the lignin-containing material portions other than wood and bamboo with adhesives or other fixing methods to form composite materials.

[0287] Fiber-reinforced composite (FRC) is made from rice-derived fibers and plastics.

[0288] Wood-plastic composites (WPCs) are composite materials made of wood fibers or wood flour and thermoplastic polymers such as polyethylene, polypropylene, polyvinyl chloride, or polyacetic acid.

[0289] More preferably, the substrate is selected from the group consisting of: wood substrate, engineered wood substrate, engineered cellulose substrate other than engineered wood or engineered bamboo substrate, fiber reinforced composite (FRC) substrate, wood-plastic composite (WPC) substrate, plastic substrate (such as melamine-formaldehyde substrate), paper substrate, recycled paper substrate, paperboard (also known as cardboard) substrate, recycled paperboard (also known as recycled cardboard) substrate, metal substrate, glass substrate, and ceramic substrate.

[0290] Most preferably, the substrate is selected from the group consisting of: wood substrate, engineered wood substrate and wood-plastic composite substrate (WPC).

[0291] Preferably, the substrate is flat and has a uniform surface.

[0292] Another part of the invention is a substrate coated with the curing layer of the invention.

[0293] Another part of the invention is the use of the coating compositions of the invention as paint or varnish compositions.

[0294] The reactive diluent of the present invention is advantageous because a curable composition comprising the reactive diluent of the present invention and at least one free radical polymer (P) curable oligomer or polymer curable by free radical polymerization has an acceptable viscosity and simultaneously forms a cured layer wherein the hardness of the cured layer does not change or only changes in a negligible range of ratios of free radical polymer curable oligomer or polymer (P) to reactive diluent. Example

[0295] Irgacure 184: 1-Hydroxy-cyclohexylphenyl ketone

[0296] Example 1

[0297] Preparation of compound 3a

[0298]

[0299] An aqueous solution of n-heptanal (91.4 g, 0.8 mol) and formaldehyde (37%, 487.0 g, 6.0 mol) was stirred at room temperature for one hour. Then, potassium hydroxide (44.8 g, 0.4 mol) was dissolved in water (200 mL) and added dropwise while the reaction mixture was cooled in an ice bath to a maximum temperature of 27°C. The reaction mixture was stirred at room temperature for three hours, then at 50°C for two hours, and finally at room temperature for 12 hours. The two-phase mixture was extracted with methyl tert-butyl ether. The combined organic phases were washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated. After purification by vacuum distillation and recrystallization from methyl tert-butyl ether and cyclohexane, compound 3a was given as a colorless solid (yield: 27.0%). 1 H NMR (500MHz, DMSO-d6): δ 0.86 (t, 3H), 1.10-1.40 (m, 8H), 3.25 (d, 6H), 4.20 (s, 3H)ppm. 13 C NMR (125 MHz, DMSO-d6): δ 13.9, 21.9, 22.1, 29.1, 32.5, 43.2, 62.1ppm.

[0300] Example 2

[0301] Preparation of compound 3b

[0302]

[0303] Nononal (113.0 g, 0.8 mol) and an aqueous solution of formaldehyde (37%, 245.0 g, 3.0 mol) were stirred at room temperature for one hour. Then, potassium hydroxide (44.8 g, 0.4 mol) was dissolved in water (200 mL) and added dropwise while the reaction mixture was cooled in an ice bath to a maximum temperature of 27°C. The reaction mixture was stirred at room temperature for three hours, then at 50°C for two hours, and finally at room temperature for 12 hours. The two-phase mixture was extracted with methyl tert-butyl ether. The combined organic phases were washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated. After purification by vacuum distillation and recrystallization from methyl tert-butyl ether and cyclohexane, compound 3b was given as a colorless solid (yield: 35.5%). 1 H NMR (500MHz, DMSO-d6): δ 0.87 (t, 3H), 1.10-1.40 (m, 12H), 3.25 (d, 6H), 4.20 (s, 3H)ppm. 13C NMR (125 MHz, DMSO-d6): δ 13.9, 22.0, 22.3, 28.8, 29.1, 30.2, 31.3, 43.3, 62.1 ppm.

