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EP1036105A1 - Preparation de polyesters et d'esters a partir de composes renfermant des groupes hydroxyles secondaires - Google Patents

Preparation de polyesters et d'esters a partir de composes renfermant des groupes hydroxyles secondaires

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Publication number
EP1036105A1
EP1036105A1 EP98961869A EP98961869A EP1036105A1 EP 1036105 A1 EP1036105 A1 EP 1036105A1 EP 98961869 A EP98961869 A EP 98961869A EP 98961869 A EP98961869 A EP 98961869A EP 1036105 A1 EP1036105 A1 EP 1036105A1
Authority
EP
European Patent Office
Prior art keywords
alkyltin
acid
oxide
mixture
process according
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Withdrawn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
EP98961869A
Other languages
German (de)
English (en)
Inventor
James Thomas Tanner, Iii
Angela Hartley Honeycutt
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.)
Eastman Chemical Co
Original Assignee
Eastman Chemical Co
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 Eastman Chemical Co filed Critical Eastman Chemical Co
Publication of EP1036105A1 publication Critical patent/EP1036105A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

Definitions

  • esters and polyesters are prepared in high yield and with improved esterification rates in the presence of at least one C,-C 3 alkyltin catalyst.
  • Esters and polyesters may be prepared by direct esterification or by transesterification reactions. In direct esterification, carboxylic acids are converted into esters by reaction with an alcohol. Similarly, polyesters may be prepared from the direct esterification between dihydridic or polyhydridic alcohols and dicarboxylic or polycarboxylic acids or anhydrides.
  • esters are prepared by reacting monocarboxylic esters with monohydridic alcohols and polyesters are prepared by reacting dicarboxylic esters or polycarboxylic esters with dihydridic or polyhydridic alcohols.
  • the esters and polyesters prepared by either process are useful in molded articles, fibers, coatings, and adhesives.
  • Tin compounds have been used as esterification catalysts in both direct esterification and transesterification reactions to prepare esters and polyesters.
  • U.S. Patent Nos. 2,720,507; 3,162,616; 4,970,288 and 5,166,310 describe the preparation of polyesters in the presence of an organotin catalyst.
  • U.S. Patent Nos. 3,345,333 and 3,716,523 describe the preparation of polyesters in a two-stage process which uses a tin catalyst to increase the efficiency of the process.
  • dialkyltin oxide and dialkyltin dichloride as a catalyst for the transesterification of esters of monocarboxylic acids with 1,2 and 1,3-polyols to prepare a polyol ester is described in U.S. Patent No. 5,498,751. Although the patent teaches that products with high yield and excellent purity are obtained, the process is limited to the transesterification of esters of monocarboxylic acid with 1,2- and 1,3-polyols.
  • U.S. Patent No. 4,554,344 discloses a process for the preparation of polyesters from aromatic dicarboxylic acids or derivatives thereof and diols containing vicinal hydroxyl groups at least one of which is secondary.
  • polyesters prepared from aromatic dicarboxylic acids and diols containing vicinal hydroxyl groups having at least one secondary hydroxyl group typically have relatively low molecular weights.
  • the low molecular weights severely limit their usefulness in the manufacture of molded articles, fibers, coatings and other shaped articles.
  • the inherent viscosity and molecular weight of the polyester prepared from aromatic dicarboxylic acid and diols containing vicinal hydroxyl groups are greatly increased by using a tin catalyst.
  • the tin catalysts include both inorganic and organic tin compounds with butylstannoic acid being particularly preferred.
  • esters and polyesters can be prepared in high yield and with improved esterification rates from polyols containing at least one secondary hydroxyl group when the esterification process is conducted in the presence of at least one Cj-C 3 alkyltin catalyst.
  • the invention relates to an improved process for the preparation of a polyester from polyols having secondary hydroxyl groups.
  • the process reacts at least one polyol containing at least one secondary hydroxyl group with at least one polycarboxyl compound in the presence of at least one C r C 3 alkyltin catalyst.
