Recycled mma and its use for the production of higher alkyl methacrylate monomers

Abstract

The present invention relates to a novel process for the isolation of C2-C18 alkyl (meth)acrylates. In this process, a polymer composition containing at least one poly(alkyl (meth)acrylate) is first thermally cleaved to obtain at least one alkyl (meth)acrylate and at least one additional alkyl ester. This mixture is subsequently condensed and mixed with a stream from a C2-C18 alkyl (meth)acrylate production process. The C2-C18 alkyl (meth)acrylate is obtained by reaction with a C2-C18 alcohol in the presence of a catalyst.

Description

[0001] 202200004 1

[0002] Recycle MMA and its use in the production of higher alkyl methacrylate monomers

[0003] Description

[0004] Field of invention

[0005] The present invention relates to a novel process for the isolation of C2-C18 alkyl(meth)acrylates. In this process, a polymer composition containing at least one poly(alkyl(meth)acrylate) is first thermally cleaved to obtain at least one alkyl(meth)acrylate and at least one further alkyl ester. This mixture is then condensed and mixed with a stream from a C2-C18 alkyl(meth)acrylate production process. The C2-C18 alkyl(meth)acrylate is obtained by reaction with a C2-C18 alcohol in the presence of a catalyst.

[0006] State of the art

[0007] Alkyl(meth)acrylates, especially methyl methacrylate (MMA), have a wide range of applications.

[0008] MMA is used in particular for the production of polymethyl methacrylate (PMMA), which is characterized by excellent optical (acrylic glass) and other physical properties. Its applications include glazing and facades in architecture, lighting elements and vehicle taillights in the automotive sector, aircraft windows, decorative, design, or furniture elements, flat screens and displays, noise barriers, and illuminated advertising.

[0009] The processing of PMMA generates production waste, known as post-industrial waste. Furthermore, post-consumer waste, such as electronic waste and scrap metal, also contains PMMA, often alongside other plastics and additives. The proportion of MMA building blocks in the PMMA polymers contained in this waste varies and can range from 75% to over 99%.

[0010] PMMA, whether post-industrial or post-consumer waste, can generally be depolymerized into its monomers and reused as so-called recycled MMA. Various depolymerization processes are described in the prior art, such as depolymerization in metal baths, rotary kilns, fluidized bed reactors, or extruders.

[0011] For example, the publications DE 642289 C, US 2,030,901, DE 3146194 A1, EP 3635 043 and US 2,470,361 describe the thermal depolymerization of PMMA, in some cases with subsequent purification of the resulting monomers, for example by distillation. 202200004 2

[0012] Thermal-catalytic depolymerizations of PMMA with subsequent purification of the obtained monomers are described, for example, in US 2,858,255, DE 2132716, WO 2019 / 003253, DE 19729065 and EP 2 895 576.

[0013] The depolymerization of PMMA, sometimes together with other polymers, in a fluidized bed is also well known. This is described, for example, in US 5,663,420, WO 2000 / 017149 and US 8,304,573.

[0014] US 3,494,958 describes a thermal depolymerization process for PMMA. The resulting monomer can then be purified by distillation. US 3,494,958 describes that the purification can be carried out, for example, analogously to purification in an ACH process (Cs process).

[0015] In the processes described above, the yield of monomers is sometimes insufficient. Furthermore, the processes described in the prior art produce recycled alkyl(meth)acrylates whose purity is insufficient for the production of poly(alkyl(meth)acrylates) of adequate quality. This is particularly the case when poly(methyl methacrylate) containing a large proportion of additives, such as impact modifiers or pigments and / or other polymers, is used in the depolymerization processes.

[0016] Processes for the production of higher alkyl(meth)acrylates starting from high-purity lower alkyl(meth)acrylates are described in the prior art.

[0017] DE 100 26 644 A1 describes the production of an ester of an unsaturated carboxylic acid by transesterification with a C4-C2o alcohol in the presence of a transesterification catalyst containing a 2,2,6,6-tetraalkyl-1-oxyl-piperidine-4 residue.

[0018] German patent DE 102 00 171 A1 describes a process for the continuous production of higher (meth)acrylic acid esters by reacting a methyl (meth)acrylate with a C2-Ci2 alcohol. The product is purified by distillation and subsequent transfer of the resulting distillation residue to an evaporator.

[0019] EP 1 583 733 B1 describes a process for the continuous production of higher (meth)acrylic acid esters by transesterification of (meth)acrylic acid methyl esters with higher alcohols in the presence of a catalyst.

[0020] The methods described in the prior art for producing higher

[0021] Alkyl(meth)acrylates are all derived from highly purified lower alkyl(meth)acrylates. None of the described processes can handle the specific requirements posed by the use of depolymerized PMMA (recycled MMA) with reduced purity. This makes the processes expensive and unsustainable.

[0022] Task

[0023] Therefore, there was a need to provide an improved method for the isolation of C2-C18 alkyl(meth)acrylates that does not exhibit the disadvantages of the prior art methods described, or only to a lesser extent. In particular, the method should result in lower emissions of climate-relevant waste products such as CO2.

[0024] Solution

[0025] This problem was solved by a process for isolating C2-C18 alkyl(meth)acrylates comprising the following steps a) to e): a) thermal cleavage of at least one polymer composition containing at least one poly(alkyl(meth)acrylate) to obtain a first gas stream containing at least one alkyl(meth)acrylate and at least one further alkyl ester; b) condensation of the first gas stream obtained in step a) to obtain a liquid first stream containing the at least one alkyl(meth)acrylate and the at least one further alkyl ester; c) mixing of the liquid first stream obtained in step b) with a further stream containing at least one further alkyl(meth)acrylate, wherein the further stream is part of a C2-C18 alkyl(meth)acrylate manufacturing process, to obtain a mixed stream comprising the liquid first stream and the further stream.d) Reacting the mixture obtained in step c) with a C2-cis alcohol in the presence of a catalyst to obtain a product stream containing at least one alkyl(meth)acrylate, at least one further alkyl(meth)acrylate, the C2-C18 alkyl(meth)acrylate, the catalyst, at least one alkyl ester, the C2-cis alcohol and at least one further alcohol; e) Separating the C2-Ci8 alkyl(meth)acrylate from the product stream.

[0026] It was surprisingly found that C2-C18 alkyl(meth)acrylates with a purity of > 99.4% are obtained by the process according to the invention.

[0027] In particular, the process according to the invention surprisingly enables the efficient removal of byproducts such as further alkyl esters, as well as their mixtures and azeotropes, even if their normal boiling point differs only slightly, for example by + / - 1 K (Kelvin), preferably + / - 0.6 K, from the normal boiling point of the alkyl(meth)acrylate and / or its azeotropes. This is due in particular to process steps d) and e).

[0028] Additives and chain regulators that may be present in the polymer composition, and the products obtained from them during the thermal cleavage of the polymer composition, such as mercaptans, can be easily and cost-effectively separated using the process according to the invention. For example, the C2-Ci8-alkyl(meth)acrylates obtained using the process according to the invention contain a maximum of 0.6% byproducts, of which a maximum of 0.5% are critical unsaturated byproducts. Due to the process according to the invention and the resulting efficient separation of the byproducts, the C2-Ci8-alkyl(meth)acrylates produced according to the invention have no or only a very slight odor, despite the mercaptans contained in the polymer composition.

[0029] The process according to the invention and the C2-C18 alkyl(meth)acrylates produced by the process according to the invention also exhibit lower CO2 emissions and thus a particularly low carbon footprint. This is achieved in particular because the process according to the invention also allows the use of polymer compositions with a relatively high proportion of additives and other impurities and because the raw material source is reusable.

[0030] The method according to the invention is therefore superior to those known to date, as it meets the requirement of being able to reuse itself in the circular economy.

[0031] Furthermore, the by-products obtained during depolymerization can be further recycled after separation, thus further reducing the carbon footprint and therefore the global warming potential (GWP).

[0032] The method according to the invention is described in more detail below.

[0033] In step a) of the process according to the invention, at least one polymer composition is thermally cleaved to obtain a first gas stream. The at least one polymer composition contains at least one poly(alkyl(meth)acrylate). The gas stream contains at least one alkyl(meth)acrylate and at least one further alkyl ester.

[0034] Within the scope of the present invention, the term "at least one polymer composition" means both exactly one polymer composition and a mixture of two or more polymer compositions. A mixture of two or more polymer compositions is preferred according to the invention.

[0035] The at least one polymer composition contains at least one poly(alkyl(meth)acrylate). 202200004 5

[0036] In the context of the present invention, “at least one poly(alkyl(meth)acrylate)” means both exactly one poly(alkyl(meth)acrylate) and a mixture of two or more poly(alkyl(meth)acrylates. Within the context of the present invention, “poly(alkyl(meth)acrylates)” refers to polymers and copolymers of alkyl(meth)acrylates.

[0037] Examples of copolymers of alkyl(meth)acrylates are copolymers of alkyl(meth)acrylates with 1-alkenes, other alkyl(meth)acrylates, (meth)acrylic acid, styrene, polyesters and / or polyurethane(meth)acrylates.

[0038] 1-Alkenes that can copolymerize with alkyl(meth)acrylates are known as such and include, for example, 1-hexene, 1-heptene, vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene and 4-methylpentene-1.

[0039] Within the scope of the present invention, the term "styrene" is understood to include not only styrene as such, but also substituted styrenes such as α-methylstyrene, α-ethylstyrene, vinyltoluene, p-methylstyrene, monochlorostyrenes, dichlorostyrenes and tribromostyrene.

[0040] Suitable polyesters are known as such and are preferably available via polycondensation or ring-opening polymerization.

