EP1537162A1 - Procede de production de copolymeres de tetrahydrofurane - Google Patents

Procede de production de copolymeres de tetrahydrofurane

Info

Publication number
EP1537162A1
EP1537162A1 EP03790835A EP03790835A EP1537162A1 EP 1537162 A1 EP1537162 A1 EP 1537162A1 EP 03790835 A EP03790835 A EP 03790835A EP 03790835 A EP03790835 A EP 03790835A EP 1537162 A1 EP1537162 A1 EP 1537162A1
Authority
EP
European Patent Office
Prior art keywords
hydrocarbon
water
copolymerization
reaction
thf
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Withdrawn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
EP03790835A
Other languages
German (de)
English (en)
Inventor
Martin Haubner
Rolf Pinkos
Alexander Weck
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1537162A1 publication Critical patent/EP1537162A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/20—Tetrahydrofuran
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used

Definitions

  • the present invention relates to a new process for the preparation of polyoxyalkylene glycols (polyalkylene ether glycols) by copolymerization of tetrahydrofuran and alpha, omega-diols in the presence of heteropolyacids and hydrocarbons, in which water is removed directly from the copolymerization as a mixture of the hydrocarbon.
  • Polyoxyalkylene glycols are important raw materials for the production of elastic fibers, elastic construction materials and coatings. They are prepared by polymerizing tetrahydrofuran (hereinafter referred to as "THF") or by copolymerizing THF with oxiranes such as ethylene oxide or propylene oxide or with alpha, omega-diols in the presence of cationic catalysts. It is known, for example, from EP-A 126 471 to use heteropolyacids as catalysts.
  • THF tetrahydrofuran
  • oxiranes such as ethylene oxide or propylene oxide
  • alpha, omega-diols alpha, omega-diols
  • This process makes polyalkylene ether glycols accessible in one stage, while other processes initially give the esters of polyoxyalkylene glycols which have to be hydrolyzed to give the polyoxyalkylene glycols before they can be used in the field of polymers.
  • heteropolyacids When THF is copolymerized with alpha, omega-diols, water of reaction is released.
  • the commercially available heteropolyacids contain 10 to 40 moles of water of crystallization per mole of heteropolyacid. Since water on the one hand negatively influences the catalyst activity and on the other hand acts as chain termination reagents (so-called "telogen"), it is necessary to remove the water of reaction and the water of crystallization from the copolymerization.
  • a batch process for the preparation of THF copolymers with alpha, omega-diols in the presence of a heteropolyacid, in which water is removed, is known from JP-A 10-87811: Part of the copolymerization solution is continuously removed from the polymerization reactor and subjected to a process for water separation. For this purpose, phase separation is first effected in a decanter and the lower phase containing the catalyst is returned to the polymerization reactor. The upper phase obtained is passed into a distillation unit in which the solid boilers are separated off. The bottom discharge, mainly copolymers, is returned to the copolymerization. The mixture is calibrated with suitable adsorption dried and also returned to the polymerization.
  • This discontinuous polymerization stage is very easy, but also complex and costly, since three recirculations (catalyst recycle, prepolymer recycle from evaporation and solvent recycle) are necessary to achieve a steady state. This means that a large number of devices is required.
  • the present invention was therefore based on the object of making the copolymerization of THF with alpha, omega-diols easier and more economical in the presence of heteropolyacids.
  • a way should be found to use polyoxyal--
  • the new process should enable polyoxyalkylene glycols with diol comonomer incorporation rates of 14 to 60% by weight, based on the copolymer.
  • the polyoxyalkylene glycols should also have low color numbers and low residual contamination
  • a mixture is understood to mean a hydrocarbon-water azeotrope in addition to conventional non-azeotropic mixtures.
  • hydrocarbons used are said to be suitable for azeotroping with water.
  • the hydrocarbons are the fresh feed of the copolymerization in an amount of 1 ⁇ 10 ⁇ 4 wt .-% (corresponding to 1 ppm) to 30 wt .-%, based on the fresh feed of alpha, omega-diol and 45 THF, preferably 1 ppm to 16 % By weight, particularly preferably 1 to 10% by weight, is added.
  • the respective molecular weight can be set via the total amount of water which is discharged from the copolymerization. In general, 1 mol of heteropolyacid " binds 10 to 40 molecules of water by coordinative binding.
  • heteropolyacids used as catalysts should contain about 1 to 10 molecules of water per molecule of heteropolyacid.
  • copolymerization with the alpha, omega-used as co-monomer The higher the water content of the copolymer solution, the lower the molecular weight of the copolymer obtained.
