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WO1996006067A1 - Utilisation d'acide phosphinique ou d'acide organophosphonique pour stabiliser les couleurs d'esters d'acides carboxyliques c3-c5 insatures - Google Patents

Utilisation d'acide phosphinique ou d'acide organophosphonique pour stabiliser les couleurs d'esters d'acides carboxyliques c3-c5 insatures Download PDF

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Publication number
WO1996006067A1
WO1996006067A1 PCT/EP1995/003258 EP9503258W WO9606067A1 WO 1996006067 A1 WO1996006067 A1 WO 1996006067A1 EP 9503258 W EP9503258 W EP 9503258W WO 9606067 A1 WO9606067 A1 WO 9606067A1
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WO
WIPO (PCT)
Prior art keywords
acid
esters
color
phosphinic acid
organophosphonic
Prior art date
Application number
PCT/EP1995/003258
Other languages
German (de)
English (en)
Inventor
Wolfgang Ritter
Thomas Reichert
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to JP8507772A priority Critical patent/JPH10504554A/ja
Priority to EP95930474A priority patent/EP0777643A1/fr
Publication of WO1996006067A1 publication Critical patent/WO1996006067A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation

Definitions

  • the invention relates to the use of phosphinic acid or organophosphonic acids or their mixtures for the color stabilization of esters of unsaturated carboxylic acids containing 3 5 C atoms containing polymerization inhibitors and to a process for the preparation of color stable (eth) acrylic acid esters of polyhydric alcohols by adding phosphinic acid or organophosphonic acids or mixtures thereof.
  • esters of unsaturated carboxylic acids with 3 to 5 carbon atoms e.g. Acrylic acid, methacrylic acid or maleic acid are used in a variety of ways, especially in polymerization technology. They are generally prepared by esterification in the presence of a catalyst and - because of the risk of undesired polymerization - in the presence of a polymerization inhibitor.
  • esters of methacrylic or acrylic acid - hereinafter referred to as (meth) acrylic acid - with polyhydric alcohols, so-called polyols, are also known.
  • esters for example, polyfunctional alcohols, as described, for example, in DE-A1 29 13 218, are esterified with (meth) acrylic acid in the presence of suitable catalysts and inhibitors and in the presence of an entrainer, for example toluene and / or xylene.
  • an entrainer for example toluene and / or xylene.
  • DE-A1 38 43 938 This problem was recognized at an early stage and attempts have already been made in DE-A1 38 43 938 to solve it by carrying out the esterification in the presence of activated carbon.
  • DE-A1 40 19 788 teaches to remove certain residual discolorations by treatment with a suitable aluminum oxide.
  • the problem of color instability is not eliminated by the methods mentioned, since only visible color bodies can be removed in this way, while obviously those substances which are responsible for the subsequent discoloration remain in the mixture.
  • the object of the invention is to provide a process for the treatment of polyol methacrylic acid esters with which light-colored and, in particular, storage stable in the dark can be produced.
  • the invention relates to the use of phosphinic acid or organophosphonic acids or mixtures thereof for the color stabilization of esters of unsaturated carboxylic acids containing 3 to 5 carbon atoms containing polymer inhibitors.
  • the invention further relates to a process for the preparation of color-stable (meth) acrylic acid esters of mono- and / or polyhydric alcohols, by reacting (meth) acrylic acid with the alcohols in the presence of acidic esterification catalysts and with the addition of polymerization inhibitors from the class of the phenols and / or hydroquinone compounds, characterized in that phosphinic acid or organophosphonic acids or mixtures thereof are added at the beginning and / or after the end of the esterification and / or neutralization reaction.
  • Examples of unsaturated carboxylic acids with 3 to 5 carbon atoms are acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid.
  • Acrylic acid and methacrylic acid are preferred.
  • the esters can be derived from linear or branched aliphatic alcohols with 1 to 22 carbon atoms, for example from methanol, ethanol, propanol, isopropanol, butanol, hexanol, 2-ethylhexanol, fatty alcohols with 6 to 22 carbon atoms, cyclohexanol or benzyl alcohol .
  • Suitable alcohols are also diols, such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol or neopentyl glycol and polyols, such as trimethylolpropane, glycerol, trimethylolethane, Pentaerythritol, sorbitol, oligomeric glycerols and their alkoxylation products.
  • the polyol esters of (meth) acrylic acid are particularly preferred. Like the previously mentioned esters with monofunctional alcohols, they contain, in a known manner, polymerization inhibitors from the class of the phenol and / or hydroquinone compounds in limited amounts, for example in the range from 200 to 3,000 ppm, preferably 500 to 2,000 ppm.