[0041] Within the scope of the present invention, "polyurethane (meth)acrylates" are understood to be (meth)acrylates linked to one another via urethane groups. They are obtainable by reacting hydroxyalkyl (meth)acrylates with polyisocyanates and polyoxyalkylenes having at least two hydroxy functionalities. Instead of hydroxyalkyl (meth)acrylates, esters of (meth)acrylic acid with oxiranes, such as ethylene oxide or propylene oxide, or corresponding oligooxiranes or polyoxiranes can also be used. Suitable polyurethane (meth)acrylates are known as such.

[0042] At least one polymer composition can, for example, originate from production waste. In this case, the polymer composition is typically so-called post-industrial waste, such as sprues, start-up lumps from extrusion, dust, chips, partially polymerized polymer syrups, edge trimmings, offcuts from sheets, rejects from sheets, films, blocks, semi-finished products, defective molded parts, or waste from injection molding.

[0043] It is also possible that at least one polymer composition originates from so-called post-consumer waste. This typically includes waste from sources such as electrical and electronic waste, greenhouses, exhibition stands, shop fittings, or illuminated advertising. 202200004 6

[0044] The at least one polymer composition therefore typically contains at least one further component. This at least one further component is, for example, selected from the group consisting of polymers other than poly(alkyl(meth)acrylate), pigments, dyes, fillers, additives, regulators, initiators, impact modifiers, release agents, and UV additives.

[0045] A preferred method is therefore also one in which the polymer composition in step a) contains at least one further component selected from the group consisting of polymers other than poly(alkyl(meth)acrylate), pigments, dyes, fillers, additives, regulators, initiators, impact strengtheners, release agents and UV additives.

[0046] Polymers other than poly(alkyl(meth)acrylate) are particularly suitable if they are commonly used as blends with poly(alkyl(meth)acrylate). Examples include polyethylene, polyvinyl chloride, polystyrene, polyamides, and biopolymers such as α-polysaccharides (starch), β-polysaccharides (cellulose, chitin), lignin, and polylactide.

[0047] Examples of pigments include white, red, blue, green, and / or yellow inorganic pigments. White inorganic pigments such as titanium dioxide are particularly preferred.

[0048] Dyes, for example, are organic dyes known to experts.

[0049] Typical fillers are primarily mineral fillers. Mineral fillers are preferably selected from the group consisting of calcium carbonate, barium sulfate, quartz, quartz flour, precipitated silicas, pyrogenic silicas, corundum, glass beads, and cristobalite.

[0050] Typical auxiliary substances are known as such and are selected, for example, from the group consisting of plasticizers, paraffins and / or inhibitors.

[0051] Esters, polyols, oils, low molecular weight polyethers or phthalates are preferably used as plasticizers.

[0052] Paraffins that may be present in the polymer composition are known as such. For example, several paraffins with different melting points may be present in varying concentrations.

[0053] The group of inhibitors preferably includes substituted phenols, hydroquinone derivatives, phosphines and / or phosphites. 202200004 7

[0054] Chain regulators, particularly those known from radical polymerization, which control chain lengths, are suitable candidates. Chain regulators typically include mercaptans such as n-dodecyl mercaptan, but also multivalent mercapto compounds such as pentaerythroletetrathioglycolate.

[0055] Initiators are also known as such and are selected, for example, from the group consisting of peroxides, azo compounds, persulfates and mixtures thereof.

[0056] Impact tougheners are known as such and are, for example, polymer particles containing an elastomer.

[0057] Suitable separating agents include, in particular, long-chain wax acids such as stearic acid, palmitic acid or lauric acid, as well as monohydric fatty or wax alcohols such as diethylene glycol monopropyl ether.

[0058] Suitable UV additives include, in particular, UV stabilizers. Preferably, the UV stabilizers are selected from the group consisting of benzophenone derivatives, benzotriazole derivatives, thioxanthonate derivatives, piperidinol carboxylic acid ester derivatives, and cinnamon acid ester derivatives.

[0059] The thermal decomposition of the at least one polymer composition can be carried out according to methods known to those skilled in the art.

[0060] Thermal cracking can be carried out in reactors known to those skilled in the art. For example, thermal cracking can be carried out in a pyrolysis reactor, in an extruder, in a rotary kiln, in fluidized bed pyrolysis, in a metal bath and / or as dry distillation.

[0061] The polymer composition can be in solid or liquid form during thermal decomposition. If the polymer composition is in solid form, it can exist as a pure solid. It is also possible for the polymer composition to be dispersed in a medium. This medium can be, for example, a solid such as quartz, metal shavings, or diatomaceous earth. It is also possible for the medium to be a gas such as nitrogen or a liquid such as water or a hydrocarbon. It is possible that the medium is a liquid at room temperature but exists as a gas under the conditions of thermal decomposition in step a).

[0062] The polymer composition is present in liquid (molten) form, for example, when thermal decomposition takes place in an extruder. 202200004 8

[0063] The polymer composition, particularly when in solid form, can be mechanically comminuted before thermal decomposition, for example to an average particle size distribution of less than 6 mm (Qr, d50), preferably less than 1.5 mm (Qr, d50), or to a particle size distribution in the range of 0.1 mm (Qr, d50) to 6 mm (Qr, d50). Preferably, the particle size distribution is determined by laser diffractometry.

[0064] The temperature (T) during the thermal cracking in step a) is, for example, in a range of 240 °C to 800 °C, preferably in a temperature in the range of 300 °C to 500 °C, particularly preferably in a temperature in the range of 325 °C to 400 °C.

[0065] The pressure during thermal cracking in step a) is, for example, in the range of 200 mbar to 1000 bar, preferably in the range of 400 mbar to 500 bar.

[0066] A method is therefore also preferred according to the invention in which the temperature during thermal cracking in step a) is in the range of 240 °C to 800 °C and / or the pressure during thermal cracking in step a) is in the range of 400 mbar to 500 bar.

[0067] The thermal decomposition in step a) can be carried out in the presence of a catalyst. Catalysts suitable for thermal decomposition are known as such and can be selected, for example, from the group consisting of molten metal, peroxides, potassium salts such as potassium acetate, and alkali metal persulfates such as potassium monopersulfate. Lead and / or eutectic lead / tin mixtures are particularly suitable as molten metals.

[0068] If the thermal cracking in step a) takes place in the presence of a catalyst, the cracking in step a) is also referred to as thermally catalytic cracking.

[0069] A method in which the thermal cracking in step a) is a thermally catalytic cracking is therefore also preferred according to the invention.

[0070] In the thermal cleavage in step a), the poly(alkyl(meth)acrylate) is cleaved. This cleavage is also called depolymerization. Depolymerizations as such are known to those skilled in the art. In depolymerizations, a polymer is cleaved into its monomer and oligomer units.

[0071] In the thermal cleavage in step a), the poly(alkyl(meth)acrylate) is cleaved into its monomer and oligomer units. As explained above, the poly(alkyl(meth)acrylate) is a polymer or copolymer of at least one alkyl(meth)acrylate. Therefore, at least one alkyl(meth)acrylate is formed during the thermal cleavage. 202200004 9

[0072] During the thermal cleavage of the polymer composition, at least one further alkyl ester is formed. Within the scope of the present invention, "at least one further alkyl ester" means both exactly one further alkyl ester and a mixture of two or more further alkyl esters. A mixture of two or more further alkyl esters is preferred according to the invention.

[0073] The first gas stream therefore contains the at least one alkyl(meth)acrylate formed during thermal cracking and the at least one further alkyl ester.

[0074] The at least one alkyl(meth)acrylate is, as explained above, derived from the poly(alkyl(meth)acrylate).

[0075] In the context of the present invention, "at least one alkyl(meth)acrylate" means exactly one alkyl(meth)acrylate as well as a mixture of two or more alkyl(meth)acrylates. A mixture of two or more alkyl(meth)acrylates is preferred.

[0076] Within the scope of the present invention, "alkyl(meth)acrylates" are understood to be alkyl esters of (meth)acrylic acid having 1 to 18, preferably 1 to 12, and particularly preferably 1 to 4, carbon atoms in the alkyl group. The alkyl group can be linear, cyclic, and / or branched. Furthermore, it can contain aromatic groups. The alkyl group can also contain heteroatoms within the alkyl group and / or be substituted with heteroatoms, as is the case, for example, with hydroxypropyl(meth)acrylate and / or hydroxyethyl(meth)acrylate. For example, alkyl(meth)acrylates according to the invention are selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, 1-methyl-ethyl(meth)acrylate, propyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isopentyl(meth)acrylate, cyclohexyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, allyl(meth)acrylate,

[0077] Polyethylene glycol (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, vinyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate and lauryl (meth)acrylate.

[0078] In a further embodiment of the present invention, the term "alkyl(meth)acrylates" also includes polyethylene glycol(meth)acrylates with a weight-average molecular weight Mw in the range of 250 g / mol to 10,000 g / mol.

[0079] Within the scope of the present invention, the term "(meth)acrylic acid" encompasses both acrylic acid and methacrylic acid. Within the scope of the present invention, the term "(meth)acrylates" encompasses both acrylates and methacrylates.

[0080] Within the scope of the present invention, the term "alkyl(meth)acrylates" is understood to mean both alkyl methacrylates and alkyl acrylates. According to the invention, alkyl methacrylates are preferred. The at least one alkyl(meth)acrylate is, for example, a Ci-Ci8 alkyl(meth)acrylate, preferably a Ci-Ci2 alkyl(meth)acrylate, and particularly preferably a Ci-C4 alkyl(meth)acrylate. Most preferably, according to the invention, the at least one alkyl(meth)acrylate comprises methyl(meth)acrylate.

