One pot synthesis of urea (METH)acrylates

Abstract

To provide the one-pot synthesis of polymerizable and acyclic urea (meth)acrylates, preferably mono(meth)acrylates, via in-situ synthesis of urea alcohols or amines followed by direct reaction with a (meth)acrylate reactive diluent.SOLUTION: The urea alcohol / amine is obtained from isocyanates and alcohols, amines, or hydroxyamines. Subsequently, the reaction with the (meth)acrylate reactive diluent takes place and the urea (meth)acrylate is directly obtained as either solution in the reactive diluent or as pure material after removal of the reactive diluent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to the one-pot synthesis of polymerizable, acyclic urea (meth)acrylates, preferably mono(meth)acrylates, by in situ synthesis of urea alcohol or amines, followed by direct reaction with a (meth)acrylate reactive diluent. [Background technology]

[0002] Among the vast number of polymerizable functional groups, the (meth)acrylate moieties are of particular interest because they can be arbitrarily modified, additionally functionalized, exhibit a beneficial safety profile, and are typically liquid or low-melting-point substances.

[0003] Among (meth)acrylates, polymerizable molecules containing a urea moiety are of particular interest because their polymerizable properties ultimately allow the urea moiety to be incorporated into polymer materials. These polymer materials then possess polarity, hydrophilicity, and hydrogen bonding properties, making them suitable for use in adhesives, coatings, and pharmaceutical / biological applications.

[0004] The term “wet adhesion” is used in the paint industry to describe a paint’s ability to maintain an adhesive bond to a substrate under wet or high-humidity conditions. While oil-based paints are known to retain their adhesive properties under wet or humid conditions, the tendency of many water-based coatings (i.e., latex) to lose their adhesive properties when wet has limited the usefulness of such coatings. The poor wet adhesion of latex paints also makes surfaces painted with such paints less washable than those painted with organic solvent-based paints.

[0005] The use of aqueous emulsion polymer systems as protective and decorative coatings for many types of surfaces is widespread, and since such systems are used by individuals at home and in industry, there is a great demand for improving their wet adhesion. In recent years, the industry has recognized the problem of adhesion loss in latex paints, and various modifications of such latex systems have been proposed to improve wet adhesion. The chemical incorporation of amine, amide, and acetacetate functional groups into latex polymers has been reported to improve the wet adhesion properties of latex paints. For example, numerous cyclic ureid compounds are known to impart wet adhesion properties.

[0006] One of the most important and industrially relevant examples is N-(2-methacryloyloxyethyl)ethylene urea (MEEU), in which the cyclic urea portion is bonded to the methacrylate via a C2 unit. Its applications are found in polymerization and / or copolymerization in bulk, suspension, emulsion, and solution, resulting in materials used in the plastics, paint, leather, paper, and textile industries. In many applications, MEEU is used to improve the wet adhesion and cohesive properties of emulsion polymers and the wet scrub resistance of some products. MEEU also contributes to corrosion protection in its formulations.

[0007] A slight modification of N-(2-methacryloyloxyethyl)ethyleneurea is N-(2-methacrylamidoethyl)ethyleneurea (N-MEEU), which is simply methacrylamido instead of ester. It is also used as a wet-bond monomer for latex paints and promotes the adhesion of polymer resins to metals, glass, concrete, and other inorganic substrates in many applications, including industrial, maintenance, automotive, and construction. It improves wet-bond properties and solvent resistance in a wide range of latex systems. It provides high adhesive strength, enhanced mechanical properties, and improved chemical and water resistance to the polymer systems.

[0008] Although MEEU or N-MEEU have been under development for several decades, both monomers remain cutting-edge and play a crucial role in current research and invention. For coatings and adhesives, see, for example, U.S. Patent Publication No. 2020 / 017725 (US2020017725 (A1)), European Patent Publication No. 3643729 (EP3643729 (A1)), European Patent No. 2935485 (EP2935485 (B1)), U.S. Patent No. 10421872 (US10421872 B1), or U.S. Patent Publication No. 2020 / 392381 (US2020392381 (A1)).

