• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    The present invention provides the production of vinyl esters from butene oligomers, which consists of oligomerizing butenes, separating butene oligomers from oligomeric water, converting butene oligomers to carboxylic acids as long as carbon atoms, and converting carboxylic acids to corresponding vinyl esters. It is about how to. Butene oligomers are di-, tri- and tetrabutenes. The invention also relates to the use of vinyl esters as softeners or as comonomers in polymerization reactions.
    公开号:KR20000058191A
    申请号:KR1020000009301
    申请日:2000-02-25
    公开日:2000-09-25
    发明作者:비제클라우스-디터；올브리히파울；가브리엘위르겐
    申请人:뮐러 리하르트, 슈베르트페거；옥세노 올레핀케미 게엠베하；
    IPC主号:
    专利说明:

    Method for preparing vinyl ester from butene oligomers {Method for the preparation of vinylester from buteneoligomer}
    The present invention relates to a process for the production of vinyl esters based on butene oligomers, in particular based on dibutene and tributene and the use of vinyl esters.
    Vinyl esters of tertiary carboxylic acids have long been established in the industry as comonomers, especially as internal softeners for the production of environmentally friendly water dispersible lacquers and pigments based on vinyl acetate. This ester, in addition to acting as a softener, imparts further advantageous properties to the comonomer, such as high satisfactory stability which makes it suitable for use under conditions of such comonomers. For example, mention may be made of exterior paint and insulating cob of a building.
    The softener properties of the vinyl esters, especially of tertiary carboxylic acids, depend on their chain length and the type and position of the branching portions. It is the glass transition point of the corresponding homopolymer (single polymer) that is a measure of the internal softness of the copolymer. Comparing the softness of vinyl esters of different chain lengths by the glass transition point (Tg) of the various homopolymers, the results show that the softness depends on the molar mass and degree of branching.
    Chain length of carboxylic acid Linear vinyl ester Glass transition temperature [℃] Tertiary vinyl ester Glass transition temperature [℃] C 2 -vinyl ester Vinyl acetate +38 (33) * C 3 -vinyl ester Vinyl propionate -7 (-7) * C 4 -vinyl ester Vinyl butyrate -5 C 5 -vinyl ester -15 *** 2,2-dimethylpropanoic acid 86 (70) *C 6 -vinyl ester Vinyl hexanoate -20 2,2-dimethylbutanoic acid 41 **C 10 -vinyl ester Vinyl decanoate -60 C 12 -vinyl ester Vinyl laurate -75 (-53) * (Encyclopedia of Polymer Science and Engineering, Vol. 17, S. 439 (1989), J. Wiley & Sons. Inc.), * Ullmann's Encyclopedia of Industrial Chemistry, Vol. A22, S. 2, 5 Ed. (1993) ), Verlag Chemie), (** CEL Feeder, Surface Coating Austral 228, 1985), 8, 5. 11-16, (*** Self-Measurement)
    These values are only suitable as comparative data between each other because they may vary depending on the preparation method and the test method of the sample. However, it has been shown that the softener properties improve with increasing chain length of the vinyl esters up to alkyl residues having 12 carbon atoms in the case of linear chains. Vinyl esters, especially from linear carboxylic acids, have very good softener properties but are less suitable for many applications because they can be easily subtracted.
    Vinyl esters of tertiary carboxylic acids, on the other hand, can be used in various ways because of their high sensitivity, temperature, and oxidation stability. Tertiary branching, of course, significantly lowers the softener action, but further branching in the chain prevents further deterioration, as can be seen in the following homopolymer of the vinyl ester of tertiary-C 9 -carboxylic acid.
    Tertiary C 9 -carboxylic acid Glass transition temperature [℃] 2,3-dimethyl-2-isopropyl-butanoic acid 119 2-Ethyl-2,3,3-trimethyl-butanoic acid 115 2,2,3,3-tetramethyl-pentanoic acid 91 (VeoVa 9, Shell) 70 (60) *2,4,4-tetramethyl-pentanoic acid 55 2,2,4-trimethyl-hexanoic acid 10 (HPH Scholten, J. Vermeulen, WJ van Westrenen, "Recent Development in Laticesbased on Viny Esters of branched Monocarboxylic Acids", International Conference on "Water-borne Coatings 7, 26-28. 10.98, Penta Hotel, London), (* W. Lau, VeoVa Vinyl Ester Monomer Polymers.com Magazine, Vol. 2, Nr. 2, Feb. 1996)
    Today, mainly vinyl esters made from isomeric mixtures of tertiary C 10 -carboxylic acids which form homopolymers with a glass transition temperature of -3 ° C are used industrially. Such mixtures are very suitable and in demand for use, for example, for internal softening of polyvinyl acetate while simultaneously increasing the sag stability.