[0081] A preferred method is therefore also one in which the at least one alkyl(meth)acrylate contained in the first gas stream in step a) is selected from the group consisting of Ci- to C4- alkyl(meth)acrylates.

[0082] The at least one alkyl(meth)acrylate, for example, has a boiling point at normal pressure in the range of 50 °C to 300 °C, preferably in the range of 80 °C to 250 °C.

[0083] It goes without saying that the at least one further alkyl ester is different from the at least one alkyl(meth)acrylate. The at least one further alkyl ester preferably does not comprise a (meth)acrylate unit.

[0084] For example, at least one further alkyl ester is selected from the group consisting of Ci-C4 alkyl isobutyrates, Ci-C4 alkyl propionates, Ci-C4 alkyl pivalates and dicarbonate esters.

[0085] Within the scope of the present invention, Ci-C4 alkyl isobutyrates are understood to be alkyl esters of isobutyric acid having 1 to 4 carbon atoms in the alkyl group. The alkyl group may be linear or branched. It may also contain heteroatoms within the alkyl group and / or be substituted with heteroatoms. Examples of Ci-C4 alkyl isobutyrates containing heteroatoms within the alkyl group are methyl 2-methoxyisobutyrate and methyl 3-methoxyisobutyrate. Ci-C4 alkyl isobutyrates according to the invention are selected, for example, from the group consisting of methyl isobutyrate, ethyl isobutyrate, methyl 2-methoxyisobutyrate, and methyl 3-methoxyisobutyrate.

[0086] Within the scope of the present invention, Ci-C4 alkylpropionates are understood to be alkyl esters of propionic acid having 1 to 4 carbon atoms in the alkyl group. The alkyl group can be linear or branched. It can also contain heteroatoms within the alkyl group and / or be substituted with heteroatoms. Ci-C4 alkylpropionates according to the invention are, for example, selected from the group consisting of methyl propionate and ethyl propionate.

[0087] Within the scope of the present invention, Ci-C4 alkyl pivalates are understood to be alkyl esters of pivalic acid having 1 to 4 carbon atoms in the alkyl group. The alkyl group may be linear or branched. It may also contain heteroatoms within the alkyl group and / or be substituted with heteroatoms. Ci-C4 alkyl pivalates according to the invention are, for example, selected from the group consisting of methyl pivalate and ethyl pivalate. 202200004 11

[0088] Within the scope of the present invention, dicarboxylic acid diesters are understood to be alkyl esters of dicarboxylic acids having 1 to 4 carbons in the alkyl group. Likewise, dicarboxylic acid diesters are understood to be carboxylic acid esters of diols in which both hydroxyl groups are esterified with a carboxylic acid. Dicarboxylic acid diesters according to the invention are, for example, selected from the group consisting of dimethyl propanedioate, dimethyl pentanedioate, dimethyl hexanedioate, and dimethyl heptanedioate.

[0089] Preferably, the at least one further alkyl ester is selected from the group consisting of methyl propionate, ethyl propionate, methyl isobutyrate, methyl pivalate, methyl 3-methoxyisobutyrate and dicaronic acid esters.

[0090] A preferred method is therefore also one in which the at least one further alkyl ester is selected from the group consisting of methyl propionate, methyl isobutyrate, methyl pivalate, methyl 3-methoxyisobutyrate and dicarboxylic acid diesters.

[0091] The at least one further alkyl ester, for example, has a boiling point at normal pressure in the range of 50 °C to 200 °C, preferably in the range of 75 °C to 150 °C.

[0092] According to the invention, the boiling point at normal pressure of at least one further alkyl ester differs from the boiling point at normal pressure of at least one alkyl(meth)acrylate by a difference in the range of -20 °C to +20 °C, preferably by a difference in the range of -1 °C to +1 °C, and particularly preferably by a difference in the range of -0.6 °C to +0.6 °C.

[0093] Equally preferably, the boiling point of an azeotrope consisting of at least one further alkyl ester with the C2-Cia alcohol and / or the at least one further alcohol differs from the boiling point of an azeotrope consisting of at least one alkyl(meth)acrylate with the C2-Cia alcohol and / or the at least one further alcohol by a difference in the range of -20 °C to +20 °C, preferably by a difference in the range of -1 °C to +1 °C, and particularly preferably by a difference in the range of -0.6 °C to +0.6 °C, wherein the boiling point is in each case referenced to the boiling point at normal pressure.

[0094] As explained above, the first gas stream is obtained by thermal decomposition of the at least one polymer composition. Therefore, the first gas stream typically contains at least one further component. It is understood that this at least one further component is different from the at least one alkyl(meth)acrylate and the at least one further alkyl ester.

[0095] The at least one further component is formed, for example, by thermal cleavage of copolymers of alkyl(meth)acrylate and / or by thermal cleavage of the at least one further component optionally contained in the polymer composition. In addition, oligomers of alkyl(meth)acrylate can also be formed during thermal cleavage; these also fall under the term "at least one further component" within the scope of the present invention.

[0096] For example, the at least one further component is selected from the group consisting of styrene, (meth)acrylic acid, sulfur-containing compounds, oligomers, dimers, C1-C4 alkyl acids, di(meth)acrylate diesters, Ci-C4 alcohols, high-boiling aromatics, aldehydes and ketones; preferably, the at least one further component is selected from the group consisting of styrene, (meth)acrylic acid, sulfur-containing compounds, oligomers and dimers.

[0097] A preferred method is therefore one in which the first gas stream contains at least one further component selected from the group consisting of styrene, (meth)acrylic acid, sulfur-containing compounds, oligomers and dimers.

[0098] For the purposes of the present invention, high-boiling aromatics are understood to be, for example, phenols, anilines, benzophenones, naphthalenes and / or pyridines, which may each be substituted or unsubstituted.

[0099] For styrene as at least one additional component, the above-described statements and preferences for styrene apply accordingly.

[0100] Sulfur-containing compounds are derived in particular from sulfur-containing regulators that may be present in the at least one polymer composition and are in particular mercaptans such as dodecyl mercaptan and multivalent mercapto compounds such as pentaerythroletetrathioglycolate.

[0101] Within the scope of the present invention, the term "oligomers" refers in particular to oligomers of at least one alkyl(meth)acrylate, of (meth)acrylic acid, and of mixtures thereof. The term "oligomer" encompasses not only higher oligomers but also lower oligomers, such as trimers, tetramers, and pentamers. In particular, the term "oligomer" includes a molecule composed of three to ten units, wherein the units are obtainable from the at least one alkyl(meth)acrylate, (meth)acrylic acid, or mixtures thereof.

[0102] In the context of the present invention, dimers are understood to be, in particular, dimers of at least one alkyl(meth)acrylate, of (meth)acrylic acid, and of mixtures thereof. 202200004 13

[0103] Ci-C4 alkyl acids are aliphatic carboxylic acids with 1 to 4 carbon atoms. Ci-C4 alkyl acids can exhibit branching. For example, the C1-C4 alkyl acid is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, and isobutyric acid.

[0104] The term di(meth)acrylate diesters encompasses not only esters of (meth)acrylic acid with a diol, but also esters of (meth)acrylic acid with a polyol, such as a triol. For example, di(meth)acrylate diester is selected from the group consisting of ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,3-butanediol di(meth)acrylate.

[0105] Ci-C4 alcohols are defined as alcohols that have 1 to 4 carbon atoms in the alkyl group. The alkyl group can be linear or branched. It is also possible that it is substituted with heteroatoms. Examples of Ci-C4 alcohols are methanol, ethanol, ethylene glycol, n-butanol, and isobutanol.

[0106] Aldehydes are well known to those skilled in the art. For example, aldehydes are selected from the group consisting of formaldehyde, acetaldehyde, methacrolein, and acrolein.

[0107] Within the scope of the present invention, the term ketones refers to both monoketones, such as acetone, and diketones, such as diacetyl. Ketones according to the invention are, for example, selected from the group consisting of diacetyl, acetone, acetylacetone, and methyl ethyl ketone.

[0108] For example, the first gas stream obtained during thermal cracking contains 60 to 99 wt. %, preferably 80 to 98 wt. %, of the at least one alkyl(meth)acrylate, in each case based on the total weight of the first gas stream.

[0109] For example, the first gas stream obtained during thermal cracking contains 0.1 to 10 wt. %, preferably 0.5 to 5 wt. %, of at least one further alkyl ester, in each case based on the total weight of the first gas stream.

[0110] For example, the first gas stream obtained during thermal cracking contains 0.1 to 30 wt.-%, preferably 0.5 to 18 wt.-%, of at least one further component, in each case based on the total weight of the first gas stream.

[0111] In step b), the first gas stream obtained in step a) is condensed to obtain a liquid first stream. The liquid first stream contains at least one alkyl(meth)acrylate and at least one other alkyl ester. 202200004 14

[0112] The first gas stream can be condensed using methods known to experts; for example, condensation can take place in a condenser.

[0113] For example, the first gas stream in step b) is condensed at a temperature in the range of -10 °C to 100 °C; preferably in the range of 0 °C to 90 °C, particularly preferably in the range of 20 °C to 80 °C.

[0114] The pressure during the condensation of the first gas stream in step b) is, for example, in the range of 0.1 bar to 1.1 bar, preferably in the range of 0.3 bar to 1 bar and particularly preferably in the range of 0.4 bar to 0.8 bar.