[0009] However, both the molecules and their manufacturing methods have significant drawbacks. First, the general synthetic procedures for the starting materials 2-hydroxyethyl ethylene urea and 2-aminoethyl ethylene urea can hardly be modified and are virtually restricted to 5-membered cyclic ureas (imidazolidin-2-one) and amino / hydroxyethyl substituents on one nitrogen atom of the imidazolidin-2-one moiety. Therefore, the range of urea-containing (meth)acrylates is, precisely speaking, restricted to the above two molecules, which are known, for example, as VISIOMER® MEEU (Evonik) or SIPOMER® WAM II (Solvay). Additionally, both starting materials 2-hydroxyethyl ethylene urea and 2-aminoethyl ethylene urea have to be manufactured in separate synthetic steps. Second, both products are usually obtained (and commercially distributed) as solutions in aqueous solutions or organic solvents or reactive diluents, which interfere with subsequent processes in non-aqueous media (such as 3D printing) and applications that do not require solvents or reactive diluents. Third, N-(2-methacrylamidoethyl)ethylene urea is usually produced from 2-aminoethyl ethylene urea and activated methacrylic acid derivatives (such as methacrylic anhydride, methacryloyl chloride), which often give rise to undesired and hardly removable by-products (such as methacrylic acid, hydrochloric acid), and these by-products have to be separated from the product with effort. As a result, the solution to these drawbacks is a significant challenge, and a synthetic route towards anhydrous (water-free) and easily purified urea (meth)acrylates is still needed.

[0010] Moreover, known structural derivatives of ethylene urea ethyl (meth)acrylate / (meth)acrylamide are particularly desirable, and the derivatives can ultimately result in polymer materials having, for example, improved (wetting) adhesion and cohesion, improved corrosion resistance properties, or improved scrub resistance. This might be achieved by chemical tailoring of the urea (meth)acrylate, and various synthetic routes can be considered depending on the targeted modification.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Non-Patent Documents

[0012]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0013] According to the above, an object of the present invention is to provide a novel production method of a novel (meth)acrylate-based monomer for (aqueous) emulsion polymers applied in coatings or adhesives.

Means for Solving the Problems

[0014] As a result, the inventors unexpectedly discovered that a variety of less polar molecules are available that are alternative to MEEU, and that one alternative method, though largely unfollowed, for the synthesis of urea-functionalized (meth)acrylates or (meth)acrylamides is the synthesis of urea-containing (long-chain) alcohols or amines, followed by subsequent (meth)acrylication by direct reaction (e.g., transesterification) with a (meth)acrylate reactive diluent. Unfortunately, the urea-containing (long-chain) alcohols or amines required for this must be synthesized through laborious means, making the synthesis of urea-containing (long-chain) (meth)acrylates a costly multi-step process. The inventors unexpectedly discovered that the in situ synthesis of the aforementioned urea-containing (long-chain) alcohols or amines in alkyl (meth)acrylates as reactive diluents is possible, enabling subsequent transesterification to obtain urea-containing (long-chain) (meth)acrylates in a one-pot process. The intermediate (II) is formed in situ with extremely high purity and yield by the reaction of an amino alcohol or diamine of general formula (V) with an isocyanate of general formula (VI) in a (meth)acrylate reactive diluent of general formula (III), thus allowing the intermediate to be subsequently converted to directly obtain (I) in high yield and purity.

[0015] More specifically, the present invention relates to general formula (I) [ka] [In the formula, R 1 The option is selected from -H or -Me; R 2 H, or C1-C 20 Selected from linear, branched, or cyclic alkyl or aryl groups; R 2′ is -H; R 3 H, or C1-C 20a linear, branched or cyclic alkyl or aryl group, and selected from benzene-sulfonyl, tosyl, p-chlorophenyl, adamantyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, and 2,6-dipropylphenyl; R 2 and R 3 are the same or different, X is selected from -O- or -NH-; and L is selected from linear, branched or cyclic alkyl or aryl groups of C2-C 20 in which one or more carbon atoms in the carbon chain may be substituted by one or more -O-, -NH- or -S- heteroatoms] relates to a one-pot process for producing (meth)acrylates, General formula (II)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0016] Detailed description of the invention In relation to the present invention, the term (meth)acrylate includes acrylates (i.e., esters of acrylic acid) and methacrylates (i.e., esters of methacrylic acid), as well as mixtures of methacrylic acid and acrylic acid, and mixtures of acrylates and methacrylates.

[0017] As used herein, the term "aryl" includes substituted aryl groups, and in particular alkylaryl groups, such as Ph-CH2-CH2-. An example of a linear alkyl group in which carbon atoms in the carbon chain are substituted with an O heteroatom is -CH2CH2-O-CH2CH2-; an example of a linear alkyl group in which carbon atoms in the carbon chain are substituted with an N heteroatom is -CH2CH2-NH-CH2CH2-.

[0018] Preferably, the (meth)acrylate of general formula (I) is urea mono It is a (meth)acrylate (different from cross-linking di(meth)acrylate, tri(meth)acrylate, or tetra(meth)acrylate).

