WO2005102519A1 - Procede de polycondensation utilisant un catalyseur et catalyseur convenant a ce procede - Google Patents

Procede de polycondensation utilisant un catalyseur et catalyseur convenant a ce procede Download PDF

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Publication number
WO2005102519A1
WO2005102519A1 PCT/EP2005/004355 EP2005004355W WO2005102519A1 WO 2005102519 A1 WO2005102519 A1 WO 2005102519A1 EP 2005004355 W EP2005004355 W EP 2005004355W WO 2005102519 A1 WO2005102519 A1 WO 2005102519A1
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catalyst
tri
tetra
penta
group
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PCT/EP2005/004355
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German (de)
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Rudolf Kaempf
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Zimmer Aktiengesellschaft
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/52—Antimony

Definitions

  • the invention relates to a method for producing polycondensates using a catalyst and the catalyst which can be used therefor.
  • the invention relates in particular to catalysts for use in polycondensation, these being able to have polymeric structures and not to carry groups which are not present in the production of polycondensates, such as polyesters, for example polyethylene terephthalate (PET), polybutylene terephthalate (PBT) or polytrimethylene terephthalate (PTT). , Polycarbonates, polyamides.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PTT polytrimethylene terephthalate
  • Polycarbonates polyamides.
  • the polycondensates are generally by reacting dialcohols, such as ethylene glycol, propylene glycol, butanediol, polyethers, such as polyethylene glycol, polypropylene glycol, polytetrahydrofuran, and also di- or bisphenols, and / or diamines with dicarboxylic acids, such as terephthalic, isophthalic, phthalic acid, or with adipic acid get their esterified dicarboxylic acids, such as dimethyl terephthalate or dicarbonates.
  • dialcohols such as ethylene glycol, propylene glycol, butanediol
  • polyethers such as polyethylene glycol, polypropylene glycol, polytetrahydrofuran, and also di- or bisphenols
  • dicarboxylic acids such as terephthalic, isophthalic, phthalic acid, or with adipic acid get their esterified dicarboxylic acids, such as dimethyl terephthal
  • a mixture of at least two of the monomers in the presence of bi-, tri- or tetraalkyloxy metal catalysts such as boron (III) phenolate, boron (III) butylate, titanium (IV) butylate or tin (IV)
  • Catalyst solution containing isopropylate is subjected to esterification or transesterification at temperatures in the range from 100 to 350 ° C. and then subjected to polycondensation.
  • the specialty plastics polybutylene terephthalate (PBT) and polytrimethylene terephthalate (PTT) and the bulk plastic polyethylene terephthalate (PET) from the range of polyesters are produced by reacting terephthalic acid (TPA) or dimethyl terephthalate (DMT) with butanediol, propanediol and ethylene glycol using catalysts.
  • TPA terephthalic acid
  • DMT dimethyl terephthalate
  • esters of the two, three or higher metal acids associated with monohydric alcohols of low chain length have the disadvantage that these types of catalysts are entrained in the fission product vapors due to their low boiling points and low volatility. Since they decompose thermally or can be easily reduced, dark-colored deposits can appear on the apparatus walls, heated metallic surfaces or areas with poor flow. Especially on heated reactor walls, in process columns and in collecting tanks, these deposits, which impair the quality of the manufactured product, can occur.
  • WO 02/42537 discloses a process for producing polyester, in which a mixture is used as the catalyst, which comprises a) an organometallic compound which comprises the reaction product of an orthoester or a condensed orthoester of titanium, Is zirconium or aluminum, an alcohol with at least two hydroxyl groups, a 2-hydroxycarboxylic acid and a base, and b) at least one compound of germanium, antimony or tin.
  • WO 02/44243 describes catalysts for the production of polyesters for the production of which a) orthoesters or condensed orthoesters of titanium and / or zirconium with b) one or more polyols which contain at least two hydroxyl groups and a number average molecular weight of at least 180 g / moles are implemented.
  • EP-A-1 308 208 describes activated titanium catalysts suitable for use in esterification or transesterification which are gel-like and which comprise a mixture of an alkoxytitanium, a water-soluble polyol and water or are a reaction product thereof.
  • Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol or other higher monohydric alcohols are present as chain lengths limiting or terminating, since they react with the carboxyl groups of the carboxylic acids to form a monoester which is no longer viable ,
  • the alkanols liberated from the catalyst cause additional costs when disposing of the cleavage products, such as water, since the alcohols contained therein are present in a very dilute form. They represent an unnecessary problem in waste water treatment due to higher chemical and biological oxygen consumption. With the low concentration, stripping processes or further rectification are cost-intensive and ineffective, so that they are usually disposed of with the waste water. There, in addition to the biological and chemical oxygen demand, they also increase the amount of sewage sludge. If valuable by-products, such as tetrahydrofuran or acrolein, are obtained during polymer production, the alkanols derived from the catalyst make cleaning them more difficult by extraction, distillation and rectification. In many cases, together with by-products, they form azeotropic mixtures with valuable side reaction products that can be recovered, which can only be remedied by increased energy and apparatus expenditure.
  • the invention is therefore based on the object of firstly providing storage-stable catalysts with specifically adjusted and improved reactivity, secondly, in the production of polymers, in particular during esterification, that no additional non-reactive substances and / or compounds are introduced into the reaction, thirdly, no impurities of the fission product (s) or distillate or wastewater and fourthly bring economic benefits.