[0115] Preferably, the first gas stream is condensed by being drawn into a previously condensed and cooled first gas stream, where it then condenses. A portion of the condensed first gas stream can then be separated as a liquid first stream, and the first gas stream can be drawn back into the condensed and cooled first gas stream.

[0116] During condensation, the first gas stream transitions from the gas phase to the liquid phase, while retaining the liquid first stream.

[0117] Typically, the at least one alkyl(meth)acrylate contained in the liquid first stream is the same at least one alkyl(meth)acrylate that was contained in the first gas stream. Therefore, the explanations and preferences previously described for the at least one alkyl(meth)acrylate contained in the first gas stream apply accordingly to the at least one alkyl(meth)acrylate contained in the liquid first stream.

[0118] Typically, the at least one additional alkyl ester contained in the first liquid stream is the same at least one additional alkyl ester that was contained in the first gas stream. Therefore, the previously described explanations and preferences apply to the at least one additional alkyl ester contained in the first liquid stream as they do to the at least one additional alkyl ester contained in the first gas stream.

[0119] The liquid first stream may additionally contain at least one further component that may be present in the first gas stream. The previously described provisions and preferences apply accordingly to this at least one further component.

[0120] Preferably according to the invention, the first gas stream is distilled after step a) and before step b). A first overhead stream containing the at least one alkyl(meth)acrylate and the at least one further alkyl ester, and a first bottom stream containing at least one other alkyl(meth)acrylate and the at least one further alkyl ester are distilled.

[0121] The component is obtained. In this embodiment, the first overhead stream obtained during distillation is then condensed in step b).

[0122] A preferred method is therefore also a process in which the first gas stream is distilled after step a) and before step b) to obtain a first overhead stream containing the at least one alkyl(meth)acrylate and the at least one further alkyl ester, and a first bottom stream containing at least one component different from the at least one alkyl(meth)acrylate and the at least one further alkyl ester, wherein the first overhead stream is condensed in step b).

[0123] The first gas stream can be condensed before it is distilled according to step a) and before step b). Methods for condensing the first gas stream are known as such and are described, for example, above. Therefore, within the scope of the present invention, "distillation of the first gas stream" refers not only to the distillation of the first gas stream in the gas phase, but also, and in particular, to the distillation of the first gas stream after it has been condensed.

[0124] The distillation of the first gas stream can be carried out using methods and reactors known to those skilled in the art. For example, the first gas stream can be transferred to a distillation column and / or a rectification column and distilled there. During the distillation of the first gas stream, components contained in the first gas stream that have a higher boiling point than the at least one alkyl(meth)acrylate are obtained in the first bottom stream, while components contained in the first gas stream that have the same or a lower boiling point than the at least one alkyl(meth)acrylate are obtained in the first top stream.

[0125] Distillation can take place, for example, at a temperature in the range of 40 to 140 °C. Preferably, the bottoms temperature during distillation is in the range of 95 to 130 °C, and particularly preferably in the range of 97 to 126 °C.

[0126] Distillation can take place, for example, at a pressure in the range of 10 to 250 mbar, preferably in the range of 15 to 150 mbar.

[0127] Distillation of the first gas stream yields a first overhead stream. This first overhead stream contains the at least one alkyl(meth)acrylate and the at least one other alkyl ester that were already present in the first gas stream.

[0128] The first overhead stream may also contain further components. In particular, the first overhead stream contains at least one further component present in the first gas stream, which has a lower or the same boiling point as the at least one alkyl(meth)acrylate and the at least one further alkyl ester. Therefore, the first overhead stream typically contains at least one further component selected from the group consisting of methyl propionate, ethyl propionate, methyl isobutyrate, methyl pivalate, methyl 3-methoxyisobutyrate, and dicaronic acid dies.

[0129] For example, the first overhead stream obtained by distillation contains 60 to 99 wt.%, preferably 80 to 98 wt.%, of the at least one alkyl(meth)acrylate, in each case based on the total weight of the first overhead stream.

[0130] For example, the first overhead stream obtained by distillation contains 0.1 to 10 wt.%, preferably 0.5 to 5 wt.%, of the at least one further alkyl ester, in each case based on the total weight of the first overhead stream.

[0131] For example, the first overhead stream obtained by distillation contains 0.1 to 30 wt.%, preferably 0.5 to 18 wt.%, of at least one further component, in each case based on the total weight of the first overhead stream.

[0132] Furthermore, a first bottom stream is obtained. Within the scope of the present invention, a "bottom stream" is understood to mean not only a bottom product that is continuously removed from the distillation, in particular from the reactor, but also a bottom product that, for example in batch operation, remains in the reactor as a distillation residue and is only removed from the reactor at a later time.

[0133] The first gas stream contains at least one component different from the at least one alkyl(meth)acrylate and the at least one other alkyl ester. This component is usually at least one of the at least one other component contained in the first gas stream. In particular, this at least one other component usually has a higher boiling point than the at least one alkyl(meth)acrylate and the at least one other alkyl ester contained in the first gas stream. For example, this at least one other component is selected from the group consisting of sulfur-containing compounds, high-boiling aromatics, oligomers, and dimers.The statements and preferences previously described for the sulfur-containing compounds, high-boiling aromatics, oligomers and dimers contained in the first gas stream apply accordingly to the sulfur-containing compounds, high-boiling aromatics, oligomers and dimers.

[0134] The first swamp stream therefore preferentially contains sulfur-containing compounds, high-boiling aromatics, oligomers and / or dimers.

[0135] In step c), the liquid first stream obtained in step b) is mixed with another stream to obtain a mixed stream. The further stream contains at least one additional 202200004 17

[0136] Alkyl(meth)acrylate and is part of a C2-Ci8-alkyl(meth)acrylate manufacturing process. The resulting mixed stream comprises the liquid first stream and the subsequent stream.

[0137] For example, up to 90 wt.%, preferably up to 60 wt.% of the liquid first stream is mixed with the further stream based on the total weight of the resulting mixed stream.

[0138] The subsequent stream with which the first liquid stream is mixed contains at least one further alkyl(meth)acrylate. "At least one further alkyl(meth)acrylate" within the scope of the present invention means both exactly one further alkyl(meth)acrylate and a mixture of two or more further alkyl(meth)acrylates. Exactly one further alkyl(meth)acrylate is preferred.

[0139] The specifications and preferences previously described for the at least one further alkyl(meth)acrylate contained in the first gas stream apply accordingly to the at least one further alkyl(meth)acrylate contained in the subsequent stream. The at least one further alkyl(meth)acrylate is therefore, for example, selected from the group consisting of Ci-C4 alkyl(meth)acrylates. Methyl(meth)acrylate is particularly preferred as the alkyl(meth)acrylate contained in the subsequent stream.

[0140] The at least one alkyl(meth)acrylate contained in the liquid first stream preferably comprises the same alkyl(meth)acrylate as the alkyl(meth)acrylate that comprises the at least one further alkyl(meth)acrylate of the further stream.

[0141] According to the invention, it is preferred that, based on the total weight of the at least one alkyl(meth)acrylate contained in the liquid first stream, at least 80 wt.%, preferably at least 90 wt.% of the at least one alkyl(meth)acrylate contained in the liquid first stream, is the same alkyl(meth)acrylate as the at least one further alkyl(meth)acrylate contained in the further stream.

[0142] The further stream is part of a C2-C18 alkyl(meth)acrylate manufacturing process. Within the scope of the present invention, a "C2-C18 alkyl(meth)acrylate manufacturing process" is understood to be a process for the production of C2-C18 alkyl(meth)acrylates by transesterification of alkyl(meth)acrylates. The previously described features and preferences apply accordingly to the alkyl(meth)acrylates. Accordingly, a C2-C18 alkyl(meth)acrylate manufacturing process is preferably a process for the production of C2-C18 alkyl(meth)acrylates by transesterification of Ci-C4 alkyl(meth)acrylates. It is understood that the alkyl(meth)acrylates transesterified in the process are different from the C2-C18 alkyl(meth)acrylates that are produced.The alkyl(meth)acrylates that are transesterified are usually the at least one further alkyl(meth)acrylate contained in the further stream and the at least one alkyl(meth)acrylate contained in the liquid first stream. 202200004 18.

[0143] The liquid first stream can be mixed with the further stream using methods known to those skilled in the art. For example, and preferably according to the invention, the liquid first stream is fed into a plant for the production of a C2-Ci8-alkyl(meth)acrylate, which contains the further stream. The resulting mixed stream is then preferably also included in the plant for the production of a C2-Ci8-alkyl(meth)acrylate. The mixed stream is then preferably also part of the C2-Ci8-alkyl(meth)acrylate production process.

[0144] A preferred method is therefore one in which the mixed stream obtained in step c) is part of the C2-Ci8-alkyl(meth)acrylate manufacturing process.

[0145] The mixed stream comprises the liquid first stream and the subsequent stream. Therefore, the mixed stream typically includes the same components that were present in both the liquid first stream and the subsequent stream. Thus, the mixed stream typically includes the at least one alkyl(meth)acrylate, the at least one further alkyl ester, the at least one further alkyl(meth)acrylate, and optionally the at least one further component.

[0146] The liquid first stream can be mixed with the subsequent stream at any point in the C2-Ci8-alkyl(meth)acrylate production process. For example, the liquid first stream is mixed with the subsequent stream upstream of the reactor described below in the C2-Ci8-alkyl(meth)acrylate production plant. It is also possible for the liquid first stream to be mixed with the subsequent stream within the reactor described below.

[0147] If the liquid first stream is mixed with the subsequent stream in the reactor described below, steps c) and d) are usually carried out simultaneously.

[0148] A method in which steps c) and d) are carried out simultaneously is therefore also preferred.

