JP2008508205A - Catalytic process for producing (meth) acrylates from N-hydroxyalkylated amides - Google Patents

Abstract

  The present invention relates to a catalytic process for producing (meth) acrylates from N-hydroxyalkylated amides and the use thereof.

Description

  The present invention relates to a process for the catalytic production of (meth) acrylates from N-hydroxyalkylated amides and their use.

  The production of (meth) acrylic esters is often carried out by catalytic esterification of (meth) acrylic acid with alcohols in the presence of strong acids or strong bases or by transesterification of other (meth) acrylic esters. Accordingly, (meth) acrylic acid esters that are sensitive to acids or bases are often generally not intentionally prepared by esterification or transesterification.

A ureido alcohol in the sense of the present invention is a compound having at least one N— (C═O) —N— group and at least one hydroxyl group (—OH). Similarly, an N-hydroxyalkylated amide in the sense of the present invention is a compound having at least one Z ^1- (C═O) —N— group and at least one hydroxyl group (—OH). The hydroxyl group is bonded to the nitrogen atom of the Z ¹ — (C═O) —N— group, and Z ¹ is defined as described below.

  Such ureido alcohols and N-hydroxyalkylated amides hydrolyze very easily under the action of acids or bases. Furthermore, in particular in the case of reaction with bases in the presence of (meth) acrylates, for example side reactions in the sense of Michael addition are considered, see eg EP 1 236 994, page 3, line 47 et seq.

  EP 1 236 994 describes the preparation of ureido (meth) acrylates by transesterification of (meth) acrylates in the presence of titanium alcoholates of titanium, zirconium, iron or zinc or 1,3-dicarbonyl chelates.

  The disadvantage of these compounds is that the metal compounds are sensitive to moisture and are therefore easily deactivated. In addition, trace amounts of catalyst remaining in the product can optionally affect subsequent polymerization and must therefore be costly removed from the product. Such removal can often be done by aqueous washing and the product must subsequently be dried.

  JP 62-185059 and JP 62-175448 describe the reaction of (meth) acrylates with alkylamino alcohols in the presence of alkali metal carbonates. JP 62-230755 describes the reaction of (meth) acrylates with alkylamino alcohols in the presence of alkali metal phosphates.

  This disclosure is limited to alkyl and dialkylamino alcohols, and no suggestion of ureido alcohols or N-hydroxyalkylated amides is described.

  U.S. Pat. No. 2,871,223 discloses the production of ureido (meth) acrylates by reaction of ureido alcohol with (meth) acrylic acid chloride.

  The use of (meth) acrylic acid chloride in the reaction forms a salt, resulting in a reaction that is not selected because of this high reactivity, such as diacrylation.

  The production of (meth) acrylic acid esters by enzymatic esterification or transesterification is generally known, for example from EP 1999229.

  Derango et al., Biotechnol. Lett. 1994, 16, 241-246 describes the lipase catalyzed preparation of carbamoyloxyethyl methacrylate by transesterification of 2-hydroxyethyl carbamate and vinyl methacrylate. Since the free vinyl alcohol is removed from the reaction equilibrium as acetaldehyde, a complete reaction is achieved with a given educt vinyl methacrylate. The disadvantage of this method is that vinyl methacrylate is not commercially available. In addition, O-hydroxyalkylated carbamoyl is used here, which is a separate reaction system from the ureido alcohol and N-hydroxyalkylated amide to be treated here.

  In WO 2004/50888, O-hydroxyalkylated carbamoyl is enzymatically esterified or transesterified using (meth) acrylic acid (ester). Again, a reaction system separate from the ureido alcohol and N-hydroxyalkylated amide treated here is used.

  The object of the present invention is to provide another process by which the (meth) acrylates of N-hydroxyalkylated amides can be produced from simple educts with high reaction rates and high purity. This synthesis should proceed under mild conditions, resulting in a product with a low color number and high purity. In particular, the proportion of products that have been (meth) acrylated several times should be suppressed. Furthermore, the necessary catalyst can be easily separated and should not result in a subsequent work-up, for example in the form of a work-up step of the reaction product.