  • Polycondensate obtainable from the reaction of at least one monomer A) with the general formula R 1 (X) m where R 1 is selected from the group consisting of linear or branched alkylene, alkenylene, alkynylene, arylene, polyether and
  • X is a functional group, which can be the same or different, is selected from the group consisting of hydroxyl, -O - , amino, carboxyl, carboxylate and mercapto groups and, m is an integer> (greater than or equal to) 2 , with at least one monomer B) with the general formula R 2 (Y) 2 , where R 2 is selected from the group consisting of alkylene,
  • Y is a group which can react with the functional groups X of the monomer A) by means of a condensation reaction, and z is an integer> (greater than or equal to) 2, or at least a monomer B) with the general formula R 2 ' -O-
  • R 2 ' and R 2" may be the same or different and are selected from the group consisting of alkyl, alkenyl, alkynyl, aryl and
  • M is selected from at least one element from main group I, II, III, IV, V and subgroup III, IV, V, VI, VII, VIII of the periodic table
  • R is the same or different and is selected from the group consisting of alkyl, alkenyl, aryl and alkylaryl radicals
  • n is 1, 2, 4, 5 or 6, with b) at least one of the monomers A), which in the production of the polycondensate can be used.
  • R 1 (X) m and R 2 (Y) Z mean that the radicals R 1 and R 2 form the basic body of the monomer A) or B) comprising carbon atoms, which is branched or linear, saturated or unsaturated, aliphatic and / or aromatic and interrupted by oxygen atoms, in the case of polyether, and the functional groups X or Y can be bound to any carbon atom of the base body of the monomer A) or B).
  • the polycondensates obtainable by the process according to the invention are preferably selected from the group consisting of polyesters, polycarbonates, polyarylates, polyarylene sulfones, polyether sulfones, polysulfonates, polyethers, polyphenyl sulfones,
  • Polyester phosphates polyester phosphonates, polycarbonate phosphates, polycarbonate phosphonates, polybisphenyl phosphonates, polyurethanes, polyanhydrides, polyetherimides, polyetheramides, polyamides, polyamideimides, polyimides, polycarbodiamides, polycarbodiimides and polysiloxanes and polyamides.
  • polycondensates are polyesters, they are preferably selected from the group consisting of polyethylene, polytrimethylene, polybutylene, polybutylene polyTHF, polydimethylcyclohexyl, polyphenylene terephthalate, isophthalate, phthalate and naphthalate. If di p PnlvknnH n ⁇ at.
  • Pnlvoarbonate are, these are preferably selected from the group consisting of poly-bisphenoxy, poly-bisphenoxypropane, poly-hydroquinone, poly-bisphenoxycyclohexylpropane, polyethylene, polybutylene, polynapthoxy and polyphosphonatocarbonates, and if the polycondensates are polyamides, these are preferably selected from the group consisting of Group consisting of polyphenylene isophthalamide, polyphenylene phthalamide, polynaphtamide polyether amide terephthalate, isophthalate, phthalate, naphthalate and polyphenylene adipate.
  • the present invention particularly preferably relates to a process for producing polyesters, polyamides and polycarbonates, in particular polyesters and polycarbonates.
  • alkane preferably means an alkane, alkyl or alkylene radical having 1 to 10, preferably 1 to 6 and in particular 1 to 4 carbon atoms.
  • Alkinylene preferably means an alkene, alkenyl or alkenylene radical or an alkyne, alkynyl or alkinylene radical having 2 to 10, preferably 2 to 6 and in particular 2 to 4, carbon atoms.
  • aryl or arylene preferably means a mono- or polynuclear aromatic radical.
  • the aryl or arylene radical preferably has 6 to 24, particularly preferably 6 to 10 and in particular 6, carbon atoms.
  • polyether preferably means a polyether glycol or amine having 1 to 500, more preferably 1 to 50, particularly preferably 4 to 40 and in particular 1 to 10 repeating units and in particular one O atom per monomer unit of the polyether.
  • a condensation reaction in the sense of the present invention is understood to mean any reaction of a monomer A) with a monomer B) in which water, alcohols, phenols, mercaptans or amines are released.
  • a monomer B either water is released in the polyester production, if a free carboxylic acid or a carboxylic acid anhydride is used, or alcohol if a carboxylic acid ester is used.
  • a free carboxylic acid or a carboxylic acid anhydride is used, or alcohol if a carboxylic acid ester is used.
  • the same applies to the Polycarbonate production is generally alcohol-free if, for example, a dialkyl carbonate is used as the carbonate.
  • the radical R 1 is preferably selected from the group consisting of alkyl, aryl and alkylaryl radicals.
  • the radicals X are preferably the same.
  • the radical X is particularly preferably a hydroxyl, -O ⁇ or amino group, in particular a hydroxyl group or -O - .
  • m is preferably 2 to 6, more preferably 2 to 4 and in particular 2 or 3, particularly preferably 2, i.e. the monomers A) preferably have the number m of functional groups mentioned.
  • the monomers A) are preferably selected from the group consisting of di-, tri-, tetra-, penta-, hexaalkanols, di-, tri-, tetra-, penta-, hexaalkenols, di-, tri- , Tetra-, penta-, hexaalkynols, di-, tri-, tetra-, penta-, hexa-aminoalkanes, di-, tri-, tetra-, penta-, hexa-aminoalkenes, di-, tri-, tetra-, Penta-, Hexa- aminoalkynes, Di-, Tri-, Tetra-, Penta-, Hexa-mercaptoalkanes, Di-, Tri-, Tetra-, Penta-, Hexa-mercaptoalkanes, Di-, Tri-, Tetra-, Penta-, Hexa
  • the monomer A) is particularly preferably selected from the group consisting of dialkanols, in particular ethylene glycol, propylene glycol and butanediol, hexanediol, naphthalenediol, polyethers, in particular polyethylene glycol, polypropylene glycol and polytetrahydrofuran, and di- or bisphenols such as bisphenol A to Z, hydroquinone, dihydroxydiphenyl, bishydroxyphenylcyclohexylpropane, diamines, hexamethylene diamine, phenylene diamine, diaminodiphenyl ether, diaminocyclohexane, bisaminocyclohexyl methane, and naphthalene diamine.