[0149] In step d), the mixed stream obtained in step c) is reacted with a C2-cis alcohol in the presence of a catalyst. This yields a product stream containing at least one alkyl(meth)acrylate, at least one further alkyl(meth)acrylate, the C2-Ci8-alkyl(meth)acrylate, the catalyst, at least one alkyl ester, the C2-cis alcohol, and at least one further alcohol.

[0150] Within the scope of the present invention, the term "a C2-Ci8 alcohol" includes both exactly one C2-Cis alcohol and a mixture of two or more C2-Cis alcohols. According to the invention, exactly one C2-Cis alcohol is preferred. 202200004 19

[0151] Within the scope of the present invention, a "C2-Ci8 alcohol" is understood to be an alcohol having 2 to 18 carbon atoms in the alkyl group. The alkyl group can be cyclic or linear, and branching is also possible. The alkyl group with 2 to 18 carbon atoms can also be substituted with heteroatoms within the alkyl group. Within the scope of the present invention, "C2-cis alcohols" also includes alcohols having an aromatic group in the alkyl group, such that the alkyl group and the aromatic group together have 2 to 18 carbon atoms. Benzyl alcohol is an example of such a C2-cis alcohol with an aromatic group in the alkyl group. The C2-cis alcohol can have exactly one hydroxyl group (OH group). It can also have two or more hydroxyl groups. If the C2-cis alcohol has two or more hydroxyl groups, the alcohol is also called a polyol.It is therefore possible that the C2-cis alcohol comprises a polyol.

[0152] A method in which the C2-cis alcohol in step d) comprises a polyol is therefore also preferred according to the invention.

[0153] If the C2-cis alcohol contains exactly two hydroxyl groups, it is also called a diol. If the C2-cis alcohol contains exactly three hydroxyl groups, it is also called a triol.

[0154] The C2-Cis alcohol is preferably a C4-Ci2 alcohol.

[0155] Examples of C2-cis alcohols are ethanol, propanol, isopropanol, n-butanol, tert-butanol, isobutanol, pentanol, cyclohexanol, hexanol, heptanol, octanol, isooctanol, isodecanol, 2-ethylhexanol, isoborneol, benzyl alcohol, tetrahydrofurfurol, 3,3,4-trimethylcyclohexanol, phenylethanol, tert-butylaminoethanol, diethylaminoethanol, ethylene glycol, ethylene triglycol, methylene triglycol, butyl diglycol, 1,3-butanediol, 1,4-butanediol, trimethylolpropane and isopropylidene glycerol.

[0156] The C2-cis alcohol in step d) is preferably selected from the group consisting of ethanol, n-butanol, isobutanol, 2-ethylhexanol, tert-butanol, isodecanol and cyclohexanol.

[0157] In particular, the C2-cis alcohol selected in step d) from the group consisting of n-butanol, isobutanol and 2-ethylhexanol is preferred.

[0158] For example, the molar ratio of the mixture stream, in particular of the at least one alkyl(meth)acrylate and at least one further alkyl(meth)acrylate contained in the mixture stream, to the C2-cis alcohol in the reactor is in the range of 2 to 1 to 1 to 2, preferably in the range of 1.1 to 1 to 1.2 to 1.

[0159] It is self-evident that the stoichiometric ratio of the mixture stream, in particular of the at least one alkyl(meth)acrylate and at least one further alkyl(meth)acrylate contained in the mixture stream, to the C2-Ci8 alcohol refers to the stoichiometric ratio before the mixture stream was reacted with the C2-Ci8 alcohol. It is clear to those skilled in the art that the stoichiometric ratio can change during the reaction, for example, due to side reactions and / or distillation of a component.

[0160] The mixed stream is reacted in step d) in the presence of a catalyst. Within the scope of the present invention, "a catalyst" means both exactly one catalyst and a mixture of two or more catalysts. Exactly one catalyst is preferred according to the invention.

[0161] It is clear to those skilled in the art that the composition of the catalyst can change during the reaction in step d), for example through transesterification. Therefore, it is possible that the reaction in step d) begins in the presence of exactly one catalyst, but that the composition of the first catalyst can change during the course of the reaction, so that a mixture of two or more first catalysts can be formed during the reaction in step d), and the reaction in step d) then takes place in the presence of a mixture of two or more catalysts.

[0162] For example, the reaction in step d) takes place in the presence of 0.01 to 5 wt.% of the catalyst, preferably in the range of 0.1 to 0.5 wt.% of the catalyst, in each case based on the total weight of at least one alkyl(meth)acrylate and at least one further alkyl(meth)acrylate.

[0163] All catalysts known to those skilled in the art are suitable as catalysts that catalyze the reaction of the components contained in the mixture stream, in particular the at least one alkyl(meth)acrylate and at least one further alkyl(meth)acrylate contained in the mixture stream, with the C2-cis alcohol.

[0164] Preferably, the catalyst is selected from the group consisting of metal salts and organic compounds, each of which is selected from the group consisting of tin, titanium, zirconium, alkali metals and alkaline earth metals.

[0165] A preferred method is therefore one in which the catalyst is selected from the group consisting of metal salts and organic compounds, each of which is selected from the group consisting of tin, titanium, zirconium, alkali metals and alkaline earth metals.

[0166] Suitable metal salts of metals selected from the group consisting of tin, titanium, zirconium, alkali metals and alkaline earth metals are known to those skilled in the art and include, for example, lithium hydroxide, calcium hydroxide, calcium oxide, lithium amide, lithium chloride, sodium hydroxide and / or potassium hydroxide; alkali metal chlorides and / or alkali metal hydroxides are preferred; mixtures of alkali metal chlorides and / or alkali metal hydroxides with alkaline earth metal oxides are particularly preferred.

[0167] Suitable organic compounds of metals selected from the group consisting of tin, titanium, zirconium, alkali metals and alkaline earth metals are known to those skilled in the art and include, for example, dibutyltin oxide, dioctyltin oxide, tetraisopropyl titanate and / or zirconium acetonyl acetonate, preferably tetraisopropyl titanate and / or zirconium acetonyl acetonate.

[0168] The implementation in step d) takes place, for example, at a temperature in the range of 80 °C to 160 °C, preferably at a temperature in the range of 110 °C to 135 °C.

[0169] The implementation in step d) can take place in reactors for transesterification known to those skilled in the art. Transesterification processes and reactors for this purpose are described, for example, in EP 1 583 733 and DE 1 200 171.

[0170] For example, the reaction in step d) can take place in a reactor that includes a vapor extraction system leading to a first distillation column. This first distillation column is also known as an azeotropic distillation column.

[0171] The reaction in step d) can take place in any reactor. It can be carried out continuously, but a batch reaction is also possible. Preferably, the reaction in step d) is carried out continuously. In this context, "continuous" means that the mixed stream or the liquid first stream and the subsequent stream are continuously fed into the reactor, while at the same time the product stream is continuously discharged from the reactor.

[0172] The implementation in step d) can take place in the presence of other components. Such additional components are known as stabilizers, for example.

[0173] Suitable stabilizers are compounds that inhibit the polymerization of the mixture, especially of the at least one alkyl(meth)acrylate and at least one other alkyl(meth)acrylate contained therein. These stabilizers are therefore also referred to as polymerization inhibitors.

[0174] Suitable stabilizers include, for example, hydroquinone monomethyl ether in combination with oxygen, phenol, hydroquinone, nitrophenol and / or butyl hydroxytoluene.

[0175] Preferred stabilizers include, in particular, phenolic compounds, such as...

[0176] Examples include hydroquinones, hydroquinone ethers, such as hydroquinone monomethyl ether, tert-

[0177] Butylhydroquinone, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,4-dimethyl-6-tert-butylphenol or di-tert-butylcatechol; p-phenylenediamines, such as N,N'-diphenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-p-tolyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine and N-1,4-dimethylpentyl-N'-phenyl-p-phenylenediamine; amines, such as thiodiphenylamine and phenothiazine; Copper dialkyldithiocarbamates, such as copper dimethyldithiocarbamates, copper diethyldithiocarbamates and copper dibutyldithiocarbamates; nitroso compounds, such as nitrosodiphenylamine, isoamyl nitrite, N-nitrosocyclohexylhydroxylamine, N-nitroso-N-phenyl-N-hydroxylamine and their salts;and N-oxyl compounds, such as 2,2,4,4-tetramethylazetidine-1-oxyl, 2,2-dimethyl-4,4-dipropylazetidine-1-oxyl, 2,2,5,5-tetramethylpyrrolidine-1-oxyl, 2,2,5,5-tetramethyl-3-oxopyrrolidine-1-oxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 6-aza-7,7-dimethylspiro[4,5]decane-6-oxyl, 2,2,6,6-tetramethyl-4-acetoxypiperidine-1-oxyl and 2,2,6,6-tetramethyl-4-benzoyloxypiperidine-1-oxyl; Methylene blue, nigrosine base BA, 1,4-benzoquinone, sterically hindered phenols, for example 2,4-dimethyl-6-tert-butylphenol and / or tocopherol compounds, preferably α-tocopherol.;

[0178] Stabilizers can be used individually or in mixtures and are generally commercially available. For further details, please refer to standard reference works, in particular the Römpp Lexicon of Chemistry; editors: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996); entry "Antioxidants" and the references cited here.

[0179] For example, the reaction in step d) takes place in the presence of 1 to 5000 wt. ppm stabilizer, preferably 5 to 1000 wt. ppm, particularly preferably 10 to 100 wt. ppm, in each case based on the total weight of the mixed stream, in particular on the at least one alkyl(meth)acrylate and the at least one further alkyl(meth)acrylate.