  • average molecular weight or “average molecular weight” is understood to mean the number average M n of the molecular weight of the polymers contained in the polymer formed.
  • Alpha, omega-diols such as, for example, C- to Cio-alkanediols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 2-methylbutanediol, 1,4-butanediol, 1,5-pentanediol are used as comonomers.
  • C- to Cio-alkanediols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 2-methylbutanediol, 1,4-butanediol, 1,5-pentanediol are used as comonomers.
  • Mixtures of tetrahydrofuran, 1,4-butanediol and 2-methylbutanediol can also be used, it being possible for the proportion of 2-methylbutanediol in such mixtures to be between 100 ppm and 60% by weight, based on the mixture.
  • 1 to 60% by weight of the alpha, omega-diol, based on the tetrahydrofuran used preferably 2 to 40% by weight, particularly preferably 3 to 20% by weight, are used in the copolymerization.
  • Heteropolyacids which are used according to the invention are inorganic polyacids which, in contrast to isopolyacids, have at least two different central atoms.
  • Heteropolyacids arise from weak polybasic oxygen acids a metal, such as chromium, molybdenum, vanadium and tungsten, and a non-metal, such as arsenic, iodine, phosphorus, selenium, silicon, boron and tellurium as partially mixed anhydrides. Examples include the dodecotungstophosphoric acid " H 3 (PW ⁇ 2 0 o) or the decamolybdophosphoric acid H 3 (PMo ⁇ 2 0 4 o).
  • the heteropolyacids can also contain actionoids or lanthanoids as the second central atom (sZ Chemie 17 (1977), pages 353 to 357 and 19 (1979), 308.
  • Phosphotungstic acid, phosphoromolybdic acid, silicon molybdic acid and silicon tungsten acid are particularly suitable as catalysts for the process according to the invention.
  • heteropolyacids used as catalysts can be used in the copolymerization either dried (1 to 10 mol water / mol heteropolyacid) or undried (10 to 40 mol water / heteropolyacid).
  • the water present in the copolymerization reactor which is partly water of crystallization from the heteropolyacid and partly water formed during the reaction, is mixed with the freshly added hydrocarbon with water at a temperature of 40 ° to 120 ° C, particularly preferably from 50 to 70 ° C. and a pressure of 150 mbar to 2 bar, preferably 230 mbar, separated off directly from the copolymerization, that is to say from the copolymerization reactor, without intermediate work-up steps such as phase separations, using a conventional distillation device.
  • the resulting vapor is preferably deposited in a surface condenser; however, quench and injection capacitors are also possible.
  • the resulting condensate is fed to the solvent processing in order to remove the water.
  • a partial return of the condensate to the reactor i.e. dissipation of the heat of reaction by means of evaporative cooling.
  • a multi-stage countercurrent rectification column with the return condensate as the reflux can be inserted between the reactor and the condenser.
  • THF is distilled off simultaneously with the mixture of the hydrocarbon used in the copolymerization with water, which, depending on the hydrocarbon, can form a ternary azeotrope.
  • the hydrocarbon distilled off in a mixture with water or the mixtures of water and hydrocarbon with tetrahydrofuran can be dried with a suitable solid adsorbent, for example on molecular sieves, and returned to the copolymerization.
  • Phase separation into an aqueous phase and the hydrocarbon is also conceivable.
  • the aqueous phase contains up to 5% by weight of THF, preferably ⁇ 1% by weight. It also contains the respective hydrocarbon in concentrations of ⁇ 1% by weight.
  • THF and the hydrocarbon can be recovered and recycled by working up the aqueous phase by distillation. However, the aqueous phase can also be discarded.
  • the copolymer solution remaining after the hydrocarbon / water mixture has been separated off is preferably transferred to a phase separator.
  • the heteropolyacid is separated from the product phase by adding further amounts of hydrocarbon. This process, known per se, for example from EP-A 181 621, leads to the reprecipitation of the heteropolyacid from the organic phase.
  • the hydrocarbon already used in the copolymerization is preferably used as the hydrocarbon.
  • the catalyst phase remains in the reaction apparatus in a continuous mode of operation and is continuously supplemented by adding new and / or possibly recirculating the discharged catalyst in accordance with the catalyst losses which result from the discharge of small amounts of catalyst with the product-containing upper phase.
  • the upper phase contains the main amount of the copolymer and THF as well as small residual amounts of heteropolyacid or its secondary products. Their proportion generally does not exceed 0.03% by weight, based on the copolymerization output. Nevertheless, it was recognized that these residual amounts of the catalyst and its secondary products have to be separated off, since they adversely affect the properties of the copolymers for their further processing.