  • dialkanols in particular ethylene glycol, propylene glycol and butanediol, hexanediol, naphthalenediol
  • polyethers in particular polyethylene glycol,
  • the abovementioned monomers A) can be substituted one or more times, preferably 1 to 3 times, by preferably one of the radicals selected from the group consisting of halogen, such as fluorine, chlorine or bromine, cyano, nitro, C t _ -alkyl , C ⁇ - alkoxy, azo and carboxy groups.
  • halogen such as fluorine, chlorine or bromine
  • cyano nitro
  • C t _ -alkyl C ⁇ - alkoxy
  • azo and carboxy groups azo and carboxy groups.
  • the substituents can be the same or different.
  • the radical R 2 in the monomers B) which can be used according to the invention is preferably selected from the group consisting of alkylene, arylene, alkylarylene and dialkyl carbonate radicals.
  • the residues Y of the monomer B) can be the same or different, the residues Y are preferably the same.
  • the radical Y which can react with the functional groups X of the monomer A) by means of a condensation reaction, is preferably a carboxyl, carboxylate, carboxylic acid ester, carboxylic acid anhydride, sulfonic acid,
  • Y radical is a carboxylic acid anhydride group, then at least two R 2 radicals are present.
  • radical X in the monomer A) is a hydroxyl, -O - , amino or mercapto group
  • radical Y of the monomer B) is preferably a carboxyl, carboxylate, carboxylic acid ester, carboxylic acid anhydride and / or sulfonic acid group. If the radical X in the monomer A) is a
  • Carboxyl or carboxylate group is that the radical Y of the monomer B) is preferably -O ⁇ or a hydroxyl group.
  • z is preferably at least 2 to 6, in particular 2 to 4, particularly preferably 2 or 3, in particular 2, ie the monomer B) preferably has the stated number z at positions which can react with the functional groups of the monomer A) by means of a condensation reaction.
  • the radicals R 2' and R 2" are preferably selected from the group consisting of alkyl, aryl and alkylaryl radicals,
  • monomer B) is preferably selected from the group consisting of dicarboxylic acids, in particular terephthalic, isophthalic, phthalic acid, naphthalenedicarboxylic acid and adipic acid, and their esterified dicarboxylic acids, in particular dimethyl terephthalate, dimethyl naphthalate and carbonates and dicarbonates, in particular methyl ethyl and methyl phenyl , Ethylene, propylene, butylene, dimethyl, diethyl, dipropyl, dibutyl, diphenyl, dibisphenyl carbonate from the group of higher carboxylic acids and anhydrides and their esters, such as trimellitic, trimesic, pyromellitic acid, and benzophenonetetracarboxylic acid dianhydride, the group of carbosulfonic acids, sulfonic acids, their salts and esters, such as sodium isophthalic acid, dimethyl sodium
  • the process according to the invention for producing the polycondensates preferably comprises the steps of esterification and / or transesterification, precondensation or precondensation and polycondensation.
  • a catalyst which esterifies the reaction product of a two, three, four or higher metal acid ester, advantageously with a monovalent alkyloxy group having not more than 4 carbon atoms, with at least one of the substances used as monomers A) in the preparation of the polymer, which can come from the group of di- or higher alkoxides, amines, mercaptans or phenols.
  • the compounds are brought to a reaction with one another and displaced by the latter and it a linear and / or triple, quadruple or higher branched polymer is formed with the metallic acid in the center.
  • M is preferably at least one element selected from the group consisting of V, Ta, Ti, Zr, Mn, Zn, B, Al, Si, Ge, S , P, Sb, Fe, Co, Ca, Ba, Sr, In, Nb, Y, Sc, Pr, Hf, Mo, W, Cr, Mg, Sn, Li, Na, K, Cu, Ni, Pt, Er and Ag more preferably at least one element selected from the group consisting of Mn, Sb, P, Ge, Sn, Ti, Mg, Ca, Na and B.
  • the radical R in the compound M (OR) n is preferably an alkyl radical, particularly preferably a C 1. 12 alkyl, in particular a Cve alkyl radical.
  • n is preferably 1, 2, 3, 4 or 5.
  • the reaction a) of the at least one compound of the general formula M (OR) ⁇ with b) the at least one monomer A) is preferably carried out at a temperature above the boiling point of the compound ROH.
  • the alcohol ROH formed during the reaction is distilled off from the compound M (OR) n in the course of the reaction. Since the alcohol ROH generally forms an azeotrope with the water which may be present, this is simultaneously removed from the reaction mixture.
  • the catalyst obtained after the reaction thus preferably contains essentially no water.
  • Particularly preferred compounds M (OR) n compounds selected from the group consisting of barium di-i-propylate, calcium dimethylate, calcium di-i-propylate, magnesium dimethylate, diethylate, strontium diisopropylate, Aluminum triethylate, Al tri-i-propylate, Al tributylate, Al sec-butoxide, Al tert-butoxide, Al triphenolate, antimony trimethylate, antimony triethylate, antimony tri-i-propylate, antimony tripropylate .
  • the catalytic activity and the Hydrolysis stability can be set.