    The C 10 -carboxylic acids themselves used in the preparation of the vinyl esters are prepared by contacting carbon monoxide and water with tripropene (hydrocarboxylation, in particular the so-called KOCH-reaction) under pressure and catalyzed by an extremely acidic catalyst.
    Tripropene, eventually a mixture of isomer C 9 -olefins, is obtained in a mixture with other olefin fractions (C 6- , C 12- , C 13 -olefins) by oligomerizing propene with an acidic catalyst. As the catalyst, for example, acidic zeolite or phosphoric acid on a solid carrier can be considered.
    C 10 - is a point defect that in the production method of a vinyl ester of a carboxylic acid, a relatively expensive raw material with propene demand. In addition, in the case of acidic catalytic oligomerization, apparent raw material loss due to by-product generation must be taken into account. Finally, it can be pointed out that the analyte fraction is already high in the tripropene fraction in the oligomer, making it difficult to control the assay itself. When converted to carboxylic acids, a large number of isomers are eventually produced, resulting in product mixtures that are difficult to define.
    Vinyl esters of tertiary carboxylic acids with more than 10 carbon atoms have been studied in part (eg WO 95/22353). This vinyl ester has on average an emollient action as can be expected based on its long carbon chain. On the one hand, however, the necessary raw materials are often not fully available at reasonable prices and on the other hand, the so-called incompatibility in the copolymer increases as the chain length increases.
    Vinyl esters of tertiary carboxylic acids having less than 10 carbon atoms are also known in part and their suitability as softeners has been studied. So based on pivalinic acid (a kind of tertiary C 5 -acid) and also tertiary C 9 -acid (VeoVa Vinyl esters based on) have a certain technical meaning, in both cases the main concern is the curable comonomer compared to vinyl acetate.
    Thus, there is a need to develop propene for preparing vinyl esters and other raw material sources as oligomers thereof, for example having the same or better properties as vinyl esters of C 10 -carboxylic acids based on tripropene.
    It has surprisingly been found that tertiary carboxylic acids prepared from butene oligomers are excellently suitable as emollients.
    Therefore, the object of the present invention,
    a) oligomerizing butenes,
    b) separating the butene oligomer from the oligomer water,
    c) converting the butene oligomers to carboxylic acids as long as carbon atoms,
    d) a process for the conversion of vinyl esters which converts carboxylic acids to the corresponding vinyl esters.
    Vinyl esters prepared according to the process of the invention are excellently suitable as comonomers for the production of internal softening polymers. For example, copolymerization of C 9 -carboxylic acid vinyl esters with vinyl chloride or copolymerization with vinyl acetate may be mentioned. Trimers with acrylates are also potential applications. The fraction of vinyl esters prepared according to the invention can vary over a wide range depending on the desired physical properties. It also includes, for example, the use of esters thereof as homopolymers in the manufacture of flexible films.
    The process according to the invention first oligomerizes butenes, in which mainly dibutene (C 8 -olefins) is produced. Tributene (C 12 -olefin) and tetrabutene (C 16 -olefin) are also formed by trimerization and tetramerization of butenes. In this case, all industrial C 4 -olefin streams such as, for example, pyrolysis-C 4 , C 4 -olefins from the Fischer Trophy method, dehydrogenation of butane or C 4 -olefins from other industrial processes Can be used as
    Thus, in the process according to the invention, di-, tri-, tetrabutene or higher higher oligomers can be used as butene oligomers. Separation of the butene oligomers from the oligomeric water can be done technically simply and by distillation with high purity.
    The method of the present invention de-butene and the corresponding C 9 which - as well as the manufacture of a carboxylic acid vinyl ester tree-butene and the corresponding C 13 to - - C 9 from the acid C 13 from the acid-also be used to produce a carboxylic acid vinyl ester to be used Can be.
    In order to obtain slightly branched vinyl esters, it is obvious that such raw materials which are generally high in linear C 4 -stream, i.e., n-butene components, should be used for oligomerization.
