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WO2003029325A1 - Procede de fabrication de polycarbonates aliphatiques - Google Patents

Procede de fabrication de polycarbonates aliphatiques Download PDF

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Publication number
WO2003029325A1
WO2003029325A1 PCT/EP2002/010406 EP0210406W WO03029325A1 WO 2003029325 A1 WO2003029325 A1 WO 2003029325A1 EP 0210406 W EP0210406 W EP 0210406W WO 03029325 A1 WO03029325 A1 WO 03029325A1
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Prior art keywords
catalyst
polycarbonates
zinc
group
reactor
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German (de)
English (en)
Inventor
Johannes Heinemann
Gerrit Luinstra
Edward Bohres
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BASF SE
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BASF SE
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    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/183—Block or graft polymers containing polyether sequences
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers

Definitions

  • the invention relates to a process for the production of high molecular weight aliphatic polycarbonates with the following properties
  • radicals R independently of one another represent hydrogen, halogen, -N0, -CN, -COOR or a hydrocarbon group with 1 to 30 20 C atoms, which may be substituted,
  • At least one catalyst selected from the group consisting of zinc carboxylates and multimetal cyanide compounds.
  • the invention also relates to aliphatic polycarbonates obtainable by this process and to thermoplastic molding compositions which contain these polycarbonates. Finally, the invention relates to the use of these thermoplastic molding compositions
  • thermoplastic molding compositions for the production of moldings, foils, films, coatings and fibers, and also these moldings, foils, films, coatings and fibers from the thermoplastic molding compositions.
  • Copolymers of epoxides such as ethylene oxide (abbreviated EO) or 5 propylene oxide (abbreviated PO) and carbon dioxide (C0 2 ) and processes for their production are known.
  • EO ethylene oxide
  • PO propylene oxide
  • C0 2 carbon dioxide
  • the copolymers are called aliphatic polycarbonates or aliphatic polyether carbonates.
  • Common catalysts for these polymerization reactions are in particular organic zinc compounds such as Zinc carboxylates, or cyanide complexes with two or more metal atoms, e.g. Double metal cyanide complexes.
  • DE-A 197 37 547 describes a process for the preparation of polyalkylene carbonates using a catalyst which is prepared from zinc oxide or other inorganic zinc compounds and a mixture of two aliphatic or aromatic dicarboxylic acids. First the epoxide and then CO 2 are metered into the reactor, ie the catalyst first comes into contact with the epoxy before CO 2 is added.
  • the US-A 5 026 676 discloses a process for the copolymerization of CO 2 and epoxides in the presence of zinc carboxylate catalysts, the epoxy and then the CO 2 being added to the reactor.
  • ÜS-A 4 943 677 describes a similar process in which the zinc carboxylate catalyst is placed in the reactor and heated in a stream of nitrogen for several hours before the epoxide and then the CO 2 are added.
  • the US-A 5 041 469 describes the copolymerization of epoxy and C0 in methylene chloride of the solvent, wherein epoxy, C0 2 and the zinc carboxylate catalyst are presented together.
  • the three WO-A documents 01/04178, 01/04179 and 01/04183 describe a process for the preparation of polyoxyalkylenes from epoxides in the presence of metal cyanide complexes as a catalyst, it also being possible to use C0 as well.
  • the catalyst and epoxide are initially introduced and left to activate the catalyst. Then the reaction starts and further epoxy is added.
  • EP-A 222 453 discloses a process for the production of polycarbonates from epoxides and CO 2 using a
  • Catalyst system of double metal cyanide compounds and a cocatalyst such as zinc sulfate The polymerization is initiated by bringing a small part of the epoxide into contact with the catalyst system. Only then the remaining amount of epoxy and the C0 are metered in simultaneously, the copolymerization taking place (p. 3, lines 53-57 and examples).
  • US Pat. No. 4,500,704 describes a process for the preparation of epoxy-CO 2 copolymers in which double metal cyanide complexes are used as catalysts. Again, before the actual copolymerization, the double metal cyanide catalyst is first activated by contacting it with the epoxy for up to 45 minutes. Only then is C0 2 pressed on and copolymerized (column 5, lines 46-50). According to Example 1, the PO-CO 2 copolymer obtained has a number average molecular weight (molar mass) M n of 23,000.
  • the activity of the catalysts is insufficient, i.e. so few grams of polymer are produced per gram of catalyst used that the process is uneconomical.
  • the polymerization times are four to 84 hours so long that the process is uneconomical.
  • the molecular weights of the polycarbonates obtained are so low that their properties of use (in particular the mechanical properties) are at an unacceptably low level. That the polycarbonates are hardly suitable for the production of molding compounds or molded parts.
  • undesirable by-products are also formed, in particular epoxy homopolymers (i.e. polyethers) and cyclic (mostly monomeric) carbonates.
  • the by-products reduce the yield of polycarbonate and may have to be separated from the main product at great expense. In addition, they significantly deteriorate the mechanical properties of the polymer mixture obtained. Cyclic carbonates, for example, significantly lower the glass transition temperature of the polycarbonate, which prevents certain possible uses.
  • indices n and k are integers greater than or equal to 1 and indicate the number of repetition units.
  • the polyethers III and the cyclic carbonates IV are undesirable by-products.
  • polycarbonates I and the polyether carbonates II are the desired process products and are referred to collectively as "polycarbonates”. “Polycarbonates” in the sense of the invention accordingly include both strictly alternating polycarbonates I and polycarbonates II with polyether segments (polyether carbonates).
  • the task was to remedy the disadvantages described. In particular, the task was to provide a process for the production of polycarbonates from epoxides and C0, in which the catalyst activity (mass of polymer obtained per mass unit of catalyst) is improved.
  • Another object was to provide an economical process with shorter polymerization times, in particular times of up to four hours.
  • the process should provide higher molecular weight polycarbonates than the prior art processes.
  • the polycarbonates obtainable by the process should have better mechanical properties.
  • the process defined at the outset was found. It is characterized in that the catalyst is used in anhydrous form and that the catalyst is first brought into contact with at least a portion of the carbon dioxide before the epoxy is added.
  • the weight average molecular weight M w of the polycarbonates is determined by means of gel permeation chromatography (GPC, also referred to as size exclusion chromatography (SEC)) using hexafluoroisopropanol (HFiP) as eluent and calibration with polymethyl methacrylate (PMMA) standards.
  • GPC gel permeation chromatography
  • HFiP hexafluoroisopropanol
  • PMMA polymethyl methacrylate
  • the polycarbonates produced by the process according to the invention have a weight-average molecular weight M w of 30,000 to 1,000,000.
  • Molecular weights M w are preferably 200,000 to 500,000 for propylene oxide as epoxide and 30,000 to 300,000 for ethylene oxide as epoxide.
  • the content of cyclic carbonates and polyethers can be determined in a known manner.
  • Nuclear magnetic resonance (NMR) is usually used for this, in particular ⁇ H NMR.
  • An X H-NMR spectrum of the process - product polycarbonate indicates by appropriate bands (peaks) whether cyclic carbonates and / or polyethers are present in the polycarbonate. Their amount can be determined in a known manner by quantitative analysis of the spectra.
  • Carbon dioxide C0 2 is inexpensive as a component of the air and is available almost indefinitely.