  • n moles of monomer A) per mole of compound M (OR) n it is particularly preferred to use less than n moles of monomer A) per mole of compound M (OR) n .
  • Particular preference is given to using n-0.01 mol to n / m mol of monomer A) per mol of compound M (OR) n , where m is the number of functional groups on monomer A, as described above in relation to monomer A) described.
  • the catalyst which can be used in the process according to the invention, obtainable after steps a) and b), as described above, can have a mnnnmom nnlvm rp linpar «nnd / nHer spatial structure
  • the catalyst preferably has a polymeric structure, preferably at least one metal M being present, as described above in relation to the compound M (OR) n .
  • Two to four metals M are particularly preferably present in the catalyst according to the invention.
  • the catalyst according to the invention can preferably contain at least Mn and Sb, more preferably Mn, Sb and P.
  • the catalyst which can be used according to the invention can preferably contain Sb, Ge, Sn and Ti or Ti, Na, P and B.
  • the systems manganese (II), antimony (III) and phosphoric, phosphoric acid esters are used in the production of PET from DMT, while only antimony (III), germanium (III), tin (IV) and Titan (IV), for PC titanium (IV), Na (l), phosphoric, phosphorous acid esters and boron (III) are used.
  • the catalyst which can be used according to the invention has a shell-like structure. This can be achieved, for example, by repeating steps a) and b) several times, preferably 2 to 4 times, in particular 2 to 3 times, particularly preferably 2 times, to prepare the catalyst, a compound M (OR) n is used, in which only one metal M is present and in the repetition of steps a) and b) a compound M (OR) "is used, the metal M being a different metal M than in each time the previous steps a) and b) used.
  • the catalyst thus obtained thus preferably has a core and at least one shell, the core and each of the at least one shell differing in that different metal atoms are present therein.
  • the catalyst preferably has 2 to 4, more preferably 2 to 3 and in particular 2 shells.
  • metal B Zr, Sn. If more than one metal is present in the core, preferably 2 to 4, more preferably 2, metals are present. If two metals are present, these are preferably Sb and Ti, Al and B, Ti and Si, Sb and Si, Sb and B, Ti and B, or Sn and B.
  • the first shell there is preferably at least one metal selected from Li, Na, Mg, Ca, Ba, K, Mn, Co, Cu, Ni, Pt and Ag, more preferably Li, Na, Mg, Mn, Co and Ag. If more than one metal is present in the first shell, preferably 2 to 4, more preferably 2, metals are present. If two metals are present, these are preferably Mg and Li, Na and Mg, Mg and Ti, Mn and Ti, Sb and Co, Ti and Ag, Sb and Si and Co, Ti, or Si and Mg.
  • the metals are preferred as indicated in relation to the first shell. If more than one metal is present in a third or further shell, preferably 2 to 4, more preferably 3, metals are present. If two or three metals are present, these are preferably Ti and Si and B, Ti and Al and B, Sb and Co, Ti and Ag, Sb and Si and Co, or Ti and Si and Mg.
  • the core of the catalyst comprises approximately 2 to approximately 1000 metal atoms, preferably approximately 3 to approximately 500 metal atoms and particularly preferably approximately 5 to approximately 200 metal atoms, while the shell preferably comprises approximately 2 to approximately 10000 metal atoms, preferably approximately 3 to about 5000 metal atoms, and more preferably about 5 to about 2000 metal atoms.
  • Such a coated catalyst then has a three-dimensional, one-dimensional, two-dimensional or multi-dimensional framework as an inner core, depending on the molar ratio of the metal ester and the valence of the metal atom to the monomer A) used, with particular differences in chain length, chain length distribution or molecular weight and molecular weight distribution affect the structure.
  • the chain length is preferably in the range from about 2 to about 1000, more preferably from about 3 to about 500 and particularly preferably from about 5 to about 200 repeating units.
  • the non-uniformity of the distribution of the repeating units is preferably in the range from approximately 1 to approximately 25, more preferably approximately 1.3 to approximately 10 and particularly preferably approximately 1.5 to approximately 8 and the degree of crosslinking is preferably in the range of about 0.1% to 100%, more preferably about 2% to about 60% and particularly preferably from about 5% to about 25%.
  • the degree of crosslinking is determined by the ratio of the metal atom bonds linked to one another via the monomer end groups. The methods for determining the degree of crosslinking are those customary in polymerization technology.
  • a catalyst can be built up that is only slightly hydrolyzed due to its polymeric structure in the esterification - where a lot of water is produced - and only develops its full activity in the precondensation / precondensation by decomposition of the polymeric structure and still carries residual activity into the final reactor.
  • This behavior can advantageously reduce the amounts of catalyst or increase the throughput due to the higher activity.
  • This measure allows the catalyst properties to be tailored to the requirements of esterification or transesterification, and the monomers B) or cleavage products can be selectively prevented from penetrating by the cavity size in the polymeric catalyst structure. This means selective reaction control and control through the design of the spatial structure of the catalyst.
  • Another possibility is to produce the outermost shell, the catalyst after the, if necessary multiple, steps a) and b) with a monomer B), for example TPA, reacting, by reacting the external OH group, the acidity of the Controlled catalyst by the catalyst is acidic by the outstanding carboxyl group.
  • a monomer B for example TPA
  • a suitable application for a shell-shaped catalyst is the production of PET from dimethyl terephthalate and ethylene glycol.
  • the problem here is that the transesterification of DMT with terephthalic acid has to be catalyzed with Mn (II), but the subsequent precondensation and polycondensation relies on Sb. Adding both together interferes with the course of the reaction or leads to losses of volatile Sb-trimethylate.