または開環状Ｎ−ヒドロキシアルキル化アミド（Ｏ）

［式中、
Ｚ^１は酸素、硫黄、非置換または置換された燐またはモノ置換されたまたは置換されていない窒素（Ｎ−Ｒ^３）を表し、
Ｒ^１およびＲ^２はそれぞれ互いに独立にＣ_２〜Ｃ_２０−アルキレン、Ｃ_５〜Ｃ_１２−シクロアルキレン、Ｃ_６〜Ｃ_１２−アリーレンまたは１個以上の酸素原子および／または硫黄原子によりおよび／または１個以上の置換されたまたは置換されていないイミノ基によりおよび／または１個以上のシクロアルキル、−（ＣＯ）−、−Ｏ（ＣＯ）Ｏ−、−（ＮＨ）（ＣＯ）Ｏ−、−Ｏ（ＣＯ）（ＮＨ）−、−Ｏ（ＣＯ）−または−（ＣＯ）Ｏ−基により中断されたＣ_２〜Ｃ_２０−アルキレンを表し、その際前記基はそれぞれアリール、アルキル、アリールオキシ、アルキルオキシ、ヘテロ原子および／または複素環により置換されていてもよく、または
Ｒ^２−ＯＨは式−［Ｘ_ｉ］_ｋ−Ｈの基を表し、
Ｒ^３、Ｒ^４およびＲ^５は互いに独立にそれぞれ水素、Ｃ_１〜Ｃ_１８−アルキル、１個以上の酸素原子および／または硫黄原子によりおよび／または１個以上の置換されたまたは置換されていないイミノ基により中断されていてもよいＣ_２〜Ｃ_１８−アルキル、Ｃ_２〜Ｃ_１８−アルケニル、Ｃ_８〜Ｃ_１２−アリール、Ｃ_５〜Ｃ_１２−シクロアルキル、または５員から６員の、酸素原子、窒素原子および／または硫黄原子を有する複素環を表し、その際前記基はそれぞれアリール、アルキル、アリールオキシ、アルキルオキシ、へテロ原子および／または複素環により置換されていてもよく、その際Ｒ^３およびＲ^５は一緒に５員から１２員までの環を形成してもよく、
ただしＺ^１がＯである場合は、Ｒ^５は非置換Ｃ_１〜Ｃ_１８−アルキル、Ｃ_６〜Ｃ_１２−アリールまたはＣ_５〜Ｃ_１２−シクロアルキルであり、
ｋは１〜５０の数であり、
Ｘ_ｉはｉ＝１〜ｋであり、互いに独立に、
−ＣＨ_２−ＣＨ_２Ｏ−、−ＣＨ_２−ＣＨ_２−Ｎ（Ｈ）−、−ＣＨ_２−ＣＨ_２−ＣＨ_２−Ｎ（Ｈ）−、−ＣＨ_２−ＣＨ（ＮＨ_２）−、−ＣＨ_２−ＣＨ（ＮＨＣＨＯ）−、−ＣＨ_２−ＣＨ（ＣＨ_３）−Ｏ−、−ＣＨ（ＣＨ_３）−ＣＨ_２−Ｏ−、−ＣＨ_２−Ｃ（ＣＨ_３）_２−Ｏ−、−Ｃ（ＣＨ_３）_２−ＣＨ_２−Ｏ−、−ＣＨ_２−ＣＨ_２−ＣＨ_２−Ｏ−、−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２−Ｏ−、−ＣＨ_２−ＣＨＶｉｎ−Ｏ−、−ＣＨＶｉｎ−ＣＨ_２−Ｏ−、−ＣＨ_２−ＣＨＰｈ−Ｏ−、および−ＣＨＰｈ−ＣＨ_２−Ｏ−の群から選択されてもよく、式中、Ｐｈはフェニルであり、Ｖｉｎはビニルである］を、無機塩（Ｓ）および酵素（Ｅ）からなる群から選択される少なくとも１個の不均一触媒の存在で（メタ）アクリル酸を用いてエステル化するかまたは少なくとも１個の（メタ）アクリル酸エステル（Ｄ）を用いてエステル交換することを特徴とする。 The problem is solved by a process for producing (meth) acrylates from N-hydroxyalkylated amides, wherein the cyclic N-hydroxyalkylated amide (C)

Or an open cyclic N-hydroxyalkylated amide (O)

[Where:
Z ¹ represents oxygen, sulfur, unsubstituted or substituted phosphorus or mono-substituted or unsubstituted nitrogen (N—R ³ );
R ¹ and R ² are each independently of each other by C ₂ -C ₂₀ -alkylene, C ₅ -C ₁₂ -cycloalkylene, C ₆ -C ₁₂ -arylene or one or more oxygen and / or sulfur atoms and / or By one or more substituted or unsubstituted imino groups and / or one or more cycloalkyl, — (CO) —, —O (CO) O—, — (NH) (CO) O—, — O (CO) (NH) - , - O (CO) - or - (CO) is interrupted by O- groups were _C 2 _{-C 20} - alkylene, where each of said groups are aryl, alkyl, aryloxy, Optionally substituted by alkyloxy, heteroatoms and / or heterocycles, or R ² —OH represents a group of formula — [X _i ] _k —H;
R ³ , R ⁴ and R ⁵ are each independently of one another hydrogen, C ₁ -C ₁₈ -alkyl, one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted which may be interrupted by imino group _C 2 _{-C 18} - _alkyl, C 2 _{-C 18} - _alkenyl, C 8 _{-C 12} - _aryl, C 5 _{-C 12} - 6 membered cycloalkyl or 5-membered, Represents a heterocycle having an oxygen atom, a nitrogen atom and / or a sulfur atom, wherein said groups may each be substituted by an aryl, alkyl, aryloxy, alkyloxy, heteroatom and / or heterocycle, R ³ and R ⁵ may form a 5- to 12-membered ring together,
Provided that when Z ¹ is O, R ⁵ is unsubstituted C ₁ -C ₁₈ -alkyl, C ₆ -C ₁₂ -aryl or C ₅ -C ₁₂ -cycloalkyl;
k is a number from 1 to 50;
X _i is i = 1 to k, and independently of each other,
_{-CH 2 -CH 2 O -, -} CH 2 -CH 2 -N (H) -, - CH 2 -CH 2 -CH 2 -N (H) -, - CH 2 -CH (NH 2) -, - _{CH 2 -CH (NHCHO) -,} - CH 2 -CH (CH 3) -O -, - CH (CH 3) -CH 2 -O -, - CH 2 -C (CH 3) 2 -O -, - _{C (CH 3) 2 -CH 2} -O -, - CH 2 -CH 2 -CH 2 -O -, - CH 2 -CH 2 -CH 2 -CH 2 -O -, - CH 2 -CHVin-O- _{, -CHVin-CH 2 -O -,} - CH 2 -CHPh-O-, and _-CHPh-CH 2 -O- may be selected from the group of wherein, Ph is phenyl, Vin is vinyl The presence of at least one heterogeneous catalyst selected from the group consisting of inorganic salts (S) and enzymes (E) In characterized by transesterification using an esterification or at least one (meth) acrylic acid ester (D) with (meth) acrylic acid.