[0019] In the (meth)acrylate of general formula (I), R 1 is preferably methyl and R 2 Preferably, it is selected from hydrogen and linear or branched alkyl groups of C1-C8. 2 It is particularly preferable that R is hydrogen. 3 The methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, cyclohexyl, and phenyl compounds are preferably selected from methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, cyclohexyl, and phenyl compounds. 3 It is particularly preferable that X is cyclohexyl or phenyl. X is preferably oxygen; and L is preferably selected from ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and ethoxyethyl.

[0020] Accordingly, an example of a (meth)acrylate of general formula (I) is as follows: [ka]

[0021] For example, one carbon atom is replaced by a heteroatom, such as O or NH, and a linker is formed, such as L=C5(C4 + heteroatom);R 1 =H, Me;R 2 Suitable acyclic alkylurea (meth)acrylates that are H = are, for example: [ka]

[0022] Linkers, e.g., L=C4 and C6;R 1 =H, Me;R 2 Suitable acyclic alkyl and arylurea (meth)acrylates that are H = are, for example: [ka]

[0023] As shown above, the aforementioned intermediate urea-containing alcohol and amine are, for example, an amino alcohol or diamine and an isocyanate, for example C1-C 30It can be obtained in situ by reaction with monoisocyanate compounds, such as benzene-sulfonyl isocyanate, tosyl isocyanate, methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, and 2,6-dipropylphenyl isocyanate, where the (meth)acrylate species is selected from the group consisting of alkyl (meth)acrylates of general formula (III).

[0024] Thus, the method according to the present invention eliminates the need for the use of functionalized (meth)acrylate precursors, such as isocyanatoethyl (meth)acrylate, and urea-containing alcohols or amines synthesized in a separate step.

[0025] The reaction with the (meth)acrylate reactive diluent described above is preferably carried out in the presence of at least one catalyst.

[0026] Suitable catalysts include zirconium acetylacetonate and, furthermore, zirconium or calcium 1,3-diketonates. These catalysts are disclosed, for example, in West German Patent Application Publication No. 2805702 (DE 28 05 702 A1).

[0027] Further examples of suitable catalysts include mixtures of alkali metal cyanates or alkali metal thiocyanates with alkali metal halides (e.g., LiCl); zinc compounds; alkaline earth metal oxides or alkaline earth metal hydroxides (e.g., CaO, Ca(OH)2, MgO, Mg(OH)2 or mixtures of the above compounds); alkali metal hydroxides; mixtures of alkali metal alkoxides with lithium chloride and / or lithium hydroxide; dialkyltin oxides (e.g., dioctyltin oxide (DOTO)), dibutyltin dilaurate (DBTL), alkali metal carbonates; quaternary ammonium salts ( Alkali metal carbonates together with (for example, tetrabutylammonium hydroxide or hexadecyltrimethylammonium bromide); mixed catalysts of diorganyl tin oxides and organyl tin halides; acidic ion exchangers; phosphomolybdenum heteropoly acids; titanium alcohols, such as titanium isopropoxide; chelate compounds of metallic titanium, zirconium, iron, or zinc with 1,3-di-carbonyl compounds; lead compounds (e.g., lead oxide, lead hydroxide, lead alkoxide, lead carbonate, or lead salts of carboxylic acids), amides of the first major metals (e.g., lithium amide); or mixtures of the above catalysts.

[0028] Furthermore, an acid or base may be used to catalyze the transesterification, where exemplary reaction conditions are described in West German Patent Application Publication No. 3423443 (DE 34 23 443) and European Patent Application Publication No. 0534666 (EP-A-0 534 666).

[0029] Particularly preferred catalysts for the method according to the present invention are tetraalkyl titanates, such as titanium isopropoxide, and alkaline earth metal oxides and hydroxides, such as calcium oxide and calcium hydroxide, which can be combined with alkali metal salts, such as lithium hydroxide or lithium chloride.

[0030] Accordingly, the method according to the present invention is advantageously carried out in the presence of at least one catalyst selected from the group consisting of Zr(acac)2, LiOH, CaO, dioctyl tin oxide (DOTO), dibutyl tin laurate (DBTL), titanium isopropoxide, and combinations thereof. Preferably, the catalyst is titanium isopropoxide, CaO / LiOH, CaO / LiCl, DOTO, or DBTL.

[0031] [5] The catalyst may be present in an amount of 0.01 to 5% by weight, or 0.1 to 3% by weight, preferably 0.3 to 2% by weight, based on the amount of compound (V).