    Typically, butadiene is first separated from crude decomposition-C 4 by extraction or converted to linear butene by selective hydrogenation. Selective hydrogenation is not necessary in this case but it is of particular advantage since doing so can significantly increase the content of n-butene for oligomerization. In both cases the butadiene removed C 4 -fragment is obtained as raffinate (extract residue) I. In the next step, isobutene can be separated from the C 4 -stream, for example by the production of methyl-tert-butylether (MTBE) by reaction with methanol. MTBE is a fuel component of overdemand. Another possible method is to react isobutene from raffinate I with water to convert it to TBA (tert-butanol) or to produce diisobutene by oligomerization of isobutene with an acidic catalyst. Raffinate II, now an isobutene removed C 4 -fragment, contains only 1-butene and 2-butene as desired. Alternatively 1-butene can also be obtained distillatively, wherein the 1-butene removed fragment is named raffinate III.
    Simple distillative separation of isobutene from C 4 -fragments with the following further treatment is not normally possible because 1-butene and isobutene have almost the same boiling point. However, distillation separation of 2-butene and isobutene is possible. Thus, when 1-butene is hydrogenated isomerized to convert to 2-butene, simple distillation separation of isobutene can successfully yield a C 4 -stream containing only linear butenes.
    Raffinate II or III is preferably used to oligomerize butene to dibutene. If the stream does not contain other unsaturated compounds other than linear butenes, other industrial C 4 -streams may be used. Particularly preferred raw materials used for butene oligomerization are n-butenes, since the vinyl esters of tertiary carboxylic acids produced therefrom have better softening properties as evidenced by the examples.
    Of course, where the softening action of vinyl esters is not critical or rather a curing action is desired, an isobutene containing C 4 -stream can be used wherein the preferred starting material is raffinate I.
    By the process of the present invention, with the existing industrial C 4 -streams which have so far been rarely used chemically, economical raw materials can be used for the production of vinyl esters.
    It is known in principle to oligomerize a butene containing C 4 -stream into a mixture containing C 8- , C 12 -and higher olefins. There are three ways in principle.
    Oligomerization using acidic catalysts has long been known, industrially for example, zeolites or phosphoric acid supported on carriers are used. In this case, an isomer mixture of branched olefins is obtained. Even under optimization conditions dimethylhexene is the main product [WO 92/13818].
    As shown in the examples, the C 8 -olefins separated at this time can be converted to the corresponding carboxylic acid and vinyl esters thereof. However, only homopolymers with high glass transition temperatures are also obtained, thus also having poor softening or rather comonomers having curability.
    The method, which is also carried out worldwide, is known as the DIMERSOL-method (s. Yves Chauvin, Helene Olivier; "Applied Homogeneous Catalysis with Organometallic Compounds", Boy Cornils, Wolfgang A. Hermann; Verlag Chemie, 1996, 258-268). Oligomerization by Nickel-Compound Compounds Vinyl esters of C 9 -carboxylic acids prepared from de C 8 -fractions have a distinctly softening effect than the vinyl esters produced by the process (see Examples).
    Finally, oligomerization using a nickel solid layer catalyst by the method of OXENO GmbH is also mentioned. This method is described in Hydrocarbon Process, Int. (1986) 65 (2, Sect. 1, 31-33), are described in the OCTOL process introduction, tertiary carboxylic acids prepared therefrom can be converted to vinyl esters which cause particularly good internal softening in the copolymer. have.
    The use of butene oligomers, in particular dibutene and tributene, in vinyl esters yields a series of notable advantages: inexpensive industrial applications such as raffinate II, raffinate III or other C 4 -olefin containing raw materials as starting materials. C 8 -streams may be used. Fragments containing virtually only n-butane as oligopolymerizable components, such as raffinate II or raffinate III, can be suitably used for the preparation of comonomers for internal softening. Particularly surprising and unexpected was the softening action of the vinyl esters produced according to the invention, based on the C 9 -carboxylic acids obtained from dibutene, when copolymerizing with vinyl acetate or vinyl chloride, giving a standard based on tripropene. At least equivalent to the substance. Further improvements can be obtained with similarly prepared tributene based vinyl esters.