  • the distillation of the THF from the copolymer can be carried out before or after the removal of the catalyst components and / or secondary catalyst products by filtration, such as, for example, ultrafiltration, adsorption on solid adsorbents and / or with the aid of ion exchangers, with filtration and adsorption on solid adsorbents is preferred.
  • the filtration is preferably carried out by distillation without prior removal of the THF.
  • the adsorption on the solid adsorbent mentioned can also be combined with a neutralization of the polymerization output by bases. Suitable bases are, for example, the hydroxides and carbonates of the alkali and alkaline earth metals.
  • the adsorption is preferably carried out on activated carbon and / or metal oxides and / or ion exchangers at temperatures of 10 to 75 ° C, preferably at 20 ° C to 70 ° C.
  • the separation in processing stage a) is particularly preferably carried out on ion exchangers and / or activated carbon.
  • Sodium hydroxide, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, lanthanum oxide and / or calcium oxide are preferably used as metal oxides.
  • Suitable activated carbon can be obtained, for example, from Merck, Darmstadt or in the form of the commercial product activated carbon type CPG UF 8x30 from Chemviron Carbon.
  • Suitable ion exchangers are, for example, anion exchangers such as the commercial product Lewatit MP 600®, which can be obtained from Bayer AG, Leverkusen, mixed ion exchangers such as, for example, the commercial product Serdolit®, which can be obtained from Serva, Heidelberg, or molecular sieves Pore sizes from 3 to 10 ⁇ .
  • anion exchangers such as the commercial product Lewatit MP 600®, which can be obtained from Bayer AG, Leverkusen, mixed ion exchangers such as, for example, the commercial product Serdolit®, which can be obtained from Serva, Heidelberg, or molecular sieves Pore sizes from 3 to 10 ⁇ .
  • the inventive separation of the catalyst components and / or catalyst secondary products by adsorption on solid adsorbents is preferred in a fixed bed at a load of generally 0.2 to 5 kg / l * h, in particular 0.4 to 4 kg / Ah (kg of polymerization output per 1 adsorbent per hour).
  • the process according to the invention can be carried out either continuously or batchwise or in a semi-batch mode.
  • the semi-batch mode or semi-continuous mode is understood to mean that the heteropolyacid is initially charged with 20 to 50% by weight of the other starting materials. The remainder of the starting materials is then metered in over the course of the reaction time.
  • the heteropolyacid is expediently used in amounts of 10 to 300 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the monomers used (THF and alpha, omega-diols) , used. It is also possible to add larger amounts of heteropolyacid to the reaction mixture.
  • the heteropolyacid can be fed to the reaction in solid form, whereupon it is gradually brought into contact with the other reactants to form the liquid Catalyst phase is solvated.
  • Both the catalyst phase and the monomeric starting material can be placed in the reactor. However, both components can also be introduced into the reactor at the same time.
  • fresh monomer is usually metered into the reactor in a controlled manner via a fill level control.
  • Fresh monomer is expediently fed in to the extent that product and unreacted monomer are discharged from the reaction apparatus.
  • the residence time, and hence the polymerization time can also be controlled, so that a further means for influencing and adjusting the average molecular weight of the resulting polymer is available.
  • the copolymerization is carried out for a period of from 0.5 to 70 hours, preferably from 5 to 50 hours and particularly preferably from 10 to 40 hours.
  • residence times of 1 to 50 and preferably 10 to 40 hours are usually set.
  • the reaction system described takes a certain time until a steady state equilibrium has been reached and during which it can be advantageous to keep the reactor outlet closed, that is to say not to discharge any product solution from the reaction apparatus.
  • the copolymerization is usually carried out at temperatures from 20 to 100 ° C., preferably at 30 to 80 ° C. It is advantageous to work under atmospheric pressure, but the reaction under pressure, primarily under the autogenous pressure of the reaction system, can likewise prove expedient and advantageous.
  • the reactors should be equipped with powerful mixing devices, for example agitators, both in batch, semi-batch mode and in continuous mode.
  • All liquid reactors known to those skilled in the art with an inert and / or external free liquid surface for the necessary evaporation of the vapors containing water, in which sufficiently high shear forces in the liquid to suspend the catalyst phase in the homogeneous monomer / polymer phase are used as the reactor are suitable (stirred tanks, circulation reactors, jet loops, pulsed internals).
  • a particularly favorable design is the design as a jet loop, since the necessary temperature control of the reactor can be easily integrated into the liquid circulation flow.
