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CA1264050A - Carrier-supported catalyst for making monocarboxylic anhydrides - Google Patents

Carrier-supported catalyst for making monocarboxylic anhydrides

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Publication number
CA1264050A
CA1264050A CA000493173A CA493173A CA1264050A CA 1264050 A CA1264050 A CA 1264050A CA 000493173 A CA000493173 A CA 000493173A CA 493173 A CA493173 A CA 493173A CA 1264050 A CA1264050 A CA 1264050A
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Canada
Prior art keywords
carrier
supported catalyst
stands
alkyl
compound
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.)
Expired
Application number
CA000493173A
Other languages
French (fr)
Inventor
Gerhard Luft
Gebhard Ritter
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Hoechst AG
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Hoechst AG
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Filing date
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/54—Preparation of carboxylic acid anhydrides
    • C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Furan Compounds (AREA)

Abstract

CARRIER-SUPPORTED CATALYST FOR MAKING MONOCARBOXYLIC
ANHYDRIDES

ABSTRACT OF THE DISCLOSURE

Carrier-supported catalyst for making monocarboxylic anhydrides by subjecting a suitable ester or ether to a carbonylation reaction. The carrier-supported catalyst has an organosilicon compound containing an alkoxy or halogen group and also an organonitrogen, organophosphorus, organo-arsenic, organosulfur, mercapto or thioether group as a po-lyfunctional adhesion promoter additively combined with the carrier material on the one hand, and with a nickel compound, on the other hand.

Description

~6~5~

This invention relates to a carrier-supported catalyst for making monocarboxylic anhydrides by subjecting a suit-able ester or ether to a carbonylation reaction, the catalyst having an organosilicon compound containing an alkoxy or ha-logen group and also an organonitrogen, organophosphorus,organoarsenic, organosulfur, mercapto or thioether group as a polyfunctional adhesion promoter additively combined with -the carrier material on the one hand, and with a nickel com-pound on the other hand.
The preparation of such nickel compound has already been described (cf. A.K. Smith et al., J. Mol. Catalysis 2 (1977), pages 223-226).
The carrier-supported catalyst of this invention is more especially used for making monocarboxylic anhydrides of the general formula (RCO)20 by reacting a carboxylic acid ester or dialkylether of the general formulae RCOOR and ROR, re-spectively, in which R each stands for one and the same alkyl group having from 1 to 4 carbon atoms, with carbon mon-oxide in gas phase in the presence of iodine or bromine or their compounds as a reaction promoter and in the presence of a carrier-supported catalyst, at temperatures of from 130 to ~00C under pressures of from 1 - 150 bars.
A process of this kind carried out in gas phase with the use of a carrier-supported catalyst has already been disclosed in German Specification DE-OS 24 50 965 and Ja-panese Specification JP-OS No. 47921/1975, which permits the disadvantages eccompanying liquid-phase methods, namely the difficult separation and recycle of suspended and partially dissolved catalyst and optionally promoter, to be avoided.

, .

~.2~ 5~) The gas phase processes described in the two specifi-cations use solid carrier-supported catalysts made by im-pregnating the carrier with a catalyst solution containing noble metals. In this way, it is not possible, however, e.g. for organonitrogen or organophosphorus compounds con-taining trivalent nitrogen and phosphorus, respectively, to be fixed in the carrier-supported catalyst, and this has been found generally to affect the activity of the ca-talyst and selectivity of the reaction, lû The present invention also permits the above deficien-cies to be obviated, however, by the use of so-called poly-func-tional adhesion promoters (spacers) which already have promoters of group V, e.g. organylamines or phosphines, in-tegrated therein, and permit nickel compounds to be fixed to the catalyst surface.
Further preferred and optional features of the carrier-supported catalyst of this invention provide:
a) for it to additionally contain as promoter,a metal com-pound selected from the 1st through 3rd principal 2û groups or the 4th through 7th subgroups of the Perio-dic System of the elements;
b) for the organosilicon compound as the polyfunctional adhesion promoter in the carrier-supported catalyst to be additively combined with the carrier material on the one hand, and alternately with the nickel compound and a metal compound salected from the 5th through 7th subgroups of the Periodic System of the elements;
c) for the polyfunctional adhesion promoter to be an or-ganosilicon compound corresponding to one of the ~;~6~)5~

following formulae:

