EP1399410A1 - Farbstabilisierung von grundstabilisierten ethylenisch ungesättigten monomeren - Google Patents

Farbstabilisierung von grundstabilisierten ethylenisch ungesättigten monomeren

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Publication number
EP1399410A1
EP1399410A1 EP02743030A EP02743030A EP1399410A1 EP 1399410 A1 EP1399410 A1 EP 1399410A1 EP 02743030 A EP02743030 A EP 02743030A EP 02743030 A EP02743030 A EP 02743030A EP 1399410 A1 EP1399410 A1 EP 1399410A1
Authority
EP
European Patent Office
Prior art keywords
stabilization
color
tocopherol
use according
meth
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Withdrawn
Application number
EP02743030A
Other languages
German (de)
English (en)
French (fr)
Inventor
Bardo Schmitt
Joachim Knebel
Marianne Omeis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
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 Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1399410A1 publication Critical patent/EP1399410A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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 is in the field of stabilizing polymerizable compounds, so-called monomers.
  • the invention relates to the color stabilization of ethylenically unsaturated monomers, in particular of
  • Hydroxyalkyl (meth) crylates which already have at least one polymerization inhibitor for basic stabilization or storage stabilization.
  • Ethylenically unsaturated monomers tend to polymerize more or less spontaneously.
  • the polymerization reaction is a chain reaction that is generally triggered by free radicals. Their formation can be promoted by light and / or the influence of temperature.
  • monomers are stabilized both during their preparation and during storage by adding polymerization inhibitors. The number of polymerization inhibitors for basic or storage stabilization of ethylenically unsaturated monomers is legion.
  • the undesired spontaneous polymerization of ethylenically unsaturated monomers is evident, for example, from an increase in the viscosity of the monomer, which is often liquid under standard conditions of pressure and temperature (atmospheric pressure and room temperature). Whether a liquid monomer contains polymer components or whether this proportion of polymer components changes, usually increases during a storage period, can be determined very precisely, for example, by means of nephelometric measurements. For many applications, however, spontaneous premature polymerization of the monomers is not only problematic, the color of the monomers is also of interest. Paints often contain free-radically curing (polymerizable) monomers.
  • the Dl deals with the inhibition of the polymerization of monomers.
  • Dl in particular discloses a method for preventing the polymerization of vinyl monomers during production, storage and transportation.
  • the Dl shows that alpha-tocopherol very effectively inhibits the polymerization of isoprene and acrylonitrile.
  • the DI describes that alpha-tocopherol and hydroquinone have a synergistic, ie superadditive, effect in inhibiting the polymerization of acrylonitrile.
  • an induction time was measured in the DI. This is the time until it was possible to suppress polymerization of the monomer by adding the inhibitors under defined conditions.
  • the D3 relates to the prevention of discoloration ("browning") of polymers.
  • a composition for lacquers or binders is disclosed which has a copolymer of dimethylaminomethyl methacrylate and methyl ethacrylate units and tocopherol. The "browning" of the readily soluble in organic solvents and water Copolymers are prevented by the addition of tocopherol.
  • the D4 relates to the stabilization of polymers (organic materials), in particular polyolefins, against thermal, oxidative or light-induced degradation (degradation), with a stabilizer mixture comprising at least one monomeric or oligomeric organic bisphosphite together with at least one benzofuran-2 on or alpha-tocopherol (vitamin E).
  • a stabilizer mixture comprising at least one monomeric or oligomeric organic bisphosphite together with at least one benzofuran-2 on or alpha-tocopherol (vitamin E).
  • D5 Another document from the prior art which deals with the stabilization of polymeric material is the D5. This describes the stabilization of polymers of styrene or of a (meth) acrylic compound against degradation by light and / or heat and / or atmospheric oxygen with a mixture of an organic phosphite and alpha-tocopherol. None is said about the color stability of the stabilized molding compound during storage.
  • the tocopherol compounds which can be used in the context of the invention are chroman-6-oles (3, 4-dihydro-2H-1-benzopyran-6-ole) substituted in the 2-position with a 4, 8, 12-trimethyltridecyl radical.
  • the tocopherols which can preferably be used according to the invention include alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol, zeta2-tocopherol and eta-tocopherol, all of the abovementioned compounds each in the (2R, 4'R, 8'R) - Form, as well as alpha-tocopherol in the (all-rac) form.