  • radicals R here independently of one another denote hydrogen, halogen, nitro group -N0 2 , cyano group -CN, ester group -COOR or a hydrocarbon group with 1 to 20 C atoms, which can be substituted.
  • Such hydrocarbon groups are especially C ⁇ _o -alkyl, C 2-20 -alkenyl, C 3 -C 20 cycloalkyl, C 6 _ 18 aryl, and C 7 _ 0 arylalkyl.
  • two radicals R if they are attached to different C atoms of the epoxy group
  • the following groups are particularly suitable as substituents with which the C 2 O hydrocarbon group can be substituted: halogen, cyano, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, arylalkyloxy, carbonyldioxyalkyl, carbonyldioxyaryl, carbonyldioxyarylalkyl, alkoxycarbonyl, aryloxycarbonyl , Arylalkyloxycarbonyl, alkylcarbonyl, arylcarbonyl, arylalkylcarbonyl, alkylsulfinyl, arylsulfinyl, arylalkylsulfinyl, alkylsulfonyl, arylsulfonyl and arylalkylsulfonyl.
  • the epoxide used is preferably ethylene oxide, propylene oxide, butylene oxide (1-butene oxide, BuO), cyclopentene oxide, cyclohexene oxide (CHO), cycloheptene oxide, 2,3-epoxypropylphenyl ether, epichlorohydrin, epibromohydrin, i-butene oxide (IBO), or acrylic oxides.
  • Ethylene oxide (EO), propylene oxide (PO), butylene oxide, cyclopentene oxide, cyclohexene oxide or i-butene oxide are particularly preferably used. Very particularly preferably ethylene oxide and propylene oxide. It is understood that mixtures of the aforementioned epoxides can also be used.
  • polycarbonate terpolymers are formed. If, for example, the epoxides ethylene oxide and cyclohexene oxide are used in addition to C0 2 , C0 / E0 / cyclohexenoxide terpolymers are formed. Examples of suitable mixtures of two epoxides are: EO and PO (a C0 2 / E ⁇ / PO terpolymer is formed), EO and cyclene hexene oxide, PO and cyclohexene oxide, i-butene oxide and EO or PO, butylene oxide and EO or PO, etc.
  • the two or more epoxides can be added as a mixture or separately.
  • the C0 2 : epoxy ratio can be varied within wide limits.
  • C0 is usually used in excess, ie more than 1 mol of C0 per 1 mol of epoxide.
  • the catalyst is selected from the group consisting of zinc carboxylates and multimetal cyanide compounds.
  • Zinc carboxylates are zinc salts of carboxylic acids.
  • Particularly suitable carboxylic acids are dicarboxylic acids, especially aliphatic dicarboxylic acids.
  • Adipic acid and glutaric acid are particularly suitable. Accordingly, zinc adipate and zinc glutarate are very particularly suitable zinc carboxylates.
  • the zinc carboxylates are prepared in a manner known per se from zinc compounds (inorganic such as e.g. zinc oxide, zinc hydroxide, zinc halide or organic such as e.g. zinc acetate, zinc propionate) and the carboxylic acids corresponding to the carboxylate residue.
  • carboxylic acid derivatives such as e.g. Use carboxylic acid anhydrides or lower carboxylic acid esters such as acetates or propionates.
  • Corresponding production processes for zinc carboxylates are e.g. in the documents US-A 4 783 445 and DE-A 197 37 547.
  • Multimetal cyanide compounds are complexes which contain at least two metals complexly coordinated with cyanide ions per formula unit, and possibly further ligands. With exactly two metals coordinated with cyanide per formula unit, one also speaks of double metal cyanide complexes (DMC).
  • DMC double metal cyanide complexes
  • Suitable multimetal cyanide compounds are known and are described in the following A documents: US 3,278,457, US 3,278,458, US 3,278,459, US 3,427,256, US 3,427,334, US 3,404,109, US
  • Multimetal cyanide complexes are also e.g. in the documents DD-A 148 957, EP-A 862 947, EP-A 654 302, EP-A 700 949, WO-A 97/40086, WO-A 98/16310, EP-A 222 453, EP-A 90 444, EP-A 90 445, WO-A 01/04177, WO-A 01/04181, WO-A 01/04182, WO-A 01/03830, DE-A 199 53 546.
  • multimetal cyanide catalysts are double metal cyanide compounds, in particular those of the formula 2
  • M, A, X, L and P stand for atoms or groups of atoms.
  • CN and H 2 0 are cyanide and water.
  • the superscript indices 1 and 2 are used to distinguish between the different M.
  • Indices a , t > , C / ⁇ ⁇ , g, n are stoichiometric indices and the letters f, h, e and k are mole numbers.
  • M 1 at least one metal ion selected from the group comprising Zn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ni 2+ , Mn 2+ , Sn + , Pb 2+ , Mo + , Mo6 + , A13 +, v + , V5 + , Sr 2+ , W 4+ , W 6+ , Cr 2+ , Cr 3+ , Cd 2+ , La 3+ , Ce 3+ , Ce 4+ , Eu 3+ , Mg 2+ , Ti 3+ , Ti 4+ , Ag + , Rh 2+ , Ru + , Ru 3+ ,
  • M 2 at least one metal ion selected from the group comprising Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , V + , V 5+ , Cr 2+ , Cr 3+ , Rh 3 +, Ru + , Ir3 +,
  • M 1 and M 2 can be the same or different
  • X at least one anion selected from the group comprising halide, hydroxide, sulfate, carbonate, hydrogen carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate,
  • L at least one water-miscible ligand selected from the group comprising alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonates, ureas, amides, nitriles, sulfides, amines, ligands with pyridine nitrogen, phosphides, phosphites, phosphines , Phosphonates, phosphates,
  • P at least one organic additive selected from the group comprising polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates , Polyalkyl methacrylates, polyvinyl methether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinyl pyrrolidone, poly (N-vinyl pyrrolodone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-sty - rol), oxazoline polymers, polyalkyleneimines, maleic acid, maleic anhydride copolymer, hydroxyethyl cellulose, polyacetates, i
  • the multimetal cyanide compounds can be crystalline or amorphous.
  • the multimetal cyanide compounds are generally crystalline or predominantly crystalline.
  • they are crystalline in general, partially crystalline or amorphous WE ⁇ sentliehen.
  • the primary particles of the multimetal cyanide compounds preferably have a crystalline structure and a content of platelet-shaped particles of more than 30% by weight, based on the total weight of the multimetal cyanide compound.
  • the platelet shape of the particles leads to an increase in the proportion of catalytically active surface, based on the total surface, and thus an increase in the mass-specific activity.
  • primary particle is understood to mean the individual crystallite as it e.g. can be seen on the scanning electron micrographs. These primary particles can then assemble to form agglomerates, the so-called secondary particles.
  • platelet-shaped is understood to mean that the length and width of the primary particles are at least three times greater than the thickness of these particles.
  • crystalline structure is understood to mean that not only a short-range order, such as an arrangement of, for example, 6 carbon atoms around a metal atom, but also a long-range order exists in the solid state, that is to say an ever-recurring unit, too referred to as a unit cell, define from which the entire solid can be built. If a solid is crystalline, this is expressed, among other things in the X-ray diffractogram. In the case of a crystalline substance, the X-ray diffractogram shows "sharp" reflections, the intensities of which are clearly, ie at least three times, greater than that of the background.