I. RlX3 Si-(CR23) -Y or II. RnX3_nSi-(CR2)m-cHy2 or III. / RnX3 nsi~(CR2)m 72Z

in which X stands for -Cl, -Br or -oR2;
Y stands for -NR24, a nitrogen-containing aryl group, -PR2, -AsR42, -SR4 or -SH;
Z stands for -NR4-, PR4-, -AsR4- or -S-;
R1 stands for a C1 - C5-alkyl;
R2 stands for a C1 - C3-alkyl;
R3 stands for -H, a C1-C5-alkyl or -C6H5;
R4 stands for a C1-C6-alkyl, a C5-C8-cycloalkyl or -C6H5 or C6H5CH~- which may be substituted .with a halogen, methoxy, ethoxy or a C1-C3-alkyl;
n stands for 0 or 1 or 2;
m stands fo~r 0 through 8, preferably 1 through 3;
d) for it to contain an inorganic oxidic carrier or an active carbon carrier the residual active hydroxygroups of which were inactivated by esterification or etherifi-cation;
25 e) for it to contain from 0.01 to 50 wgt %, preferably 0,1 to 20 wgt %, nickel compound, adhesion promoter and further non noble mPtal compound, if desired.
The catalyst carriers should preferably be selected from inorganic oxides, e.g. SiO2, Al203, MgO, TiO2, La203, ~' .

, ' 05() ZrO2, zeolites, clay, NiO, Cr203, W03 or corresponding mixed oxides but also active carbon having a BET-surface area of from 1 to 1000 m2/g, preferably 30 to 400 mZ/g, and present-ing OH-groups. These OH-groups undergo reaction with the functional group or groups X of the adhesion promoter with formation of oxygen bridges between carrier and adhesion promoter. The promoters of the 5th or 6th principal group are chemically combined with the adhesion promoter and are themselves one of its functional groups which have the nickel compounds linked thereto, if desired alternately with metal compounds from the 5th to 7th subgroups, especially vanadium, bromium or rhenium. These nickel compounds and further non-noble metal compounds, if any, may well form bridges between individual adhesion promoter molecules fixed to the carrier.
An advantage of the present invention resides in the fact that the promoters increasing the catalyst activi.ty and selectivity, which are selected from principal group V
or VI of the Periodic System of the elements, form a func-tional group Y or Z in a polyfunctional adhesion promoterand can thus be fixed up to maximum concentration which is determined by the number of OH-groups on the carrier surface.
This is the reason why it is not necessary for an organoni-trogen or organophosphorus promoter, for example, to be separated and recycled. The process for making monocarboxy-lic anhydrides catalyzed by the carrier-supported catalyst of this invention compares favorably in catalyst activity and selectivity with the prior processes referred to herein-above carried out in gas phase with the use of a carrier-, '~'- ' .