[0032] The reaction temperature in the first reaction step can be maintained at 0°C to 80°C, or 0°C to 50°C, preferably 0°C to 30°C, whereas the reaction temperature in the second reaction step (transesterification step) can be maintained at 30°C to 180°C, or 50°C to 150°C, very preferably 80°C to 130°C. In this step, the reaction mixture is advantageously heated to a boil and separated from the alcohol R 4 The OH group is continuously removed by distillation in the form of the ester and its azeotrope. Depending on the reaction temperature, the catalyst, and the amount of catalyst, the reaction time ranges from about 2 to 15 hours. The reaction can also be carried out in the presence of an inert solvent, such as toluene or cyclohexane, but this is usually unnecessary. The reaction can be carried out under standard pressure, under greater pressure, or in partial vacuum.

[0033] The reactive diluent is an alkyl (meth)acrylate selected from the group consisting of propyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, and methyl (meth)acrylate. Preferably, the reactive diluent is methyl (meth)acrylate.

[0034] According to the above formula, equimolar amounts of reaction partners (II) and (III) react to form the desired final product. However, in practice, it has been found that it is always practical to maintain an excess of the reactive diluent, i.e., the starting ester (III), during the reaction. The amount of reactive diluent used may be 1 to 50 mol, or 2 to 20 mol, preferably 3 to 10 mol, per mole of compound (V).

[0035] The amount of isocyanate (VI) may be 0.80 to 1.20 equivalents, or 0.90 to 1.10 equivalents, preferably 0.95 to 1.05 equivalents, per equivalent of compound (V).

[0036] Advantageously, the method according to the present invention is carried out in the presence of at least one polymerization inhibitor. In relation to the present invention, the terms "(polymerization) inhibitor" and "stabilizer" are used synonymously.

[0037] The aforementioned at least one polymerization inhibitor may be selected from the group consisting of hydroquinone, hydroquinone ether, e.g., hydroquinone monomethyl ether or di-tert-butylcatechol, phenothiazine, N,N′-(diphenyl)-p-phenylenediamine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, p-phenylenediamine, methylene blue, or sterically hindered phenol, all of which are well known in the art. For further details, refer to the usual specialized literature, in particular Kroehnke, C., Schacker, O., and Zaeh, M. (2015). Antioxidants. Ullmann's Encyclopedia of Industrial Chemistry, (Ed.).

[0038] Preferably, the polymerization inhibitor is selected from the group consisting of hydroquinone monomethyl ether, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and mixtures thereof. Hydroquinone monomethyl ether is particularly preferred.

[0039] The amount of polymerization inhibitor at the start of the reaction may be adjusted to 0 to 5000 ppm, preferably 100 ppm to 3000 ppm, based on the amount of product theoretically expected from complete conversion. Additional inhibitors may be added, preferably in an amount adjusted to 0 to 1000 ppm based on the amount of stabilizer added additionally at the start of the reaction, based on the amount of product theoretically expected from complete conversion, and most preferably in an amount adjusted to 100 to 1000 ppm based on the amount of stabilizer added additionally at the start of the reaction, based on the amount of product theoretically expected from complete conversion.

[0040] The reaction can preferably be carried out with stirring, and the stirring speed is particularly preferably in the range of 50 to 2000 rpm, and most particularly preferably in the range of 100 to 500 rpm.

[0041] The reaction can be carried out continuously, semi-continuously, or in batches. The continuous method can preferably be carried out in a plant having several reactors, thereby, in particular, the reaction temperature can be varied and the alcohol or water released from the low-boiling point (meth)acrylic acid ester can be separated from the reaction system.

[0042] Of particular interest is the semi-batch method in which a portion of the reaction mixture is charged. In a further step or continuously after the start of the reaction, a low-boiling point ester of (meth)acrylic acid can be added to the reaction mixture.

[0043] The reaction is preferably carried out in an atmosphere containing at most 20% by weight of oxygen, preferably at most 10% by weight, and most preferably at most 3% by weight. In this way, complex safety measures can be avoided during implementation, thus achieving many cost advantages.

[0044] After the completion of the reaction, any excess reactive diluent (III) can be completely or partially removed by distillation. The dispersed catalyst is usually removed by filtration, and it is advantageous to do so before distillation of the reactive diluent (III), which is usually present in excess. However, it can also be removed only after the partial or complete removal of the excess reactive diluent (III). If the catalyst is recovered in filtered form, it can be used in other alcoholization batches after being dried as needed.