    In the process according to the invention, the butane oligomer is separated from the oligomerization product and converted to a carboxylic acid corresponding to the carbon atom length. This is done by acid catalyzed hydrocarboxylation (KOCH-reaction) or hydroformylation and then by oxidation of the oxoaldehyde thus obtained. KOCH-synthesis, such as described in Falbe, "New Synthesis with Carbon Monooxide", Spring Verlag, Berlin 1980, p. 372, may be the preferred method in practice. In this case, the olefin is reacted with carbon monoxide to convert to tertiary carboxylic acid in the presence of a strong acid such as sulfuric acid or boron fluoride hydrate. By the use of Cu + as a cocatalyst, the reaction occurs early at standard pressure and at ambient temperature [Y. Souma, H. Sano; Bull. Chem. Soc. Jpn. 1974, 17, 1717.
    The carboxylic acid thus obtained is then converted to the corresponding vinyl ester. This reaction is carried out, for example, by reacting the carboxylic acid with acetylene in the presence of a zinc salt of the acid to be vinylated at standard pressure and 200-250 ° C. [eg Encyl. Polym. Sci. Eng. 17, S., 426-434].
    Alternatively, the vinyl esters can be transesterified with additional vinyl esters such as acetic acid vinyl esters or propionic acid vinyl esters [eg, Ullmann, 4, Auflage, Band 19, S. 368 ff. ] Can also be obtained.
    The softness of vinyl esters is affected by its branching as already mentioned. Again the branching of the vinyl esters is influenced by the branching of the olefins used. Thus, in a particular embodiment of the invention, dibutene, for example dimethylhexene, having up to 35% by weight, preferably up to 25% by weight, of multiple branched olefins can be used.
    The vinyl esters produced by the process according to the invention can be used as polymerization comonomers in polymerization reactions, for example in the production of polyvinyl acetates, where such vinyl acetates cause internal softening while simultaneously increasing hydrolytic stability. . Copolymerization with ethylene or preparation of tetramers with acrylates is a further use of the use of vinyl esters prepared according to the invention as comonomers for internal softening.
    The following examples will illustrate the invention in detail without limiting its scope.
    Examples 1 to 3
    In the following, typical compositions of dibutene resulting from three different oligomerization methods from n-butene are shown. It can be seen that the product composition largely depends only on the oligomerization method. For example, raffinate II or raffinate III or other n butene containing streams can be used unless they contain large amounts of branched butenes. Raffinate III is used as a raw material for the following examples.
    Dibutene obtained by oligomerizing raffinate III in olefin A montmorillonite (acid catalysis).
    Dibutene obtained by oligomerizing Raffinate III according to the Olefin B DIMRESOL-method.
    Dibutene obtained by oligomerizing raffinate III according to the Olefin C OCTOL-method.
    Example 1Example 2Example 3Olefin AOlefin BOlefin C n-octene～ 0%～ 6%～ 13% 3-methyl-heptene～ 5%~ 59%～ 62% 3,4-dimethyl-hexene～ 70%～ 34%～ 24% Other C 8 -olefins～ 25%-1%-1% The linear and extremely simply branched olefin content is about 5% in olefin A, about 65% in olefin B and also about 75% in olefin C. All indications are in weight percent.
    Examples 4-6
    Tertiary carboxylic acids are prepared from olefins A, B and C according to DE 23 39 947. As the catalyst, a complex compound consisting of boron-fluoride and water was used, and Cu + was used as the cocatalyst. The reaction conversion is carried out in a stirred autoclave at a temperature of 20 to 35 ° C. and a CO-pressure of 30 bar. And olefin is added uniformly over the period of 6 hours. The pressure is kept constant by supplemental supply of CO. The reaction is terminated as soon as CO consumption is no longer observed.
    After removal of the catalyst layer, washing with water and distillatively finishing the crude carboxylic acid, several sets of products of the following composition are obtained (value in mass%).
    Example 4Example 5Example 6 Isomers of C 9 -carboxylic AcidMountain AMountain BMountain C 2,2-dimethyl-heptanoic acid0.5%6.5%7.4% 2-Methyl-2-ethyl-hexanoic acid3.7%48.1%55.2% 2-Methyl-2-propyl-pentanoic acid0.5%6.3%7.2% 2,2-diethyl-pentanoic acid0.2%3.0%3.5% 2,2,5-trimethyl-hexanoic acid2.1%1.1%0.8% 2,2,4-trimethyl-hexanoic acid2.0%1.0%0.8% 2,4-dimethyl-2-ethyl-pentanoic acid4.4%2.2%1.6% 2,2,3-trimethyl-hexanoic acid6.4%3.2%2.4% 2-Methyl-2-isopropyl-pentanoic acid13.7%6.9%5.1% 2,3-dimethyl-2-ethyl-pentanoic acid37.5%19.0%13.8% 2-Ethyl-2-isopropyl-butanoic acid3.0%1.5%1.1% Other unknown mountain25.8%1.2%1.3%
    Examples 7-9
    The mixture of tertiary carboxylic acids obtained in Examples 4 to 6 was reacted with acetylene according to the following formula at a standard pressure and a temperature of 190 to 220 ° C. in the presence of a zinc salt of the acid to be converted.