  • the primary particles can also e.g. be bar-shaped, cube-shaped or spherical.
  • Preferred multimetal cyanide compounds contain:
  • M 1 at least one metal ion selected from the group comprising Zn 2+ , Fe 2+ , Fe 3+ ,
  • M 2 at least one metal ion selected from the group comprising Co 2+ , Fe 2+ , Fe 3+ ,
  • X at least one anion selected from the group containing formate, acetate, propionate,
  • L at least one water-miscible ligand selected from the group containing tert-butanol, monoethylene glycol dimethyl ether (Gly e)
  • Multimetal cyanide compounds of the above formula 2 in which k and e are greater than zero are particularly preferred. These compounds contain the multimetal cyanide, at least one ligand L and at least one organic additive P.
  • multimetal cyanide compounds of the above formula 2 in which k is zero and optionally e is zero. These compounds contain no organic additive P and optionally no ligand L.
  • Multimetal cyanide compounds with k and e equal to zero, in which X is selected from the group consisting of formate, acetate and propionate, are very particularly preferred. These compounds contain no organic additive P and no ligand L. Details can be found in WO-A 99/16775. In this embodiment, crystalline double metal cyanide catalysts are preferred; and double metal cyanide catalysts which are crystalline and platelet-shaped (see WO-A 00/74845). Also particularly preferred are multimetal cyanide compounds of the formula 2 in which f, e and k are not equal to zero. Ie these compounds contain the metal salt M ⁇ - g X n , a ligand L and organic additives P. ' See WO-A 98/06312. 5
  • the preparation of the multimetal cyanide compounds is e.g. described in WO-A 00/74843, WO-A 00/74844, WO-A 00/74845, EP-A 862 947, WO-A 99/16775, WO-A 98/06312 and US-A 5 158 922.
  • an aqueous solution of the metal salt is combined
  • cyanometalate H a M 2 (CN) b A c
  • H is hydrogen, alkali metal, alkaline earth metal or ammonium.
  • the metal salt solution and / or the cyanometalate solution can contain the water-miscible ligand L and / or the organic additive P.
  • ligand L and / or additive P may be added.
  • catalyst production it is advantageous to stir vigorously, e.g. with high speed stirrer.
  • the precipitate is separated off in a conventional manner and, if necessary, dried.
  • cyanometalate hydrogen acids can be produced from the corresponding alkali or alkaline earth metal cyanometalates, for example via acidic ion exchangers, see for example WO-A 99 / 16,775th
  • a compound which can be obtained by reacting aqueous hexacyanocobaltoic acid H 3 [Co (CN) g] with aqueous zinc acetate solution is very particularly preferably used as the multimetal cyanide compound. This reaction can be carried out, for example, under the conditions specified in the examples, see, for example, the manufacturing instructions there. 0
  • the catalyst is used in anhydrous form. This means that the catalyst - apart from the chemically bound water (for example h mol crystal water in the general formula 2 above) - contains no water or only insignificant traces of water, in particular no water which adheres to the surface or is physically enclosed in cavities.
  • the catalyst is therefore made anhydrous before it is used. This is particularly preferably done by heating the catalyst in a stream of inert gas or in vacuo until it is free of water before starting the polymerization. Nitrogen, argon or other customary inert gases are usually used as the inert gas.
  • the temperature up to which the catalyst is heated is usually 80 to 130 ° C.
  • the duration of the heating is usually 20 to 300 minutes. Typical values are 2 hours at 120 ° C for zinc carboxylate and 4 hours at 130 ° C for multimetal cyanide catalysts.
  • the catalyst can e.g. Place in the polymerization reactor, make anhydrous in the inert gas stream (bake out) and - if necessary after cooling - carry out the polymerization in the same reactor, i.e. anhydrous the catalyst and polymerization can be easily done in the same vessel.
  • the catalyst can also be made anhydrous by heating in vacuo or other suitable drying methods.
  • the anhydrous catalyst is then dissolved or dispersed (suspended or emulsified) in an inert reaction medium before the polymerization is started.
  • the dissolving or dispersing can take place with stirring.
  • Suitable as an inert reaction medium are all substances which do not adversely affect the catalyst activity, in particular aromatic hydrocarbons such as toluene, xylenes, benzene, also aliphatic hydrocarbons such as hexane, cyclohexane, and halogenated hydrocarbons such as dichloromethane, chloroform, isobutyl chloride. Also suitable are ethers such as diethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether (diglyme), dioxane, and nitro compounds such as nitromethane. Toluene is preferably used.
  • the inert medium can be pressed, for example, as such or preferably with a gas stream into the polymerization reactor, it being possible to use an inert gas such as nitrogen or the reactant C0 2 as the gas.
  • the catalyst is preferably first placed in the reactor, made anhydrous by heating in an inert gas stream, allowed to cool if necessary, and the inert reaction medium is forced into the reactor with gas while stirring.
  • the catalyst concentration is preferably 0.01 to 20, in particular 0.1 to 10% by weight. Based on the sum of epoxy and inert reaction medium, the catalyst concentration is preferably 0.01 to 10, particularly preferably 0.1 to 1% by weight.
  • the catalyst is first brought into contact with at least a portion of the CO before the epoxide is added.
  • “with at least a partial amount” means that, before adding the epoxy, either a partial amount of the total amount of CO 2 used is added, or the total amount of CO 2 is already added.
  • this subset is particularly preferably 20 to 80, in particular 55 to 65% by weight of the total CO amount.
  • C0 2 as a gas and the amount of C0 2 is - depending on the temperature - adjusted via the C0 gas pressure.
  • C0 2 -Teilmenge which is the preferred C0 2 -Teilmenge corresponds, when using the zinc carboxylate catalysts 5 to 70, particularly 10 to 30 bar, and when using the multimetal cyanide catalysts 5 to 70, in particular 10 to 50 bar.
  • Typical values for the CO 2 admission pressure are 15 bar for zinc carboxylate catalysts and 50 bar for multimetal cyanide catalysts, both at 23 ° C.
  • the CO 2 pre-pressure can be set discontinuously at one time or divided into several steps, or also set continuously over a certain period of time linearly or following a linear exponential or stepwise gradient.
  • the C0 2 admission pressure eg at 23 ° C
  • the C0 2 admission pressure should be selected so that the desired C0 2 end pressure at the reaction temperature (eg 80 ° C) is not exceeded.
  • the catalyst is generally brought into contact with CO at temperatures of 20 to 80 ° C., preferably 20 to 40 ° C. It is particularly preferred to work at room temperature (23 ° C.).
  • the duration of the contacting of catalyst and CO 2 is dependent on the reactor volume and is usually 30 seconds to 120 minutes.
  • the catalyst or the solution or dispersion of the catalyst is stirred in the inert reaction medium while being brought into contact with the CO.
  • the epoxy is usually pressed as such or preferably with a small amount of inert gas or CO 2 into the reactor.
  • the epoxide is usually added with stirring and can be carried out all at once (in particular in the case of a small reactor volume) or continuously over a period of generally 1 to 100 min, preferably 10 to 40 min, the addition being constant over time or a gradient can follow the example can be ascending or descending, linear, exponential or gradual.
  • the temperature when the epoxide is added is generally 20 to 100, preferably 20 to 70 ° C.
  • Variant a) is preferred.