supported catalyst. ~n adaition to this, the carrier-support-ed catalysts of this invention are free from expensive noble metals of group VIII of the Periodic System of the e].ements.
The carrier-supported catalyst of this invention is more especially used for making acetic anhydride from methyl acetate or dimethylether in the presence of methyl iodide or methyl bromide as a reaction promoter. HI, HBr or more gene-rally RI or RBr, where R stands for an alkyl group having from 1 to 4 carbon atoms, can also be used as a reaction promoter.
In the general formulae defining the organosilicon com-pounds which should conveniently be used as adhesion promoters (spacers), X preferably stands for _oR2 and more preferably for methoxy and ethoxy. If n stands for 1 or 2, R1 preferably stands for an unbranched alkyl group, especially methyl, ethyl or propyl.
The useful carrier materials have already been specified hereinabove; useful mixed oxides are e.g. Cr203 - A1203, 3 2 3 9 A1203, SiO2 - Al203 or ZrO2 - Al2û3 The carrier-supported catalyst preferably contains from 0.01 to 5 wgt % nickel and is conveniently used in form of particlec with a size of 1 to 20 mm.
The nickel compounds useful for making the carrier-sup-ported catalyst comprise e.g. the following compounds:
Ni(C0)4~ /-P(C6H5)3 72Ni(Co)2~ Ni(C8H12)2, 2 The metal compounds from the first to third principal groups or from the 4th through 7th subgroups of the Periodic System, preferably of Li, Na, Mg, Ca, Al, Ti, Zr, V, Cr, W, Re, should conveniently be selected from hydroxides, carbonates, o~ ~
carbonyls, hydrides, halides and further salts. The metal compounds can be used in form of a solution for impregnat-ing the catalyst carrier therewith.
~or preparation of the carrier-supported catalyst of this invention, it is necessary to have the polyfunctional adhesion promoter (organosilicon compound) which is a commercially available product or can be made by methods described in literature. Speaking generally, one of the nickel compounds specified and, if desired, one of the me-lû tal compounds of the 5th to 7th subgroups is linked to theadhesion promoter, namely to promoter group Y or Z contain-ing an element selected from the 5th or 6th principal group. Next, the nickel-containing intermediary product is reactively combined with the hydroxy groups of the carrier material with escape of a group X as a compound XH (e.g.
HCl, HBr, or R20H). This is achieved by heating the com-pounds suspended in an unpolar solvent (e.g. benzane, toluena, xylene) over a period of 24 to lûO hours until decolorized.
2û Alternatively, it is also possible first reactively to combine the polyfunctional adhesion promoter (organo-silicon compound) with the hydroxy groups of the carrier with escape of a group X as a compound XH, and then additi-vely to combine the nickel compound and, if desired, one of the metal compounds of the 5th to 7th subgroup with the promoter group Y or Z of the intermediary product.
Details are indicated in the catalyst description hereinafter.
In order to increase the selectivity and supprass . , ' .' ' '' .

~L~,6~5~

side reactions, it is good practice, especially for discon-tinuous operation but also for the initial phase in a con-tinuous process, to inactivate those residual OH-groups on the surface of the catalyst carrier which have not reacted with the functional groups X of the adhesion promoter. This can be done e.g. by silylation with trimethylchlorosilane, methylation with methyl iodide or acetylation with acetic anhydride.
The quantitative ratio of carboxylic acid ester or di-alkylether and iodine(compound) or bromine(compound) inthe reaction zone may vary within wide limits. Generally, however, 1 to 500 mols, preferably 1 to 100 mols, carboxy-lic acid ester and/or dialkylether is used per 1 mol iodine~compound) or bromine(compound). The temperature se-lected for the reaction zone should be high enough to al-ways have a gaseous reaction mixture therein, irrespective of the conversion rate, and preferably is between 170 and 250C. The preferred pressure is between 10 and 4û bars.
The reaction mixture should conveniently be contacted with the solid carrier-supported catalyst over a period of from 1 to 1000 seconds, preferably 1 to 180 seconds. The conversion should suitably be effected in a flow tube arranged in upright position, packed with the carrier-supported catalyst or in an autoclave provided with a stirrer or in a shaking autoclave, having the carrier-supported catalyst placed therein.
The reaction mixture coming from the carbonylation zone is gaseous and contains carbon monoxide, methyl iodide, acetic anhydride, unreacted methyl acetate or dimethylether .... . ... . . , . . , .. , . .. _, ~.2~S~