  • the C r C 3 alkyltin catalyst is selected from a C r C 3 alkyltin salt of a carboxylic acid, a C,-C 3 alkylstannoic acid, a C r C 3 alkyltin oxide, a C,-C 3 alkyltin halide and mixtures thereof.
  • the invention in another embodiment relates to a process for the preparation of an ester from a secondary alcohol comprising reacting at least one secondary alcohol with at least one carboxyl compound in the presence of at least one C r C 3 alkyltin catalyst as described above.
  • the process of the invention can be used for the preparation of a linear high molecular weight polyester useful in molding and fiber applications.
  • Polyesters prepared by a process of the invention may also be used as precursors in the preparation of lower molecular weight carboxylic or hydroxyl functional polyesters.
  • the carboxylic and hydroxyl functional polyesters may be linear or optionally branched by addition of a trifunctional or polyfunctional hydroxyl or carboxyl compound.
  • polyesters prepared according to the invention are also useful in coatings and adhesive applications.
  • Figure 1 is a plot of acid number vs. time showing the effect of organotin compounds on processing IPA/AD/TMP/TMPD high solids polyester resins in the final four hours of polyesterification.
  • Figure 2 is a plot of natural log of acid concentration (Ln [acid]) vs. time showing the effect of organotin compounds on precessing IPA/AD/TMP/TMPD high solids polyester resin in the final four hours of polyesterification.
  • Figure 3 is a plot of acid number vs. time showing the effect of organotin compounds on processing IPA/AD/TMP/PG high solids polyester resins in the final three hours of polyesterification.
  • Figure 4 is a plot of natural log of acid concentration (Ln [acid]) vs. time showing the effect of organotin compounds on precessing IPA AD/TMP/PG high solids polyester resins in the final three hours of polyesterification.
  • Figure 5 is a plot of acid number vs. time showing effect of organotin compounds on processing IPA AD/TMP/NPG polyester resin in the final four hours of polyesterification.
  • Figure 6 is a plot of acid number vs. time showing effect of organotin compounds on processing IPA AD/TMP/BEPD polyester resin in the final two hours of polyesterification.
  • the invention relates to a process for preparing a polyester comprising reacting at least one polyol having at least one secondary hydroxyl group and at least one polycarboxyl compound in the presence of a catalytically effective amount of at least one C,-C 3 alkyltin catalyst selected from a C r C 3 alkyltin salt of a carboxylic acid, a C,-C 3 alkylstannoic acid, a C ⁇ C 3 alkyltin oxide, a C r C 3 alkyltin halide and mixtures thereof.
  • a catalytically effective amount of at least one C,-C 3 alkyltin catalyst selected from a C r C 3 alkyltin salt of a carboxylic acid, a C,-C 3 alkylstannoic acid, a C ⁇ C 3 alkyltin oxide, a C r C 3 alkyltin halide and mixtures thereof.
  • the polyol compound employed in the process of the invention contains at least one 5 secondary hydroxyl group and preferably from about 2 to about 40 carbon atoms, more preferably from about 3 to about 26 carbon atoms.
  • Suitable polyols include triols such as 1,2,3-trihydroxypropane (glycerol); 1,2,4-butanetriol; 1,2,6-trihydroxyhexane; and 1,3,5- cyclohexanetriol.
  • the preferred polyol employed in the invention is a diol containing from about 3 to about 20 carbon atoms, preferably from about 3 to about 8 carbon atoms. Suitable
  • diols may be aliphatic, cycloaliphatic or aromatic, and may or may not contain unsaturation. Examples include, but are not limited to 1,2-propanediol, 1,2-butanediol, 1,4- cyclohexanediol, 2,2,4,4-tetramethylcyclobutanediol, 2,2,4-trimethyl-l,3-pentanediol or mixtures thereof. Particularly suitable diols include 2,2,4-trimethyl-l,3-pentanediol, 1,2- propanediol, and 2,2,4,4-tetramethylcyclobutanediol.
  • Polyesters containing both secondary and primary polyols may also be prepared by the process of the invention.
  • Polyols without secondary hydroxyl groups suitable for use in the invention include aliphatic, cycloaliphatic or aromatic polyols which can be either saturated or unsaturated and contain from about 2 to about 40 carbon atoms.