  • the use of a shell-shaped catalyst with a core in which the metal is M Sb and the shell contains Mn is advantageous in the production of PET from nMT I mr.
  • Fthvlpn ⁇ lvknl The incorporation of higher or lower value metal ester linkages can also create voids in the spatial structure.
  • the size of the cavities depends on the length of the monomers A) which connect or form the network and can be controlled by adding more or less long chains, such as, for example, the polymethylene ether glycols with different chain lengths, further distances between the Metals are generated that can range from about 2 to about 1000 ⁇ , more preferably from about 3 to about 500 ⁇ , and most preferably from about 5 to about 100 ⁇ .
  • Solvents, monomers A) and / or B) can then penetrate into these cavities and react with the catalyst and the monomers A) bound thereto.
  • the catalyst chelates by breaking up the macromolecular structure and further reacting the monomer A) with the monomer B). If monomers B) penetrate into the cavities and free the monomer A) bound to the metal from the polymer structure by means of a competitive reaction, these can then react to form a polyester molecule.
  • Na, Li, K, Cu, Mg, Ca and / or Ag can be present in the outermost shell of a shell-shaped catalyst, inter alia additionally monovalent metals of the first main and subgroup of the periodic table. They can be applied as the outermost layer after the production of the degree of branching, chain length or the molecular weight distribution and are particularly suitable for rapidly catalyzing the reaction of the monomers A) and B) on the surface. They are characterized in that they do not have any functional end groups of the monomers A) or B) on the outside.
  • the catalyst thus has a structure in which the core contains Ti and / or B and the shell contains alkali metals, in particular Li, Na, K, Cu, Mg, Ca and Ag.
  • chelation takes place in the reaction space, i.e. the catalyst is degraded to a limited extent and, because of the polymeric structure, the chelation proceeds slowly, since only there is the chelating agent, monomer A, present in a sufficiently high concentration.
  • monomer A present in a sufficiently high concentration.
  • a trivalent metal catalyst for example, when a trivalent metal catalyst is selected, molar ratios of more than 3 are only achieved and, if the polymer structure, residence time and temperature are within certain limits, the polymer structure of the catalyst is not yet completely broken down here.
  • the chelation reaction of monomer A suppresses the competition reaction of hydrolysis with cleavage products such as water or limits it to at most one valence of the catalyst metal. Due to the lower boiling point of the leaving group water in comparison to monomer A, in the ambient conditions far above the boiling point, water is displaced by monomer A during the chelation which takes place.
  • the polymeric catalysts have no groups other than those present in the product, they are already the first precursors in the catalytic activity / structure and become with the progressing residence time and monomer concentration in the reactor or in the course of the process by reaction with that available in the process Monomer A) is converted from the polymeric, spatially handicapped and less active state into a more accessible and catalytically active monomeric state.
  • divalent metal atom 0.5 molecule diol per valence O - M - O ⁇ / (CH 2 ) n divalent metal atom, 1/3 molecule triol per valence (CH 2 ) n -O / ⁇ HO- (CH 2 ) - C - HM ⁇ / (CH 2 ) n - O divalent metal atom, between 0.5 and 1 molecule of diol per valence: linear chain, polymeric structure HO- (CH 2 ) n -O- M -O- (CH 2 ) n -O - M -O- (CH 2 ) n -O- O- (CH 2 ) n -O-
  • tetravalent metal atom between 0.5 and 1 molecule of diol per valence: tetrafunctional branched chain, polymeric structure -O- (CH 2 ) n -O / (CH 2 ) n - O - M- O- (CH 2 ) n - OH / ⁇ HO - (CH 2 ) n - OO O- (CH 2 ) n -O- ⁇ / HO - (CH 2 ) n - O - M - O - (CH 2 ) n -O - M - O- ( CH 2 ) n -O- / ⁇ -O - (CH 2 ) n - OO O- (CH 2 ) ⁇ -O- / / (CH 2 ) n -O - M- O- (CH 2 ) ⁇ -O- / (CH 2 ) n -O - M- O- (CH 2 )
  • Example of a polymeric catalyst with germanium, Ge (IV) core and partial saturation of the outer shell by lithium Li (I) Li-O- (CH 2 ) n -O /. (CH 2 ) n - O-Ge-O- (CH 2 ) n -OH / ⁇ HO - (CH 2 ) n - OO O- (CH 2 ) n -OH ⁇ / HO- (CH 2 ) n - O - Ge - O - (CH 2 ) n -O - Ge - O- (CH 2 ) n -O- / ⁇ Li-O - (CH 2 ) n - OO O- (CH 2 ) n -OH / / ( CH 2 ) n -O - Ge O- (CH 2 ) n -O- Li ⁇ Li-O- (CH 2 ) n -O /.
  • the catalyst can be added in any stage of the polycondensation process, that is to say the transesterification or esterification, the precondensation or precondensation and the polycondensation. Regardless of which stage of the polycondensation process the catalyst is added to, the catalyst is not removed again from the reaction mixture, since it is chelated or gradually dissolves as described above and it is advantageous for the further stages of the polycondensation process that further active catalyst is available.
  • the catalyst is added in the transesterification or esterification stage, it can be added separately or mixed with monomer A) and / or B).
  • the catalyst is advantageously added in an amount of 10 "12 mol / mol to 10 " 1 mol / mol based on one of the monomers A and / or B.
  • the transesterification or esterification preferably takes place at temperatures in the range from approximately 100 to approximately 350 ° C., more preferably from approximately 100 to approximately 300 ° C., particularly preferably from approximately 180 to approximately 260 ° C.
