WO2001056694A1 - Compositions de catalyseur d'esterification - Google Patents

Compositions de catalyseur d'esterification Download PDF

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Publication number
WO2001056694A1
WO2001056694A1 PCT/GB2001/000001 GB0100001W WO0156694A1 WO 2001056694 A1 WO2001056694 A1 WO 2001056694A1 GB 0100001 W GB0100001 W GB 0100001W WO 0156694 A1 WO0156694 A1 WO 0156694A1
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acid
catalyst composition
alcohol
metal
titanium
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PCT/GB2001/000001
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English (en)
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Charles Mark Lindall
John Ridland
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Acma Limited
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Publication of WO2001056694A1 publication Critical patent/WO2001056694A1/fr

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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0212—Alkoxylates
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0202—Polynuclearity
    • B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • 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
    • B01J2531/46—Titanium
    • 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
    • B01J2531/48—Zirconium
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds

Definitions

  • este ⁇ fication catalyst compositions and in particular este ⁇ fication catalyst compositions which comprise novel organometaUic compositions based on a combination of titanium or zirconium with other metals
  • Organotitanium compounds and, in particular, titanium alkoxides or orthoesters are known as catalysts for este ⁇ fication processes During the este ⁇ fication, these compounds are frequently converted to insoluble compounds of titanium which result in a hazy product The presence of a haze is a particular disadvantage in polyesters which have a high viscosity and/or high melting point and are therefore difficult to filter Furthermore, many organotitanium compounds which re effective catalysts in the manufacture of polyesters such as polyethylene terephthalate are known to produce unacceptable yellowing in the final polymer GB-A-2314081 relates to an este ⁇ fication process in which these problems are partially solved but there is still a need for a catalyst which induces little or no yellowing in a polyester produced using the catalyst
  • a catalyst composition suitable for use as a catalyst for the preparation of an ester comprises an organometaUic compound which is a complex of a first metal selected from the group consisting of titanium or zirconium, a second metal selected from the group consisting of germanium, antimony or tin, and a carboxyhc acid
  • a process for the preparation of an ester comprises carrying out an este ⁇ fication reaction in the presence of a catalyst composition comprising an organometaUic compound which is a complex of a first metal selected from the group consisting of titanium and zirconium, a second metal selected from the group consisting of germanium, antimony and tin, and a carboxyhc acid
  • the first metal is titanium or zirconium and, preferably, is titanium
  • the second metal is selected from the group consisting of germanium, antimony and tin but is preferably germanium or antimony It is preferably present in an amount such that the molar ratio of first metal to second metal is in the range 99 1 to 1 99 More preferably, the molar ratio of first metal to second metal is in the range 50 1 to 1 50
  • a number of carboxyhc acids, having one or more than one carboxyl group, can be used to form the complexes which comprise the catalysts of the invention, but preferably, the acid contains from 1 to 20, more preferably from 1 to 12 carbon atoms
  • Suitable unsubstituted carboxyhc acids include acetic acid, oxalic acid, cap ⁇ c acid and lau ⁇ c acid
  • a useful class of acids is hydroxy carboxyhc acids and, preferably, 2-hydroxy carboxyhc acids In this class, preferred acids include lactic acid, citric acid, malic acid and tarta ⁇ c acid
  • the preferred molar ratio of acid to total metal in the complex is 4 1 to
  • the catalyst composition of the invention includes as a further component a solubihsing compound
  • a preferred solubihsing compound is an alcohol containing at least two hydroxyl groups
  • the alcohol is a dihydnc alcohol and may be a 1 ,2-d ⁇ ol such as 1 ,2-ethaned ⁇ ol or 1 ,2- propanediol, a 1 ,3-d ⁇ ol such as 1 ,3-propaned ⁇ ol, a 1 ,4-d ⁇ ol such as 1 ,4-butaned ⁇ ol, a diol containing non-terminal hydroxyl groups such as 2-methyl-2,4-pentaned ⁇ ol, cyclohexane dimethanol, or a dihydnc alcohol containing a longer chain such as diethylene glycol or a polyethylene glycol Preferred dihydnc alcohols are 1 ,2-ethaned ⁇ ol and diethylene glycol
