EP1924547A1 - Verfahren zur herstellung von (meth) acrylaten vier- oder mehrwertiger alkohole - Google Patents
Verfahren zur herstellung von (meth) acrylaten vier- oder mehrwertiger alkoholeInfo
- Publication number
- EP1924547A1 EP1924547A1 EP06792846A EP06792846A EP1924547A1 EP 1924547 A1 EP1924547 A1 EP 1924547A1 EP 06792846 A EP06792846 A EP 06792846A EP 06792846 A EP06792846 A EP 06792846A EP 1924547 A1 EP1924547 A1 EP 1924547A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- meth
- transesterification
- alkanols
- formula
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
Definitions
- the invention relates to a process for the transesterification of (meth) acrylic acid esters with in particular polyfunctional alkanols using a catalyst.
- diorganyltin oxides or of organyltin halides as transesterification catalysts is known.
- DE-AS 1005947 describes that di- and triorganotin compounds effectively catalyze esterification and transesterification reactions of (meth) acrylic acid or (meth) acrylic acid esters.
- the advantageous effects of the catalysts described therein include high catalytic activity, low tendency to dehydration especially secondary alcohols and high ester yields.
- EP 663386 describes a process for the transesterification of (meth) acrylic acid esters with in particular polyfunctional alkanols using a mixed catalyst consisting of diorganyltin oxide and organyltin halide. For example, a reaction time of 14 hours is given in EP 663386 for the preparation of pentaerythritol tetramethacrylate. In addition, only 78 mol% of pentaerythritol tetramethacrylate are isolated.
- the object was to provide a process for the transesterification of (meth) acrylic acid esters with, in particular, polyfunctional alkanols using a catalyst which can, within acceptable reaction times, form reaction products in acceptable purities.
- R 1 is H or CH 3 and R 2 is an alkyl radical having 1 to 6 carbon atoms, with alkanols having four or more esterifiable hydroxyl group, characterized in that as the transesterification catalyst 0.01 to 10 wt .-% based on the entire reaction mixture lithium amide catalysts are used.
- (meth) acrylic acid esters can be prepared in significantly improved purities by the process.
- the notation (meth) acrylate stands for the esters of (meth) acrylic acid and means here both methacrylate, such as methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, such as methyl acrylate, ethyl acrylate, etc., as well as mixtures of the two.
- the alkanols used in the transesterification preferably have four or more esterifiable hydroxyl groups, for example pentaerythritol, erythritol or threitol.
- Examples of representatives of penta- and hexafunctional alkanols which can be used as transesterification components are: arabinitol, ribitol, xylitol, sorbitol, glucitol and mannitol, all also known as sugar alcohols (cf., for example, Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 1, pp. 754-789, John Wiley, New York, 1978).
- the reaction of acrylic or methacrylic esters of the formula I with the tetra- or polyfunctional alkanols in the presence of from 0.01 to 10% by weight of catalyst is preferably from 0.1 to 5% by weight, particularly preferably from 0.2 to 2 wt .-% catalyst based on the total reaction mixture.
- the reaction of acrylic or Methacrylklam of formula I with the tetra- or polyfunctional alkanols is at temperatures between 30 and 180 0 C, preferably between 50 and 130 degrees in the presence of 0.01 to 10 wt .-%, preferably from 0, 1 to 5 wt .-%, particularly preferably from 0.2 to 2 wt .-%, based on the total reaction mixture of the lithium amide carried out catalyst.
- the process can be carried out in any inert aprotic solvent. Preference is given to aliphatic or aromatic solvents, particularly preferably xylene, toluene or cyclohexane.
- inhibitors which prevent free-radical polymerization of the (meth) acrylic groups during the reaction. These inhibitors are well known in the art.
- inhibitors are used mainly 1, 4-dihydroxybenzenes. However, it is also possible to use differently substituted dihydroxybenzenes.