  • the residence time in the transesterification or esterification is preferably between about 5 minutes and about 36 hours
  • the precondensation preferably takes place at temperatures in the range from approximately 120 to approximately 360 ° C., more preferably from approximately 140 to approximately 320 ° C., particularly preferably from approximately 190 to approximately 290 ° C.
  • the residence time in the precondensation is between 5 minutes and 36 hours.
  • the polycondensation preferably takes place at temperatures in the range from approximately 150 to approximately 380 ° C., more preferably from approximately 200 to approximately 330 ° C., particularly preferably from approximately 200 to approximately 310 ° C.
  • the residence time in the polycondensation is between 5 minutes and 36 hours.
  • the method according to the invention can be carried out as follows:
  • a first stirred kettle is fed with the mostly liquid or melted monomeric diol component, for example ethylene glycol or another
  • Monomer A in the form of a paste mixed with monomer B for example a dicarboxylic acid such as terephthalic acid.
  • the catalyst is either introduced directly into the reactor through an additional line or already added to the paste, the concentration ratio for manganese (II), for example, being set from 10 "2 to 10 " 6 mol of metal atom to mol of monomer B.
  • concentration ratio for manganese (II) for example, being set from 10 "2 to 10 " 6 mol of metal atom to mol of monomer B.
  • the components are mixed in the stirred tank, the transesterification or esterification reaction commencing.
  • cleavage products released in the transesterification or esterification reaction and from the catalyst escape as vapors such as water, methanol, propanol, acetic acid or their esters, are removed from the reaction space and drawn off via a so-called vapor line.
  • the product produced in the first reactor is conveyed to a precondensation reactor in the next reaction stage with continuous plant operation.
  • a precondensation reactor in the next reaction stage with continuous plant operation.
  • polycondensation with chain growth takes place in this reactor.
  • catalyst is fed into this reactor again, either the same in a modified form or usually a different one than that in the first transesterification or esterification stage - for example antimony (III) in a concentration of 10 "2 to 10 ⁇ mol Metal atom to mole of monomer B - since there are fewer fission products with which it can react, which impair its effectiveness.
  • Molecules with average chain lengths of up to 10 structural units are usually generated in this reaction section.
  • the technical designs of the precondensation reactor can correspond to the shape of the stirred tank , Designs that have a horizontal stirrer shaft with wheel-like stirring elements, how to she knows from the literature of polycondensation reactors, have also proven to be excellent.
  • a melt residence time of up to 6 hours is ensured in the precondensation reactor; temperatures are usually in the range of 220 to 300 ° C.
  • a blower sucks off the vapors generated during the reaction and ensures a pressure in the range of 100 to 800 mbar. Since the vapors also contain monomers in addition to the cleavage products released during the reaction, the vapors are fed to a rectifying work-up with condensation.
  • the so-called pre-condensate is fed to a so-called prepolycondensation reactor, which, for example, is designed similarly to the precondensation reactor.
  • the melt residence times in the prepolycondensation reactor are in the range of a few hours, as in the previous reactor.
  • the polycondensation reaction proceeds at temperatures in the range from 230 to 320 ° C. and a negative pressure of up to 5 mbar, which is maintained with the aid of the suction fan.
  • the intermediate product leaving the prepolycondensation reactor has molecules with an average chain length of 30 to 100 structural units and is fed to a final reactor.
  • the final reactor preferably also has stationary elements for producing high shear rates and thorough mixing of the highly viscous mass.
  • the temperatures in the final reactor are in the range from 240 to 350 ° C and the pressure is usually up to 0.1 mbar.
  • a blower extracts vapors from the final reactor and, together with the vapors from the previous reactors, feeds them for rectification.
  • the melted product is pumpable and consists of molecules with average chain lengths in the range of up to 300 structural units and is pressed into strands by nozzles, which are cooled and processed into chips by a cutting device.
  • M is selected from at least one element of the I, II, III, IV, V main group and the III, IV, V, VI, VII, VIII subgroup of the periodic table
  • R is the same or different and is selected from the group consisting of alkyl -, Alkenyl, aryl and alkylaryl radicals
  • n is 1, 2, 4, 5 or 6, with b) at least one of the monomers A) which are used in the preparation of the polycondensate.
  • the catalyst is preferred, as described above in relation to the process according to the invention.
  • the catalyst according to the invention is particularly preferably a shell-shaped catalyst, as described above.
  • the catalysts of the invention can be prepared in a specially designed reactor in which the starting components are mixed with one another and heated to above the boiling point of the alkanol to be split off.
  • the mixing ratio of the metal acid ester used with the alcohol, amine, mercaptan or phenol carrying several functional groups is chosen so that there is at least 0.5 mol and up to at most 1 mol of the monomer per valence of the metal acid.
  • the mixture is heated at least 5 ° C and up to 100 ° C above the boiling point of the alkanol or phenol contained in the metal acid ester used.
  • the alcohols, amines or phenols which generally boil less than the functional groups and boil only one functional group-bearing alkanols, monoamines or monophenols, are distilled off and the polyfunctional alkanols, alkenols, alkynols, amines, mercaptans or phenols on the metal replaced.
  • the metal acid ester which is equipped with monofunctional groups, can decompose at excessively high temperatures, so care must be taken. that, for example, exceeding 250 ° C
  • Use of antimony (III) or tin (IV) propylate is avoided. It is also conceivable to allow the exchange reaction to take place under reduced pressure, for example between 1 mbar and 980 mbar and temperatures below 200 ° C.
  • composition of the catalyst obtained can be monitored by spectroscopic, optical or electrochemical methods.