  • the improvement in color stability is achieved according to the invention by adding phosphinic acid or organophosphonic acids or mixtures thereof.
  • organophosphonic acids are to be understood as meaning alkyl-substituted phosphonic acids.
  • Organophosphonic acids whose alkyl substituents have 1 to 6 carbon atoms and which in turn may contain substituents such as hydroxyl, nitrile and / or amino groups or else carboxyl groups are preferred here.
  • Examples of such organophosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, nitrilotrismethylenephosphonic acid, aminobismethylenephosphonic acid, ethylene-diamintetramethylenephosphonic acid, diethylenetriamine-pentamethylenephosphonic acid and phosphonobutane tricarboxylic acid.
  • 1-Hydroxyethane-1,1-diphosphonic acid is particularly preferred here.
  • phosphinic acid in conjunction with the use of hydroquinone as a polymerization inhibitor-containing reaction products and mixtures of the type specified has proven to be particularly effective with regard to color stabilization.
  • the combination of these auxiliaries or active ingredients is a particularly preferred embodiment in terms of the teaching according to the invention.
  • the stabilization according to the invention of the esters of unsaturated carboxylic acids with 3 to 5 carbon atoms is carried out by adding the phosphinic acid or organophosphonic acids or mixtures thereof, preferably already for the esterification reaction or also before and / or after the neutralization of the reaction products.
  • the amounts of phosphinic acid can be between 0.01 and 3% by weight, based on the ester. Quantities of 0.1 to 2% by weight and in particular 0.5 to 1% by weight are preferred.
  • organophosphonic acids can be between 0.1 and 3.5% by weight, based on the ester. Quantities of 1.5 to 2.5% by weight are preferred.
  • the unsaturated esters of carboxylic acids with 3 to 5 carbon atoms are prepared in a known manner by esterification in the presence of a catalyst, usually a strong acid such as p-toluenesulfonic acid or sulfuric acid, and a polymerization inhibitor.
  • a catalyst usually a strong acid such as p-toluenesulfonic acid or sulfuric acid, and a polymerization inhibitor.
  • the water of reaction can be separated off azeotropically using an entrainer.
  • the preferred polyol (meth) acrylic acid esters are prepared from polyfunctional alcohols such as glycerol or trimethylolpropane or their alkoxylation products and (meth) acrylic acid by esterification.
  • the esterification generally also takes place here in the presence of an acidic esterification catalyst, usually p-toluenesulfonic acid, and one Inhibitors instead and is carried out without the addition of solvents or azeotropic entraining agents.
  • suitable inhibitors are, in particular, phenol and / or hydroquinone compounds.
  • An important example of the alkyl-substituted hydroquinones is 2,5-ditertbutylhydroquinone.
  • the particularly preferred inhibitor in combination with the addition of the phosphinic acid H3PO2 is the unsubstituted hydroquinone.
  • the water of reaction is separated off in an inert gas stream to which small amounts of oxygen have been added in order to avoid undesired polymerization reactions.
  • the neutralization of the acidic constituents of the reaction mixture - essentially (meth) acrylic acid and esterification catalyst - is generally carried out by adding oxides, hydroxides and / or carbonates of the alkali and / or alkaline earth metals and, if desired, limited amounts of water with salt formation.
  • the neutralization water formed in the reaction is then withdrawn from the reaction mixture.
  • Finely divided oxides and / or hydroxides of calcium and / or magnesium are used in particular as the solid phase for binding the acidic constituents in the course of the neutralization reaction, with the calcium compounds being preferred.
  • the neutralization reaction can be carried out in the temperature range from about 60 to 100 ° C. with a treatment time of advantageously not more than about 3 hours, a treatment time in the range from a few minutes to 1 hour being generally preferred.
  • the amount of neutralizing agent - based on the acid number of the feed material - is 1 to 1.5 times, preferably about 1.1 to 1.3 times the stoichiometrically required amount.
  • water can be added in amounts of about 0.5 to 15% by weight, based on the feed, to facilitate the neutralization reaction.
  • the solids content is usually separated off by pressure filtration, in particular temperatures of the reaction material above 50 ° C. and in particular working temperatures in the range from about 70 to 90 ° C. are suitable here.
  • the distillation of the water formed by neutralization and optionally added water from the hot reaction material is preferably carried out under reduced pressure, final pressures in the range from about 1 to 150 mbar being important here.