[0180] In step d), a product stream is obtained. The product stream contains at least one alkyl(meth)acrylate, at least one further alkyl(meth)acrylate, the C2-Ci8-alkyl(meth)acrylate, the catalyst, at least one alkyl ester, the C2-Cis alcohol, and at least one further alcohol.

[0181] It goes without saying that the at least one alkyl(meth)acrylate, the at least one further alkyl(meth)acrylate, and the at least one alkyl ester contained in the product stream are the same at least one alkyl(meth)acrylate, at least one further alkyl(meth)acrylate, and at least one alkyl ester that were present in the mixed stream and have not (yet) reacted. It also goes without saying that the C2-cis alcohol contained in the product stream is the same C2-cis alcohol with which the mixed stream was reacted. The catalyst contained in the product stream is the same catalyst in whose presence the mixed stream was reacted with the C2-cis alcohol.

[0182] Upon reaction of the mixed stream, in particular the at least one alkyl(meth)acrylate and the at least one further alkyl(meth)acrylate, with the C2-Ci8 alcohol in the presence of the catalyst, the C2-Ci8 alkyl(meth)acrylate is formed. Simultaneously, at least one further alcohol of the alkyl group of the at least one alkyl(meth)acrylate and the at least one further alkyl(meth)acrylate is formed. The at least one further alcohol formed is therefore typically a Ci-Cis alcohol, preferably a Ci-Ci2 alcohol, and particularly preferably a C1-C4 alcohol.

[0183] It goes without saying that at least one other alcohol is different from the C2-cis alcohol.

[0184] Likewise, the C2-Ci8-alkyl(meth)acrylate differs from the at least one alkyl(meth)acrylate and the at least one other alkyl(meth)acrylate.

[0185] For example, the product stream obtained in step d) contains

[0186] 1 to 30 wt% at least one alkyl(meth)acrylate and at least one other alkyl(meth)acrylate,

[0187] 47 to 88 wt% C2-Ci8-alkyl(meth)acrylate,

[0188] 0.05 to 0.4 wt% catalyst,

[0189] 0.01 to 1 wt% at least one alkyl ester,

[0190] 2 to 22 wt% C2-cis alcohol and

[0191] 0.1 to 1.1% by weight of at least one other alcohol, each based on the total weight of the product stream.

[0192] Preferably, in the implementation in step d), a second top stream and a second bottom stream are obtained.

[0193] The second headstream then contains at least one alkyl(meth)acrylate, at least one further alkyl(meth)acrylate, at least one alkyl ester and at least one further alcohol.

[0194] The second sump stream comprises the product stream.

[0195] A preferred method is therefore also one in which, during the reaction in step d), a second overhead stream is obtained, containing the at least one alkyl(meth)acrylate, the at least one further alkyl(meth)acrylate, the at least one alkyl ester and the at least one further alcohol, and a second bottom stream comprising the product stream.

[0196] The second overhead stream and the second bottom stream are usually formed by distillation during the reaction in step d). As explained above, the reactor in which the 202200004 24

[0197] The conversion process in step d) takes place, for example, in a first distillation column. The distillation during the conversion in step d) then preferably takes place in the first distillation column.

[0198] The second overhead stream can be at least partially removed from the reaction in step d). This is particularly advantageous because it shifts the reaction equilibrium of the reaction in step d) towards the product stream.

[0199] The received second head current can be at least partially fed back in step c) and / or d).

[0200] Furthermore, it is possible that the second headstream is at least partially fed into a process for the production of a Ci-C2 alkyl(meth)acrylate, in particular methyl(meth)acrylate.

[0201] A preferred method is therefore one in which the obtained second headstream is recycled in step c) and / or step d) and / or fed into a process for the production of a C1-C2 alkyl(meth)acrylate.

[0202] Methods for the preparation of Ci-C2 alkyl(meth)acrylates, in particular methyl(meth)acrylate, are known to those skilled in the art. These are usually prepared using various methods starting from C2, C3, or C4 building blocks.

[0203] In step e), the C2-Ci8-alkyl(meth)acrylate is separated from the product stream.

[0204] The C2-Ci8-alkyl(meth)acrylate can be separated from the product stream by methods known to those skilled in the art. Preferably, the C2-Ci8-alkyl(meth)acrylate is separated from the product stream by distillation.

[0205] For example, step e) includes the following step e1): e1) Distillation of the product stream to obtain a third overhead stream containing the at least one alkyl(meth)acrylate, the at least one further alkyl(meth)acrylate, the at least one alkyl ester, the C2-Cis alcohol and the at least one further alcohol, and a third bottom stream containing the C2-Ci8-alkyl(meth)acrylate, residues of the at least one alkyl ester and the catalyst.

[0206] A preferred method is therefore also one in which step e) comprises the following step e1): e1) distillation of the product stream to obtain a third overhead stream containing the at least one alkyl(meth)acrylate, the at least one further alkyl(meth)acrylate, the at least one alkyl ester, the C2-C18 alcohol and the at least one further alcohol, and a 202200004 25 third bottom stream containing the C2-C18 alkyl(meth)acrylate, residues of the at least one alkyl ester and the catalyst.

[0207] The distillation in step e1) takes place, for example, in a second distillation column. The components of the third overhead stream have a lower boiling point than the C2-C18 alkyl(meth)acrylate and are separated from the C2-C18 alkyl(meth)acrylate. Therefore, the second distillation column is also referred to as the low-boiling-point distillation column.

[0208] Typically, following step e), the second mixture is transferred to the second distillation column, preferably continuously, and distilled there according to step e1).

[0209] The distillation in step e1) is usually carried out at a temperature in the range of 45 °C to 130 °C. Preferably, the bottoms temperature during distillation is in the range of 50 °C to 180 °C, particularly preferably in the range of 100 °C to 150 °C.

[0210] The distillation in step e1) is preferably carried out at reduced pressure, in particular at a pressure in the range of 10 mbar to 200 mbar.

[0211] The third overhead stream obtained in step e1) can, for example, be recycled in step c) and / or d) of the process according to the invention. This allows the at least one alkyl(meth)acrylate, the at least one further alkyl(meth)acrylate, and the C2-cis alcohol contained in the third overhead stream to be reacted according to step d), thus saving resources and ensuring that the overall conversion of the process according to the invention is largely complete.

[0212] Furthermore, it is possible to feed at least part of the third headstream into a process for the production of a Ci-C2 alkyl(meth)acrylate.

[0213] A preferred method is therefore one in which the third headstream is recycled in step c) and / or step d) and / or fed into a process for the production of a C1-C2 alkyl(meth)acrylate.

[0214] Preferably, the third head current is recycled in step c) and / or d) of the method according to the invention.

[0215] The third bottom stream obtained in step e1) preferably contains more than 98 wt% C2-C18-alkyl(meth)acrylate, based on the total weight of the third bottom stream. 202200004 26

[0216] If the reaction in step d) takes place in the presence of at least one polymerization inhibitor, the third bottom stream usually also contains the at least one polymerization inhibitor.

[0217] According to the invention, it is preferred that following step e1) the following step e2) is carried out: e2) Distillation of the third bottom stream obtained in step e1) to obtain a fourth top stream containing the C2-Ci8-alkyl(meth)acrylate and a fourth bottom stream containing the residues of the at least one alkyl ester and the catalyst.

[0218] A method is therefore also preferred according to the invention in which, following step e1), the following step e2) is carried out: e2) Distillation of the third bottom stream obtained in step e1) to obtain a fourth top stream containing the C2-C18 alkyl(meth)acrylate and a fourth bottom stream containing the residues of the at least one alkyl ester and the catalyst.

[0219] The distillation in step e2) takes place, for example, in a third distillation column. The C2-Ci8-alkyl(meth)acrylate is obtained in the fourth overhead stream. The components of the fourth bottom stream have a higher boiling point than the C2-Ci8-alkyl(meth)acrylate and are separated from it. Therefore, the third distillation column is also referred to as the high-boiling distillation column.

[0220] Typically, the third bottom stream obtained in step e1) is continuously transferred to the third distillation column and distilled there according to step e2).

[0221] The distillation in step e2) usually takes place at a temperature in the range of 85 to 120 °C.

[0222] The distillation in step e2) is preferably carried out at reduced pressure, in particular at a pressure in the range of 20 mbar to 200 mbar.

[0223] The distillation in step e2) can, for example, include film evaporation. Suitable film evaporators are known as such and have been selected, for example, from the group consisting of falling film evaporators, thin-film evaporators, and short-path evaporators.

[0224] The fourth bottom stream obtained in step e2) contains the catalyst. Preferably, the fourth bottom stream is recycled in step d). This makes the process according to the invention particularly economical. 202200004 27

[0225] A method in which the fourth sump stream is recycled in step d) is therefore also preferred.

[0226] The fourth sump stream can be purified before being recycled in step d), for example in a vacuum evaporation stage. Such vacuum evaporation stages are known as such and include, for example, film evaporators such as falling film evaporators, thin-film evaporators and / or short-path evaporators.

[0227] In the vacuum evaporation stage, any remaining C2-Ci8-alkyl(meth)acrylate contained in the fourth bottom stream can also be removed, further increasing the yield of C2-Ci8-alkyl(meth)acrylate.

[0228] In step e), the C2-Ci8-alkyl(meth)acrylate is separated. In particular, the C2-Ci8-alkyl(meth)acrylate is preferably obtained in the fourth overhead stream in step e2).