  Esterification using (meth) acrylic acid in the presence of at least one heterogeneous catalyst selected from the group consisting of inorganic salts (S) and enzymes (E), or at least one (meth) acrylic acid ester Transesterify using (D).

  The production of (meth) acrylates of N-hydroxyalkylated amides using the process of the present invention is possible in high yield, under mild conditions, with good color number and without a washing step to work up the product. Is possible.

  (Meth) acrylic acid in the present invention is methacrylic acid and acrylic acid, preferably methacrylic acid.

In the above definition, the following are represented.
C ₂ -C ₂₀ -alkylene optionally substituted by aryl, alkyl, aryloxy, heteroatom and / or heterocycle, for example 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4 -Butylene, 1,6-hexylene, 2-methyl-1,3-propylene, 2-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, 2,2-dimethyl-1,4 -Butylene,
C ₅ -C ₁₂ -cycloalkylene optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatom and / or heterocycle, such as cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclododecylene,
Optionally substituted by aryl, alkyl, aryloxy, heteroatoms and / or heterocycles, one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or Or one or more cycloalkyl,-(CO)-, -O (CO) O-,-(NH) (CO) O-, -O (CO) (NH)-, -O (CO)-or- C2-C20-alkylene interrupted by (CO) O-groups, such as 1-oxa-1,3-propylene, 1,4-dioxa-1.6-hexylene, 1,4,7-trioxa-1,9 -Nonylene, 1-oxa-1,4-butylene, 1,5-dioxa-1,8-octylene, 1-oxa-1,5-pentylene, 1-oxa-1,7-heptylene, 1,6-dioxa -1, 0-decylene, 1-oxa-3-methyl-1,3-propylene, 1-oxa-3-methyl-1,4-butylene, 1-oxa-3,3-dimethyl-1,4-butylene, 1- Oxa-3,3-dimethyl-1,5-pentylene, 1,4-dioxa-3,6-dimethyl-1,6-hexylene, 1-oxa-2-methyl-1,3-pyropylene, 1,4- Dioxa-2,5-dimethyl-1,6-hexylene, 1-oxa-1,5-pent-3-enylene, 1-oxa-1,5-pent-3-ynylene, 1,1-, 1,2 -, 1,3- or 1,4-cyclohexylene, 1,2- or 1,3-cyclopentylene, 1,2-, 1,3- or 1,4-phenylene, 4,4'-biphenylene, 1,4-diaza-1,4-butylene, 1-aza-1,3-propylene 1,4,7-triaza-1,7-heptylene, 1,4-diaza-1,6-hexylene, 1,4-diaza-7-oxa-1,7-heptylene, 4,7-diaza 1-oxa-1,7-heptylene, 4-aza-1-oxa-1,6-hexylene, 1-aza-4-oxa-1,4-butylene, 1-aza-1,3-propylene, 4- Aza-1-oxa-1,4-butylene, 4-aza-1,7-dioxa-1,7-heptylene, 4-aza-1-oxa-4-methyl-1,6-hexylene, 4-aza- 1,7-dioxa-4-methyl-1,7-heptylene, 4-aza-1,7-dioxa-4 (2′-hydroxyethyl) -1,7-heptylene, 4-aza-1-oxa- ( 2'-hydroxyethyl) -1,6-hexylene or 1,4-piperazinylene,
C ₆ -C ₁₂ -arylene optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatom and / or heterocycle, for example 1,2-, 1,3- or 1,4-phenylene, 4, 4'-biphenylene, toluylene or xylylene,
C ₁ -C ₁₈ -alkyl or optionally C ₂ -C ₁₈ -alkyl interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, For example, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hexadecyl, Octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p -Tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chloroben 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2- Di (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropylethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2- Chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroe 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3 -Hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2 -Hydroxy-2,2-dimethylethyl, 2- Phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2- Ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, or 6-ethoxyhexyl,
C ₂ -C ₁₈ -alkenyl optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, for example vinyl, 1-propenyl, allyl , Methallyl, 1,1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, undecenyl, dodecenyl, octadecenyl, 2-phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl 2-ethoxyallyl, 3-ethoxyallyl, or 1- or 2-chlorovinyl,
C ₆ -C ₁₂ -aryl optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, such as phenyl, tolyl, xylyl, α -Naphthyl, β-naphthyl, 4-diphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, t-butylphenyl, dodecylphenyl, methoxyphenyl, Dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, , 6-Dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethyl Phenyl or ethoxymethylphenyl,
C ₅ -C ₁₂ -cycloalkyl optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, eg cyclopentyl, cyclohexyl, cyclooctyl , Cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, and saturated or unsaturated Bicyclic systems such as norbornyl or norbornyl, and optionally one or more oxygen atoms and / or sulfur sources And / or heterocycles having 5- to 6-membered oxygen, nitrogen and / or sulfur atoms interrupted by one or more substituted or unsubstituted imino groups, such as furyl, thiophenyl, pyryl, Pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxyfuryl, dimethylpyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl, or t-butylthiophenyl.

Examples of R ¹ are 1,2-ethylene, 1,2-propylene, 1,1-dimethyl-1,2-ethylene, 1-hydroxymethyl-1,2-ethylene, 2-hydroxy-1,3-propylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 2-methyl-1,3-propylene, 2-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, And 2,2-dimethyl-1,4-butylene, 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, and orthophenylene, 1,2-ethylene, 1,2-propylene and 1,3-propylene, in particular 1,2-ethylene and 1,2-propylene, particularly preferably 1,2-ethylene.