  • alpha-tocopherol in the (2R, 4'R, 8'R) form (Trivialna.me: RRR-alpha-tocopherol) and the synthetic racemic alpha-tocopherol (all-rac-alpha-tocopherol).
  • RRR-alpha-tocopherol Trivialna.me: RRR-alpha-tocopherol
  • all-rac-alpha-tocopherol all-rac-alpha-tocopherol
  • the amount of tocopherol compound which can be used to stabilize the color of stabilized monomers can vary over a wide range depending on the monomer and the desired efficiency. For many areas of application, amounts of up to 1000 ppm, based on the sum of the weights of monomer and tocopherol compound, are sufficient. Very small additions of 10 ppm are often sufficient to achieve a noticeable improvement in color stability. Should one use less than 10 ppm, however, a substantial color stabilization is generally not perceptible. A favorable range for the amount to be added is therefore between 10 and 1000 ppm of tocopherol compound, based on the sum the weights of monomer and tocopherol compound. Very good results are achieved in the 100 to 800 ppm addition range. A particular embodiment of the invention provides for use in an amount of 200 to 600 ppm. About 400 ppm of tocopherol compound are very particularly advantageously used.
  • ethylenically unsaturated monomers are compounds which have at least one free-radically polymerizable double bond.
  • These ethylenically unsaturated monomers include Vinyl esters, (meth) acrylic acid, esters of (meth) acrylic acid, e.g. methyl and ethyl (meth) acrylate, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, substituted styrenes with an alkyl substituent in the side chain, e.g.
  • styrenes substituted styrenes with an alkyl substituent on the ring, such as, for example, vinyl toluene and p-methylstyrene, halogenated styrenes, such as, for example, monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes, vinyl and isopropenyl ethers, maleic acid derivatives, such as maleic acid anhydride, such as maleic acid maleic acid, for example maleic anhydride, Maleimide, methyl maleimide, and dienes such as divinylbenzene.
  • an alkyl substituent on the ring such as, for example, vinyl toluene and p-methylstyrene
  • halogenated styrenes such as, for example, monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes
  • the notation (meth) acrylic includes methacrylic, acrylic and mixtures of both.
  • Preferred ethylenically unsaturated monomers are (meth) acrylic acid and derivatives of (meth) acrylic acid. These compounds can be represented, for example, according to formula 1
  • the radical R 1 is hydrogen or a methyl group
  • the radical R 2 is hydrogen, an aryl radical which can also contain heteroatoms, such as phenyl and imidazole, and a straight-chain, branched or cyclic alkyl radical with up to 30 carbon atoms which is both saturated can also be unsaturated, and can also contain heteroatoms, such as, for example, nitrogen and / or oxygen, such as, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, isobornyl, vinyl, propenyl, butinyl, 2- (N , N-dimethylamino) ethyl, 2- (N, N-dimethylamino) propyl, 2-hydroxypropyl and 2-hydroxyethyl.
  • DMAEMA dimethylaminoethyl methacrylate
  • the (meth) acrylic acid amides corresponding to the (meth) acrylic acid esters are also a preferred group of ethylenically unsaturated monomers. For this belongs, for example, to N-dimethylaminopropyl methacrylamide (DMAPMA).
  • DMAPMA N-dimethylaminopropyl methacrylamide
  • the ethylenically unsaturated monomers can be present individually or as a mixture in the composition according to the invention.
  • a very particularly preferred group of compounds whose color is stabilized according to the principle of the invention are the hydroxyalkyl (meth) acrylates.
  • HSA hydroxyethyl acrylate
  • HEMA Hydroxyethyl methacrylate
  • the (meth) acrylic acid esters of are particularly preferred to be stabilized esterification products
  • the monomers to be stabilized according to the invention with regard to the discoloration already have at least one stabilizing compound for basic stabilization. This is used to inhibit the polymerization.
  • Polymerization inhibitors are already known. For example, 1,4-dihydroxybenzenes can be added for stabilization. However, differently substituted dihydroxybenzenes can also be used. Such inhibitors can generally be represented by the general formula (II)
  • R 1 is hydrogen, 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, particularly preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl , sec-butyl, tert-butyl, Cl, F or Br;
  • n is an integer ranging from one to four, preferably one or two; and R 2 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, particularly preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec - Butyl or tert-butyl.
  • R 1 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, particularly preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec -Butyl, tert-butyl, Cl, F or Br; and
  • n is an integer in the range from one to four, preferably one or two.
  • Phenols of the general structure (IV) are also used.