[0045] The method product of formula (I) thus obtained can be used directly, i.e., without costly and qualitatively troublesome removal steps—for example, as a solution in the acrylic or methacrylate—as a comonomer, particularly in the production of dispersed polymers. Using the above method, the compound of formula (I) can also be produced by this method as a neat liquid or solid, for example, by evaporation from a solution or crystallization from its solvent. Preferably, the (meth)acrylate of general formula (I) is obtained by evaporation of the reactive diluent. Alternatively, the (meth)acrylate of general formula (I) can be obtained as a solid upon cooling of the reaction mixture (after filtration in the case of a heterogeneous mixture) or by precipitation upon addition of an antisolvent (e.g., hexane, heptane, petroleum ether, etc.). The polymerization inhibitor may coprecipitate with the product (meth)acrylate of general formula (I), which has the effect of avoiding spontaneous polymerization in the final product.

[0046] The monomers obtained by the method of the present invention may, more specifically, be used to produce or modify polymers, for example, in binder compositions. The polymerization may be carried out by any known method.

[0047] Such methods more specifically include free radical addition polymerization, cationic addition polymerization, or anionic addition polymerization, and variations of these addition polymerization methods, such as ATRP (atom transfer radical polymerization), NMP (nitroxide-mediated polymerization), or RAFT (reversible addition-cleavage chain transfer), can also be used. [Examples]

[0048] General synthesis procedure for monomers All reaction and product operations were carried out under standard conditions in standard laboratory glassware. Methyl (meth)acrylate, catalyst, and solvent were obtained from commercial / industrial suppliers and used as received without further purification.

[0049] NMR spectra were recorded at 300 K using a Bruker Avance 300 or 400 spectrometer unless otherwise noted, and the resonance of the residual solvent was used as an internal reference. 1 ¹H NMR: THF-d8: 1.72 ppm, C6D6: 7.16 ppm, Toluene-d8 (tol-d8): 2.08 ppm; CDCl3: 7.26 ppm. 13 C{ 1 ¹H} NMR: THF-d8: 25.31 ppm, C6D6: 128.06 ppm, CDCl3: 77.16 ppm). Chemical shift δ is tetramethylsilane ( 1 H, 13 C{ 1 Refer to the external standard of H) and it is given in ppm. 1 H and 13 The 1C NMR signal is converted to a 2D NMR spectrum ( 1 H, 1 H-COSY; 1 H, 13 C-HSQC; 1 H, 13Partial attribution was made based on C-HMQC.

[0050] General procedure for the synthesis of intermediate (II)—supporting the concept: One equivalent of the isocyanate of general formula (VI) is mixed with a reactive diluent of general formula (III) (e.g., methyl methacrylate), and the mixture is preferably cooled to 0-20°C and stirred. Optionally, a polymerization inhibitor (e.g., MEHQ) is added. One equivalent of the amino alcohol or diamine of general formula (V) is added either as a pure substance or as a solution in the reactive diluent of general formula (III), so the temperature of the reaction mixture does not exceed approximately 30°C.

[0051] Alternatively, weigh out 1 equivalent of an amino alcohol or diamine of general formula (V) into the reaction vessel, either as a pure substance or as a solution in a reactive diluent of general formula (III), and preferably cool to 0-20°C and stir. Optionally, a polymerization inhibitor (e.g., MEHQ) may be added. Since 1 equivalent of an isocyanate of general formula (VI) is added either as a pure substance or as a solution in a reactive diluent of general formula (III), the temperature of this reaction mixture does not exceed approximately 30°C.

[0052] After all ingredients have been added and mixed completely, stir the resulting homogeneous or heterogeneous mixture for a further 30-60 minutes and allow it to reach ambient temperature.

[0053] Intermediate (II) is obtained either as a colorless solid or oily substance by removing the reactive diluent (III) under vacuum, or by filtration of the formed solid, followed by drying. Yield: >90%.

[0054] Example 1 :1-(2-hydroxyethyl)-3-phenylurea (HEPU) [ka]

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[0055] Example 2 :1-(1-hydroxy-2-methylpropan-2-yl)-3-phenylurea [ka]

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[0056] Example 3 :1-(2-(2-hydroxyethoxy)ethyl)-3-phenylurea [ka]

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[0057] Example 4 :1-Cyclohexyl-3-(2-(2-hydroxyethoxy)ethyl)urea [ka]

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[0058] Example 5 :1-(6-hydroxyhexyl)-3-phenylurea [ka]

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[0059] Example 6 :1-Cyclohexyl-3-(6-hydroxyhexyl)urea [ka]

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[0060] General procedure for the synthesis of monomer (I): One equivalent of the isocyanate of general formula (VI) is mixed with a reactive diluent of general formula (III) (e.g., methyl methacrylate), and the mixture is preferably cooled to 0-20°C and stirred. Optionally, a polymerization inhibitor (e.g., MEHQ) is added. One equivalent of the amino alcohol or diamine of general formula (V) is added either as a pure substance or as a solution in the reactive diluent of general formula (III), so the temperature of the reaction mixture does not exceed approximately 30°C.