[0229] The term "C2-Ci8-alkyl(meth)acrylate" refers to alkyl esters of (meth)acrylic acid that have 2 to 18 carbon atoms in the alkyl group. The alkyl group can be cyclic or linear, and branching is also possible. The alkyl group with 2 to 18 carbon atoms can also be substituted with heteroatoms and, in particular, may contain hydroxyl groups (OH groups).

[0230] For example, C2-Ci8-alkyl(meth)acrylate is selected from the group consisting of ethyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, stearyl(meth)acrylate, cyclohexyl(meth)acrylate, benzyl(meth)acrylate, isodecyl(meth)acrylate and lauryl(meth)acrylate.

[0231] It goes without saying that the alkyl group with the 2 to 18 carbon atoms is derived from the C2-cis alcohol reacted in step d).

[0232] For example, if isobutanol is reacted as the C2-cis alcohol in step d), the resulting C2-Ci8 alkyl(meth)acrylate is isobutyl(meth)acrylate. Similarly, the resulting C2-C18 alkyl(meth)acrylate is, for example, cyclohexyl(meth)acrylate if cyclohexanol is reacted as the C2-cis alcohol.

[0233] The C2-Ci8-alkyl(meth)acrylate separated in step e) typically still contains residues of the at least one alkyl ester. For example, the C2-Ci8-alkyl(meth)acrylate contains, in the range of 50 wt. ppm to 8500 wt. ppm, preferably in the range of 75 wt. ppm to 4700 wt. ppm, the at least one alkyl ester, based on the total weight of the C2-Ci8-alkyl(meth)acrylate.

[0234] The present invention therefore also relates to a C2-Ci8-alkyl(meth)acrylate obtainable according to the inventive process, wherein the C2-Ci8-alkyl(meth)acrylate has a concentration of 28%.

[0235] Contains 50 ppm to 10000 ppm of at least one alkyl ester, based on the total weight of the C2-Ci8-alkyl(meth)acrylate.

[0236] A further object of the present invention is a process for isolating C2-C18 alkyl(meth)acrylates comprising the following steps c1) to e): c1) Mixing a liquid first stream containing at least one alkyl(meth)acrylate and at least one further alkyl ester, wherein the liquid first stream is obtainable by thermal cleavage of at least one polymer composition, with a further stream containing at least one further alkyl(meth)acrylate, wherein the further stream is part of a C2-C18 alkyl(meth)acrylate manufacturing process, to obtain a mixed stream comprising the liquid first stream and the further stream; d) Reacting the mixed stream obtained in step c) with a C2-cis alcohol in the presence of a catalyst to obtain a product stream comprising the at least one alkyl(meth)acrylate, the at least one further alkyl(meth)acrylate, the C2-C18 alkyl(meth)acrylate, the catalyst, the at least one alkyl ester,containing the C2-cis alcohol and at least one other alcohol, e) separation of the C2-Ci8 alkyl(meth)acrylate from the product stream.

[0237] In step c1), the liquid first stream is mixed with the subsequent stream. The liquid first stream is obtained by thermal cracking of at least one polymer composition. The previously described specifications and preferences apply to the polymer composition.

[0238] Preferably, the liquid first stream is therefore obtainable by the following steps a) and b): a) thermal cracking of at least one polymer composition containing at least one poly(alkyl(meth)acrylate) to obtain a first gas stream containing at least one alkyl(meth)acrylate and at least one further alkyl ester, b) condensation of the first gas stream obtained in step a) to obtain the liquid first stream containing the at least one alkyl(meth)acrylate and the at least one further alkyl ester.

[0239] The explanations and preferences described above apply accordingly to steps a) and b).

[0240] The previously described explanations and preferences also apply to the liquid first stream. Similarly, the previously described explanations and preferences for step c) apply to step c1).

[0241] The explanations described above apply accordingly to steps d) and e). 202200004 29

[0242] Reference symbol list

[0243] The reference symbols in the figures have the following meaning:

[0244] 1 liquid first stream

[0245] 2 more electricity

[0246] 3 Mixed flow

[0247] 4 C2-Cia-Alcohol

[0248] 5 first distillation column

[0249] 6 Reactor

[0250] 7 second headstream

[0251] 8 second swamp stream

[0252] 9 Low-boiling-point distillation column

[0253] 10 third headstream

[0254] 11 third swamp stream

[0255] 12 High-boiling-point distillation column

[0256] 13 fourth headstream

[0257] 14 fourth swamp stream

[0258] 15 Catalyst

[0259] 16 Product flow

[0260] Figures

[0261] Figure 1 shows an embodiment of steps c) to e) of the method according to the invention.

[0262] The liquid first stream 1 is mixed with the further stream 2 to obtain a mixed stream 3. In the illustrated embodiment, steps c) and d) of the method according to the invention are carried out successively. The third head stream 10 is used as the further stream 2.

[0263] The mixed stream is reacted with the C2-cis alcohol 4 in reactor 6. The C2-cis alcohol 4 can be fed directly into reactor 6 (feed line 4b). Additionally or alternatively, it is possible to introduce the C2-cis alcohol 4 into the first distillation column 5 (feed line 4a). Additionally or alternatively, it is possible to mix the C2-cis alcohol 4 with the mixed stream 3 (feed line 4c) and / or the other stream 2 (feed line 4d).

[0264] In reactor 6, the mixed stream 3 is reacted with the C2-cis alcohol 4 in the presence of a catalyst 15, yielding a second overhead stream 7, which is drawn off via the first distillation column 5, and a second bottom stream 8, which comprises the product stream 16. The second bottom stream 8 is transferred to the low-boiling distillation column 9 (second distillation column) 202200004 30 and distilled there, yielding the third overhead stream 10 and the third

[0265] Bottom stream 11. The third overhead stream 10 is recycled in step c) and mixed with the liquid first stream 1. The third bottom stream 11 is transferred to the high-boiling distillation column 12 (third distillation column) and distilled there to obtain the fourth overhead stream 13, which contains the C2-Ci8-alkyl(meth)acrylate, and a fourth bottom stream 14. The fourth bottom stream 14 can be recycled in step d) (not shown in Figure 1).

[0266] Examples

[0267] Examples of depolymerization

[0268] Example 1 - 5 - Depolymerization as a function of temperature:

[0269] Approximately 50 mg of PMMA molding compound (type: Y7H) was cleaved at different temperatures, and the collected condensate was analyzed by GC-MS. The components were quantitatively determined by headspace GC-MS analysis. The results are shown in Table 1.

[0270] Table 1

[0271] General description Example 6 - 13 continuous depolymerization

[0272] Reactor: consisting of two pipes (DN 100, made of steel 1.4571, each approx. 80 cm long) with attached sight glasses (Schott glass components, DN 100), connected via a 90° elbow (DN 100, 1.4571). Equipped with thermocouples for temperature measurement.

[0273] Heating: Melting and cracking tubes, each with an electric heating sleeve (KJT, 220 V, 3000 W, 54 cm long), pipe bends and distillate transfer with electric heating bands. Heating temperature regulated via Eurotherm controller. Granule inlet: Metal container with ball valve and 202200004 31

[0274] Nitrogen purge (homemade, approx. 5 l capacity) mounted on a glass cooler (Schott, DN 100) with inserted funnel (PE powder funnel extended with Teflon tube).

[0275] Description:

[0276] PMMA granules (polymer composition) are fed into the reactor's preheater via a nitrogen-purged feed hopper and a hopper. To generate a sufficiently fluid melt, temperatures in the preheater are necessary at which pyrolysis begins (slightly at 250 °C, increasingly so from 300 °C onwards). If the heating jacket temperature is too low, insufficient energy input occurs (heat exchange surface too small), and the cracking reactor (temperatured at 300–350 °C) is not adequately supplied with melt. Furthermore, the nitrogen flow prevents the gases produced by depolymerization from mixing back into the reactor and carries them into the reaction zone where the PMMA contained in the melt is cracked.The melt flows by gravity into the reaction zone and separates into a non-vaporizable fraction and gaseous polymer. The latter is condensed and collected to obtain a condensate representative of the depolymerization process. Depending on the initial composition and purity of the PMMA used, the purity and composition of the condensed liquid first stream ("cracked MMA") differ significantly. The various compositions were determined by GC and are shown in Table 2.

[0277] Table 2 202200004 32

[0278] It is clearly evident that non-organically modified PMMA residues are preferable, while inorganic impurities (Ex. 13) hardly cause any problems.

[0279] Example 14 - 21: continuous rectification of “Crack-MMA”

[0280] In a rectification process, the separation of low- and high-boiling components to produce pure MMA from the liquid first stream ("cracked MMA") was simulated. A packed column was used for the experiments, equipped with wire mesh packing from Sulzer (type DX, DN 50; 2.3 m packing height). The individual packing beds were equipped with a liquid sampling system. The feed was preheated and fed into the center of the column. A Robert evaporator operated with heat transfer oil was used. The overhead product was withdrawn via a reflux divider (NGW). The reflux ratio was set via a predefined time interval of the control unit. A combination of water and brine chillers was used for vapor condensation. The inlet water temperature was approximately 9°C, and the brine temperature was approximately -12°C. To ensure complete condensation of the vapors, a cold trap filled with acetone / dry ice was installed downstream.The bottoms product flowed freely into a receiving flask. The liquid level in the evaporator was determined by the arrangement of the overflow. The column was stabilized by bubbling air into the column bottoms and adding a stabilizer solution to the top of the column. The distillation was separated into two stages: first, to remove the lighter-boiling components, and then to remove the higher-boiling components, with the pure product ultimately being collected as the first overhead stream.