  • R 1 is a linear or branched alkyl radical with one to eight carbon atoms, aryl or aralkyl, propionic acid ester with 1 to 4 polyhydric alcohols, which may also contain heteroatoms such as S, O and N, preferably an alkyl radical with one to four carbon atoms, particularly preferably methyl, Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl means.
  • Another advantageous class of substances are sterically hindered phenols based on triazine derivatives of the formula (V):
  • R C n H 2 n + l
  • Another group of known inhibitors are amines, especially sterically hindered amines.
  • R 1 , R 2 , R 3 and R 4 independently represent hydrogen and alkyl, aryl, alkaryl, aralkyl radicals each having up to 40, preferably up to 20 carbon atoms, preferably at least one of the radicals R 1 , R 2 , R 3 and R 4 is hydrogen.
  • Exemplary p-phenylenediamines include p-phenylenediamine wherein R 1 , R 2 , R 3 and R 4 are hydrogen;
  • N-phenyl-N'-alkyl-p-phenylenediamines N-phenyl-N '-methyl-p-phenylenediamine, N-phenyl-' -ethyl-p-phenylenediamine, N-phenyl-N '-propyl-p- phenylenediamine, N-phenyl-N '-isopropyl-p-phenylenediamine, N-phenyl-N' - n-butyl-p-phenylenediamines, N-phenyl-N 'isobutyl-p-phenylenediamine, N-phenyl' -sec-butyl-p-phenylenediamine.
  • N-phenyl-N'-tert-butyl-p-phenylene diamine N-phenyl-N '-n-pentyl-p-phenylene diamine, N-phenyl-N' -n-hexyl-p-phenylene diamine ' n, N-phenyl -N '- (1-methylhexyl) -p-phenylenediamine, N-phenyl-N' - (1,3-dimethylbutyl) -p-phenylenediamine, N-phenyl-N '- (1,4-dimethyl-pentyl) - p-phenylenediamine;
  • N-phenyl-N ', N' -dialkyl-p-phenylenediamines such as, for example, N-phenyl-N ', N' -dimethyl-p-phenylenedia in, N-phenyl- ', N' -diethyl-p- phenylenediamine, N-phenyl-N ', N' -di-n-butyl-p-phenylenediamine N-phenyl-N ', N' -di-sec-butyl-p-phenylenediamine, N-phenyl- '- methyl-N '-ethyl-p-phenylenediamine;
  • N, N-dialkyl-p-phenylenediamines such as, for example, N, N-dimethyl-p-phenylenediamine and N, N '-diethyl-p-phenylenediamine;
  • N, N '-dialkyl-p-phenylenediamines such as, for example, N,' -diisopropyl-p-phenylenediamine, N, N '-diisobutyl-p-phenylenediamine;
  • N, N '-diaryl-phenylenediamines such as N, N' -diphenyl-p-phenylenediamine
  • N, N, N '-trialkyl-p-phenylenediamines such as, for example, N, N,' -trimethyl-p-phenylenediamine, N, N, N '-triethyl-p-phenylenediamine.
  • phenazine dyes form another preferred group. These include in particular indulin and nigrosine. Nigrosine is created by heating nitrobenzene, aniline and hydrochloric aniline with metallic iron and FeCl 3 .
  • alcohol-soluble aniline dyes preferred, which may comprise, for example, 5 benzene nuclei, such as dianilido-N, N-diphenylphenosafranine. These substances are well known and can be obtained commercially.
  • the inhibitors mentioned are commercially available.
  • the compounds mentioned can be used alone or in a mixture of two or more compounds.
  • the proportion of the inhibitors responsible for the basic stabilization of the monomers is 0.01-0.5% (wt / wt) for many applications.
  • N-Nitroso-N-phenylhydroxylamine is an acidic compound, its salts , such as the ammonium, aluminum, copper, lithium, sodium, potassium and rubidium salt, can also be used.
  • Synergism here means that the inhibitory effect of the combination is greater than the inhibition which can be expected on the basis of the activity of the individual compounds.
  • the ratio of color stabilizer to basic stabilizer is variable when used according to the invention.
  • use in a ratio (w / w) of compound from the group of tocopherols to polymerization inhibitor (basic stabilizer) such as 1:10 to 10: 1, preferably 1: 1 to 8: 1, is expedient.
  • the monomer composition stabilized according to the invention can contain further constituents. These include solvents such as benzene, toluene, n-hexane, cyclohexane, methyl isobutyl ketone and methyl ethyl ketone.
  • solvents such as benzene, toluene, n-hexane, cyclohexane, methyl isobutyl ketone and methyl ethyl ketone.
  • additives such as anti-binding agents, antistatic agents, antioxidants, bio-stabilizers, chemical blowing agents, mold release agents, flame retardants, lubricants, colorants, casting improvers, fillers, lubricants, adhesion promoters, catalysts, light stabilizers, optical brighteners, organic phosphorus compounds, oils, pigments, toughening agents Reinforcing agents, reinforcing fibers, weathering protection agents and plasticizers are preferred components of the monomer composition stabilized according to the use according to the invention.
  • compositions stabilized by the use according to the invention can be obtained by mixing at least one ethylenically unsaturated monomer and a stabilizing amount of a basic stabilizer and at least one tocopherol compound.
  • Vinyl monomers especially HEMA, are used in clearcoat and high solid coatings.
  • the use of colorless starting materials has a particularly favorable effect on the color of the end product.
  • the use of certain hydroxyalkyl (meth) acrylates in the abovementioned applications has already been described in EP 0882750 and US 5753756.