[0061] Alternatively, weigh out 1 equivalent of an amino alcohol or diamine of general formula (V) into the reaction vessel, either as a pure substance or as a solution in a reactive diluent of general formula (III), and preferably cool to 0-20°C and stir. Optionally, a polymerization inhibitor (e.g., MEHQ) may be added. Since 1 equivalent of an isocyanate of general formula (VI) is added either as a pure substance or as a solution in a reactive diluent of general formula (III), the temperature of this reaction mixture does not exceed approximately 30°C.

[0062] After all ingredients have been added and mixed completely, the resulting homogeneous or heterogeneous mixture should be stirred for a further 30-60 minutes and allowed to reach ambient temperature. Additional inhibitors may be added.

[0063] In a reactor equipped with mechanical stirring, an air supply, a liquid temperature display, a topped packing column, and an automatically controlled top section with reflux and distillate condenser, the mixture is then heated to a boil, and the reactive diluent (III) = methyl methacrylate is first distilled off until no more azeotrope distillate is observed and instead pure methyl methacrylate distillate is observed (this azeotropic distillation step of removing water is unnecessary when using anhydrous starting materials). This batch is cooled to about 10-20°C, and a catalyst (e.g., titanium isopropoxide (IPT) (1% relative to the intermediate urea-containing alcohol or amine (II))) and methyl methacrylate are added, in amounts corresponding to the mass of the lost azeotrope distillate.

[0064] The mixture is heated again to a boil, and the resulting methyl methacrylate-methanol azeotrope is removed by reflux at a 2:1 ratio to a maximum top temperature of 70°C, and then by reflux at a 10:1 ratio to a constant top temperature of 98–101°C. The reaction is typically completed within 2–16 hours. This batch is cooled to 80°C. If titanium alkoxide is used as a catalyst, dilute sulfuric acid, followed by sodium carbonate, is added. Tonsil, Celatom, or Celite may be added as an option. This batch is filtered by pressure filtration (EKS pressure filter). A clear filtrate is optionally obtained as a solution in methyl methacrylate, or concentrated under vacuum (room temperature (RT)–125°C, ambient pressure, or up to 1 mbar) until the product is obtained as a colorless oil or solid. Optionally, the product may be obtained as a crystalline material upon cooling of the solution. Optionally, the product may be recrystallized from a suitable common organic solvent, such as ethyl acetate, methanol, ethanol, and acetone. Optionally, the product may be washed with a suitable organic solvent, such as pentane, hexane, heptane, diethyl ether, or toluene.

[0065] Example 1Synthesis of 2-(3-phenylureido)ethyl methacrylate [ka]

[0066] Phenyl isocyanate (49.3 g, 0.414 mol, 1.00 equivalent) is dissolved in methyl methacrylate (331 g, 3.31 mol, 8.00 equivalent). MEHQ (44 mg, 200 ppm relative to the product) is added. The temperature of this mixture is kept below 20°C, and ethanolamine (25.53 g, 0.418 mol, 1.01 equivalent) is added dropwise over 15 minutes. This heterogeneous mixture is further diluted with methyl methacrylate (84.6 g, 0.84 mol, 2.00 equivalent), brought to room temperature, and then heated to 100°C to remove all water as water-methyl methacrylate azeotrope. The mixture is cooled to 80°C, and a catalyst (e.g., IPT (1% relative to urea alcohol), Zr(acac)2 (1% relative to urea alcohol), or LiOH (1% relative to urea alcohol) is added. The mixture is heated to 120°C, and methanol-methyl methacrylate is gradually removed with an azeotrope (at a controlled reflux ratio) until complete conversion is obtained after 6 hours. Optionally, the pure product can be obtained as a crystalline solid upon cooling of the reaction mixture. Typically, the catalyst is removed directly by filtration of the reaction solution (e.g., through Celite, Celatome, Arbocell), or, in the case of IPT, by first precipitation with dilute sulfuric acid and then removal by filtration of the reaction solution (e.g., through Celite, Celatome, Arbocell).