[0304] Example 3

[0305] Preparation of compound 1a (1,1,1-trimethylolhexane triacrylate (TMHTA))

[0306]

[0307] 51.3 g of compound 3a from Example 1, 22.8 g of cyclohexane, 68.7 g of acrylic acid, 0.096 g of a 31.5% solution of copper(II) chloride in water, 0.47 g of H3PO2, and 0.035 g of methylhydroquinone were added as a template and the mixture was heated to 75°C. At this temperature, 5.16 g of a 65% aqueous solution of p-toluenesulfonic acid was added. The temperature was raised to 96°C to 97°C and maintained at this level by adding additional cyclohexane. The reaction progress was determined by the amount of reaction water formed. The reaction was completed after approximately 10 hours. Post-treatment was performed as follows: excess acrylic acid was extracted aqueously, the solvent was removed under reduced pressure, and the liquid compound 1a (1,1,1-trimethylolhexane triacrylate (TMHTA)) was then filtered through a Seitz K300 filter. The esterification yield was 84%. 1 ¹H NMR (400 MHz, CDCL₃): δ 0.88 (t, 3H), 1.16–1.22 (m, 8H), 4.01 (s, 6H), 5.83 (d, 3H), 6.12 (m, 3H), 6.41 (d, 3H) ppm. EI-MS m / z: for C 18 H 26 O6 of [M + H] + Calculated value: 338.17; Measured value: 338.17.

[0308] Comparison Example 1

[0309] Preparation of ethoxylated 1,1,1-trimethylolpropane triacrylate (TMPEOTA)

[0310] The mixture was loaded with 679 g of ethoxylated 1,1,1-trimethylolpropane (average degree of ethoxylation 3.5), 108 g of cyclohexane, 521 g of acrylic acid, 0.96 g of a 31.5% solution of copper(II) chloride in water, 3.58 g of H3PO2, and 0.27 g of methylhydroquinone as a template and heated to 75°C. At this temperature, a catalyst (39.69 g of a 65% aqueous solution of p-toluenesulfonic acid) was added. The temperature was raised to 96°C to 97°C and maintained at this level by adding additional cyclohexane. The reaction progress was determined by the amount of reaction water formed. The reaction was completed after approximately 10 hours. Post-treatment was performed as follows: excess acrylic acid was extracted aqueously, the solvent was removed under reduced pressure, and liquid TMPEOTA was subsequently filtered through a Seitz K300 filter. The esterification yield was 92%.

[0311] Comparison Example 2

[0312] Preparation of 1,1,1-trimethylolpropane triacrylate (TMPTA)

[0313]

[0314] 43.3 g of 1,1,1-trimethylolpropane, 10.8 g of cyclohexane, 76.7 g of acrylic acid, 0.096 g of a 31.5% solution of copper(II) chloride in water, 0.47 g of H3PO2, and 0.035 g of methylhydroquinone were added as a template and the mixture was heated to 75°C. At this temperature, a catalyst (5.16 g of a 65% aqueous solution of p-toluenesulfonic acid) was added. The temperature was raised to 96°C to 97°C and maintained at this level by adding additional cyclohexane. The reaction progress was determined by the amount of reaction water formed. The reaction was completed after approximately 10 hours. Post-treatment was performed as follows: excess acrylic acid was extracted aqueously, the solvent was removed under reduced pressure, and liquid TMPTA was subsequently filtered through a Seitz K300 filter. The esterification yield was 87%.

[0315] Comparison Example 3

[0316] Preparation of 1,1,1-trimethylolethane triacrylate (TMETA)

[0317]

[0318] 40.3 g of 1,1,1-trimethylolethane, 10.8 g of cyclohexane, 79.7 g of acrylic acid, 0.096 g of a 31.5% solution of copper(II) chloride in water, 0.47 g of H3PO2, and 0.035 g of methylhydroquinone were added as a template and the mixture was heated to 75°C. At this temperature, a catalyst (5.16 g of a 65% aqueous solution of p-toluenesulfonic acid) was added. The temperature was raised to 96°C to 97°C and maintained at this level by adding additional cyclohexane. The reaction progress was determined by the amount of reaction water formed. The reaction was completed after approximately 10 hours. Post-treatment was performed as follows: excess acrylic acid was extracted aqueously, the solvent was removed under reduced pressure, and liquid TMETA was subsequently filtered through a Seitz K300 filter. The esterification yield was 86%.