    R-COOH + HC≡CH → R-COO-CH = CH 2
    The reaction is carried out according to G. Hubner, Fette, Seifen, Anstrichmittel, 68 (4), S. 290-292 (1966).
    After distillation of the crude product, a vinyl ester having a purity of at least 99.8% is obtained, and the vinyl ester is subjected to a gas chromatography test and has a degree of branching comparable to or substantially equivalent to that of carboxylic acid. The vinyl ester thus obtained is hereinafter referred to as vinyl ester A (basic acid A, Example 7), vinyl ester B (basic acid B, Example 8), and vinyl ester C (basic acid C, Example 9).
    Examples 10 to 14.
    Homopolymers are prepared from the vinyl esters according to Examples 7-9 according to standard methods (Examples 12-14) and the glass transition temperature is measured as a measure of suitability as copolymer for internal softening.
    Used raw materials
    MonomerParts by weight Vinyl ester of C 9 -carboxylic acid100.00 AwardsVE-number70.00 Anionic detergents for example Marlon A 390 (85% active ingredient)0.03 Nonionic detergents such as Marlophen 820 (25% solution)8.00 Potassium persulfate (K 2 S 2 O 8 )0.10 Potassium carbonate0.25 Hydroxyethylcellulose, for example Natrosol 250 L (or LR)2.00 Acetic acid (100%)0.20 Initiator solutionPotassium persulfate0.23 VE-number12.00
    Conduct method
    About 10% of the aqueous phase and monomers are heated to 75 ° C. under stirring. After 15 minutes at this temperature the remaining monomer and initiator solution are added in separate streams. The monomer is added evenly for 120 minutes and the starting solution is added for 135 minutes. The temperature during addition is maintained at 75 to 80 ° C. After stirring for an additional 120 minutes at the same temperature, the whole is cooled to room temperature. From the resulting emulsion, if necessary, a molded body is produced after filtration, and the glass transition point is measured from the molded body by torsional vibration analysis (by DIN 53445).
    In addition, to ensure the comparability of the test procedure, two commercial vinyl esters having known glass transition points are measured by the above procedure. One of them is, for example, tertiary C 10 -acid (VeoVa, which is widely used as an internal softener for vinyl acetate. 10, basic tripropene, and the vinyl ester of Comparative Example 10). The other is Class 3 C 9 -San (VeoVa 9, the commercially available vinyl esters from Comparative Example 11) resulted in the use of vinyl esters having the same degree of branching as the overall formula but with different vinyl esters prepared according to the previous examples.
    The following data were measured:
    Example 10Example 11Example 12Example 13Example 14 Raw material(Comparative Example)(Comparative Example)From mountain AFrom mountain BFrom mountain C Glass transition point-3 ℃～ + 60 ℃～ + 38 ℃+ 1 ℃-3 ℃
    Thus, vinyl ester A based on oligomerized butene using acidic catalysts is a hard comonomer. Vinyl ester B from oligomerized butenes according to the Dimersol method is clearly a softening comonomer. With vinyl esters prepared from dibutene according to the Octol method a good softening action can be achieved and is equivalent to a comparative product based on basic tripropene (Comparative Example 10). Note the comparison between Example 11 and Example 14. In both cases tertiary carboxylic acids of 9 carbon atoms with the same general formula are used. However, Example 14 of the vinyl esters prepared according to the present invention achieves excellent softening, while Comparative Example 11 shows obvious hard comonomers.
    Example 15
    Raffinate III is oligomerized by Octol-method. Tributene was separated from the oligomer and a C 13 -carboxylic acid mixture was prepared by Koch-synthesis (similar to Examples 4-6). This mixture is reacted as described in Examples 7-9 to convert to vinyl esters corresponding to acetylene. A homopolymer is prepared from the vinyl ester mixture thus obtained in analogy to the methods of Examples 10-14 with a glass transition point of -13 ° C. Vinyl esters of C 13 -carboxylic acids based on tributene thus have a clearly good function despite the high degree of branching.