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[0067] Example 2 :2-methyl-2-(3-phenylureido)propyl methacrylate [ka]

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[0068] Example 3 :3-(3-phenylureido)propyl methacrylate [ka]

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[0069] Example 4 :2-(2-(3-phenylureido)ethoxy)ethyl methacrylate [ka]

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[0070] Example 5 :6-(3-phenylureido)hexyl methacrylate [ka]

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[0071] Example 6 :6-(3-cyclohexylureido)hexyl methacrylate [ka]

[0072] 6-aminohexanol (0.40 mol, 1.00 equivalent), methyl methacrylate (602 g, 6.02 mol, 15 equivalents), and MEHQ (0.02 g, 200 ppm relative to the product) are weighed into a reactor equipped with mechanical stirring, an air supply, a liquid temperature display, a top-mounted packed column, and an automatically controlled top section with reflux and distillate condenser. The mixture is cooled to 9°C, and cyclohexyl isocyanate (49.76 g, 0.398 mol, 0.99 equivalents, 50 wt% of methyl methacrylate) is added within 20 minutes, so the temperature does not exceed 20°C. After complete addition, the mixture is stirred for a further 30 minutes to bring it to room temperature, and then heated to 100°C to remove any water as water-methyl methacrylate azeotrope. The mixture is cooled to 80°C, and catalyst IPT (0.96 g, 1% based on the intermediate alcohol) and methyl methacrylate (35 g, azeotrope loss) are added. The mixture is heated again to a boil, and the resulting methyl methacrylate-methanol azeotrope is removed by reflux at a 2:1 ratio to a maximum top temperature of 75°C, and then by reflux at a 10:1 ratio to a constant top temperature of 98-101°C. The mixture is cooled to 80°C, and dilute sulfuric acid (3.84 g), followed by sodium carbonate (5.76 g). The mixture is filtered, and the product, obtained as a colorless precipitate upon cooling of its mother liquor, is filtered off and dried. Yield: 115.7 g (94%).

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[0073] Embodiments of the present invention are as follows: 1. General formula (I) [ka] [In the formula, R 1 The option is selected from -H or -Me; R 2 is -H, or C1~C 20Selected from linear, branched, or cyclic alkyl or aryl groups; R 2′ is -H; R 3 is -H, or C1~C 20 Linear, branched, or cyclic alkyl or aryl groups, and Selected from benzenesulfonyl, tosyl, p-chlorophenyl, adamantyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, and 2,6-dipropylphenyl; R 2 and R 3 They are the same or different. X is selected from -O- or -NH-; and L is C2~C 20 A one-pot method for producing (meth)acrylates [selected from linear, branched, or cyclic alkyl or aryl groups, wherein one or more carbon atoms in the carbon chain of the group may be substituted with one or more -O-, -NH-, or -S- heteroatoms], General formula (II) [ka] [where X, R 2 , R 2′ , R 3 L is defined above] as an intermediate compound, General formula (V) [ka] [where X, R 2 L is an amino alcohol or diamine as defined above. and general formula (VI) [ka] [In the formula, R 3 The isocyanate of [as defined above] General formula (III) [ka] [In the formula, R 4 It is formed in situ by reacting with a reactive diluent of a C1-C4 alkyl group; The method wherein the intermediate compound (II) is immediately reacted with a reactive diluent (III) to form a product compound (I). 2. R 1 However, it is methyl, R 2 However, it is selected from hydrogen and linear or branched alkyl groups of C1-C8, R 3 However, these are selected from methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, cyclohexyl, and phenyl. X is oxygen; and The method according to 1, wherein L is selected from ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethoxyethyl. 3. The method according to any one of the above, wherein the method is carried out in the presence of at least one catalyst selected from the group consisting of Zr(acac)2, LiOH, CaO, dioctyl tin oxide (DOTO), dibutyl tin laurate (DBTL), titanium isopropoxide, and combinations thereof. 4. The method according to any one of the above, wherein the catalyst is titanium isopropoxide, CaO / LiOH, CaO / LiCl, DOTO, or DBTL. 5. The method according to any one of the above, wherein the catalyst is present in an amount of 0.01 to 5% by weight, based on the amount of compound (V). 6. The method according to any one of the above, wherein the reaction temperature in the first reaction step is maintained at 0°C to 80°C, or 0°C to 50°C, preferably 0°C to 30°C. 7. The method according to any one of the above, wherein the reaction temperature in the second reaction step is maintained at 30°C to 180°C, or 50°C to 150°C, preferably 80°C to 130°C. 8. The method according to any one of the above, wherein the reactive diluent is an alkyl (meth)acrylate selected from the group consisting of propyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, and methyl (meth)acrylate. 9. The method according to any one of the above, wherein the reactive diluent is methyl (meth)acrylate. 10. The method according to any one of the above, wherein the amount of reactive diluent used is 1 to 50 mol, or 2 to 20 mol, preferably 3 to 10 mol, per mole of compound (V). 11. The method according to any one of the above, wherein the amount of isocyanate (VI) is 0.80 to 1.20 equivalents, or 0.90 to 1.10 equivalents, preferably 0.95 to 1.05 equivalents, per equivalent of compound (V). 12. The method according to any one of the above, wherein the method is carried out in the presence of at least one polymerization inhibitor selected from the group consisting of hydroquinone monomethyl ether, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and mixtures thereof. 13. The method according to 12, wherein the at least one polymerization inhibitor is hydroquinone monomethyl ether. 14. The method according to 12. or 13., wherein the amount of polymerization inhibitor at the start of the reaction is adjusted to 0 to 5000 ppm, preferably 100 ppm to 3000 ppm, based on the amount of product theoretically expected by complete conversion. 15. The method according to any one of the above, wherein a (meth)acrylate of general formula (I) is obtained by precipitation, and preferably at least one of the inhibitors is co-precipitated with the (meth)acrylate of general formula (I).