  • the experiments were carried out by adding additives to finished monomers which had a basic stabilization (stabilization with 200 ppm hydroquinone monomethyl ether (HQME)) indicated in the examples to inhibit polymerization, with the concentrations listed in the table.
  • the samples were subjected to a storage test at 50 ° C in comparison to the corresponding blank value samples.
  • the Pt / Co color number was determined in accordance with DIN / ISO 6271 at certain intervals.
  • the turbidity of the samples was determined using nephelometry in order to check the polymerization inhibition.
  • a light beam is passed through the sample.
  • the light scattered at an angle of 90 °, the light scattered forward and the transmitted light are measured with photocells.
  • the ratio of the output of the photocell for the 90 ° measurement to the sum of the outputs of the other two photocells is formed electronically, thus achieving excellent linearity and eliminating the influence of color.
  • the stray light is negligible due to the construction of the optical system.
  • Scattered light in nephelometric measurements is the part of the light that the photo element reached, but not due to light scattering in the sample. is due.
  • the samples to be examined are measured using a turbidity meter.
  • the HACH * Ratio Turbidity Meter is a laboratory nephelometer that can be used to measure turbidity up to 199 turbidity units (NTU) based on formazin, even in colored samples. Even solutions with a higher turbidity can be measured after dilution of the sample with filtered sample solution and using a simple calculation.
  • NTU turbidity units
  • Calibration standard Formazin Sample size: 30 ml cuvette: 25 x 95 mm; Glass bottle with screw cap
  • the visual comparison with color standard solutions of the platinum-cobalt scale is replaced by a measurement of the absorbance of the sample at the wavelengths 460 and 620 nm.
  • ⁇ E a calibration line is obtained, the pitch of which is used directly as a "factor" for the calculation the color number serves.
  • the prerequisite is that the sample to be examined corresponds largely to the color characteristic, ie the color tone, to the platinum / cobalt scale. Synonyms for the platinum-cobalt color number are APHA or Hazen number.
  • Spectrophotometer or filter photometer with filters for the ranges 460 or 620nm; 5 cm and 1 cm cuvette scales (d lmg); Volumetric flask; measuring cylinders
  • Pt / Co standard comparison solutions for the required measuring range (0 - 500 of the color scale) can be prepared from the Pt / Co stock solution by adding corresponding volumes of standard solution to 100 ml volumetric flasks, which are filled with deionized water up to the calibration mark become.
  • the volumes of stock solution for the desired Pt-Co standard comparison solutions can be found in the following table:
  • the Pt-Co standard comparison solutions produced are measured in 5 cm cuvettes with the spectrophotometer or a filter photometer with the corresponding filters at 460 and 620 nm. (Reference cuvette contains demineralized water).
  • the Pt / Co color numbers and the associated measured extinction differences (E460nm - E620nm) result in a linear relationship.
  • the liquid to be measured is placed in a 5 cm cell and the cell is closed. It must be free of air bubbles or streaks. Now the extinction of the sample is measured with a spectrophotometer or a filter photometer with the appropriate filters at 460 and 620 nm against demineralized water and the extinction difference is calculated.
  • the factor can have different values depending on the device, it is according to 1.3.3.3. to be determined in each case. If extinctions ⁇ 0 occur at 620 nm, the difference is also formed; ie the numerical value of the absorbance at 620 nm is added to the absorbance value at 460 nm. 1.3.2.6 Results
  • the immersion depth is reproducibly set using a plastic grate.
  • the level of the oil bath is at least 1 cm above the liquid level in the test tube.
  • a PC-based temperature measuring point with six measuring points is switched on simultaneously with the insertion of the test tube in the oil bath.
  • the temperature / time curve is recorded and evaluated. After the polymerization has largely ended, the measurement is stopped.
  • the time until the maximum temperature is reached and the peak temperature of the polymerization are obtained and recorded as measured values.
  • HEMA - polymer test on stored samples Turbidity measurement according to 1.2. namely 1: 9 in Die.thylether. Specification of the NTU values.
  • the improvement in the turbidity value by adding tocopherol is only minimal. This means that the addition of tocopherol does not make a significant contribution to stabilization before polymerization.
  • HEMA Hydroxyethyl methacrylate
  • HEMA Hydroxyethyl methacrylate
  • Initiator 1.0% (w / w) tert-butyl peroctoate
  • Comparative sample polymerization time: 2.8 min; Temperature maximum: 175.5 ° C; Sample acc. Invention: Polymerization time: 3.0 min; Temperature maximum: 168.8 ° C;