  • the water-containing mixture of the hydrocarbon is evaporated continuously or discontinuously from the reaction mixture and the water content of the reactor content is thus adjusted to values which are favorable in terms of reaction technology.
  • inert gas atmosphere carried out, wherein any inert gases such as nitrogen or argon can be used.
  • the reactants are freed of any water and peroxides contained therein before they are used.
  • the continuous procedure is preferably used.
  • the reaction can be carried out in conventional reactors or reactor arrangements suitable for continuous processes, for example in tubular reactors which are equipped with interior fittings which ensure thorough mixing of the emulsion-like copolymerization batch or can also be carried out in stirred tank cascades.
  • An emulsion-like copolymerization approach means one with water contents of 2 to 10 mol water / per mol heteropolyacid.
  • polyoxyalkylene glycols in particular copolymers of THF and neopentyl glycol, can be obtained economically and in good yield, selectively and with a narrow molecular weight distribution and in pure form with low color numbers.
  • the copolymers have installation rates of the alpha, omega-diol comonomer of 10 to 50% by weight, based on the copolymer, and average molecular weights M n of 600 to 6000.
  • the polyoxyalkylene glycols which can be prepared according to the invention are used, for example, to produce special polyurethanes which are suitable as highly elastic composite materials.
  • a polyurethane polymer which contains the copolymers which can be prepared according to the invention has a high elongation after breakage, a slight change in tension when elongated, a low hysteresis loss when expanding and contracting and a high elasticity even in extreme cold.
  • the sample solution is subjected to a digestion process in which the sample is first treated with concentrated sulfuric acid. After the mineral acids have been consumed, the W remains in a hydrochloric acid solution. In this solution, the tungsten content is determined by mass spectrometry with inductively coupled plasma (ICP-MS).
  • ICP-MS inductively coupled plasma
  • the polymer freed from the solvent is untreated in a liquid color measuring device LICO 200 from Dr. Measured for a long time.
  • Precision cuvettes type no. 100-QS layer thickness 50 mm, from Helma are used.
  • the hydroxyl number is understood to mean the amount of potassium hydroxide in mg which is equivalent to the amount of acetic acid bound in the acetylation of 1 g of substance.
  • the hydroxyl number is determined by the esterification of the hydroxyl groups present with an excess of acetic anhydride. After the reaction, the excess acetic anhydride is hydrolyzed with water and back-titrated as acetic acid with sodium hydroxide solution.
  • the copolymerization ratio was determined by 1 H-NMR using a device from Bruker, device type: dpx 400; 400 MHz, log. Default:
  • Tetra ethylsilane determined using the solvent CDC1.
  • the continuously obtained reaction discharge from the polymerization reactor was mixed with 250 g of pentane in a work-up vessel and phase separation was brought about.
  • the heavy, aqueous phase was returned to the polymerization vessel.
  • the upper phase was passed at 20 ° C. over activated carbon (Chemviron Carbon; type CPG UF 8 x 30), which was arranged in a 2.5 1 container as a fixed bed.
  • the top stream was condensed, forming two liquid phases.
  • the water phase was partially removed (57.3 g / h, pentane and THF contained only in traces).
  • the remaining water phase and part of the organic phase were added to the column as reflux. Pentane losses were supplemented in a return pentane stream for reaction and phase separation. To adjust the water content in the reaction or phase separation, part of the water phase was possibly introduced into the back pentane stream.
  • the THF was first evaporated in one stage at 1.2 bar and 75 ° C. and returned to the reaction, and then the NPG was likewise evaporated in one stage at 15 mbar and 170 ° C. and returned to the reaction.
  • a copolymer with an OH number of 58 mg KOH / g, a color number of 10 APHA and a W content of ⁇ 1 ppm was obtained.
  • Example 2 Discontinuous process control
  • the reaction apparatus consists of a distillation device which has a 50 cm distillation column, a condenser and reflux valves, and a heatable 10 1 reactor.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne un procédé de production en une étape de polyoxylalkylène glycols par copolymérisation de tétrahydrofurane et de alpha,oméga-diols en présence d'un hétéropolyacide et un carbure d'hydrogène. L'invention est caractérisée en ce que l'eau mélangée à ce carbure d'hydrogène est éliminée par distillation de la copolymérisation.
EP03790835A 2002-08-30 2003-07-30 Procede de production de copolymeres de tetrahydrofurane Withdrawn EP1537162A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10239947 2002-08-30
DE10239947A DE10239947A1 (de) 2002-08-30 2002-08-30 Verfahren zur Herstellung von Tetrahydrofuran-Copolymeren
PCT/EP2003/008406 WO2004020499A1 (fr) 2002-08-30 2003-07-30 Procede de production de copolymeres de tetrahydrofurane