Examples of R ² are 1,2-ethylene, 1,2-propylene, 1,1-dimethyl-1,2-ethylene, 1-hydroxymethyl-1,2-ethylene, 2-hydroxy-1,3-propylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 2-methyl-1,3-propylene, 2-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, And 2,2-dimethyl-1,4-butylene, 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene and orthophenylene, preferably 1,2-ethylene, 1,2-propylene, 1,3-propylene, in particular 1,2-ethylene and 1,2-propylene, particularly preferably 1,2-ethylene.

Examples of R ³ and R ⁵ are independently of each other hydrogen or C ₁ -C ₄ -alkyl, and within the scope of the invention are methyl, ethyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl. Hydrogen, methyl, ethyl, n-propyl and n-butyl, especially hydrogen, methyl, ethyl and n-butyl, particularly preferably hydrogen, methyl and ethyl, especially hydrogen.

When R ³ and R ⁵ together form a ring, R ³ and R ⁵ together represent 1,4-butylene, 1,5-pentylene or 3-oxa-1,5-pentylene.

Examples of R ⁴ are hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, s-butyl, t-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl. , N-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, phenyl, naphthyl, or benzyl.

Z ¹ is preferably O or NR ³ , in particular NR ³ .

  The cyclic alcohol (C) is preferably present opposite the open-chain alcohol (O).

  Preferred individual (C) are 2'-hydroxyethyl-ethyleneurea, 3'-hydroxypropyl-ethyleneurea, 2'-hydroxypropyl-ethyleneurea, 2'-hydroxyethyl-1,3-propyleneurea, 2 ' -Hydroxypropyl-1,3-propylene urea, 3'-hydroxypropyl-1,3-propylene urea, 2'-hydroxyethyl-1,2-propylene urea, 2'-hydroxypropyl-1,2-propylene urea, 3′-hydroxypropyl-1,2-propyleneurea, 1- (2′-hydroxyethyl) imidazolidine-2,4-dione, 1- (2′-hydroxyethyl) dihydropyrimidine-2,4-dione, or 3- (2-hydroxyethyl) -oxazolidine-2-one. Particularly preferred are 2'-hydroxyethyl-ethyleneurea, 3'-hydroxypropyl-ethyleneurea, 2'-hydroxyethyl-1,3-propyleneurea, and 3'-hydroxypropyl-1,3-propyleneurea.

  Preferred individual (O) are N- (2-hydroxyethyl) urea, N- (2-hydroxypropyl) urea, N- (3-hydroxypropyl) urea, N ′, N′-dimethyl-N- (2 -Hydroxyethyl) urea, N ', N'-dimethyl-N- (2-hydroxypropyl) urea, N', N'-diethyl-N- (2-hydroxyethyl) urea, N ', N'-diethyl- N- (2-hydroxypropyl) urea, N ′, N′-diethyl-N- (3-hydroxypropyl) urea, N ′, N′-di-n-butyl-N- (2-hydroxyethyl) urea, N ′, N′-di-n-butyl-N- (2-hydroxypropyl) urea N ′, N′-di-n-butyl-N- (2-hydroxypropyl) urea, and N ′, N′- Di-n-butyl-N- (3-hydroxypropyl) urea, especially N- (2-hydroxyethyl) urea, N- (2-hydroxypropyl) urea, and N- (3-hydroxypropyl) urea.

  In step c) esterification with (meth) acrylic acid or preferably transesterification of the alcohol (C) or (O) with at least one, preferably (meth) acrylate (D), is carried out with the inorganic salt (S) And in the presence of at least one heterogeneous catalyst selected from the group consisting of enzyme (E).

Compound (D) is (meth) acrylic acid or an ester of (meth) acrylic acid and a saturated alcohol, preferably a saturated C ₁ -C ₁₀ -alkyl ester of (meth) acrylic acid, especially a saturated C ₁ of (meth) acrylic acid. -C ₄ - may be an alkyl ester.

  Saturation means within the scope of the present invention a compound without C—C multiple bonds (except of course the C═C double bond in the (meth) acryl unit).

  Examples of compound (D) are methyl (meth) acrylate, -ethyl, -n-butyl, -isobutyl, -t-butyl, -n-octyl and -2-ethylhexyl esters, 1,2-ethylene glycol di- and -Mono (meth) acrylate, 1,4-butanediol di- and -mono (meth) acrylate, 1,6-hexanediol di- and -mono (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol Slit tetra (meth) acrylate.

  Particularly methyl (meth) acrylates-, -ethyl, -n-butyl and -2-ethylhexyl esters, preferably methyl (meth) acrylate-, -ethyl and -n-butyl esters, especially (meth) ) Methyl acrylate and -ethyl esters, especially (meth) acrylic acid methyl esters.

Inorganic salts which can be used according to the invention (S) is not more than 7.0, preferably not more than 6.1, particularly preferably salts contain not more pK _B value than 4.0. At the same time pK _B value should not fall below 1.0, preferably not be less than 1.5, no particular advantage be less than 1.6.

  Heterogeneous catalysts within the scope of the present invention have a solubility in the reaction medium at 25 ° C. of not greater than 1 g / l, preferably not greater than 0.5 g / l, particularly preferably greater than 0.25 g / l. There is no catalyst.