- such inhibitors can be represented by the general formula (III)
- R 6 is a linear or branched alkyl radical having one to eight carbon atoms, halogen or aryl, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec Butyl, tert -butyl, Cl, F or Br; o is an integer in the range of one to four, preferably one or two; and
- R 7 is hydrogen, a linear or branched alkyl radical having one to eight carbon atoms or aryl, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec Butyl or tert-butyl.
- R 7 is hydrogen, a linear or branched alkyl radical having one to eight carbon atoms or aryl, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec Butyl or tert-butyl.
- 1,4-benzoquinone as the parent compound.
- R 6 and o have the meaning given above.
- R 8 denotes a linear or branched alkyl radical having one to eight carbon atoms, aryl or aralkyl, propionic acid esters with 1 to 4 valent alcohols, which may also contain heteroatoms such as S, O and N, preferably an alkyl radical having one to four carbon atoms, particularly preferably methyl, Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl.
- Another advantageous class of substances are hindered phenols based on triazine derivatives of the formula (VI)
- the proportion of inhibitors individually or as a mixture is generally 0.01-0.50% (wt / wt), wherein the concentration of the inhibitors is preferably selected so that the color number according to DIN 55945 is not impaired becomes. Many of these inhibitors are commercially available.
- (Meth) acrylic esters of the formula I and hydroxyl groups of the tetra- or polyfunctional alkanols react to give the desired end products.
- the reaction can be carried out under atmospheric pressure, underpressure or overpressure, it being possible for the reaction to be carried out batchwise or continuously.
- the starting materials, (meth) acrylic acid esters I and tetra- or polyfunctional alkanol are heated together in the presence of the lithium amide catalyst to reaction temperature and thereby continuously the eliminated alkanol R 2 OH and the excess (meth) acrylic ester I, preferably together in one Azeotrope, distilled off.
- the reaction times are generally between 1 and 20 hours, preferably between 2 and 8 hours, and depend on the reaction temperature or on the amount of catalyst used.
- an inert solvent such as, for example, toluene or cyclohexane.
- the excess (meth) acrylic ester I is partially or preferably completely, for example distilled off, removed from the reaction product. Subsequently, the separation of the catalyst is carried out by filtration.
- the tetra- or polyfunctional (meth) acrylic esters are excellent copolymers for reactions in which crosslinking during polymerization is desired.
- they are used in paints, dental applications, adhesives, in vulcanization or in radiation curing.
- the mixture is introduced into the reaction apparatus except for lithium amide and dehydrated, then the batch is cooled. At about 80 0 C is added to the lithium amide and the reaction temperature is increased again. The resulting methanol is distilled as MMA / methanol azeotrope over a column top. After the column head temperature no longer falls, the reaction is stopped after a reaction time of 6.7 h and a reaction temperature of 101 0 C to 113 0 C.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005044250A DE102005044250A1 (de) | 2005-09-15 | 2005-09-15 | Verfahren zur Herstellung von Methacrylaten mit reaktiven Doppelbindungen |