[0319] Example 4

[0320] Preparation of oligomer 2a (BADGEDA)

[0321] 859.12 g of Epikote 828 (an epoxy resin derived from bisphenol A and epichlorohydrin, with an epoxy group content of 5260 to 5420 mmol / kg and a viscosity at 25°C of 12 to 14 Pa•s at 25°C, Epikote 828 without any diluent) (7a), 1.2 g of Kerobit TBK (2,6-di-tert-butyl-4-methylphenol), 0.6 g of 4-methoxyphenol, and 0.12 g of phenothiazine were placed in a 2 L four-necked round-bottom flask equipped with a stirrer, thermometer, condenser, and dropping funnel. The mixture was stirred and heated to 100°C. Then, 6.0 g of tetraethylammonium bromide dissolved in 34.09 g of acrylic acid was added, followed by 306.79 g of acrylic acid being added dropwise to the mixture via a dropping funnel at 103°C–107°C. After the addition of acrylic acid, the reaction was maintained at 103°C to 107°C for 35 minutes. The acid value of the mixture in the flask was determined at defined time intervals, and the reaction was stopped when the acid value was below 5 mg KOH / g. Oligomer 2a (BADGEDA) was obtained as a pale yellow viscous liquid. The final acid value was 2.2 mg KOH / g, and its viscosity at 23°C was approximately 250 Pa•s.

[0322] Example 5

[0323] Preparation of coating compositions comprising compounds 1a (TMHTA), TMPEOTA, TMPTA and TMETA (respectively) and 2a (BADGEDA)

[0324] Compound 1a (TMHTA) of Example 3 was mixed with Irgacure 184 (photoinitiator) to produce a coating composition (0 wt% 2a (BADGEDA)). The concentration of Irgacure 184 was 4% by weight based on the weight of the coating composition.

[0325] Compound 1a (TMHTA) of Example 3 was mixed with compound 2a (BADGEDA) of Example 4. The weight ratios of compound 2a (BADGEDA) of Example 4 to the mixtures of compound 2a (BADGEDA) of Example 4 and compound 1a (TMHTA) of Example 3 were 10% (10 wt% BADGEDA content), 20% (20 wt% BADGEDA content), 30% (30 wt% BADGEDA content), 40% (40 wt% BADGEDA content), and 50% (50 wt% BADGEDA content), respectively. Irgacure 184 (photoinitiator) was added at a concentration of 4 wt% based on the weight of the coating composition.

[0326] Similar to TMPEOTA in Comparative Example 1, TMPTA in Comparative Example 2 and TMETA in Comparative Example 3 were mixed with Irgacure 184 (photoinitiator) to produce coating compositions (0 wt% BADGEDA content). The concentration of Irgacure 184 was 4% by weight based on the weight of the coating composition.

[0327] Similar to TMPEOTA in Comparative Example 1, TMPTA in Comparative Example 2 and TMETA in Comparative Example 3 were mixed with oligomer 2a (BADGEDA) in Example 4, respectively. The weight ratios of oligomer 2a (BADGEDA) in Example 4 and the mixtures of oligomer 2a (BADGEDA) in Example 4 with TMPEOTA in Comparative Example 1, TMPTA in Comparative Example 2, and TMETA in Comparative Example 3 were 10% (10 wt% BADGEDA content), 20% (20 wt% BADGEDA content), 30% (30 wt% BADGEDA content), 40% (40 wt% BADGEDA content), and 50% (50 wt% BADGEDA content), respectively. Irgacure 184 (photoinitiator) was added at a concentration of 4% by weight based on the coating composition.

[0328] The viscosity of the coating composition was determined after storage in a climate chamber for at least 24 hours. According to DIN EN ISO 3219-2:2021, the viscosity was determined using a Brinell viscometer at 23°C and 1000 s⁻¹. -1 Viscosity was measured under a velocity gradient.

[0329] The results are shown inFigure 1 middle.

[0330] Figure 1 The results show that viscosity decreases with increasing reactive diluent content.

[0331] The coating composition was applied to a glass plate using a box-type doctor blade with a roller gap width of 120 μm (meaning a wet film thickness of 120 μm). The wet layer was then immediately cured twice with UV at a belt speed of 5 m / min under ambient conditions. For curing, an IST UV system (type: M-40-2xl-R-TR-SLC-SO-Inert, lamp 1: IST UV lamp M400 U2HC, lamp 2: IST UV lamp M400 U2H) was used. After storage in a climate chamber for at least 24 hours, the martensite hardness was determined. The martensite hardness was determined via microindentation using a FISCHERSCOPE HM2000 S apparatus. This apparatus measured and calculated the martensite hardness according to Annex A of DIN EN ISO 14577-1:2015 and ASTM E 2546.