and, under circumstances, minor proportions of acetic acid.
The gaseous reaction mixture is cooled with condensation of acetic anhydride and, under circumstances, acetic acid. Un-condensed gases, such as C0, CH3I, methyl acetate or dimethyl-ether are recycled to the reaction zone, the reacted esteror ether and C0 portions being continuously renewed. The an-hydrides are easy to separate, i.e. in uncomplicated fashion, by cooling the effluent reaction mixture and recycling the uncondensed gas. This is a particular advantage of the pro-cess carried out with the catalyst of this invention~ The carrier-supported catalyst is not contaminated; it remains in the reaction zone. As a result, the entire process is rendered considerably simpler.
Example Preparation of the catalyst of the formula:
l C2H5 Al203 } û-Si-CH2-CH2~P(c6H5)2-72Ni( )2 Aluminum oxide was activated by drying it over a period of 10 hours at 200C under a pressure of 0.1 to 0.2 milli-bar.
The catalyst was prepared in the presence of nitrogen with exclusion of oxygen and water, all of the reactants having been dried previously using molecular screen 4 A.
65 mg (4.4 mg Ni) of the compound of the formula L (C2HsO)3si-cH2cH2p(c6H5)2-72Ni(cû)2~ dissolved in 40 ml xylene, was added while stirring to 3~2 g activated aluminum oxide (99 % A1203) which consisted substantially of particles with a diameter of 3 mm, had an inner BET-surface area of 6~V~

125 m2/g and a pore volume of 0.9 ml per 9, and the mixture was brought to boiling. After having been refluxed over a period of 72 hours, the yellowish solution was found to have been completely decolorized. The solvent was separa-ted and the catalyst was given into a Snxhlet. After 12 h Soxhlet-extraction with benzene, the catalyst was dried over a period of 8 hours at 85C under a pressure of 1.33 millibar.
To suppress side-reactions and improve the selectivity, the catalyst was ultimately treated with trimethylchloro-silane.

Al O }OH + Cl-Si(CH3)3 ~Al23 } 3 3 To this end, the catalyst was completely covered at room temperature with trimethylchlorosilane. The suspension was heated to boiling and boiled under reflux until gas ceased to be evolved. Next, the suspension was allowed to cool, the catalyst was separated from the liquid and dried over a period of 12 hours at 85C under 1.33 millibar.
The concentrated solvents were free from nickel. The catalyst so made contained û.13 wgt % nickel.
The intermediate compound of the formula - ( 2 5 )3Si CH2CH2P(C6H5)2 72Ni(Co)2 from
2 5 3 2 H2P(C6H5)2 and Ni(C0)4 with escape of CO gas was prepared as described by A.K. Smith et al. J. mol. Catal.
2 (1977), pages 223-226. The compound of the formula (C2H5û)3SiCH2CH2P(C6H5)2 from triethoxyvinylsilane and di-phenylphosphine with exposure to ultraviolet light was made as described by H. Niebergall, Makromol. Chem. 52 (1962), : : , : ~ , - . -, ~.

pages 218-227.
Use of catalyst a) 2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl iodide and 3.15 9 catalyst were reacted with carbon monoxide in a stainless steel (Hastelloy C) autoclave having a capacity of 0.25 liter, at 200C under a C0-pressure of 20 bars. The space/time-yield after a reaction period of 1 h was 140 9 Ac20/g Ni per hour.
The yield of Ac20, based on the ester used, was 22 %
for a selectivity of 92 %.
b) 1.86 ml dimethylether, 0.5 ml (1.14 9) methyl iodide and 3.15 9 catalyst were reacted in the autoclave at 200C under a C0-pressure of 20 bars. Acetic an-hydride was obtained in a space/time-yield of 30 9 Ac20 per 9 Ni per hour. The experiment was run over a period of 5 hours.
The yield of Ac20, based on the ether used, was 6 %
for a selectivity of 19 %.