  • polyethylene terephthalate is produced by esterification of ethylene glycol with terephthalic acid.
  • the two monomers are mixed in a ratio of 1.05 to 1 as a paste in a first reactor which is operated at 250 ° C. and a slight negative pressure becomes.
  • Antimony acetate or germanium acetate are preferably used as catalysts in the established production processes.
  • a catalyst solution in the process is customary to meter a catalyst solution in the process at one point or else at several points.
  • a catalyst solution from the above-mentioned catalysts is already metered into the paste batch or the esterification stage. It is also possible to feed a catalyst solution into the EG return flow from the process column to the first process stage and, if appropriate, to one of the subsequent process stages.
  • a disadvantage of this prior art process is that the catalytically active metal atom is hydrolyzed by the water split off during the reaction and thus loses activity. Therefore, much more catalyst must be added than is necessary for the catalysis. There are also precipitations that adversely affect the product color.
  • An advantage of the present invention is that the catalytically active metal atom is protected by the polymer structure in such a way that the water liberated in the esterification reaction is prevented from making rapid contact. Furthermore, it is extremely advantageous that the monomer A used in the construction of the polymeric structure, which is also one of the basic monomers of the plastic to be produced, forms the polymeric structure of the catalyst. This prevents, on the one hand, contamination of the
  • Polymer product comes and no additional cleavage products from the catalyst complicate the purification and recycling of the monomers A and / or B and on the other hand the reaction to the polymer is hindered by blocking the functional end groups by catalyst components.
  • the catalyst according to the invention also has the advantage that, compared to other metal acid esters used as catalysts, it is less susceptible to hydrolysis, becomes less cloudy when stored for a long time and has an adaptable, improved reactivity.
  • Figure 1 shows a schematic representation of a polycondensation.
  • polyethylene terephthalate is produced by esterifying ethylene glycol with terephthalic acid by one of the known processes.
  • the two monomers are mixed in a ratio of 1.05 to 1 and introduced into a first reactor, which is operated at 250 ° C. and a slight negative pressure, and is fed to the polycondensation in scheme 1 via at least one of the lines.
  • the catalyst is customary to meter the catalyst in the process at one point or simultaneously at several points.
  • the catalyst is already metered into the paste batch (22) or into a subsequent process step (20, 23) and / or into a melt transfer line (24).
  • Polymeric antimony (III) - ethylene glycolate catalyst and line (3) ethylene glycol are fed to a stirred tank (1), mixed with one another and equipped with a stirring reactor (5) and an additional heating element (6) equipped with a stirring reactor ( 7) heated to 250 ° C.
  • Esterification produces a liquid mixture of ethylene glycol and oligomers and steam, the latter consisting essentially of water, ethylene glycol and catalyst decomposition products.
  • the esterification in the stirred reactor (7) takes place in the presence of the catalyst fed in via line (4).
  • the steam formed in the stirred reactor (7) leaves the stirred reactor (7) via line (9) and is fed to the distillation column (10), where water and the catalyst fission products are removed overhead.
  • the top product of the distillation column (10) is fed via line (11) to the cooler (12), from which the condensate runs via line (13) to the reflux distributor (14). Water is drawn off from the return distributor (14) via line (15) and the return line (16) is returned to the top of the distillation column (10).
  • the mixture leaving line (15) contains either acetic acid or alcoholic catalyst decomposition products.
  • the separation in column (10) requires because of the additional separation of acetic acid, its esters or from alkanols with additional separation stages and a higher reflux quantity.
  • the water / ethylene glycol mixture can be separated into its constituents water and ethylene glycol with fewer separation stages due to the lack of acetic acid and / or alcohol admixtures, the ethylene glycol also having a higher purity.
  • the filling process is closed, the oxygen is replaced by nitrogen and the filled mass is warmed to 120 ° C by switching on the heating. After the desired temperature has been reached, it is discharged into the subsequent reactor. After preheating to 120 ° C in a further storage tank, ethylene glycol, which is also used in the polycondensation process, is added to the antimony (III) propylate in a molar ratio of 1: 1, 43 and discharged into the subsequent reactor
  • a stirred tank apparatus In the heated reactor, a stirred tank apparatus, antimony (III) propylate and ethylene glycol are mixed by intensive stirring at 130 ° C., which produces high turbulence, which leads to high interfaces, rapid mass transfer and accelerated reaction. With a residence time of at least 85 minutes, propanol bound to the metal atom is displaced by ethylene glycol and a polymeric antimony (III) ethylene glycolate is produced. Propanol boils at 97 ° C and leaves the reactor via the vapor line, is deposited in a condenser and collected in a receiver. After obtaining at least 95% by mass of the stoichiometric amount, the
  • the polymeric antimony (III) ethylene glycolate can be used as a catalyst in the polycondensation.
  • the collected propanol has no by-products and can be used as a solvent.
  • Example 2 is carried out as described in Example 1, manganese (II) ethylate being added after the production of an antimony (III) ethylene glycolate and the temperature being maintained until all of the ethanol has escaped from the manganese (II) ethylate.
  • Example 3 is carried out as described in Example 2, using germanium tetraethylate instead of antimony (III) propylate and diethylene glycol being used as the monomer for the catalyst preparation.
  • the trapped ethanol has no by-products and can be used as a solvent, the polymeric germanium diethylene glycolate is used as a catalyst in one of the following examples.
  • a 5 liter stirred reactor is charged with 250 ppm antimony (III) acetate catalyst, 1127 g terephthalic acid (TPA) and 962 g EG. After inerting with nitrogen, the filling is heated to a temperature of 250 ° C. under normal pressure within 2 hours with stirring and esterified at this temperature for 2 hours at a pressure of 400 mbar.