  • the reactor is accordingly brought to the reaction temperature T R before or - preferably - after the addition of the epoxide.
  • the reaction temperature is usually set at 30 to 180, in particular 50 to 130 ° C. This is usually done by heating the reactor with stirring.
  • the reaction temperature is usually 40 to 120, preferably 60 to 90 ° C. Typical values are 80 ° C for zinc carboxylate and 65 to 80 ° C for multimetal cyanide catalysts.
  • the remaining amount of C0 2 is added to the reactor, preferably with stirring, unless the total amount of C0 has already been added when the catalyst is brought into contact with C0 2 (see above). Customarily as presents to the C0 2 amount again recorded the C0 2 gas pressure.
  • CO final pressure the CO pressure
  • CO final pressure the CO pressure
  • Typical values for the CO 2 end pressure are 20 to 100 bar for zinc carboxylate and 100 bar for multimetal cyanide catalysts.
  • the final C0 pressure can be set discontinuously at once or continuously as described for the C0 2 pre-pressure.
  • the time to complete the polymerization reaction is usually 60 to 500 min, preferably 120 to 300 min. A typical value for this post-reaction time is 3 to 4 hours.
  • the reaction temperature is usually kept constant; however, they can also be raised or lowered depending on the progress of the reaction.
  • the quantitative ratios used in the process C0 2 : epoxy depend in a known manner on the desired properties of the polymer. Usually the ratio (weight ratio) of total amount of CO 2 : total amount of epoxy is 1: 1 to 2: 1. In a preferred embodiment, all of the aforementioned process steps are carried out with the exclusion of water: not only the catalyst, but also the inert reaction medium, the CO 2 and the epoxide are anhydrous or are rendered anhydrous in the customary manner.
  • the contents of the reactor are worked up onto the polycarbonate. This is done in a known manner. As a rule, the reactor is allowed to cool with stirring, the pressure is equalized with the surroundings (ventilation of the reactor), and the polycarbonate polymer precipitates by placing the reactor contents in a suitable precipitation medium.
  • alcohols such as methanol, ethanol, propanol or ketones such as acetone are used as the precipitation medium.
  • Methanol is preferred. It is advantageous to acidify the precipitation medium to pH 0 to 5.5 with hydrochloric acid or another suitable acid.
  • the precipitated polymer can be separated as usual, e.g. by filtration, and dried in vacuo.
  • part of the polycarbonate reaction product is also dissolved or dispersed in the precipitation medium, for example in the acidified methanol.
  • This polycarbonate can be isolated in the usual way by removing the precipitant.
  • the methanol can be distilled off under reduced pressure, for example on a rotary evaporator.
  • Steps 5 and 6 can be interchanged (first heating, then adding epoxy).
  • the catalyst can be made anhydrous by heating under inert gas in the reactor, as a result of which steps 1 and 2 coincide.
  • the polymerization time is 1 to 10, in particular 2 to 5 hours, typically about 3 to 4 hours, considerably shorter, which greatly improves the economics of the process.
  • the weight-average molecular weights M w of the polycarbonates obtained are significantly higher at 30,000 to 1,000,000 than according to the prior art. Molding compounds or molded parts, foils, films and fibers with good usage properties, in particular good mechanical properties, can be produced from polycarbonates with these molecular weights.
  • the polymerization reaction can be controlled so that little or no undesirable by-products are formed.
  • the formation of the interfering polyether homopolymers (III in the reaction scheme given at the outset) and the interfering cyclic carbonates IV is significantly reduced or completely avoided.
  • the reduced or missing by-products III and IV increase the yield of polycarbonate and thus improve the economics of the process.
  • the lack of by-products also saves time-consuming separation from the main product. This significantly improves economy.
  • Process product polycarbonate set the ratio of alternating polycarbonate I to polyether carbonate II.
  • polycarbonates obtainable according to the invention have at least 50, preferably at least 70, in particular 75 to 95%, carbonate linkages in the polymer chain.
  • a high proportion of carbonate linkages means a low proportion of polyether segments in the polymer chain. Pure alternating polycarbonate I has 100% carbonate linkages. A high proportion of carbonate linkages in the process product therefore means that the process product comes close to the alternating polycarbonate I. If the proportion of carbonate linkages is lower, the process product comes close to polyether carbonate II.
  • the reaction conditions which control the polymerization reaction with regard to the ratio of main products I and II / by-products III and IV, and in particular with regard to the proportion of carbonate linkages in main product I and II and thus the (mechanical and other) properties include in particular the catalyst, but also the amount of epoxy and C0 2 , the C0 pressure and pressure, and the temperature control of the reaction.
  • polycarbonates with> 90% carbonate linkages They have a high modulus of elasticity and low elongation at break and are tough and tough.
  • Such tough solid polycarbonates are suitable e.g. for the production of molded parts.
  • multi-metal cyanide catalysts with PO tend to give polycarbonates with 70 to 90% carbonate linkages. They have a low modulus of elasticity and high elongation at break and are flexible. Such flexible polycarbonates are suitable e.g. for the production of foils and films.
  • the former tough polycarbonates resemble in terms of modulus of elasticity and elongation at break similar to polyesters such as polybutylene terephthalate (e.g. Ultradur® from BASF), the latter flexible polycarbonates are similar in terms of modulus of elasticity and elongation at break to aromatic-aliphatic copolyesters (e.g. Ecoflex® from BASF) or polyethylenes such as LLDPE (linear low density polyethylene) or LDPE (low density polyethylene).
  • aromatic-aliphatic copolyesters e.g. Ecoflex® from BASF
  • polyethylenes such as LLDPE (linear low density polyethylene) or LDPE (low density polyethylene).
  • the polycarbonates according to the invention insofar as they were produced using a zinc carboxylate catalyst, have a modulus of elasticity above 500 MPa, determined in a tensile test at 23 ° C. on cylindrical strands of 2.5 mm in diameter 25 mm clamping length, 10 mm measuring length standard travel, 50 mm / min pulling speed and 10 kN pulling force.
  • the polycarbonates according to the invention provided they were produced using a multimetal cyanide catalyst, have an elongation at break of more than 500%, determined in a tensile test at 23 ° C. on cylindrical strands of 2.5 mm in diameter with a clamping length of 25 mm, a measuring length of 10 mm as standard, 50 mm / min pulling speed and 10 kN pulling force.
  • the details for the production of the cylindrical strands and for the measurement of the modulus of elasticity and the elongation at break are as follows:
  • the polycarbonates are dried at 60 to 80 ° C. for 4 to 12 hours in vacuo.
  • 4 to 5 g of the material are placed in a melt flow capillary rheometer (e.g. type MP-D from Göttfert).
  • the strands with a load of 2.16 kg at 150 ° C. are extruded through the die of the rheometer (cylindrical die of 2 mm diameter) and allowed to cool in air.
  • Tensile test the approx.
  • the choice of catalyst therefore essentially determines the property profile of the polycarbonates.
  • the process according to the invention allows the production of polycarbonate molding compositions with tailored properties which can be varied within wide limits, in particular tailored and variable mechanical properties.
  • polycarbonates according to the invention are notable for good biodegradability, i.e. they are broken down comparatively quickly by microorganisms in the ground, sunlight, hydrolysis or several of these mechanisms.
  • the invention accordingly also relates to the polycarbonates obtainable by the process according to the invention, in particular also those with at least 50, in particular at least 70%, carbonate linkages in the polymer chain, and those with good biodegradability.