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
EP02743030A 2001-06-29 2002-05-16 Farbstabilisierung von grundstabilisierten ethylenisch ungesättigten monomeren Withdrawn EP1399410A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10131479A DE10131479B4 (de) 2001-06-29 2001-06-29 Farbstabilisierung von grundstabilisierten ethylenisch ungesättigten Monomeren, insbesondere von grundstabilisierten Hydroxyalkyl(meth)acrylaten
DE10131479 2001-06-29
PCT/EP2002/005376 WO2003006417A1 (de) 2001-06-29 2002-05-16 Farbstabilisierung von grundstabilisierten ethylenisch ungesättigten monomeren

Publications (1)

Publication Number Publication Date
EP1399410A1 true EP1399410A1 (de) 2004-03-24

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EP02743030A Withdrawn EP1399410A1 (de) 2001-06-29 2002-05-16 Farbstabilisierung von grundstabilisierten ethylenisch ungesättigten monomeren

Country Status (7)

Country Link
US (1) US7002035B2 (zh)
EP (1) EP1399410A1 (zh)
JP (1) JP4184954B2 (zh)
KR (1) KR100875382B1 (zh)
CN (1) CN100378060C (zh)
DE (1) DE10131479B4 (zh)
WO (1) WO2003006417A1 (zh)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10349972A1 (de) * 2003-10-24 2005-05-25 Röhm GmbH & Co. KG Verfahren zur Herstellung von polymerisierbaren Polyhydroxyverbindungen
EP2085376B1 (en) 2008-01-30 2012-09-05 Evonik Röhm GmbH Process for preparation of high purity methacrylic acid
DE102009001577A1 (de) 2009-03-16 2010-09-23 Evonik Röhm Gmbh Für eine Aufreinigung stabilisierte Zusammensetzung und Verfahren zur Aufreinigung und zur Herstellung von Hydroxyalkyl(meth)acrylaten
DE102009002861A1 (de) 2009-05-06 2010-11-18 Evonik Röhm Gmbh Verfahren und Anlage zur Aufreinigung von Monomeren
DE102012203362A1 (de) 2012-03-05 2013-09-05 Evonik Röhm Gmbh Stabilisierte (Meth)acrylmonomere
WO2013163806A1 (en) 2012-05-03 2013-11-07 Evonik Industries Ag Process for preparation of highly pure, non-yellowing methacrylic acid
CN117321027A (zh) 2021-05-19 2023-12-29 罗姆化学有限责任公司 制备易聚合化合物的方法
CN115873171B (zh) * 2021-09-29 2024-07-02 爱森（中国）絮凝剂有限公司 丙烯酸2-二甲氨基乙酯聚合物及其制备方法
WO2023169863A1 (en) 2022-03-08 2023-09-14 Röhm Gmbh Process for preparing high purity (meth)acrylates

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163113A (en) * 1977-09-29 1979-07-31 Union Carbide Corporation Ester diol alkoxylate acrylates
DE3843843A1 (de) 1988-12-24 1990-07-05 Henkel Kgaa Verfahren zur verbesserten herstellung von (meth)acrylsaeureestern mehrwertiger alkohole (iv)
DE3843930A1 (de) 1988-12-24 1990-06-28 Henkel Kgaa Verfahren zur verbesserten herstellung von (meth)acrylsaeureestern mehrwertiger alkohole (iii)
US5859280A (en) * 1997-07-01 1999-01-12 Betzdearborn Inc. Methods for inhibiting the polymerization of vinyl monomers

Non-Patent Citations (2)

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Title
None *
See also references of WO03006417A1 *

Also Published As

Publication number Publication date
DE10131479B4 (de) 2005-05-19
CN1511136A (zh) 2004-07-07
JP2004536179A (ja) 2004-12-02
US20040186311A1 (en) 2004-09-23
KR100875382B1 (ko) 2008-12-23
JP4184954B2 (ja) 2008-11-19
CN100378060C (zh) 2008-04-02
WO2003006417A1 (de) 2003-01-23
DE10131479A1 (de) 2003-02-06
KR20040013004A (ko) 2004-02-11
US7002035B2 (en) 2006-02-21

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