Claims

1. General formula (I) 【Chemical 1】 [In the formula, R １ is selected from -H or -Me; R ２ is -H or C １ ~C ２０ is selected from linear, branched or cyclic alkyl or aryl groups; R ２′ is —H; R ３ is -H or C １ ~C ２０ and benzenesulfonyl, tosyl, p-chlorophenyl, adamantyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, and 2,6-dipropylphenyl; R ２ and R ３ are the same or different, X is selected from —O— or —NH—; and L is C ２ ~C ２０ wherein one or more carbon atoms in the carbon chain of said group may be replaced by one or more -O-, -NH- or -S-heteroatoms, General formula (II) 【Chemistry 2】 [wherein, X, R ２ , R ２′ , R ３ , wherein L is as defined above, General formula (V) 【Chemistry 3】 [wherein, X, R ２ , L is as defined above], and General formula (VI) 【Chemistry 4】 [In the formula, R ３ is as defined above, General formula (III) 【Chemistry 5】 [In the formula, R ４ is C １ ~C ４ in situ by reacting in the presence of a reactive diluent of The process wherein the intermediate compound (II) is immediately reacted with the reactive diluent (III), thereby forming the product compound (I).

2. R １ is methyl, R ２ is hydrogen and C １ ~C ８ is selected from the linear or branched alkyl R ３ is selected from methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, cyclohexyl, and phenyl; X is oxygen; and 2. The method of claim 1, wherein L is selected from ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethoxyethyl.

3. The method comprises: ２ 3. The process of claim 1 or 2, carried out in the presence of at least one catalyst selected from the group consisting of LiOH, CaO, dioctyltin oxide (DOTO), dibutyltin laurate (DBTL), titanium isopropoxide, and combinations thereof.

4. 4. The method of claim 3, wherein the catalyst is titanium isopropoxide or CaO / LiOH or CaO / LiCl or DOTO or DBTL.

5. 4. The process of claim 3, wherein the catalyst is present in an amount of 0.01 to 5% by weight, based on the amount of compound (V).

6. 3. The process according to claim 1 or 2, wherein the reaction temperature in the first reaction stage is maintained at 0°C to 80°C.

7. 3. The process according to claim 1 or 2, wherein the reaction temperature in the second reaction stage is maintained at 30°C to 180°C.

8. 3. The method of claim 1 or 2, wherein the reactive diluent is an alkyl (meth)acrylate selected from the group consisting of propyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, and methyl (meth)acrylate.

9. 3. The method of claim 1 or 2, wherein the reactive diluent is methyl (meth)acrylate.

10. 3. The method according to claim 1, wherein the amount of the reactive diluent used is 1 to 50 mol per 1 mol of compound (V).

11. 3. The method according to claim 1, wherein the amount of isocyanate (VI) is 0.80 to 1.20 equivalents per equivalent of compound (V).

12. 3. The process of claim 1 or 2, wherein the process is carried out in the presence of at least one polymerization inhibitor selected from the group consisting of hydroquinone monomethyl ether, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methyl-phenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and mixtures thereof.

13. 13. The method of claim 12, wherein said at least one polymerization inhibitor is hydroquinone monomethyl ether.

14. 13. The method of claim 12, wherein the amount of polymerization inhibitor at the start of the reaction is adjusted to 0 to 5000 ppm based on the amount of product theoretically expected at complete conversion.

15. 3. The method according to claim 1, wherein the (meth)acrylate of general formula (I) is obtained by precipitation.

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