  • the invention furthermore relates to thermoplastic molding compositions which contain the polycarbonates mentioned.
  • Other constituents of these molding compositions can be polymers, for example polyesters such as polybutylene terephthalate, polyethylene, and biodegradable polymers.
  • aromatic-aliphatic copolyesters eg Ecoflex® from BASF
  • polyanhydrides polyhydroxybutyrates
  • polyethylene glycols polyvinyl alcohols
  • polyvinyl acetates polyvinyl acetates
  • cellulose acetates starch acetates called do.
  • thermoplastic molding compositions may also contain conventional additives and processing aids.
  • additives and processing aids are lubricants and mold release agents, colorants such as pigments and dyes, flame retardants, antioxidants, light stabilizers, fibrous and powdery fillers and reinforcing agents and antistatic agents in the amounts customary for these agents.
  • the molding compositions according to the invention can be produced by mixing processes known per se, for example by melting in an extruder, Banbury mixer. Kneader, roller mill or calender at temperatures from 150 to 300 ° C. However, the components can also be mixed "cold" without melting and the powdery or granular mixture is only melted and homogenized during processing.
  • Moldings of all kinds can be produced from the molding compounds.
  • the films can be produced by extrusion, rolling, calendering and other processes known to the person skilled in the art.
  • the molding compositions according to the invention are thereby heated and / or friction alone or with the use of softening or other additives to form a processable film or a sheet (plate).
  • the processing into three-dimensional shaped bodies of all kinds takes place, for example, by injection molding.
  • the coatings come e.g. Coatings of surfaces made of paper, wood, plastic, metal or glass.
  • thermoplastic molding compositions according to the invention for the production of moldings, films, films, coatings and fibers. Furthermore, the molded articles obtainable by using the thermoplastic molding compositions are films, films, coatings and fibers.
  • Zn (Glu) zinc glutarate, produced as follows:
  • 35 g of ground zinc oxide in 250 ml of absolute toluene were placed in a 1 1 four-necked flask which was provided with a stirring bone, heating bath and a water circuit. After adding 52 g of glutaric acid, the mixture was heated to 55 ° C. for 2 hours with stirring. The mixture was then heated to boiling, the water of reaction being distilled off azeotropically until no more water passed over. The toluene was distilled off and the residue was dried at 80 ° C. under high vacuum.
  • DMC double metal cyanide compound, prepared as follows:
  • the wur- 8 kg Pluronic ® PE 6200 (this is a EO-PO block copolymer having 20 wt.% EO and an average molecular weight of about 2000 to 5000, available from BASF) and 10.7 kg of water with stirring, added.
  • 67.5 kg of aqueous zinc acetate dihydrate solution (zinc content: 2.7% by weight) were metered in with stirring (stirring energy: 1W / 1) at 50 ° C. within 20 min.
  • the suspension was stirred at 55 ° C. until the pH had dropped from 3.7 to 2.7 and remained constant.
  • the precipitate suspension thus obtained was then filtered off by means of a filter press and washed in the filter press with 400 l of water.
  • the moist filter cake obtained was dried in a forced air oven at 60 ° C. to constant weight.
  • the inert reaction medium toluene was dried over sodium.
  • the catalyst (type and amount see tables) was placed in a reactor.
  • the reactor was flushed with N 2 gas, heated to 130 ° C. under a stream of N and kept at these conditions for 4 hours. Then allowed to cool to room temperature.
  • the inert reaction medium toluene (amount see tables) was pressed into the reactor with CO 2 gas. It was then pushed into the reactor at room temperature (23 ° C) as long as C0, to the bark in the Ta ⁇ mentioned C0 2 -Vortik was reached. The duration of this contacting of the catalyst with CO 2 was 1 to 120 min, depending on the CO 2 pressure and reactor volume.
  • the epoxide (type and amount see tables) was then pressed into the reactor with CO gas and the reactor was then heated to the reaction temperature T R given in the tables. Subsequently, at the reaction temperature T R, C0 2 was pressed into the reactor until the final C0 pressure given in the tables was reached. The reactor was kept at the reaction temperature T R for a certain time (time duration see tables), whereby no C0 2 was replenished. The mixture was then allowed to cool to room temperature.
  • the reactor was vented and the reactor contents were in 1 1 methanol, which was concentrated with 5 ml. Hydrochloric acid (37% by weight) was acidified, poured in. A polymer precipitated out, which was filtered off and dried in vacuo at 60 ° C. overnight.
  • the methanol liquid phase obtained on filtering was also evaporated to dryness on a rotary evaporator. A polymer-containing residue was obtained.
  • the polymer obtained is a mixture (blend) of alternating polycarbonate (I in the above-mentioned scheme) and polyether homopolymer III or a random polyether carbonate copolymer II
  • an NMR spectrometer AMX 300 from Fa Bruker 1 H and 13 C NMR spectra of pure alternating polycarbonate I, of pure polyether homopolymer III and of the polymer obtained were recorded and compared with one another.
  • the polymer precipitated was a polyether carbonate copolymer and not a blend.
  • the precipitated polymer as well as the polymer obtained from the methanol liquid phase in the case of the R examples, were examined for molecular weights, glass transition and melting temperatures, and for the proportion of carbonate linkages, and for by-products (cyclic carbonates and polyethers).
  • ERC 7510 differential refractometer from ERC
  • HFiP Gel guard column and HFiP Gel linear separation column both from Polymer Laboratories
  • the glass transition temperatures T g and melting temperatures T m given in the tables were determined by means of differential scanning calorimetry (DSC) in accordance with DIN 53765. The details were as follows: heating from room temperature to 180 ° C., cooling to -100 ° C., heating to 180 ° C., rate in each case 20 K / min, determination in the second run.
  • DSC differential scanning calorimetry
  • the tables labeled A contain the reaction conditions (see test instructions above) and the tables labeled B indicate the results.
  • M w weight average molecular weight
  • M n number average molecular weight
  • Table 1A C0 / PO copolymer, variation of C0 2 pressure and temperature, conditions
  • Example 10 was repeated to check the reproducibility.
  • Example 10 was repeated to check the reproducibility.
  • Example 2V shows that the process according to the invention did not work with a non-anhydrous catalyst. It proves that it is essential to the invention to use the catalyst in anhydrous form.
  • Examples 3 to 8V illustrate the influence of the variation in the CO 2 end pressure.
  • C0 end pressures of 150 to 50 bar (Examples 3 to 6)
  • polycarbonates with molecular weights M w over 200,000 were obtained, which contained a maximum of 5% by weight of undesired by-products (sum of cyclic carbonates and polyethers).
  • C0 end pressures of 20 bar (Examples 7V to 8RV) polycarbonates with molecular weights M w up to approx. 110,000 were obtained which contained more than 5% by weight of by-products.
  • the example pair 4/5 illustrates the variation in the amount of catalyst.
  • Examples 9V and 10 illustrate the influence of the variation in the reaction temperature T R. At temperatures of 50 ° C (example 9V) to give polycarbonates which more than 5 wt .-% unwanted 'by-products contained. In contrast, showed temperatures of 65 ° C (Example 10) polycarbonates with most 5 wt .-% by-products.
  • Examples 11 to 15 zinc glutarate was used as the catalyst, not DMC.