PCT/EP2006/065366 WO2007031384A1 (de) | 2005-09-15 | 2006-08-16 | Verfahren zur herstellung von (meth) acrylaten vier- oder mehrwertiger alkohole |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1924547A1 true EP1924547A1 (de) | 2008-05-28 |
Family
ID=37086504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06792846A Withdrawn EP1924547A1 (de) | 2005-09-15 | 2006-08-16 | Verfahren zur herstellung von (meth) acrylaten vier- oder mehrwertiger alkohole |
Country Status (14)
Country | Link |
---|---|
US (1) | US7521578B2 (ko) |
EP (1) | EP1924547A1 (ko) |
JP (1) | JP5080473B2 (ko) |
KR (1) | KR101297448B1 (ko) |
CN (1) | CN101203478B (ko) |
AU (1) | AU2006290941B2 (ko) |
BR (1) | BRPI0615874A2 (ko) |
CA (1) | CA2622353C (ko) |
DE (1) | DE102005044250A1 (ko) |
MX (1) | MX2008003169A (ko) |
NZ (1) | NZ564132A (ko) |
RU (1) | RU2446144C2 (ko) |
WO (1) | WO2007031384A1 (ko) |
ZA (1) | ZA200802414B (ko) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012160007A1 (de) | 2011-05-24 | 2012-11-29 | Evonik Röhm Gmbh | Reaktivharze für kabelvergussmassen |
DE102011081649A1 (de) | 2011-08-26 | 2013-02-28 | Evonik Röhm Gmbh | Längerkettige Methacrylate aus nachwachsenden Rohstoffen |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10314776A1 (de) * | 2003-03-31 | 2004-10-14 | Rohmax Additives Gmbh | Schmierölzusammensetzung mit guten Reibeigenschaften |
DE102004021717A1 (de) * | 2004-04-30 | 2005-11-24 | Rohmax Additives Gmbh | Verfahren zur Herstellung von Schmierfett |
DE102004034618A1 (de) * | 2004-07-16 | 2006-02-16 | Rohmax Additives Gmbh | Verwendung von Pfropfcopolymeren |
DE102004037929A1 (de) * | 2004-08-04 | 2006-03-16 | Rohmax Additives Gmbh | Verfahren zur radikalischen Polymerisation ethylenisch-ungesättigter Verbindungen |
DE102006006200B4 (de) * | 2006-02-09 | 2008-01-10 | Röhm Gmbh | Wässrige N-Methylol-methacrylamid-Methacrylamid-Mischung |
DE102006039420A1 (de) | 2006-08-23 | 2008-02-28 | Evonik Rohmax Additves Gmbh | Verfahren zur Herstellung von Methacrylatestern |
JP2008100972A (ja) * | 2006-10-20 | 2008-05-01 | Kuraray Medical Inc | 親水性単量体の製造方法 |
DE102007031473A1 (de) | 2007-07-05 | 2009-01-08 | Evonik Röhm Gmbh | Verfahren zur Herstellung von Ethylenglycoldimethacrylat |
BR112016013709A2 (pt) * | 2013-12-26 | 2017-08-08 | Dow Global Technologies Llc | Combinação de inibidor para processo de transesterificação catalisada por sal de lítio e método para remoção de sal de lítio |
WO2015159611A1 (ja) * | 2014-04-16 | 2015-10-22 | 東亞合成株式会社 | 多官能(メタ)アクリレートの製造方法 |
CN107428771B (zh) | 2015-02-26 | 2020-06-12 | 巴斯夫欧洲公司 | 制备异山梨醇二(甲基)丙烯酸酯的方法 |
JP6583413B2 (ja) * | 2015-07-02 | 2019-10-02 | 東亞合成株式会社 | 硬化型組成物 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2364126A1 (de) * | 1972-12-27 | 1974-07-11 | Ciba Geigy Ag | Verfahren zur herstellung von hydroxyalkylphenylderivaten |
DE2744641B2 (de) * | 1977-10-04 | 1979-08-02 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Verfahren zur Herstellung von Estern der Methacrylsäure |
US4618700A (en) * | 1983-12-22 | 1986-10-21 | Ciba-Geigy Corporation | Process for the preparation of a hydroxyphenylcarboxylate |
DE3423443A1 (de) * | 1984-06-26 | 1986-01-02 | Röhm GmbH, 6100 Darmstadt | Verfahren zur herstellung von estern der acryl- und methacrylsaeure durch umesterung |
US5136082A (en) * | 1990-08-03 | 1992-08-04 | Himont Incorporated | Process for preparing organic esters and amides and catalyst system therefor |