  • phosphinic acid or organophosphonic acids or mixtures thereof according to the invention is preferably carried out at the beginning of the esterification reaction, but the compounds can also be added to the finished ester after esterification and / or neutralization has ended.
  • the polyol (meth) acrylic acid esters produced in accordance with the invention can be used as a component of radiation-curing coatings and adhesives.
  • Examples are lacquer raw materials for lacquers which are hardened with the aid of electron beams, raw materials for printing inks hardening with the aid of UV light or lacquers and raw materials for fillers, molding compounds and potting compounds.
  • Turpinal R SL (Henkel) is an aqueous solution of 1-hydroxyethane-1,1-diphosphonic acid with an active substance content of 60% by weight.
  • TMPx3EO ethoxylated trimethylolpropane
  • the esterification was carried out while passing air (40 l / h) and with water being separated off. At a maximum bottom temperature of 103 ° C and a maximum pressure of 400 mbar, the esterification time was 5 hours.
  • the crude product was neutralized by adding 29.5 g Ca (OH), 62.6 g H 0 and stirring for 15 minutes at 80 ° C., then stirring for 30 minutes at 80 ° C. and a pressure of 50 mbar and then using a Filtered suction filter.
  • Example 1 The product according to Example 1 was then aftertreated after the addition of 0.1% phosphinic acid with stirring at 80 ° C. for 60 minutes.
  • this product was aftertreated for 60 minutes at 80 ° C.
  • Example 7 (Turpinal R SL) 778.7 g of acrylic acid, 746.4 g of an ethoxylated trimethylolpropane, 18.3 g of p-toluenesulfonic acid, 22.9 g of Turpinal SL and 2.46 g of 2,5-di-t-butylhydroquinone ( 2,000 ppm based on the amount of product) weighed.
  • the esterification was carried out while passing air (40 l / h) and with water being separated off. At a maximum bottom temperature of 103
  • the crude product was neutralized by adding 34.5 g of Ca (OH) 2 , 63.8 g of H 2 O and stirring for 15 minutes at 80 ° C., then stirring for 30 minutes at 80 ° C. and a pressure of 50 mbar and then with Filtered using a pressure filter.
  • Example 8 (like example 7, less neutralization agent)
  • Example 7 The approach of Example 7 was repeated.
  • the crude product was neutralized by adding 12.2 g of Ca (OH) 2 , 62.6 g of H 2 O and stirring for 15 minutes at 80 ° C., then stirring for 30 minutes at 80 ° C. and a pressure of 50 mbar and then with Filtered using a pressure filter.
  • Example 7 The approach of Example 7 was repeated.
  • the crude product was neutralized by adding 16.0 g of Ca (OH) 2 , 62.6 g of H 0 and stirring for 15 minutes at 80 ° C., then stirring for 30 minutes at 80 ° C. and a pressure of 50 mbar and then using filtered using a pressure filter.
  • the product was then filtered again at 80 ° C.
  • the esterification was carried out while passing air (40 l / h) and with water being separated off. At a maximum bottom temperature of 103 ° C and a maximum pressure of 400 mbar, the esterification time was 5 hours.
  • the crude product was precipitated by addition of 35 g Ca (OH) 2, 30 g H 2 0 and stirring for 15 minutes at 80 ° C followed by stirring for 30 minutes at 80 ⁇ C and neutralized to a pressure of 50 mbar and then with the aid of a pressure filter filtered.
  • the esterification was carried out while passing air (50 l / h) and with water being separated off. At a maximum bottom temperature of 103 ° C and a maximum pressure of 400 mbar, the esterification time was 6 hours.
  • the crude product was neutralized by adding 83.1 g of Ca (OH) 2 , 193.5 g of H 2 O and stirring for 15 minutes at 80 ° C., then stirring for 30 minutes at 80 ° C. and a pressure of 50 mbar and then with Filtered using a pressure filter.
  • the color measurement was carried out using the APHA test according to DIN ISO 6271.
  • the color number of the raw product is 8 (Gardener).
  • the color number of the neuralized and filtered product is 4.2 (Gardener).
  • the samples were stored at 60 ° C in the dark.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'addition d'acide phosphinique ou d'acide organophosphonique ou de leurs mélanges permet d'améliorer la stabilité des couleurs d'esters, contenant des inhibiteurs de polymérisation, d'acides carboxyliques C3-C5 insaturés.
PCT/EP1995/003258 1994-08-25 1995-08-16 Utilisation d'acide phosphinique ou d'acide organophosphonique pour stabiliser les couleurs d'esters d'acides carboxyliques c3-c5 insatures WO1996006067A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP8507772A JPH10504554A (ja) 1994-08-25 1995-08-16 不飽和ｃ▲下３▼−ｃ▲下５▼カルボン酸エステルの色を安定化するためのホスフィン酸または有機ホスホン酸の使用
EP95930474A EP0777643A1 (fr) 1994-08-25 1995-08-16 Utilisation d'acide phosphinique ou d'acide organophosphonique pour stabiliser les couleurs d'esters d'acides carboxyliques c 3?-c 5? insatures