[0281] Distillates were collected in several campaigns, the composition of which is shown in Table 3:

[0282] 202200004 33

[0283] Table 3

[0284] Description of the preparation of C2-Ci8-alkyl(meth)acrylate:

[0285] Reactor 6 was a steam-heated stainless steel reaction vessel with a maximum filling volume of 15 L. Reactor 6 was connected via a vapor line to an azeotropic distillation column 5 mounted above it. The azeotropic distillation column 6 (top pressure = 1 barabs) was a pilot-scale glass column with a diameter of D = 0.1 m, packed with H = 2 m Sulzer CY metal wire mesh packing. The feed 4a for the C₂-cis alcohol 4 was located in the center of the column (H = 1 m). The second bottom stream 8 was continuously fed to a low-boiling-point distillation column 9. The low-boiling distillation column 9 was a pilot-scale vacuum glass column (top pressure = 120 mbarbars) with a diameter of D = 0.1 m, equipped with H = 3.8 m Sulzer CY metal wire mesh packing. The feed was located at H = 2 m. The bottom was heated with steam.The condensed third headstream 2 was continuously recycled to reactor 6. Instead of a falling film evaporator, a thermal oil-heated glass thin-film evaporator with an evaporation area of ​​A = 0.1 m² was used for the continuous work-up of the third bottom stream 11 from the low-boiling-point distillation column 9. 2 The vapors from this glass thin-film evaporator were continuously fed into a high-boiling-point distillation column 12 mounted above it. This was a pilot-scale vacuum glass column (top pressure = 120 mbarabs) with a diameter of D = 0.05 m, packed with H = 0.5 m Sulzer EX metal wire mesh packing. The fourth bottom stream 14 was fed into a second, smaller glass thin-film evaporator (top pressure = 120 mbarabs), also heated with thermal oil, with an evaporation area of ​​A = 0.02 m². 2The vapors from this second glass thin-film evaporator were continuously condensed and, combined with 202200004 34, continuously fed into the reactor downstream of the low-boiling distillation column 9. The bottoms stream was continuously discharged from the process. The feedstocks (methyl methacrylate, MMA, as liquid first stream 1 and C2-Cia alcohol 4) were continuously metered using piston metering pumps, with the catalyst 15 (tetraalkyl titanate) being added dissolved in the (by specification anhydrous) MMA feed (mixed stream 3). The MMA / catalyst feed was fed directly into the reactor, while the C2-Cia alcohol feed was preheated (to column internal temperature) and fed into the center of the azeotropic distillation column 5. The continuous addition of 50-100 g / h of stabilizer solution (0.2 wt% hydroquinone monomethyl ether in MMA or product ester) was carried out using peristaltic pumps into the reflux stream of the distillation columns.The continuous transfer of material streams between the plant components was achieved either using piston metering pumps or by the suction effect of the vacuum. Intermediate tanks (buffer volumes) were avoided wherever possible, except for the column refluxes. The composition of the material streams was determined using a gas chromatograph.

[0286] Example 22: Production of n-butyl methacrylate

[0287] For the continuous production of n-butyl methacrylate (n-BuMA), 2.62 kg / h of MMA feed from a PMMA depolymerization (liquid first stream, first overhead stream), 2.5 g / h of tetra-n-butyl titanate (Ti(n-OBu)₄) (catalyst), and 1.78 kg / h of n-BuOH feed (C₂-Cia alcohol) were fed into the reaction vessel. Additionally, 1.84 kg / h of the recirculated effluent from the top of the low-boiling-point distillation column (third overhead stream) flowed continuously into the reactor. The molar MMA : n-BuOH ratio in the reactor feed was 1.1 : 1. With a reactor residence time of 2.67 h and an azeotrope output (second overhead stream) of 1.0 kg / h, a reactor temperature of 115 °C was reached. The resulting reactor outflow (second bottom stream) was 5.6 kg / h. Due to the recycling of low-boiling components, a crude ester (4 kg / h) was obtained in the bottom discharge of the low-boiling distillation column (third bottom stream), which already had a purity of > 98.4 wt.-% n-BuMA as well as the entire catalyst and stabilizer. The yield of n-BuOH for the entire process was therefore almost 100%. The yield of MMA was also calculated based on the total yield.

[0288] The yield of 202200004 35 for the entire process, minus the previously calculated MMA loss via the MMA / MeOH azeotrope, was also nearly 100%. With an evaporation ratio (ratio of vapor to feed stream) of approximately 90% in the first, larger thin-film evaporator, 3.4 kg / h of pure n-BuMA are ultimately obtained at the top of the high-boiling-point distillation column (fourth head stream). The total discharge (fourth bottom stream) of the process (catalyst, stabilizer, high-boiling byproducts, n-BuMA) is 20 g / h.

[0289] The composition of all the above-mentioned process streams after reaching a steady state of the plant is shown in the following Tables 4 to 6, which used different pure headstream streams from Examples 14 to 16.

[0290] Table 4 Use of the fraction from Example 14

[0291] Table 5 Use of the fraction from Example 15

[0292] Table 6 Use of the fraction from Example 16

Claims

202200004 39 Claims 1. A process for isolating C2-Ci8-alkyl(meth)acrylates comprising the following steps a) to e): a) thermal cleavage of at least one polymer composition containing at least one poly(alkyl(meth)acrylate) to obtain a first gas stream containing at least one alkyl(meth)acrylate and at least one further alkyl ester; b) condensation of the first gas stream obtained in step a) to obtain a liquid first stream containing the at least one alkyl(meth)acrylate and the at least one further alkyl ester; c) mixing the liquid first stream obtained in step b) with a further stream containing at least one further alkyl(meth)acrylate, wherein the further stream is part of a C2-Ci8-alkyl(meth)acrylate manufacturing process, to obtain a mixed stream comprising the liquid first stream and the further stream.d) Reacting the mixture obtained in step c) with a C2-cis alcohol in the presence of a catalyst to obtain a product stream containing at least one alkyl(meth)acrylate, at least one further alkyl(meth)acrylate, the C2-C18 alkyl(meth)acrylate, the catalyst, at least one alkyl ester, the C2-cis alcohol and at least one further alcohol; e) Separating the C2-Ci8 alkyl(meth)acrylate from the product stream.

2. Method according to claim 1, characterized in that the polymer composition in step a) contains at least one further component selected from the group consisting of polymers other than poly(alkyl(meth)acrylate), pigments, dyes, fillers, additives, regulators, initiators, impact strengtheners, release agents and UV additives.

3. Method according to claim 1 or 2, characterized in that the at least one alkyl(meth)acrylate contained in the first gas stream in step a) is selected from the group consisting of Ci- to C4-alkyl(meth)acrylates.

4. Method according to one of claims 1 to 3, characterized in that the at least one further alkyl ester is selected from the group consisting of methyl propionate, methyl isobutyrate, methyl pivalate, methyl 3-methoxyisobutyrate and dicaronic acid esters.

5. Method according to one of claims 1 to 4, characterized in that the first gas stream contains at least one further component selected from the group consisting of styrene, (meth)acrylic acid, sulfur-containing compounds, oligomers and dimers. 202200004 40 6. A process according to any one of claims 1 to 5, characterized in that the first gas stream is distilled after step a) and before step b) to obtain a first overhead stream containing the at least one alkyl(meth)acrylate and the at least one further alkyl ester, and a first bottom stream containing at least one component different from the at least one alkyl(meth)acrylate and the at least one further alkyl ester, wherein the first overhead stream is condensed in step b).

7. Method according to any one of claims 1 to 6, characterized in that the C2-C18 alcohol in step d) comprises a polyol.

8. Method according to any one of claims 1 to 7, characterized in that the catalyst is selected from the group consisting of metal salts and organic compounds, each of metals selected from the group consisting of tin, titanium, zirconium, alkali metals and alkaline earth metals.

9. Method according to any one of claims 1 to 8, characterized in that steps c) and d) are carried out simultaneously.

10. A process according to any one of claims 1 to 9, characterized in that, in the reaction in step d), a second overhead stream is obtained, which contains the at least one alkyl(meth)acrylate, the at least one further alkyl(meth)acrylate, the at least one alkyl ester and the at least one further alcohol, and a second bottom stream, which comprises the product stream.

11. Method according to claim 10, characterized in that the obtained second headstream is recycled in step c) and / or step d) and / or fed to a method for the production of a Ci-C2 alkyl(meth)acrylate.

12. A process according to any one of claims 1 to 11, characterized in that step e) comprises the following step e1): e1) distillation of the product stream to obtain a third overhead stream containing the at least one alkyl(meth)acrylate, the at least one further alkyl(meth)acrylate, the at least one alkyl ester, the C2-Cis alcohol and the at least one further alcohol, and a third bottom stream containing the C2-Ci8-alkyl(meth)acrylate, residues of the at least one alkyl ester and the catalyst.

13. Method according to claim 12, characterized in that the third headstream is recycled in step c) and / or step d) and / or fed to a method for the production of a Ci-C2 alkyl(meth)acrylate. 202200004 41 14. A method according to claim 12 or 13, characterized in that following step e1), the following step e2) is carried out: e2) distillation of the third bottom stream obtained in step e1) to obtain a fourth overhead stream containing the C2-Ci8-alkyl(meth)acrylate and a fourth bottom stream containing the residues of the at least one alkyl ester and the catalyst.

15. A process according to claim 14, characterized in that the fourth bottom stream is recycled in step d).

16. C2-Ci8-alkyl(meth)acrylate obtainable by a process according to any one of claims 1 to 15, characterized in that the C2-Ci8-alkyl(meth)acrylate contains, in the range of 50 ppm to 10,000 ppm, the at least one alkyl ester, based on the total weight of the C2-Ci8-alkyl(meth)acrylate.

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