Publications (1)

Publication Number Publication Date
EP1537162A1 true EP1537162A1 (fr) 2005-06-08

Family

ID=31502136

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03790835A Withdrawn EP1537162A1 (fr) 2002-08-30 2003-07-30 Procede de production de copolymeres de tetrahydrofurane

Country Status (10)

Country Link
US (1) US7094933B2 (fr)
EP (1) EP1537162A1 (fr)
JP (1) JP4327724B2 (fr)
KR (1) KR100970039B1 (fr)
CN (1) CN1276000C (fr)
AU (1) AU2003251667A1 (fr)
DE (1) DE10239947A1 (fr)
MY (1) MY135604A (fr)
TW (1) TWI328015B (fr)
WO (1) WO2004020499A1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8163680B2 (en) * 2006-09-28 2012-04-24 Chevron Oronite Company Llc Method of demulsing a natural gas dehydrator
WO2011039324A1 (fr) 2009-09-30 2011-04-07 Novozymes A/S Procédés de préparation de pain vapeur et compositions d'amélioration de pain vapeur
AU2011263706B2 (en) 2010-06-11 2014-07-24 Novozymes A/S Enzymatic flour correction
BE1022042B1 (nl) 2014-09-29 2016-02-08 Puratos Nv Verbeterde cakebeslagsoorten
US12171240B2 (en) 2018-06-12 2024-12-24 Novozymes A/S Less added sugar in baked products
AU2021372822A1 (en) 2020-11-02 2023-06-01 Novozymes A/S Baked and par-baked products with thermostable amg variants from penicillium
CN113087893B (zh) * 2021-03-23 2023-04-28 杭州三隆新材料有限公司 一种四氢呋喃共聚物及其制备方法
US20250270485A1 (en) 2022-05-04 2025-08-28 Novozymes A/S Brewing with thermostable amg variants
CN119768060A (zh) 2022-09-01 2025-04-04 诺维信公司 用热稳定amg葡糖苷酶变体（ec 3.2.1.3）和低添加或不添加乳化剂进行烘焙
WO2024046595A1 (fr) 2022-09-01 2024-03-07 Novozymes A/S Cuisson à l'aide de variants d'amyloglucosidase (amg) thermostables (ec 3.2.1.3) et à faible teneur en sucre ajouté
CA3268687A1 (fr) 2022-10-24 2024-05-02 Novozymes A/S Procédé de cuisson pour pain enrichi en protéine pulsée utilisant de l'amyloglucosidase thermostable (ec 3.2.1.3)
EP4608147A1 (fr) 2022-10-24 2025-09-03 Novozymes A/S Procédé de cuisson avec un variant d'amg thermostable et une alpha-amylase
CN120201929A (zh) 2022-10-28 2025-06-24 诺维信公司 用于获得植物基食品配料的方法
EP4626238A1 (fr) 2022-11-30 2025-10-08 Novozymes A/S Cuisson à faible ph avec des variants thermostables de glucoamylase
CN116804662B (zh) * 2023-06-21 2025-09-26 中国神华煤制油化工有限公司 一种乙交酯中水分含量测定的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1216597A (fr) 1983-05-23 1987-01-13 Atsushi Aoshima Production de polyetherglycole
DE10032264A1 (de) * 2000-07-03 2002-01-17 Basf Ag Verbessertes Verfahren zur Herstellung von Polyetrahydrofuran und THF-Copolymeren
DE10032265A1 (de) * 2000-07-03 2002-01-17 Basf Ag Verbessertes Verfahren zur Herstellung von Polytetrahydrofuran und THF-Copolymeren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004020499A1 *