  • the polyol is a diol containing from about 2 to about 20, more preferably from about 2 to about
  • Such diols include, but are not limited to, ethylene glycol, 1-4-butanediol, 1,3-butanediol, pentanediol, hexanediol, heptanediol, neopentyl glycol, nonanediol, decanediol, diethylene glycol, dipropylene glycol, cycohexanedimethanol, 2-methyl-l,3-propanediol and mixtures thereof.
  • the preferred diols containing both primary hydroxyl groups include neopentyl glycol,
  • the polycarboxyl compound may be aliphatic, cycloaliphatic or aromatic and may or may not contain unsaturation. Also suitable are the anhydrides and lower, e.g.,C r C g alkyl esters thereof. Suitable aromatic polycarboxyl compounds may be derived from single ring, multiple ring and fused ring system compounds.
  • the carboxylic acid groups may be directly
  • aromatic polycarboxyl compounds preferably contain from about 7 to about 20, more preferably from about 8 to about 12 carbon atoms.
  • the aliphatic and cycloaliphatic polycarboxyl compounds may be derived from saturated, monounsaturated and polyunsaturated carboxylic acids. These acids may be straight or branched and may be substituted with one or more of the groups listed above as being suitable for aromatic ring substitution.
  • the aliphatic and cycloaliphatic carboxyl compounds preferably contain from about 2 to about 40, more preferably from about 3 to about 26 carbon atoms.
  • suitable polycarboxyl compounds include 1,2,4-benzenetricarboxylic anhydride (trimellitic anhydride); 1,2,4-benzenetricarboxylic acid (trimellitic acid); and 1,3,5-cyclohexanetricarboxylic acid.
  • Preferred polycarboxyl compounds are dicarboxyl compounds.
  • suitable dicarboxyl compounds include, but are not limited to, terephthalic acid, isophthalic acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, dimethylterephthalate, phthalic anhydride, maleic anhydride and mixtures thereof.
  • Particularly suitable dicarboxyl containing compounds include terephthalic acid, isophthalic acid and adipic acid.
  • the mole ratio of polyol to polycarboxyl compound can be varied over a wide range.
  • the preferred mole ratio ranges from about 0.5 to about 1.5, more preferably from about 0.8 to about 1.2.
  • the C r C 3 alkyltin catalyst employed in the invention may be a C r C 3 alkyltin salt of a carboxylic acid represented by the formula (R) 2 Sn(O 2 CR') 2 , RSn(O 2 CR 1 ) 3 , or (R) 2 Sn(O 2 CR 1 )Y.
  • the R group may be the same or different and is an alkyl group having from about 1 to about 3 carbon atoms, preferably 1 carbon atom.
  • R 1 may be the same or different and is an alkyl group having from about 1 to about 20 carbon atoms which may be linear, branched, substituted or unsubstituted. Preferably R 1 contains from about 1 to about 12, more preferably from about 1 to about 8 carbon atoms. R 1 may also be an aryl group such as phenyl or naphthyl, an alkaryl group such as tolyl or phenylethyl or a cycloalkyl group such as cyclohexyl. Preferred aryl, alkaryl and cycloalkyl groups contain from about 3 to about 14 carbon atoms. Y is a halogen, preferably bromine or chlorine.
  • organotin salts of carboxylic acids include, but are not limited to, dimethyltin diacetate, diethyltin diacetate, dipropyltin diacetate, dimethyltin dilaurate, methyltin trilaurate, ethyltin trilaurate, propyltin trilaurate and mixtures thereof.
  • a C r C 3 alkylstannoic acid of the formula RSn(O)OH may also be employed as the C,-C 3 alkyltin catalyst.
  • the R group is as defined above.
  • suitable C,-C 3 alkylstannoic acids include, but are not limited to methylstannoic acid, propylstannoic acid, ethylstannoic acid and mixtures thereof.
  • the C r C 3 alkyltin catalysts may also be an C,-C 3 alkyltin oxide of the formula (R) 2 SnO.
  • R may be the same or different and is as defined above.