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A carrier supported catalyst for making monocarboxylic anhydrides by subjectlng a suitable ester or ether to a carbonylation reaction, the carrier-supported catalyst having an organosilicon compound as a polyfunctional adhesion promoter reactively combined with the carrier material, and bound to a nickel compound, the organosillcon compound corresponding to one of the following general formulae:
I. R?X3-nSi-(CR?)m-Y or II. R?X3-nSi-(CR?)m-CHY2 or III. [R?X3-nSI-(CR?)m]2Z

in which X stands for -C1, -Br or -oR2;
Y stands for -NR?, -PR?, -AsR?, -SR4 or -SH;
Z stands for -NR4-, PR4-, AsR4- or -S-;
R1 stands for a C1-C5-alkyl;
R2 stands for a C1-C3-alkyl;
R3 stands for -H, a C1-C5-alkyl or -C6H5;
R4 stands for a C1-C6-alkyl, a C5-C8-cyclo-alkyl or -C6H5 or C6H5CH2-, n stands for 0 or 1 or 2;
m stands for 0 through 8.
2. A carrier-supported catalyst as claimed in claim 1, which additionally contains, as a promoter, a metal compound selected from the 1st through 3rd principal groups or the 4th through 7th subgroups of the Periodic System of the elements.
3. A carrier-supported catalyst as claimed in claim 1, wherein the organosilicon compound as the polyfunctional adhesion promoter is reactively combined with the carrier material and alternately bound to the nickel compound and to a metal compound selected from the 5th through 7th subgroups of the Periodic System of the elements.
4. A carrier-supported catalyst as claimed in claim 1, wherein R4 stands for -C6H5 or C6H5CH2 substituted with a halogen, methoxy, ethoxy or C1 - C3-alkyl.
5. A carrier-supported catalyst as claimed in claim 1, wherein m stands for 1 or 2 or 3.
6. A carrier-supported catalyst as claimed in claim l, wherein the carrier-supported catalyst contains an inorganic oxidic carrier or an active carbon carrier, the residual active hydroxy groups of which were inactivated by esterification or etherification.
7. A carrier-supported catalyst as claimed in claim 1, containing from 0.01 to 50 wgt % nickel compound and adhesion promoter.
8. A carrier-supported catalyst as claimed in claim 2, containing a total quantity of from 0.01 to 50 wgt % nickel compound, adhesion promoter and further non noble metal compounds.
9. A carrier-supported catalyst for making monocarboxylic anhydrides by subjecting a suitable ester or ether to a carbonylation reaction, corresponding to the formula
CA000493173A 1984-11-07 1985-10-17 Carrier-supported catalyst for making monocarboxylic anhydrides Expired CA1264050A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843440643 DE3440643A1 (en) 1984-11-07 1984-11-07 Catalysts for acid anhydride prodn.
DEP3440643.3 1984-11-07

Publications (1)

Publication Number Publication Date
CA1264050A true CA1264050A (en) 1989-12-27

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ID=6249703

Family Applications (1)

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Country Status (5)

Country Link
EP (1) EP0180801B1 (en)
JP (1) JPH0628736B2 (en)
AT (1) ATE37022T1 (en)
CA (1) CA1264050A (en)
DE (2) DE3440643A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0203286B1 (en) * 1985-03-27 1988-09-14 Hoechst Aktiengesellschaft Supported catalyst and procedure for the production of monocarboxylic acid anhydrides
DE4020689A1 (en) * 1990-06-29 1992-01-02 Bayer Ag PALLADIUM-CONTAINING CARALYST PREPARATION

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2722504A (en) * 1950-12-04 1955-11-01 Union Oil Co Silicone coated catalyst and use thereof
FR2347097A1 (en) * 1976-04-05 1977-11-04 Raffinage Cie Francaise Hydrocarbon conversion catalysts based on alumina - contg. silicon and group=VIA or group=VIII metals
DE3232066A1 (en) * 1982-08-28 1984-03-01 Hoechst Ag, 6230 Frankfurt METHOD FOR PRODUCING ACETIC ACID ANHYDRIDE

Also Published As

Publication number Publication date
ATE37022T1 (en) 1988-09-15
EP0180801A3 (en) 1986-07-16
JPS61114740A (en) 1986-06-02
JPH0628736B2 (en) 1994-04-20
DE3564802D1 (en) 1988-10-13
DE3440643A1 (en) 1986-05-07
EP0180801A2 (en) 1986-05-14
EP0180801B1 (en) 1988-09-07

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