  • the organometaUic compound can
  • a base may also be used in preparing the complex which is the catalyst composition of the invention
  • the base may be useful to stabilise the complex and/or neutralise the acidic component
  • Suitable inorganic bases include sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide
  • Preferred organic bases include quaternary ammonium compounds such as tetrabutyl ammonium hydroxide, tetraethyl ammonium hydroxide (TEAH), chohne hydroxide (tr ⁇ methyl(2- hydroxyethyl)ammon ⁇ um hydroxide) or benzylt ⁇ methyl ammonium hydroxide, or alkanolamines such as monoethanolamine, diethanolamine, t ⁇ ethanolamine and trnsopropanolamine
  • Particularly preferred organic bases include chohne hydroxide and TEAH, which have been found to produce polyester having particularly good colour properties when used in the catalysts of the invention When present, the amount of base used is usually in the range 10 to
  • Condensed orthoesters suitable for preparing the organometaUic compounds used in this invention are typically prepared by careful hydrolysis of titanium or zirconium orthoesters Titanium or zirconium condensed orthoesters are frequently represented by the formula R'0[M(OR') 2 0]R' in which R' represents an alkyl group and M represents titanium or zirconium Preferably n is less than 20 and more preferably is less than 10 Preferably, R' contains 1 to 12 carbon atoms more preferably, R' contains 1 to 6 carbon atoms and useful condensed orthoesters include the compounds known as polybutyl titanate, polyisopropyl titanate and polybutyl zirconate
  • One method of preparing a complex consists of reacting an orthoester or condensed orthoester of the first metal with the hydroxy acid and a suitable source of the second metal
  • by-product alcohol e g isopropanoi when the orthoester is tetraisopropoxy titanium
  • the base and alcohol containing at least two hydroxyl groups may then be added and, if necessary, further by-product alcohol removed
  • the catalysts may be
  • a derivative of the second metal with the carboxyhc acid (for example, germanium citrate) is prepared, usually with the addition of a solvent e g water or another solvent e g an alcohol such as ethanol or methanol, to dissolve the acid and this is then reacted with the product derived from mixing together the alcohol containing at least two hydroxyl groups, the base and an orthoester or condensed orthoester of the first metal By-product alcohol and water may be removed during the preparation, normally by distillation
  • a solvent e g water or another solvent e g an alcohol such as ethanol or methanol
  • the este ⁇ fication reaction of the process of the invention can be any reaction by which an ester is produced
  • the reaction may be (i) a direct este ⁇ fication in which a carboxyhc acid or its anhydride and an alcohol react to form an ester or (n) a transeste ⁇ fication (alcoholysis) in which a first alcohol reacts with a first ester to produce an ester of the first alcohol and a second alcohol produced by cleavage of the first ester or (in) a transeste ⁇ fication reaction in which two esters are reacted to form two different esters by exchange of alkoxy radicals
  • Direct este ⁇ fication or transeste ⁇ fication can be used in the production of polymeric esters and a preferred process of the invention comprises a polyeste ⁇ fication process
  • Many carboxyhc acids and anhydrides can be used in direct este ⁇ fication including saturated and unsaturated monocarboxy c acids and anhydrides of such acids such as stearic acid, isostea ⁇ c acid, cap ⁇
  • esters employed in an alcoholysis reaction are generally the lower homologues such as methyl, ethyl and propyl esters since, during the este ⁇ fication reaction, it is usual to eliminate the displaced alcohol by distillation
  • lower homologue esters of the acids suitable for direct este ⁇ fication are suitable for use in the transeste ⁇ fication process according to the invention
  • (meth)acrylate esters of longer chain alcohols are produced by alcoholysis of esters such as methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate
  • Typical alcohols used in alcoholysis reactions include butyl, hexyl, n-octyl and 2-ethyl hexyl alcohols and substituted alcohols such as dimethyiaminoethanol
  • esters When the este ⁇ fication reaction is a transeste ⁇ fication between two esters, generally the esters will be selected so as to produce a volatile product ester which can be removed by distillation