  • suitable C r C 3 alkyltin oxides include, but are not limited to dimethyltin oxide, diethyltin oxide, dipropyltin oxide, methylethyltin oxide, methylpropyltin oxide, ethylpropyltm oxide and mixtures thereof.
  • Preferred C,-C 3 alkyltin oxides for use in the process of the invention include dimethyltin oxide, dimethyltin dilaurate and methylstannoic acid.
  • the oxides can be generated in situ by hydrolyzing an appropriate C r C 3 alkyltin halide with a base such as ammonium hydroxide. Suitable C r C 3 alkyltin halides are described below.
  • the C ⁇ -C 3 alkyltin catalysts useful in the process of the present invention also include C r C 3 alkyltin halides of the formula (R) n Sn(X) 3 _ n wherein R may be same or different and is as defined above; n is 1 or 2; and X is a halide, preferably chloride or fluoride.
  • Examples of suitable C r C 3 alkyltin halides include methyltin trifluoride, dimethyltin dichloride, diethyltin dichloride, dipropyltin dichloride, methylethyltin dichloride, ethylpropyltin dichloride, methylpropyltin dichloride or a mixture thereof.
  • the preferred C,-C 3 alkyltin halide is dimethyltin dichloride. Under certain reaction conditions, however, the use of dichlorides may generate hydrochloric acid.
  • the C,-C 3 alkyltin catalyst used in the process of the invention is present in a catalytically effective amount, preferably ranging from about 0.001 to about 3, more preferably from about 0.01 to about 1.0, and most preferably from about 0.05 to about 0.2 weight percent based upon the weight of the reactants (based on % tin in the C C 3 alkyltin catalyst).
  • the processes of the invention are conducted under conditions sufficient to form the desired polyester.
  • the temperature and pressure should be maintained such that the water of esterification or alcohol of transesterification are removed to give maximum reaction rate and allow the reaction to proceed to completion.
  • the process of the invention may be conducted as a melt of the polyol and the polycarboxyl compound under inert or nonoxidizing atmosphere using conventional polyester-forming conditions of temperature, pressure and time.
  • the temperature of the reaction varies depending on the reactants and the desired properties of the polyester. Preferably the temperature ranges from about 160°C to about 280°C, more preferably from about 180 °C to about 250 °C. Temperatures below about 150 °C are generally not sufficient to provide sufficient rate of reaction.
  • the pressure at which the reaction is carried out also varies depending on the reactants and the properties of the polyester desired. In general, the pressure ranges from about 700 mm Hg to about 1,500 mm Hg. If higher molecular weight polyesters are desired the reaction should be finished at lower pressures. Depending on the molecular weight desired, the pressure of the reaction ranges from about 100 mm Hg to below about lO m Hg.
  • Suitable solvents include, but are not limited to aromatic hydrocarbons, ethers, sulfones, halogenated aromatic hydrocarbons, ketones, sulfolanes, sulfoxides and combination thereof. Particularly suitable solvents include toluene, xylene, diphenyl ether, dimethyl sulfolane and combinations thereof.
  • the solvent may be a solvent for the reactants, products or both.
  • the solvents can be employed in amounts ranging from about 40 to about 95, preferably from about 45 to about 90, more preferably from about 50 to about 90 percent based on the weight of the reactants.
  • monofunctional compounds may be incorporated into the reaction mixture.
  • Suitable monofunctional reactants include, but are not limited to benzoic acid, tert-butylbenzoic acid, phenylbenzoic acid, stearic acid, tert- butylbenzoic acid, phenylbenzoic acid, stearic acid, tert-butylphenol, benzyl alcohol or combinations thereof.
  • the monofunctional compounds are present in amounts ranging from about 0.01 to about 10, preferably from about 1 to about 8, more preferably from about 2 to about 5 weight percent based upon the total weight of reactants.
  • the polyester prepared by the process of the invention can be used as precursors in the preparation of a lower molecular weight carboxylic or hydroxyl functional polyester which may be linear or optionally branched by the addition of a trifunctional or polyfunctional branching agent as described above.
  • a chain branching agent include tri- or poly- functional reactants.