The inorganic salts are preferably carbonates (CO ₃ ²⁻ ), bicarbonates (HCO ₃ ⁻ ), phosphates (PO ₄ ³⁻ ), hydrogen phosphates (HPO ₄ ²⁻ ), dihydrogen phosphates (H ₂ PO ₄ ^-), at least one anion selected from the group consisting of sulfate _(SO ^{4 2-),} sulfite _(SO ^{3 2-),} and carboxylates ^{(R 6} -COO-), R 6 Is C ₁ -C ₁₈ -alkyl or optionally C ₂ -C ₁₈ -alkyl interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups or _C 6 _{-C 12} - aryl.

  Carbonates and phosphates are preferred, and phosphates are particularly preferred.

  Phosphate can also be understood as condensation products such as diphosphates, triphosphates and polyphosphates.

  The inorganic salt preferably has at least one cation selected from the group consisting of alkali metals, alkaline earth metals, ammonium, cerium, iron, manganese, chromium, molybdenum, cobalt, nickel or zinc.

  Preference is given to alkali metals, in particular lithium, sodium or potassium.

Particularly preferred inorganic salts are Li ₃ PO ₄ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ CO ₃ and Na ₂ CO ₃ and their hydrates, particularly preferably K ₃ PO ₄ .

K ₃ PO ₄ is used in the water-free form and in the trihydrate, heptahydrate or nonahydrate according to the invention.

  The esterification or transesterification catalyzed by inorganic salts is generally carried out at 50 to 140 ° C., preferably 50 to 100 ° C., in particular 60 to 90 ° C., particularly preferably 60 to 80 ° C.

  If the water liberated during esterification or the low-boiling alcohol produced during transesterification is optionally separated by distillation as an azeotrope, the reaction can optionally be carried out under a weak vacuum from 300 hPa to atmospheric pressure. .

  The molar ratio of (meth) acrylic acid or (meth) moacrylic acid ester to alcohol (C) or (D) is generally 2-6: 1 mol / in the esterification or transesterification catalyzed by inorganic salts. Mol, preferably 2 to 3.5: 1 mol / mol, in particular 2.5 to 3.0: 1 mol / mol.

  The reaction time during esterification or transesterification catalyzed by inorganic salts is generally from 30 minutes to 24 hours, preferably from 45 minutes to 18 hours, in particular from 3 to 12 hours, particularly preferably from 5 to 10 hours.

  The content of inorganic salt in the reaction medium is generally about 0.01 to 5 mol%, preferably 0.1 to 1.8 mol%, in particular with respect to the sum of the components (C) or (D) used. 0.3 to 1.5 mol%.

  A polymerization inhibitor (see below) is necessarily required during esterification or transesterification.

  The presence of an oxygen-containing gas (see below) is advantageous during the reaction catalyzed by the inorganic salt.

  A product having a color number (according to DINISO 6271) of generally less than 500 APHA, preferably less than 200 APHA, in particular less than 150 APHA, is obtained during esterification or transesterification catalyzed by inorganic salts.

  The enzyme (E) used according to the present invention is, for example, selected from hydrolases (EC-3 .-.-.-), of which esterases (EC 3.1 .-.-), in particular, Selected and released from lipase (EC 3.1.1.3), glycosylase (EC 3.2 .-.-) and protease (EC 3.4 .-.-) It exists in a form or in a chemically or physically fixed form on a carrier and is preferably a lipase, an esterase or a protease, in particular an esterase (EC 3.1 .-.-). Particularly preferred Novozyme® 435 (lipase from Candida antarctia B) or Alkaligenes, Aspergillus, Mucor, Penicillium, Geotricum, Rhizopus, Burgholideria, Candida, Pseudomonas, Thermomyces Seed or porcine pancreas, particularly preferably lipase from Candida antalcia B or Burkholderia species.

  Enzymatic esterification or transesterification with (meth) acrylates is generally carried out at 20-100 ° C, preferably 20-80 ° C, particularly preferably 30-70 °, particularly preferably 40-60 ° C.

  In this case, the upper limit of the temperature is of course the boiling point of the solvent or alcohol liberated during transesterification.

  In the case where the water liberated during esterification or the low-boiling alcohol produced during transesterification is optionally separated by distillation as an azeotrope, the reaction may optionally be carried out under a weak vacuum, for example from 300 hPa to atmospheric pressure. it can.

  The enzyme content in the reaction medium is generally in the range from about 0.1 to 10% by weight, based on the sum of the components (C) or (O) and (D) used.

  The molar ratio of (meth) acrylic acid or (meth) acrylic acid ester to alcohol (C) or (D) is generally from 1 to 50: 1 mol / mol during enzyme catalyzed esterification or transesterification, advantageously 5 to 20: 1 mol / mol.

  The reaction time during the esterification or transesterification catalyzed by the enzyme is generally from 6 hours to 3 days, preferably from 8 hours to 2 days and in particular from 12 to 24 hours.

  The reaction time is preferably such that the conversion of all hydroxy functions contained in the alcohol is at least 70%, preferably at least 80%, in particular at least 90%, particularly preferably at least 95%, in particular at least 97%. Adjust.

  The reaction catalyzed by the enzyme can optionally be carried out in the absence of a stabilizer (see below), but is preferably carried out in the presence of at least one stabilizer.

  The reaction products obtained during the enzyme-catalyzed reaction generally have a color number of less than 100 APHA, preferably less than 80 APHA.

  Unless otherwise stated for reactions catalyzed by enzymes and by inorganic salts, the following reaction parameters apply.