  • Polycarbonates were obtained whose molar masses M w were comparable to the polycarbonates produced by means of DMC.
  • the proportion of carbonate linkages was 88 to 97% higher than that of polycarbonates via DMC.
  • Example 16 is identical to Example 4 from Tables 1A and 1B and was listed again for better comparability.
  • Example 16 is identical to Example 4 from Tables 1A and IB and was listed here again for better comparability.
  • Examples 16 to 19 show that a reduction in the amount of catalyst and an increase in the amount of epoxy (PO) gives polycarbonates with high molar masses M w .
  • Tables 3A and B below illustrate a scale-up of the process to larger product quantities.
  • An autoclave with 3.5 1 instead of 300 ml volume was used.
  • Example 20 is identical to Example 4 from Tables 1A and IB and was listed again for better comparability.
  • Example 20 is identical to Example 4 from Tables 1A and 1B and was listed again for better comparability.
  • Examples 20 to 23 show that a scale-up by a factor of 10 (examples 20 and 21), by a factor of 15 (examples 20 and 22) or by a factor of 21 (examples 20 and 23) was possible: 24 ml PO were used in Example 20, 240 ml PO in Example 21, 360 ml PO in Example 22 and 500 ml PO in Example 23. The profile of properties of the polycarbonates obtained was comparable.
  • the process according to the invention is therefore also flexible with regard to the amounts of substance used or obtained.
  • Table 4A CO 2 / EO copolymer, variation of CO 2 pressure and temperature, conditions
  • Examples 24 to 26 show the influence of the variation of final CO pressure and reaction temperature T R for EO as epoxy.
  • T R reaction temperature
  • Example 10 The mechanical properties of the polycarbonates from Example 10 (copolymer of CO and PO with DMC catalyst) and from Example 12 (copolymer of CO and PO with Zn (Glu) catalyst) were determined and compared with those of other polymers.
  • These other polymers were ültradur® B 4520, a polybutylene terephthalate PBT (polyester) from BASF and Ecoflex®, an aromatic-aliphatic biodegradable copolyester from BASF.
  • strands were produced from the polymers as follows: the polycarbonates were dried at 60 to 80 ° C. for 4 to 12 hours in vacuo. 4 to 5 g of the material were placed in a melt flow capillary rheometer (type MP-D from Gottfert). After 3 to 4 minutes of preheating, the strands were extruded with a load of 2.16 kg at 150 ° C. through the die of the rheometer (cylindrical die of 2 mm diameter) and allowed to cool in air.
  • the measurement was carried out in a tensile test at 23 ° C, as follows: the approx. 50 mm long strands with a diameter of 2.5 mm were examined with a tensile force of 10 kN, the clamping length (distance between the clamping jaws) 25 mm and the measuring length Standard path was 10 mm.
  • the tensile tests were carried out at two different train speeds, namely 5 mm / min and 50 mm / min, see examples 28a and 28b.
  • the measurement was carried out in accordance with DIN 53455-3.
  • Example 27 the polycarbonate from Example 10 (here Example 27) produced using DMC showed a significantly lower modulus of elasticity and a much higher elongation at break than the polycarbonate from Example produced using Zn (Glu) 12 (here example 28a).
  • the polycarbonate via DMC catalyst was therefore flexible and the polycarbonate via Zn (Glu) catalyst was tough.
  • the polycarbonate shows a modulus of elasticity via Zn (Glu) catalyst that comes close to the PBT Ultradur®.
  • the polycarbonate via DMC catalyst shows a modulus of elasticity and an elongation at break that come close to that of the Ecoflex® polyester.
  • the method according to the invention accordingly allows the production of polycarbonates with interesting and tailor-made property profiles.

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Abstract

L'invention concerne un procédé de fabrication de polycarbonates aliphatiques de poids moléculaire élevé présentant les propriétés suivantes : leur poids moléculaire moyen en poids <o>M</o>w est de 30000 à 1000000 ; et, leur teneur en carbonates cycliques et en polyéthers est de 5 % en poids max. au total. Lesdits polycarbonates sont fabriqués par polymérisation de dioxyde de carbone avec au moins un époxyde en présence d'au moins un catalyseur choisi dans le groupe des carboxylates de zinc et des composés de cyanure multimétalliques. Le procédé selon l'invention est caractérisé en ce que le catalyseur est employé sous forme anhydre et mis en contact avec au moins une quantité partielle du dioxyde de carbone avant addition de l'époxyde.
PCT/EP2002/010406 2001-09-27 2002-09-17 Procede de fabrication de polycarbonates aliphatiques Ceased WO2003029325A1 (fr)

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Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006061237A1 (fr) * 2004-12-10 2006-06-15 Basf Aktiengesellschaft Procede pour produire et utiliser des polycarbonates a haut poids moleculaire
WO2010100052A1 (fr) 2009-03-03 2010-09-10 Basf Se Carbonate de polyalkylène résistant à l'agglomération
WO2011089120A1 (fr) 2010-01-20 2011-07-28 Bayer Materialscience Ag Procédé d'activation de catalyseurs de cyanure métallique double pour produire des polyéthercarbonate polyols
WO2011101395A1 (fr) 2010-02-18 2011-08-25 Basf Se Dispersion de polymère qui contient un polycarbonate très ramifié comprenant des groupes acide gras insaturé
WO2011107499A1 (fr) 2010-03-05 2011-09-09 Basf Se Procédé de fabrication de carbonates de polyalkylène
WO2011107577A2 (fr) 2010-03-05 2011-09-09 Basf Se Sels de zinc modifiés de diacides alcane en c4-8 et leur utilisation comme catalyseur de polymérisation
WO2012032028A1 (fr) 2010-09-09 2012-03-15 Bayer Materialscience Ag Procédé de production de polyéthercarbonate polyols
EP2450407A2 (fr) 2010-11-08 2012-05-09 Basf Se Couche de protection anti-bruit comprenant du carbonate de polypropylène
EP2451860A2 (fr) 2009-07-05 2012-05-16 Novomer, Inc. Compositions de poly(carbonate de propylène) précises du point de vue de la structure
WO2012139994A1 (fr) 2011-04-13 2012-10-18 Basf Se Procédé de couplage d'époxydes et du dioxyde de carbone
EP2548905A1 (fr) 2011-07-18 2013-01-23 Bayer MaterialScience AG Procédé de activation de catalyseurs de cyanure métallique double pour la fabrication de polyols de polyéther