  • the tri- or poly-functional reactant can be either hydroxyl, acid or anhydride functional.
  • Particularly suitable tri- or poly- functional reactants include but are not limited to trimellitic anhydride, trimethylolpropane, glycerine, triethylolpropane and pentaerythritol and combinations thereof.
  • the polyfunctional compounds when desired, are employed in amounts ranging from about 0.01 to about 10, preferably from about 0.1 to about 7, more preferably from about 0.1 to about 5 weight percent based upon the total weight of reactants. These polyesters are useful in coating and adhesive applications. Accordingly, the invention also relates to materials such as metals, paper and paperboard, and synthetic polymers having coated thereon one or more of the polyester compositions described above.
  • the C r C 3 alkyltin compounds, discussed above, may also be used as catalysts in simple esterification and transesterification reactions.
  • another embodiment of the invention relates to a method for the preparation of esters comprising reacting a carboxyl compound and a secondary alcohol in the presence of a catalytically effective amount of at least one C,-C 3 alkyltin catalyst.
  • the secondary alcohols employed in the process of the invention preferably contain from about 2 to about 40 carbon atoms.
  • the preferred alcohol contains from about 3 to about 20 carbon atoms, preferably from about 3 to about 8 carbon atoms.
  • suitable secondary alcohols include 2-propanol, 2-butanol, cyclohexanol and cyclohexylmethanol.
  • the ester prepared by the process of the invention may contain a mixture of secondary alcohols and primary alcohols without a secondary hydroxyl group.
  • the carboxyl compound used for preparing esters may be aliphatic, cycloaliphatic or aromatic and may or may not contain unsaturation. Also suitable are the anhydrides and lower, e.g.,C r C g alkyl esters thereof. Suitable aromatic carboxyl compounds may be derived from the same ring system compounds as the polycarboxyl compound described above. The carboxylic acid groups may be directly substituted on an aromatic ring, or part of an alkyl group that is substituted on the ring.
  • aromatic ring may be further substituted with one or more functional groups, e.g., halogen, amino, cyano, nitro, as well as alkyl, alkoxy and alkylthio groups containing from 1 to 20 carbon atoms.
  • the aromatic carboxyl compounds preferably contain from about 7 to about 20, more preferably from about 8 to about 12 carbon atoms.
  • the aliphatic and cycloaliphatic carboxyl compounds may be derived from saturated, monounsaturated and polyunsaturated carboxylic acids. These acids may be straight or branched and may be substituted with one or more of the groups listed above as being suitable for aromatic ring substitution.
  • the aliphatic and cycloaliphatic carboxyl compounds preferably contain from about 2 to about 40, more preferably from about 3 to about 26 carbon atoms.
  • Propionic acid, butyric acid, cyclohexanecarboxylic acid and benzoic acid are particularly preferred carboxyl compounds useful in the simple esterification and transesterification process of the invention.
  • the preferred C,-C 3 alkyltin catalyst for this esterification is the same as described above.
  • the mole ratio of secondary alcohol and carboxyl compound can be varied over a wide range with a 1 :1 mole ratio being particularly preferred. In some cases, however, it may be advantageous to include an excess of secondary alcohol.
  • the reaction may be conducted in a melt or solution.
  • TMPD 2,2,4-Trimethyl-l,3-propanediol
  • TMP Trimethylolpropane
  • IP A isophthalic acid
  • the reaction mixtures were heated to 150 °C at a constant rate of 2 deg/min until all reactants were molten. The reaction mixtures were then heated to 215 °C at a constant rate of 2 deg/min and held at that temperature until an acid number less than 10 was obtained.
  • the relative activities of the three organotin catalysts were determined by monitoring the acid number of the reaction mixtures during the final four hours of polyesterification. The results of acid number vs. time is shown in Table 1 and plotted in Figure 1.
  • dimethyltin oxide gives a two fold increase in esterification rate compared with dibutyltin oxide, and a fifty percent increase in reaction rate compared with butylstannoic acid, thus providing a substantial improvement prior processes.