  The reaction can be carried out in an organic solvent or a mixture thereof or without the addition of a solvent. The batch is generally sufficiently free of water, ie a water content of less than 10% by weight, preferably less than 5% by weight, in particular less than 1% by weight, particularly preferably less than 0.5% by weight. Furthermore, the batch is sufficiently free of primary and secondary alcohols, ie an alcohol content of less than 10% by weight, preferably less than 5% by weight, in particular less than 1% by weight, particularly preferably less than 0.5% by weight.

Solvent Suitable organic solvents are known for this purpose, for example tertiary monools, for example C ₃ -C 6 _- alcohols, advantageously t-butanol, t-amyl alcohol, pyridine, poly -C ₁ -C ₄ -alkylene glycol di-C ₁ -C ₄ -alkyl ethers, preferably polyethylene glycol di-C ₁ -C ₄ -alkyl ethers such as 1,2-dimethoxyethane, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether 500, C ₁ -C ₄ - alkylene carbonates, in particular propylene carbonate, acetic _-C 3 -C ₆ - alkyl esters particularly acetic -t- butyl ester, THF, toluene, 1,3-dioxolane, acetone, isobutyl methyl ketone, ethyl methyl ketone, 1, 4-dioxane, t- Chill methyl ether, cyclohexane, methylcyclohexane, hexane, dimethoxymethane, 1,1-dimethoxyethane, acetonitrile, and 1-phase or multiphase mixture thereof.

  In a particularly advantageous embodiment of transesterification, the reaction is carried out in a (meth) acrylic ester used as an educt. Particularly advantageous as the product (C) or (O) occurs after the end of the reaction as an approximately 10-80% by weight solution, in particular as a 20-50% by weight solution, in the (meth) acrylate used as educt. The reaction is carried out.

  The educt is dissolved, suspended as a solid or present in the reaction medium in the form of an emulsion. The initial concentration of the reactants is preferably in the range of about 0.1 to 20 mol / l, in particular 0.15 to 10 mol% / l, or 0.2 to 5 mol / l.

  The reaction can be carried out continuously, for example in a tubular reactor, or in a stirred reactor cascade, or discontinuously.

  The reaction can be carried out in all reactors suitable for this reaction. These reactors are known to those skilled in the art. The reaction is preferably carried out in a stirred vessel reactor or a fixed bed reactor.

  Any method can be used to mix the reaction batches. No specific stirring device is required. Mixing can be effected, for example, by supplying a gas, preferably an oxygen-containing gas (see below). The reaction medium may be single-phase or multi-phase, in which the reactants are dissolved, suspended or emulsified, optionally pre-loaded with molecular sieves, at the start of the reaction and optionally once or several times. Enzyme preparation is added as the reaction proceeds. The temperature is adjusted to the desired value during the reaction and can be raised or lowered during the reaction if desired.

  If the reaction is carried out in a fixed bed reactor, the fixed bed reactor is preferably equipped with an immobilized enzyme, with the reaction mixture being fed by a column packed with enzyme. It is also possible to carry out the reaction in a fluidized bed reactor, in which case the enzyme is used immobilized on a carrier. The reaction mixture can be fed continuously through the column, with the flow rate being able to adjust the residence time and thereby the desired conversion. The reaction mixture can be circulated and fed by a column, whereby the alcohol liberated under vacuum can be distilled off simultaneously.

  In the case of esterification, water or in the case of transesterification, the alcohol liberated from the alkyl (meth) acrylate is removed continuously or stepwise in a manner known per se, for example vacuum, azeotropic removal, stripping, absorption. Pervaporation and membrane diffusion or extraction.

  Stripping can optionally take place additionally to the distillation, for example by passing an oxygen-containing gas, preferably air or an air-nitrogen mixture, through the reaction mixture.

  For absorption, molecular sieves or zeolites (pore size, for example in the range of about 3 to 10 liters), separation by distillation or using suitable semipermeable membranes are preferably suitable.

  The mixture separated from the alkyl (meth) acrylate and its underlying alcohol, which often forms an azeotrope, is fed directly to the apparatus for producing the alkyl (meth) acrylate, where it is esterified with (meth) acrylic acid Further use is possible.

  In an enzyme-catalyzed reaction, it is advantageous to separate the water or alcohol generated by a binary or ternary heteroazeotrope that boils as close as possible to the temperature optimum of the enzyme used. The alcohol thus removed can subsequently be removed by phase separation or membrane vapor separation.

  After completion of the reaction, the reaction mixture obtained from c) can be used further without further purification or, if necessary, can be purified in another step d).

  Generally, only the heterogeneous catalyst used in step d) is separated from the reaction mixture, and the reaction product is separated from the organic solvent optionally used.

  The separation of the heterogeneous catalyst is generally performed by filtration, electrofiltration, absorption, stretch separation, or decantation. The separated heterogeneous catalyst can subsequently be used for other reactions.

  The organic solvent is generally separated by distillation or rectification, or by filtration in the case of a solid reaction product.

  Chromatography can be performed for subsequent purification of the reaction product.

  However, it is preferred to separate only the heterogeneous catalyst and optionally used solvent in step d).

  The reaction conditions according to the invention, in particular during the esterification or transesterification with enzymes, are mild. Unfavorable radicals of (meth) acrylates used, which can be avoided by low temperature and otherwise mild conditions, in other cases for example derived from chemical catalysts or otherwise only by addition of stabilizers By-product formation in step c) due to polymerization is avoided. In addition to the storage stabilizer included in any case, the (meth) acrylic compound (D) is further added to the (meth) acrylic compound (D) when carrying out the reaction according to the invention, for example hydroquinone monomethyl ether, phenothiazine, phenol, t-butyl-4-methylphenol, 6-t-butyl-2,4-dimethylphenol or N-oxyl, such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo -2,2,6,6-tetramethylpiperidine-N-oxyl or Uvinul <(R)> 4040P, BASF, for example in an amount of 50-2000 ppm, at least to the (meth) acrylate used or to the reaction mixture can do.