    The present invention provides propene and other raw materials as oligomers thereof for the production of vinyl esters, which have the same or better emollient properties compared to the vinyl esters of C 10 -carboxylic acids based on conventional tripropene and which can be used inexpensive. Provide a source.
    权利要求:
    Claims (13)
    [1" claim-type="Currently amended] a) oligomerizing butenes,
    b) separating the butene oligomer from the oligomer water,
    c) converting the butene oligomers to carboxylic acids as long as the number of carbon atoms,
    d) a process for producing a vinyl ester from a butene oligomer, characterized in that the carboxylic acid is converted into the corresponding vinyl ester.
    [2" claim-type="Currently amended] The process of claim 1 wherein the conversion of the butene oligomers to carboxylic acids as long as the number of carbon atoms is carried out by acidic catalytic hydrocarboxylation.
    [3" claim-type="Currently amended] The process according to claim 1, wherein the conversion of the butene oligomers to carboxylic acids as long as the number of carbon atoms is carried out by hydroformylation followed by oxidation of the aldehyde thus obtained.
    [4" claim-type="Currently amended] The process according to claim 1, wherein the vinyl ester is obtained by reacting a carboxylic acid with acetylene.
    [5" claim-type="Currently amended] 5. Process according to claim 4, wherein the vinyl ester is obtained by reacting the carboxylic acid with acetylene in the presence of a zinc salt of carboxylic acid.
    [6" claim-type="Currently amended] The process according to claim 1, wherein the vinyl esters are obtained by transesterifying further vinyl esters with carboxylic acids.
    [7" claim-type="Currently amended] 7. The process of claim 6 wherein the further vinyl ester is acetic acid vinyl ester or propionic acid vinyl ester.
    [8" claim-type="Currently amended] 8. The process according to claim 1, wherein the butene oligomer is dibutene and is reaction converted to C 9 -carboxylic acid and the corresponding vinyl ester. 9 .
    [9" claim-type="Currently amended] The process according to claim 1, wherein the butene oligomer is tributene and is reaction converted to C 13 -carboxylic acid and the corresponding vinyl ester.
    [10" claim-type="Currently amended] The process according to claim 1, wherein the dibutene contains up to 35% by weight of branched olefins.
    [11" claim-type="Currently amended] The process of claim 10 wherein the dibutene contains up to 25 weight percent branched olefins.
    [12" claim-type="Currently amended] Use as a comonomer in the polymerization of vinyl esters prepared according to any one of claims 1 to 11.
    [13" claim-type="Currently amended] Use of the vinyl esters prepared according to claim 1 as an emollient.
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    同族专利:
    公开号 | 公开日
    ES2204373T3|2004-05-01|
    NO20000872D0|2000-02-22|
    CA2299587A1|2000-08-26|
    DE19908320A1|2000-08-31|
    HK1031866A1|2005-09-09|
    PL338630A1|2000-08-28|
    NO20000872L|2000-08-28|
    EP1033360B1|2003-09-17|
    CN1269352A|2000-10-11|
    JP2000248017A|2000-09-12|
    ID24863A|2000-08-31|
    JP4681095B2|2011-05-11|
    EP1033360A1|2000-09-06|
    US6281372B1|2001-08-28|
    TW482760B|2002-04-11|
    MY121144A|2005-12-30|
    ZA200000927B|2000-10-16|
    MXPA00001956A|2002-03-08|
    BR0000963A|2000-09-19|
    CN1185203C|2005-01-19|
    KR100673279B1|2007-01-24|
    AR022771A1|2002-09-04|
    SG82685A1|2001-08-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-02-26|Priority to DE19908320A
    1999-02-26|Priority to DE19908320.7
    2000-02-25|Application filed by 뮐러 리하르트, 슈베르트페거, 옥세노 올레핀케미 게엠베하
    2000-09-25|Publication of KR20000058191A
    2004-06-08|First worldwide family litigation filed
    2007-01-24|Application granted
    2007-01-24|Publication of KR100673279B1
    优先权:
    申请号 | 申请日 | 专利标题
    DE19908320A|DE19908320A1|1999-02-26|1999-02-26|Process for the production of vinyl esters from butene oligomers|
    DE19908320.7|1999-02-26|
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