[0332] The results are shown in Figure 2 middle.

[0333] Figure 2 A coating composition containing compound 1a (TMHTA) and 0 wt% BADGEDA is shown to have nearly the same martensitic hardness as a coating composition containing compound 1a (TMHTA) and 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% BADGEDA (respectively).

[0334] Therefore, the martensitic hardness of coating compositions containing compound 1a (TMHTA) and 0 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% BADGEDA is approximately the same.

[0335] Figure 2 It is also shown that, in contrast, coating compositions containing TMPEOTA of Comparative Example 1 and 0 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, and 50 wt% BADGEDA (respectively) exhibit different martensitic hardness. This also applies to coating compositions containing TMPTA of Comparative Example 2 and TMETA of Comparative Example 3 (respectively) and 0 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, and 50 wt% BADGEDA.

Claims

1. A compound having the following formula in R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl, in C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution R 2 It is H or methyl and n is between 1.0 and 6.

0.

2. The compound of claim 1, wherein, R 1 It is C 5-8 -alkyl, C 5-8 -Alkenyl or C 5-8 -Alkyne group, and R 2 It is H or methyl.

3. The compound of claim 1, wherein, R 1 It is pentyl and R 2 It's H.

4. The compound according to any one of claims 1 to 3, wherein, n is between 1.0 and 4.

0.

5. The compound according to any one of claims 1 to 3, wherein, n is between 1.0 and 2.

0.

6. A composition comprising at least one compound as claimed in any one of claims 1 to 5, at least one oligomer or polymer (P) different from compound (1), and optionally at least one free radical initiator (I), the oligomer or polymer (P) being curable by free radical polymerization.

7. The composition of claim 6, wherein, The oligomer or polymer (P) carries at least one group having the following formula Where R 3 It is H or methyl.

8. The composition of claim 7, wherein, The oligomer or polymer (P) carries at least one group having the following formula Where R 3 It is H or methyl.

9. The composition of claim 8, wherein, The oligomer or polymer (P) is at least one oligomer or polymer selected from the group consisting of: 、 as well as Where L 1 It is an organic residue. R 3 It is H or methyl, and m is between 0 and 16.

0.

10. The composition of claim 9, wherein, L 1 yes R 3 It is H or methyl, and m ranges from 0.1 to 16.

0.

11. The composition according to any one of claims 6 to 10, wherein, The composition contains The compound having formula (1) comprises 10.0% to 98.0% by weight and 2.0% to 90.0% by weight of oligomers or polymers (P) Based on the weight of the composition.

12. The composition according to any one of claims 6 to 11, wherein, The composition contains The free radical initiator (I) is 0.1% to 15.0% by weight of the compound having formula (1) and the oligomer or polymer (P).

13. A cured layer formed on a substrate by the composition as described in any one of claims 6 to 12.

14. A substrate comprising the cured layer as claimed in claim 13.

15. A method for preparing compounds having the following formula in R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl, in C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution R 2 It is H or methyl. and n is between 1.0 and 6.

0. The method includes making compounds having the following formula in R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl, in C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution and n is between 1.0 and 6.

0. Steps of reacting with compounds having the following formula Where R 2 It is H or methyl.

16. A method for preparing compounds having the following formula in R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl, in C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution The method includes the following steps: (i) Make compounds having the following formula in R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl, in C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution Reacts with formaldehyde to obtain a compound having the following formula in R 1 It is C 4-9 -alkyl, C 4-9 -Alkenyl, C 4-9 -Alynyl group, C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl or C 4-12 - Heterocyclic alkyl, in C 4-9 -alkyl groups can be phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl or C 4-8 - Heterocyclic alkyl substitution, and C 6-14 -Aryl, C 3-12 - heteroaryl, C 3-12 -cycloalkyl, C 5-12 -cycloalkenyl and C 4-12 - Heterocyclic alkyl groups can be C 1-10 -alkyl, phenyl, C 3-8 - heteroaryl, C 5-8 -cycloalkyl or C 4-8 - Heterocyclic alkyl substitution as well as (ii) Reduce the compound having formula (6) with hydrogen to obtain the compound having formula (3”).

17. Use of the composition as a paint or varnish composition as claimed in any one of claims 6 to 12.

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