  The esterification or transesterification is preferably carried out in the presence of an oxygen-containing gas, preferably air or an air-nitrogen mixture.

  The heterogeneous catalyst used according to the present invention can be removed from the final product without problems due to the low solubility of the heterogeneous catalyst according to the present invention in traces of the least important catalyst remaining in the reaction medium in the product. In this way, simple filtration or decantation is generally sufficient to work up the reaction product, and costly washing, neutralization, etc. for separating the catalyst can be omitted by the method of the present invention.

  The catalysts used according to the invention are less prone to produce by-products. Inorganic salts are sufficiently basic to catalyze esterification or transesterification, but are not basic to catalyze side reactions such as the Michael reaction described at the outset, and the process of the invention This clearly reduces the proportion of Michael adducts from the state of the art compared to known reactions.

  Furthermore, the reaction is very selective under the reaction conditions according to the invention, and by-products are generally less than 10%, preferably less than 5% (relative to conversion).

Typical by-products of the reaction of compounds (C) and (O) where Z ¹ is N—H with (meth) acrylic acid or (meth) acrylic acid ester are bonded via this nitrogen atom ( Resulting from internal or intramolecular separation of the group R5-Z1 from (meth) acrylamide, the Michael adduct bonded through this nitrogen atom, the Michael adduct bonded through the free hydroxyl group, and the compound (C) or (O) Subsequently, (D) is a product which can be esterified or transesterified again.

  A particular advantage of the catalyst according to the invention is that it can suppress the proportion of the product that has been (meth) acrylated several times, ie at least twice. This type of product is difficult to separate from the desired product that is mono (meth) acrylated. Since the desired product is used as a monomer or reaction diluent, the inclusion of a product that has been (meth) acrylated several times is not preferred, as this type of product crosslinks and the molecular weight of the product during polymerization Because it rises so as not to be able to schedule.

  The (meth) acrylates of N-hydroxyalkylated amides prepared according to the present invention can be used, for example, as monomers or comonomers in the manufacture of dispersions, such as acrylic dispersions, as reactive diluents, such as in radiation curable coating materials, or Used in dyes, preferably in external dyes, and in dispersions used in the papermaking field.

  The following examples illustrate the characteristics of the present invention, but are not limited thereto.

Examples In the present invention, parts are parts by weight unless otherwise stated.

  The apparatus consisted of a 500 ml four-necked flask with an air inlet tube, a separation column, a sample intake location, and an internal temperature measurement sensor. Stir at 300 rpm using a magnetic stirrer.

  As a separation column, a 20 cm Vigreux column having a Raschig ring (5 × 5 mm) was used. A column head with a reflux controller and a Liebig condenser was mounted on the separation column and could run without polymer deposition in all tests.

  Each batch was carried out according to the following general work description. 2-Hydroxyethylethyleneurea (HEEEH, 130 g, 1.0 mol) was melted and coated with a corresponding amount of methyl methacrylate (MMA) (5.0 mol, 560 g). Heated to an internal temperature of 1000 ° C. and added catalyst (0.8 mol%, based on urea). The resulting azeotrope from methyl methacrylate (MMA) and methanol was distilled off at a reflux ratio of 2: 1 (65 ° C.). At regular intervals, samples were taken from the distillate and bottom product and analyzed. After the end of methanol generation, it was still operated at a reflux ratio of 10: 1 until a test time of 6 hours was achieved. The distillation was subsequently interrupted and the bottom product was examined by gas chromatography for the product, 2- (2-oxo-imidazolin-1-yl) ethyl methacrylate and the resulting secondary components (total). Subcomponents measured are, for example, N- [2- (2-oxooxazolidine-3-yl) -ethyl] -methacrylamide, N- {2- [3- (methacryloyl) -2-oxoimidazolidine-1- Yl] -ethyl} -methacrylamide, 2-methyl-3- {3- [2- (methacryloylamino) -ethyl] -2-oxoimidazolidin-1-yl} -propionic acid, and 2-methyl-3- [2- (2-Oxo-imidazolidin-1-yl) -ethoxy] -propionic acid.

  A comparison of the tests clearly shows that potassium phosphate as a catalyst is superior to current systems. The reaction proceeds with a high selectivity and a high conversion with a minimum space-time yield of 2 times and a small proportion of crosslinker. The catalyst crystallizes in the form of crystals that can be well filtered, and cools, thus eliminating the washing step.

  2-hydroxyethylethyleneurea (HEEH, 1.3 g) 10 mmol, methyl methacrylate 100 mmol or 400 mmol, molecular sieve (5 cm) 2.0 g and Novozym® (an immobilized lipase from Candida antartica B, Novozym) ) 65-260 mg was shaken in a twisted lid glass at 40 ° C. for 72 hours. A colorless solution was obtained. For analysis, a uniform sample was prepared by dissolving the optional precipitate by adding 10 ml of 1.4-dioxane. The reaction to produce methacrylate from HEEH was determined by gas chromatography using the GC method.