  • TMP 1,2-Propanediol
  • IP A 1,2-Propanediol (propylene glycol, PG) 232.86 3.06
  • TMP Trimethylolpropane
  • IP A Isophthalic acid
  • the reaction mixtures were heated to 150 °C at a constant rate of 2 deg/min until all reactants were molten. The reaction mixtures were then heated to 190 °C at a constant of 2 deg/min and held at that temperature unit an acid number less than 10 was obtained.
  • the relative activities of the two organotin catalysts were determined by monitoring the acid number of the reaction mixtures during the final three hours of polyesterification. The results of acid number vs. time is shown in Table 3 and plotted in Figure 3.
  • NPG Neopentyl glycol
  • TMP Trimethylolpropane
  • IP A 519.95 3.130
  • AD Adipic acid
  • Organotin catalyst 0.05 wt.% of total charge (based on % Sn in organotin catalyst)
  • the reaction mixtures were heated to 150 °C at a constant rate of 2 deg/min until all reactants were molten. The reaction mixtures were then heated to 230 °C at a constant rate of 2 deg/min and held at that temperature until and acid number less than 10 was obtained.
  • the relative activities of the three organotin catalysts were determined by monitoring the acid number of the reaction mixtures during the final four hours of polyesterification. The results of acid number vs. time is shown in Table 5 and plotted in Figure 5. TABLE 5
  • Organotin catalyst 0.05 wt.% of total charge (based on % Sn in organotin catalyst)
  • the reaction mixtures were heated to 150°C at a constant rate of 2 deg/min until all reactants were molten.
  • the reaction mixtures were then heated to 215 °C at a constant of 2 deg/min and held at that temperature unit an acid number less than 10 was obtained.
  • the relative activities of the two organotin catalysts were determined by monitoring the acid number of the reaction mixtures during the final two hours of polyesterification. The results of acid number vs. time is shown in Table 6 and plotted in Figure 6.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation d'un polyester à partir d'un polyol renfermant un groupe hydroxyle secondaire, ce procédé permettant d'obtenir un rendement élevé et une vitesse d'estérification améliorée. Ce procédé consiste à faire réagir un composé d'un polyol, renfermant au moins un groupe hydroxyle secondaire, avec un composé polycarboxyle, et ce en présence d'au moins un composé d'alkylétain C1-C3, l'alkylétain C1-C3 étant choisi parmi un sel d'alkylétain C1-C3 d'un acide carboxylique, un acide stannique alkyle C1-C3, un oxyde d'alkylétain C1-C3, un halogénure d'alkylétain C1-C3, et un mélange de ceux-ci. Cette invention concerne également des polyesters fabriqué selon le procédé susmentionné, ces polyesters pouvant être utilisés dans des pièces moulées, des fibres, des revêtements, et des formulations adhésives. Ce procédé peut également être utilisé pour préparer un ester à partir d'un alcool secondaire. Dans un autre mode de réalisation, cette invention concerne un procédé de préparation d'esters, ce procédé consistant à faire réagir un composé carboxyle avec un alcool secondaire en présence d'une quantité catalytiquement efficace d'au moins catalyseur d'alkylétain C1-C3, tel que susmentionné.
EP98961869A 1997-12-04 1998-12-03 Preparation de polyesters et d'esters a partir de composes renfermant des groupes hydroxyles secondaires Withdrawn EP1036105A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US98522197A 1997-12-04 1997-12-04
US985221 1997-12-04
PCT/US1998/025578 WO1999028368A1 (fr) 1997-12-04 1998-12-03 Preparation de polyesters et d'esters a partir de composes renfermant des groupes hydroxyles secondaires

Publications (1)

Publication Number Publication Date
EP1036105A1 true EP1036105A1 (fr) 2000-09-20

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EP (1) EP1036105A1 (fr)
JP (1) JP2001525432A (fr)
CN (1) CN1411480A (fr)
BR (1) BR9815362A (fr)
WO (1) WO1999028368A1 (fr)

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BR9815362A (pt) 2000-10-10
JP2001525432A (ja) 2001-12-11
WO1999028368A1 (fr) 1999-06-10
CN1411480A (zh) 2003-04-16

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