Also Published As

Publication number Publication date
US20060167321A1 (en) 2006-07-27
JP2005536615A (ja) 2005-12-02
TW200406438A (en) 2004-05-01
MY135604A (en) 2008-05-30
DE10239947A1 (de) 2004-03-11
KR20050037590A (ko) 2005-04-22
CN1678659A (zh) 2005-10-05
AU2003251667A1 (en) 2004-03-19
CN1276000C (zh) 2006-09-20
US7094933B2 (en) 2006-08-22
KR100970039B1 (ko) 2010-07-16
TWI328015B (en) 2010-08-01
JP4327724B2 (ja) 2009-09-09
WO2004020499A1 (fr) 2004-03-11

Similar Documents

Publication Publication Date Title
EP1537162A1 (fr) Procede de production de copolymeres de tetrahydrofurane
EP0428003B1 (fr) Procédé de préparation de polyéther-glycols
EP2885336B1 (fr) Polyesters
EP1299449A1 (fr) Procede ameliore de preparation en une etape de polytetrahydrofurane et de copolymeres tetrahydrofurane
EP0421268B1 (fr) Procédé pour la purification de glycols polyalkylène éthers contenant des hétéropolyacides
EP1576030B1 (fr) Procede de production de copolymeres de tetrahydrofurane
DE69509360T2 (de) Polyetherglyole und alkohole aus 3,4-epoxy-1-ruten
DE69505270T2 (de) Polyätherglycole und alkohole aus 3,4-epoxy-1-burne, tetrahydrofuran und ein initiator
EP2370192A1 (fr) Dispositif de séparation par distillation
EP1613684B1 (fr) Procede de production de copolymeres de tetrahydrofurane
DE10330721A1 (de) Verfahren zur Gewinnung von Oligomeren des Polytetrahydrofurans oder der Tetrahydrofuran-Copolymere
DE10242286A1 (de) Verfahren zur Herstellung von Mono- und Diestern des Polytetrahydrofurans und der Tetrahydrofuran-Copolymere
DE10359808A1 (de) Verfahren zur Herstellung von Tetrahydrofuran-Copolymeren
DE10314649A1 (de) Verfahren zur Herstellung von Tetrahydrofuran-Copolymeren
EP1123340B1 (fr) Procede de production de polymeres de tetrahydrofurane
WO2005087840A1 (fr) Procede de production de polytetrahydrofuranne ou de copolymeres de tetrahydrofuranne
DE10210728A1 (de) Verfahren zur Herstellung von Polytetrahydrofuran mit vermindertem Gehalt an oligomeren cyclischen Ethern
WO2003076493A1 (fr) Procede de reduction de la teneur en ethers cycliques oligomeriques du polytetrahydrofurane ou des copolymeres de tetrahydrofurane
DE19502970A1 (de) Verfahren zur Herstellung von Polyoxibutylenpolyoxialkylenglykolen
DE10359810A1 (de) Verfahren zur Herstellung von Mono- und Diestern des Polytetrahydrofurans oder der Tetrahydrofuran-Copolymere

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050330

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20051101