  • polymeric esters can be produced by processes involving direct este ⁇ fication or transeste ⁇ fication and a particularly preferred embodiment of the este ⁇ fication process of the invention is a polyeste ⁇ fication reaction in the presence of the catalyst composition described hereinbefore in a polyeste ⁇ fication reaction
  • polybasic acids or esters of polybasic acids are usually reacted with polyhydric alcohols to produce a polymeric ester
  • Linear polyesters are often produced from dibasic acids such as those mentioned hereinbefore or esters of said dibasic acids and dihydnc alcohols
  • Preferred polyeste ⁇ fication reactions according to the invention include the reaction of terephthalic acid or dimethyl terephthalate, optionally with a proportion of the isophthalate or isophthahc acid, with 1 ,2-ethaned ⁇ ol (ethylene glycol) to produce polyethylene terephthalate or with 1 ,3-propaned ⁇ ol (propylene glycol) to produce polypropylene terephthalate, also known
  • este ⁇ fication reaction of the invention can be carried out using any appropriate, known technique for an este ⁇ fication reaction
  • a typical process for the preparation of polyethylene terephthalate comprises two stages In the first stage terephthalic acid or dimethyl terephthalate is reacted with 1 ,2-ethaned ⁇ ol to form a prepolymer and the by-product water or methanol is removed The prepolymer is subsequently heated in a second stage to remove 1 ,2-ethaned ⁇ ol and form a long chain polymer Either or both these stages may comprise an este ⁇ fication process according to this invention Processes may be operated either on a batch or a continuous basis
  • the ester, first alcohol and catalyst composition are mixed and, generally, the product alcohol (second alcohol) is removed by distillation, often as an azeotrope with the ester Frequently it is necessary to fractionate the vapour mixture produced from the alcoholysis in order to ensure that the second alcohol is separated effectively without significant loss of product ester or first alcohol
  • the conditions under which alcoholysis reactions are carried out depend principally upon the components of the reaction and generally components are heated to the boiling point of the mixture used
  • a preferred process of the invention is the preparation of polyethylene terephthalate
  • a typical batch production of polyethylene terephthalate is carried out by charging terephthalic acid and ethylene glycol to a reactor along with catalyst composition, if desired, and heating the contents to 260 - 270° C under a pressure of about 0 3 Mpa (40 psi) Reaction commences as the acid dissolves and water is removed The product is transferred to a second autoclave reactor and catalyst composition is added, if needed The reactor is heated to 285 - 310° C under an eventual vacuum of 100 Pa (1 mbar) to remove ethylene glycol by-product The molten product ester is discharged from the reactor cooled and chipped The chipped polyester may be then subjected to solid state polymerisation, if appropriate
  • a preferred means of adding the catalyst compositions of this invention to a polyeste ⁇ fication reaction is in the form of a solution in the glycol being used (e g ethylene glycol in the preparation of polyethylene terephthalate) This method of addition is applicable to addition of the catalyst composition to the polyestenfication reaction at the first stage or at the second stage
  • the amount of catalyst used in the este ⁇ fication process of the invention generally depends upon the total metal content (expressed as amount of first metal plus amount of second metal) of the catalyst composition Usually the amount is from 50 to 400 parts per million (ppm) of total metal based on weight of product ester for direct or transeste ⁇ fication reactions Preferably the amount is from 75 to 300 ppm of total metal based on weight of product ester In polyestenfication reactions the amount used is generally expressed as a proportion of the weight of product polyester and is usually from 3 to 500 ppm expressed as total metal (first metal plus second metal) based on product polyester Preferably the amount is from 5 to 300 ppm expressed as total metal based on product polyester
  • a colour managing compound is added to the polyestenfication reaction in order to counteract any yellowing which may occur in the finished polymer product
  • the compound used is a cobalt compound and this may be done in the preparation of PET by e g adding cobalt acetate tetrahydrate in glycol in an amount up to 100 ppm preferably 0 - 75 ppm
  • Alternative or additional colour managing compounds include organic dyes Normally phosphorus stabilisers are added to polyester at the polyestenfication stage at a level of up to about 200 ppm, preferably 0 - 100 ppm The amount used is carefully controlled in order to avoid poisoning the este ⁇ fication catalysts