JP3460259B2 (ja) * | 1992-09-18 | 2003-10-27 | 株式会社エーピーアイ コーポレーション | ペンタエリスリトールエステル化合物およびその用途 |
DE4401132A1 (de) | 1994-01-17 | 1995-07-20 | Roehm Gmbh | Verfahren zur Umesterung von (Meth)acrylsäureestern |
JPH0931018A (ja) * | 1995-07-24 | 1997-02-04 | Dainippon Ink & Chem Inc | ペンタエリスリトール(メタ)アクリルエステル類の製造法 |
JP2000302749A (ja) * | 1999-04-26 | 2000-10-31 | Hitachi Chem Co Ltd | (メタ)アクリル酸ポリオキシエチレン化ビスフェノ−ルsエステル、その製造法及び感光性樹脂組成物 |
JP4826026B2 (ja) * | 2001-05-18 | 2011-11-30 | 日立化成工業株式会社 | (メタ)アクリル酸エステルの製造法 |
JP2005213218A (ja) * | 2004-01-30 | 2005-08-11 | Hitachi Chem Co Ltd | ポリオキシアルキレン化グリコール類の(メタ)アクリル酸エステル誘導体の製造方法 |
-
2005
- 2005-09-15 DE DE102005044250A patent/DE102005044250A1/de not_active Withdrawn
-
2006
- 2006-08-16 EP EP06792846A patent/EP1924547A1/de not_active Withdrawn
- 2006-08-16 US US11/995,406 patent/US7521578B2/en not_active Expired - Fee Related
- 2006-08-16 BR BRPI0615874-9A patent/BRPI0615874A2/pt not_active Application Discontinuation
- 2006-08-16 RU RU2008114030/04A patent/RU2446144C2/ru not_active IP Right Cessation
- 2006-08-16 AU AU2006290941A patent/AU2006290941B2/en not_active Ceased
- 2006-08-16 MX MX2008003169A patent/MX2008003169A/es active IP Right Grant
- 2006-08-16 CA CA2622353A patent/CA2622353C/en not_active Expired - Fee Related
- 2006-08-16 NZ NZ564132A patent/NZ564132A/en not_active IP Right Cessation
- 2006-08-16 KR KR1020087006385A patent/KR101297448B1/ko not_active IP Right Cessation
- 2006-08-16 JP JP2008530456A patent/JP5080473B2/ja not_active Expired - Fee Related
- 2006-08-16 CN CN2006800220452A patent/CN101203478B/zh not_active Expired - Fee Related
- 2006-08-16 WO PCT/EP2006/065366 patent/WO2007031384A1/de active Application Filing
-
2008
- 2008-03-14 ZA ZA200802414A patent/ZA200802414B/xx unknown
Non-Patent Citations (1)
Title |
---|
See references of WO2007031384A1 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012160007A1 (de) | 2011-05-24 | 2012-11-29 | Evonik Röhm Gmbh | Reaktivharze für kabelvergussmassen |
DE102011081649A1 (de) | 2011-08-26 | 2013-02-28 | Evonik Röhm Gmbh | Längerkettige Methacrylate aus nachwachsenden Rohstoffen |
Also Published As
Publication number | Publication date |
---|---|
AU2006290941B2 (en) | 2012-06-14 |
ZA200802414B (en) | 2009-01-28 |
US7521578B2 (en) | 2009-04-21 |
AU2006290941A1 (en) | 2007-03-22 |
CN101203478B (zh) | 2011-05-04 |
RU2008114030A (ru) | 2009-10-20 |
JP2009507881A (ja) | 2009-02-26 |
WO2007031384A1 (de) | 2007-03-22 |
KR20080044301A (ko) | 2008-05-20 |
KR101297448B1 (ko) | 2013-08-16 |
CA2622353C (en) | 2014-04-15 |
NZ564132A (en) | 2011-04-29 |
CA2622353A1 (en) | 2007-03-22 |
MX2008003169A (es) | 2008-03-18 |
BRPI0615874A2 (pt) | 2011-05-31 |
JP5080473B2 (ja) | 2012-11-21 |
DE102005044250A1 (de) | 2007-03-29 |
US20080194861A1 (en) | 2008-08-14 |
RU2446144C2 (ru) | 2012-03-27 |
CN101203478A (zh) | 2008-06-18 |
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Legal Events
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Effective date: 20080107 |
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DAX | Request for extension of the european patent (deleted) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: EVONIK ROEHM GMBH |
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DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20150128 |
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