EP2548906A1 (fr) 2011-07-18 2013-01-23 Bayer MaterialScience AG Procédé dýactivation de catalyseurs de cyanure métallique double pour la fabrication de polyols de polyéther
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WO2013030300A1 (fr) 2011-09-02 2013-03-07 Basf Se Mousses renfermant du carbonate de polypropylène
WO2013034489A1 (fr) 2011-09-09 2013-03-14 Basf Se Procédé de préparation de dicarboxylate de zinc
EP2586818A1 (fr) 2011-10-26 2013-05-01 Basf Se Procédé de fabrication de dispersions de carbonates de polypropylène
EP2604642A1 (fr) 2011-12-16 2013-06-19 Bayer Intellectual Property GmbH Procédé destiné à la fabrication de polyéthercarbonatpolyoles
EP2604641A1 (fr) 2011-12-16 2013-06-19 Bayer Intellectual Property GmbH Procédé de fabrication de polyols de carbonate d'ester de polyéther
EP2703425A1 (fr) 2012-08-27 2014-03-05 Bayer MaterialScience AG Procédé destiné à la fabrication de polyéthercarbonatpolyoles
EP2703426A1 (fr) 2012-08-27 2014-03-05 Bayer MaterialScience AG Procédé destiné à la fabrication de polyéthercarbonatpolyoles
EP2433986A4 (fr) * 2009-05-22 2014-08-27 Lg Chemical Ltd Composition de résine pour produit moulé à jeter, et produit moulé à jeter fait de la résine
US9006425B2 (en) 2009-03-18 2015-04-14 University Of York Aluminum complexes and their use in the synthesis of cyclic carbonates
EP2865700A1 (fr) 2013-10-23 2015-04-29 Bayer MaterialScience AG Procédé destiné à la fabrication de polyéthercarbonatpolyoles
DE102014223786A1 (de) 2013-12-10 2015-06-11 Basf Se Polymermischung für Barrierefilm
EP2886572A1 (fr) 2013-12-17 2015-06-24 Bayer MaterialScience AG Utilisation d'alcools d'uréthane pour la fabrication de polyéthercarbonatepolyols
US9242955B2 (en) 2007-04-25 2016-01-26 University Of York Synthesis of cyclic carbonates
US9273024B2 (en) 2008-03-07 2016-03-01 University Of York Synthesis of cyclic carbonates
EP3023447A1 (fr) 2014-11-18 2016-05-25 Covestro Deutschland AG Procédé destiné à la fabrication de polyéthercarbonatpolyoles
EP3050907A1 (fr) 2015-01-28 2016-08-03 Covestro Deutschland AG Procédé destiné à la fabrication de polyéthercarbonatpolyoles
EP3098252A1 (fr) 2015-05-26 2016-11-30 Covestro Deutschland AG Utilisation d'alcools, comprenant au moins deux groupes uréthane, destinés à la production de polyols de carbonate de polyéther
EP3219741A1 (fr) 2016-03-18 2017-09-20 Covestro Deutschland AG Procede de production de polyethercarbonatpolyoles
US9815965B2 (en) 2013-08-02 2017-11-14 Covestro Deutschland Ag Method for producing polyether carbonate polyols
EP3260483A1 (fr) 2016-06-22 2017-12-27 Covestro Deutschland AG Procédé de production de polyéthercarbonatpolyoles
US9868816B2 (en) 2008-09-17 2018-01-16 Saudi Aramco Technologies Company Aliphatic polycarbonate quench method
WO2018073313A1 (fr) 2016-10-18 2018-04-26 Repsol, S.A. Nouveaux polymères à masse moléculaire élevée présents dans des déchets de matières premières
EP3336130A1 (fr) 2016-12-19 2018-06-20 Covestro Deutschland AG Procédé destiné à la fabrication de polyoles de thiocarbonate de polyéther
KR101902047B1 (ko) 2011-07-18 2018-09-27 바이엘 인텔렉쳐 프로퍼티 게엠베하 폴리에테르 카르보네이트 폴리올의 제조 방법

Families Citing this family (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7521521B2 (en) 2003-09-12 2009-04-21 Basf Aktiengesellschaft Highly functional highly branched or hyperbranched polycarbonates and the production and use hereof
DE102004005652A1 (de) 2004-02-04 2005-08-25 Basf Ag Fließfähige Polyesterformmassen
DE102004005657A1 (de) 2004-02-04 2005-08-25 Basf Ag Fließfähige Polyesterformmassen
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DE102005002044A1 (de) 2005-01-14 2006-07-20 Basf Ag Fließfähige Polyester mit Hydrolyseschutz
DE102005004856A1 (de) 2005-02-01 2006-08-03 Basf Ag Fliessfähige Polyester mit Carbodilmid-Stabilisatoren
DE102005009166A1 (de) 2005-02-25 2006-08-31 Basf Ag Hochfunktionelle, hoch- oder hyperverzweigte Polycarbonate sowie deren Herstellung und Verwendung
US7671228B2 (en) * 2005-03-29 2010-03-02 Basf Corporation Method of forming a polyethercarbonate polyol using a CO2-philic compound or substituent
DE102005027549A1 (de) 2005-06-14 2006-12-21 Basf Ag Mehrkomponentenformkörper mit Polyesterschichten
US7977501B2 (en) 2006-07-24 2011-07-12 Bayer Materialscience Llc Polyether carbonate polyols made via double metal cyanide (DMC) catalysis
JP5591116B2 (ja) 2007-11-19 2014-09-17 ビーエーエスエフ ソシエタス・ヨーロピア 光沢色のためのポリマー分散液における高分岐ポリマーの使用
CN101910207B (zh) 2007-11-19 2013-04-24 巴斯夫欧洲公司 高度支链化聚合物用于制备具有改进的冻结/融化稳定性的聚合物分散体的用途
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CA2716792C (fr) 2008-03-14 2017-04-18 Basf Se Elastomeres de polyurethane a grosses cellules
JP5665734B2 (ja) * 2008-05-09 2015-02-04 コーネル ユニバーシティー エチレンオキシドと二酸化炭素とのポリマー
EP2159240A2 (fr) 2008-09-01 2010-03-03 Basf Se Mousses de polyuréthane plastiquement déformables
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ATE517149T1 (de) 2009-05-11 2011-08-15 Basf Se Verstärkte styrolcopolymere
DE102009034767A1 (de) 2009-07-25 2011-01-27 Lanxess Deutschland Gmbh & Co. Kg Organoblechstrukturbauteil
KR20120102725A (ko) 2009-11-26 2012-09-18 바스프 에스이 화장품 및 피부과용 제제에서의 초분지형 폴리카르보네이트의 용도
BR112012013800B1 (pt) 2009-12-09 2019-09-03 Basf Se composição, anfifílico, processo para preparar o anfifílico, método para solubilizar um ingrediente ativo e método para controlar fungos fitopatogênicos
DE102010008410A1 (de) * 2010-02-18 2011-08-18 Bayer MaterialScience AG, 51373 Verfahren zur Herstellung von Polyethercarbonatpolyolen
KR20130100912A (ko) 2010-05-05 2013-09-12 바스프 에스이 삽입부 및 플라스틱 재킷류를 포함하는 구성요소 및 그의 제조 방법
EP2395039A1 (fr) 2010-05-21 2011-12-14 Basf Se Moyen polymère de protection contre les flammes
WO2012136657A1 (fr) * 2011-04-04 2012-10-11 Henkel Ag & Co. Kgaa Procédé pour la copolymérisation d'époxydes avec du dioxyde de carbone
EP2557104A1 (fr) * 2011-08-12 2013-02-13 Basf Se Procédé de fabrication de polyalkylène de carbonate de bas poids moléculaire
KR102118431B1 (ko) * 2014-10-31 2020-06-09 에스케이이노베이션 주식회사 고내열성 폴리알킬렌 카보네이트 수지 조성물
US10316131B2 (en) 2014-12-23 2019-06-11 Basf Se Hyperbranched polymer modified with isocyanate linker and mix of short and long chain alkyl polyether
EP3298065A4 (fr) 2015-05-21 2019-02-27 Basf Se Préparation de polycarbonate polyols hyper-ramifiés et leur utilisation