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4430086.7 1994-08-25
DE19944430086 DE4430086A1 (de) 1994-08-25 1994-08-25 Verwendung von Phosphinsäure oder Organophosphonsäuren zur Farbstabilisierung von Estern ungesättigter Carbonsäuren mit 3 - 5 C-Atomen

Publications (1)

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WO1996006067A1 true WO1996006067A1 (fr) 1996-02-29

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EP (1) EP0777643A1 (fr)
JP (1) JPH10504554A (fr)
DE (1) DE4430086A1 (fr)
WO (1) WO1996006067A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7956050B2 (en) 2005-07-15 2011-06-07 Albany Molecular Research, Inc. Aryl- and heteroaryl-substituted tetrahydrobenzazepines and use thereof to block reuptake of norepinephrine, dopamine, and serotonin

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19720257C1 (de) * 1997-05-16 1998-07-09 Henkel Kgaa Verfahren zur Herstellung hellfarbiger Carbonsäureester
DE19728898A1 (de) * 1997-07-07 1999-01-14 Henkel Kgaa Verfahren zur lösemittelfreien Herstellung von ungesättigten Polyolestern
DE19929258A1 (de) 1999-06-25 2000-12-28 Basf Ag Verfahren zur Herstellung von (Meth)acrylsäureestern
WO2002055472A1 (fr) * 2000-12-18 2002-07-18 Basf Aktiengesellschaft Procede de preparation d'esters d'acide (meth)acrylique superieurs
JP4548821B2 (ja) * 2004-03-25 2010-09-22 伯東株式会社 （メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制方法
JP5162306B2 (ja) * 2008-04-03 2013-03-13 精工化学株式会社 着色防止剤
GB0809332D0 (en) * 2008-05-22 2008-07-02 Lucite Int Uk Ltd Production of ethylenically unsaturated acids or esters thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD135193A1 (de) * 1977-11-10 1979-04-18 Brigitte Kreil Verfahren zum stabilisieren waessriger loesungen ungesaettigter carbonsaeuren und deren ester
JPS5572144A (en) * 1978-11-22 1980-05-30 Ube Ind Ltd Preparation of oligoester acrylate
JPH01106843A (ja) * 1987-10-20 1989-04-24 Nippon Oil & Fats Co Ltd ヒドロキシアリール脂肪酸類の製造法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD135193A1 (de) * 1977-11-10 1979-04-18 Brigitte Kreil Verfahren zum stabilisieren waessriger loesungen ungesaettigter carbonsaeuren und deren ester
JPS5572144A (en) * 1978-11-22 1980-05-30 Ube Ind Ltd Preparation of oligoester acrylate
JPH01106843A (ja) * 1987-10-20 1989-04-24 Nippon Oil & Fats Co Ltd ヒドロキシアリール脂肪酸類の製造法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8029, Derwent World Patents Index; AN 80-50504c *
DATABASE WPI Week 8922, Derwent World Patents Index; AN 89-162889 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7956050B2 (en) 2005-07-15 2011-06-07 Albany Molecular Research, Inc. Aryl- and heteroaryl-substituted tetrahydrobenzazepines and use thereof to block reuptake of norepinephrine, dopamine, and serotonin

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Publication number Publication date
JPH10504554A (ja) 1998-05-06
EP0777643A1 (fr) 1997-06-11
DE4430086A1 (de) 1996-02-29

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