Claims (10)

In a process for producing (meth) acrylates from N-hydroxyalkylated amides, cyclic N-hydroxyalkylated amides (C)

Or an open cyclic N-hydroxyalkylated amide (O)

[Where:
Z ¹ represents oxygen, sulfur, unsubstituted or substituted phosphorus or mono-substituted or unsubstituted nitrogen (N—R ³ );
R ¹ and R ² are each independently of each other by C ₂ -C ₂₀ -alkylene, C ₅ -C ₁₂ -cycloalkylene, C ₆ -C ₁₂ -arylene or one or more oxygen and / or sulfur atoms and / or By one or more substituted or unsubstituted imino groups and / or one or more cycloalkyl, — (CO) —, —O (CO) O—, — (NH) (CO) O—, — O (CO) (NH) - , - O (CO) - or - (CO) is interrupted by O- groups were _C 2 _{-C 20} - alkylene, where each of said groups are aryl, alkyl, aryloxy, Optionally substituted by alkyloxy, heteroatoms and / or heterocycles, or R ² —OH represents a group of formula — [X _i ] _k —H;
R ³ , R ⁴ and R ⁵ are each independently of one another hydrogen, C ₁ -C ₁₈ -alkyl, one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted which may be interrupted by imino group _C 2 _{-C 18} - _alkyl, C 2 _{-C 18} - _alkenyl, C 8 _{-C 12} - _aryl, C 5 _{-C 12} - 6 membered cycloalkyl or 5-membered, Represents a heterocycle having an oxygen atom, a nitrogen atom and / or a sulfur atom, wherein said groups may each be substituted by an aryl, alkyl, aryloxy, alkyloxy, heteroatom and / or heterocycle, R ³ and R ⁵ may form a 5- to 12-membered ring together,
Provided that when Z ¹ is O, R ⁵ is unsubstituted C ₁ -C ₁₈ -alkyl, C ₆ -C ₁₂ -aryl or C ₅ -C ₁₂ -cycloalkyl;
k is a number from 1 to 50;
X _i is i = 1 to k, and independently of each other,
_{-CH 2 -CH 2 O -, -} CH 2 -CH 2 -N (H) -, - CH 2 -CH 2 -CH 2 -N (H) -, - CH 2 -CH (NH 2) -, - _{CH 2 -CH (NHCHO) -,} - CH 2 -CH (CH 3) -O -, - CH (CH 3) -CH 2 -O -, - CH 2 -C (CH 3) 2 -O -, - _{C (CH 3) 2 -CH 2} -O -, - CH 2 -CH 2 -CH 2 -O -, - CH 2 -CH 2 -CH 2 -CH 2 -O -, - CH 2 -CHVin-O- _{, -CHVin-CH 2 -O -,} - CH 2 -CHPh-O-, and _-CHPh-CH 2 -O- may be selected from the group of wherein, Ph is phenyl, Vin is vinyl The presence of at least one heterogeneous catalyst selected from the group consisting of inorganic salts (S) and enzymes (E) A (meth) acrylate from an N-hydroxyalkylated amide characterized in that it is esterified with (meth) acrylic acid or transesterified with at least one (meth) acrylic acid ester (D) How to manufacture. The method according to claim 1, wherein Z ¹ is unsubstituted or monosubstituted nitrogen (N—R ³ ). At least one inorganic salt (S) is not greater than 7.0, according to claim 1 or 2 wherein has a solubility in the reaction medium not greater than 1 g / l at pK _B value and 25 ° C. not less than 1.0 Method. Inorganic salts are carbonate (CO ₃ ²⁻ ), bicarbonate (HCO ₃ ⁻ ), phosphate (PO ₄ ³⁻ ), hydrogen phosphate (HPO ₄ ²⁻ ), dihydrogen phosphate (H ₂ PO ₄ ⁻ ), Sulfate (SO ₄ ²⁻ ), sulfite (SO ₃ ²⁻ ), and carboxylate (R ⁶ —COO ⁻ ), and R ⁶ is C ₁ -C ₁₈ -alkyl or C ₂ -C ₁₈ -alkyl optionally interrupted by one or more oxygen and / or sulfur atoms and / or by one or more substituted or unsubstituted imino groups or _C 6 _{-C 12} - any one process of claim 1, aryl up to 3.   The inorganic salt according to any one of claims 1 to 4, wherein the inorganic salt has at least one cation selected from the group consisting of alkali metals, alkaline earth metals, ammonium, cerium, iron, manganese, chromium, molybdenum, cobalt, nickel or zinc. The method according to claim 1. Any inorganic salt from _{Li 3 PO 4, K 3 PO} 4, Na 3 PO 4, K 2 CO 3, and _Na 2 CO ₃ and claim 1 selected from the group consisting of hydrates up to 5 The method according to claim 1.   The enzyme is selected from the group consisting of esterase (EC 3.1 -.-), lipase (EC 3.1.1.3), glycosilla back (EC 3.2 -.-) and protease (EC 3.4 -.-). The method according to claim 1 or 2.   The enzyme is Novozym (registered trademark) 435 (lipase from Candida antarctia B), Alkaligenes species, Aspergillus species, Mucor species, Penicillium species, Geotricum species, Rhizopus species, Burkholderia species, Candida species, Pseudomonas species, Thermomyces species Or the method of claim 7 selected from the group consisting of lipases from porcine pancreas.   9. The reaction according to claim 1, wherein the reaction is carried out such that the product (C) or (O) occurs as a solution of about 10 to 80% by weight in (meth) acrylic acid ester used as an educt after completion of the reaction. The method according to claim 1.   Use of a compound prepared by the process according to any one of claims 1 to 8 as a (co) monomer in poly (meth) acrylate or in radiation curing.