WO2017065957A1 (fr) 2015-10-16 2017-04-20 Basf Se Résines fonctionnelles multi acrylates ou vinyléthers à forte réactivité et durcissables par application d'énergie
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EP4185627A1 (fr) 2020-07-23 2023-05-31 Basf Se Application de l'ouverture de cycle d'uretdiones à basse température et sous atmosphère ambiante
CN116848175A (zh) * 2021-09-29 2023-10-03 株式会社Lg化学 制备聚碳酸亚烷基酯树脂的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953383A (en) * 1972-07-21 1976-04-27 Nippon Oil Seal Industry Co., Ltd. Catalytic process for copolymerizing epoxy compounds with carbon dioxide
US4500704A (en) * 1983-08-15 1985-02-19 The Dow Chemical Company Carbon dioxide oxirane copolymers prepared using double metal cyanide complexes
US5026676A (en) * 1989-06-07 1991-06-25 Air Products And Chemicals, Inc. Catalyst for the copolymerization of epoxides with CO2
DE19737547A1 (de) * 1997-08-28 1999-03-04 Buna Sow Leuna Olefinverb Gmbh Katalysatorsystem zur Herstellung von Polyalkylencarbonaten

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900424A (en) * 1972-07-21 1975-08-19 Nippon Oil Seal Ind Co Ltd Catalyst for copolymerizing epoxy compounds with carbon dioxide
RU2128658C1 (ru) * 1996-08-27 1999-04-10 Ярославский государственный технический университет Способ получения циклических карбонатов с многократным использованием катализатора

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953383A (en) * 1972-07-21 1976-04-27 Nippon Oil Seal Industry Co., Ltd. Catalytic process for copolymerizing epoxy compounds with carbon dioxide
US4500704A (en) * 1983-08-15 1985-02-19 The Dow Chemical Company Carbon dioxide oxirane copolymers prepared using double metal cyanide complexes
US5026676A (en) * 1989-06-07 1991-06-25 Air Products And Chemicals, Inc. Catalyst for the copolymerization of epoxides with CO2
DE19737547A1 (de) * 1997-08-28 1999-03-04 Buna Sow Leuna Olefinverb Gmbh Katalysatorsystem zur Herstellung von Polyalkylencarbonaten

Cited By (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7728099B2 (en) 2004-12-10 2010-06-01 Basf Se Preparation and use of ultrahigh-molecular-weight polycarbonates
WO2006061237A1 (fr) * 2004-12-10 2006-06-15 Basf Aktiengesellschaft Procede pour produire et utiliser des polycarbonates a haut poids moleculaire
US9242955B2 (en) 2007-04-25 2016-01-26 University Of York Synthesis of cyclic carbonates
US9273024B2 (en) 2008-03-07 2016-03-01 University Of York Synthesis of cyclic carbonates
US9868816B2 (en) 2008-09-17 2018-01-16 Saudi Aramco Technologies Company Aliphatic polycarbonate quench method
WO2010100052A1 (fr) 2009-03-03 2010-09-10 Basf Se Carbonate de polyalkylène résistant à l'agglomération
US9006425B2 (en) 2009-03-18 2015-04-14 University Of York Aluminum complexes and their use in the synthesis of cyclic carbonates
EP2433986A4 (fr) * 2009-05-22 2014-08-27 Lg Chemical Ltd Composition de résine pour produit moulé à jeter, et produit moulé à jeter fait de la résine
US8748555B2 (en) 2009-07-05 2014-06-10 Novomer, Inc. Structurally precise poly(propylene carbonate) compositions
EP2451860A2 (fr) 2009-07-05 2012-05-16 Novomer, Inc. Compositions de poly(carbonate de propylène) précises du point de vue de la structure
US8933192B2 (en) 2010-01-20 2015-01-13 Bayer Intellectual Property Gmbh Process for the activation of double metal cyanide catalysts for the preparation of polyether carbonate polyols
WO2011089120A1 (fr) 2010-01-20 2011-07-28 Bayer Materialscience Ag Procédé d'activation de catalyseurs de cyanure métallique double pour produire des polyéthercarbonate polyols
WO2011101395A1 (fr) 2010-02-18 2011-08-25 Basf Se Dispersion de polymère qui contient un polycarbonate très ramifié comprenant des groupes acide gras insaturé
WO2011107499A1 (fr) 2010-03-05 2011-09-09 Basf Se Procédé de fabrication de carbonates de polyalkylène
CN102869444A (zh) * 2010-03-05 2013-01-09 巴斯夫欧洲公司 C4-8-链烷二羧酸的改性锌盐及其用作聚合催化剂的用途
WO2011107577A3 (fr) * 2010-03-05 2011-12-29 Basf Se Sels de zinc modifiés de diacides alcane en c4-8 et leur utilisation comme catalyseur de polymérisation
WO2011107577A2 (fr) 2010-03-05 2011-09-09 Basf Se Sels de zinc modifiés de diacides alcane en c4-8 et leur utilisation comme catalyseur de polymérisation
DE102010040517A1 (de) 2010-09-09 2012-03-15 Bayer Materialscience Aktiengesellschaft Verfahren zur Herstellung von Polyetherpolyolen
WO2012032028A1 (fr) 2010-09-09 2012-03-15 Bayer Materialscience Ag Procédé de production de polyéthercarbonate polyols
EP2450407A2 (fr) 2010-11-08 2012-05-09 Basf Se Couche de protection anti-bruit comprenant du carbonate de polypropylène
WO2012139994A1 (fr) 2011-04-13 2012-10-18 Basf Se Procédé de couplage d'époxydes et du dioxyde de carbone
KR20140053197A (ko) * 2011-07-18 2014-05-07 바이엘 인텔렉쳐 프로퍼티 게엠베하 폴리에테르 폴리올의 제조방법
WO2013010987A1 (fr) 2011-07-18 2013-01-24 Bayer Intellectual Property Gmbh Procédé d'activation de catalyseurs à base de cyanure métallique double pour produire des polyols de polyéthercarbonate
EP2548905A1 (fr) 2011-07-18 2013-01-23 Bayer MaterialScience AG Procédé de activation de catalyseurs de cyanure métallique double pour la fabrication de polyols de polyéther
US9249259B2 (en) 2011-07-18 2016-02-02 Bayer Intellectual Property Gmbh Method for activating double metal cyanide catalysts for producing polyether polyols
EP2548906A1 (fr) 2011-07-18 2013-01-23 Bayer MaterialScience AG Procédé dýactivation de catalyseurs de cyanure métallique double pour la fabrication de polyols de polyéther
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US9309356B2 (en) 2011-07-18 2016-04-12 Bayer Intellectual Property Gmbh Method for activating double metal cyanide catalysts for the production of polyether carbonate polyols
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WO2013011015A1 (fr) 2011-07-18 2013-01-24 Bayer Intellectual Property Gmbh Procédé de production de polyols polyéthers
US9120894B2 (en) 2011-07-18 2015-09-01 Bayer Intellectual Property Gmbh Method for producing polyether polyols
WO2013011014A1 (fr) 2011-07-18 2013-01-24 Bayer Intellectual Property Gmbh Procédé d'activation de catalyseurs de cyanure bimétallique pour produire des polyols polyéthers
WO2013030300A1 (fr) 2011-09-02 2013-03-07 Basf Se Mousses renfermant du carbonate de polypropylène
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