  • the melt is pressed out of the reactor by means of nitrogen as a jet and is collected on a pan cooled with liquid nitrogen and solidified.
  • the product is ground and its intrinsic viscosity and filter load value determined. The values determined are shown in Table 1 below.
  • the intrinsic viscosity (IV) is measured at 25 ° C. on a solution of 500 mg polyester in 100 ml of a mixture of phenol and 1,2-dichlorobenzene (3: 2 parts by weight) and is a measure of the molecular weight of the sample and the same dwell times for the conversion or the reaction rate. The higher the IV, the higher the conversion per unit of time and consequently, in catalyzed reactions, the activity of the catalyst.
  • FW filter load value
  • PET is produced under the same process conditions as described in Example 1, but using the catalyst from Example 1
  • PET is produced under the same process conditions as described in Example 1, but using a catalyst according to Example 2.
  • PET is produced under the same process conditions as described in Example 1, but using a catalyst according to Example 3.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé pour la production d'un polycondensat, obtenu par réaction d'au moins un monomère (A) de formule générale R1(X)m (I) avec un monomère (B) de formule générale R2(Y)z (II) ou avec un monomère (B) de formule générale R2'-O-C(O)-O-R2'' (III), en présence d'au moins un catalyseur. Dans la formule (I), R1 est sélectionné dans le groupe comprenant des restes alkylène, alcénylène, alcynylène, arylène, polyéther et alkylarylène linéaires ou ramifiés, X est un groupe fonctionnel qui peut être identique ou différent et qui est sélectionné dans le groupe comprenant des groupes hydroxyle, O-, amino, carboxyle, carboxylate et mercapto et m est un nombre entier supérieur ou égal à 2. Dans la formule (II), R2 est sélectionné dans le groupe comprenant des restes alkylène, alcénylène, alcynylène, aryle, alkylaryle et dialkylcarbonate, Y est un groupe qui peut réagir par une réaction de condensation avec les groupes fonctionnels X du monomère (A) et z est un nombre entier supérieur ou égal à 2. Dans la formule (III), R2' et R2'' sont identiques ou différents et sont sélectionnés dans le groupe comprenant des restes alkyle, alcényle, alcynyle, aryle et alkylaryle. L'invention concerne également le catalyseur utilisé dans ce procédé de polycondensation.
PCT/EP2005/004355 2004-04-27 2005-04-22 Procede de polycondensation utilisant un catalyseur et catalyseur convenant a ce procede WO2005102519A1 (fr)

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DE102004020582.5A DE102004020582B4 (de) 2004-04-27 2004-04-27 Polykondensationsverfahren unter Verwendung eines Katalysators und dafür geeigneter Katalysator

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3047515A (en) * 1956-07-09 1962-07-31 Goodyear Tire & Rubber Preparation of polyesters using titanium-containing catalysts
GB1287419A (en) * 1969-02-04 1972-08-31 Ici Ltd Catalyst for polyesterification
SU602503A1 (ru) * 1976-04-29 1978-04-15 Институт химии Уральского научного центра АН СССР Тетракис-(гидроксиалкиленокси)титан как катализатор переэтерификации и поликонденсации и способ его получени
US4705764A (en) * 1985-10-03 1987-11-10 Research Development Corporation Of Japan Esterification and/or ester interchange catalyst
WO2002044243A1 (fr) * 2000-12-01 2002-06-06 Bayer Aktiengesellschaft Catalyseurs a base de titane/zirconium et leur utilisation pour produire des esters ou des polyesters
WO2004065452A1 (fr) * 2003-01-23 2004-08-05 Saudi Basic Industries Corporation Complexe catalyseur destine a catalyser les reactions d'esterification et de trans-esterification et procede d'esterification / trans-esterification reposant sur l'utilisation dudit complexe

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE546080A (fr) * 1955-03-18
CH482752A (de) * 1968-04-10 1969-12-15 Inventa Ag Verfahren zur Herstellung von Polyestern
US6489433B2 (en) * 2001-02-23 2002-12-03 E. I. Du Pont De Nemours And Company Metal-containing composition and process therewith

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3047515A (en) * 1956-07-09 1962-07-31 Goodyear Tire & Rubber Preparation of polyesters using titanium-containing catalysts
GB1287419A (en) * 1969-02-04 1972-08-31 Ici Ltd Catalyst for polyesterification
SU602503A1 (ru) * 1976-04-29 1978-04-15 Институт химии Уральского научного центра АН СССР Тетракис-(гидроксиалкиленокси)титан как катализатор переэтерификации и поликонденсации и способ его получени
US4705764A (en) * 1985-10-03 1987-11-10 Research Development Corporation Of Japan Esterification and/or ester interchange catalyst
WO2002044243A1 (fr) * 2000-12-01 2002-06-06 Bayer Aktiengesellschaft Catalyseurs a base de titane/zirconium et leur utilisation pour produire des esters ou des polyesters
WO2004065452A1 (fr) * 2003-01-23 2004-08-05 Saudi Basic Industries Corporation Complexe catalyseur destine a catalyser les reactions d'esterification et de trans-esterification et procede d'esterification / trans-esterification reposant sur l'utilisation dudit complexe

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 197910, Derwent World Patents Index; Class A60, AN 1979-19435B, XP002338174 *

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TW200603889A (en) 2006-02-01
DE102004020582B4 (de) 2020-01-30
DE102004020582A1 (de) 2005-12-01

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