  • the phosphorous may be added in many forms, including phosphoric acid, phosphorous acid, phosphate esters, phosphonic acids, pyrophosphates, phosphites and others known in the art
  • Additional compounds may be added to the polyestenfication reaction if required Such additives include dyes, optical b ⁇ ghteners, pigments, dye pretreatments, reheat agents and delustrants such as titanium dioxide Solid state polymerisation accelerators may also be added It may also be required to control the co-products of the polyestenfication process, in particular the diethylene glycol (DEG) content of the polymer, by addition of DEG suppressants such as bases or amines, as is known in the art
  • DEG diethylene glycol
  • DEG suppressants such as bases or amines
  • the DEG content of the polymer is believed to affect the thermal properties of the polymer
  • the DEG content should be low although for textile fibre it may be desirable to control the level of DEG to 0 8 - 1 5 weight %
  • Citric acid monohydrate 131 34 g, 0 625 moles were placed in a reaction flask with 100 g of deminera sed water and stirred for approximately 15 minutes
  • titanium isopropoxide 63 95 g, 0 225 moles
  • germanium iso-propoxide 7 72 g, 0 025 moles
  • the product was then heated to reflux for 60 minutes and left to stir overnight with no heating
  • the product was then distilled at atmospheric pressure to remove water/isopropanol
  • the resultant solution was allowed to cool to room temperature and then 32% wt aqueous sodium hydroxide solution (95g, 0 76 moles) was added to it over 30 minutes
  • the solution was then diluted with ethylene glycol (125 35 g, 2 02 moles) and stirred for 20 minutes
  • the product was filtered and a second distillation was then carried out under reduced pressure to remove remaining isopropanoi and water
  • the product was a colourless, highly viscous solution having a Ti content of
  • Example 2 demineralised water and stirred for 15 minutes
  • To the solution was added 2 05 g of titanium isopropoxide (0 0072 moles) and 20 00 g of germanium iso-propoxide (0 064 moles) over 30 minutes
  • the mixture was then heated to reflux for 60 minutes and left to stir overnight with no heating
  • the product was then distilled at atmospheric pressure to remove water/isopropanol
  • the resultant solution was allowed to cool to room temperature and then 32% wt aqueous sodium hydroxide solution (27 35 g , 0 219 moles) added to it over 30 minutes
  • the solution was then diluted with ethylene glycol (36 09 g, 0 582 moles) and stirred for 20 minutes
  • the product was filtered and a second distillation was then carried out under reduced pressure to remove remaining isopropanoi and water
  • the product was a green mobile solution having a Ti content of 0 44% wt and a Ge content of 5 93% wt
  • a germanium citrate was prepared as follows germanium dioxide (3 952 g, 0 0378 moles) was placed in a round-bottomed flask and suspended in water (14 g) After stirring for 15 minutes, citric acid monohydrate (22 0 g, 0 105 moles) was added over 20 minutes The resulting mixture was stirred for 90 minutes at room temperature, then heated to 85° C over 240 minutes and then allowed to cool to room temperature overnight The product was diluted with monoethylene glycol (15 6 g) to yield a clear solution having a Ge content of 4 94% by weight
  • Monoethylene glycol 44 7 g, 0 72 mole was added to titanium tetra-n-butoxide (6 18 g, 0 018 mole) in a beaker and stirred for 20 minutes 32% wt aqueous sodium hydroxide solution (2 16 g 0 018 mole) was added dropwise over 10 minutes followed by the germanium citrate solution (2 94 g, 0 002 mole Ge) over a further 10 minutes to yield a clear colourless solution This product contained 1 55% Ti and 0 26% Ge by weight
  • Monoethylene glycol (37 25 g, 0 60 mole) was added to titanium tetra-n-butoxide (5 10 g, 0 015 mole) in a beaker and stirred for 20 minutes 32% wt aqueous sodium hydroxide solution (1 80 g 0 015 mole) was added dropwise over 10 minutes followed by germanium citrate solution as prepared in Example 3 (7 35 g, 0 005 mole Ge) over a further 10 minutes to yield a clear colourless solution
  • This product contained 1 40% Ti and 0 70% Ge by weight
  • Example 5 Monoethylene glycol (24 85 g, 0 40 mole) was added to titanium tetra-n-butoxide (3 40 g, 0 01 mole) in a beaker and stirred for 20 minutes 32% wt aqueous sodium hydroxide solution (1 2 g 0 01 mole) was added dropwise over 10 minutes followed by germanium citrate solution prepared as in Example 3 above (14 7 g, 0 01 mole Ge) over a further 10 minutes to yield a clear colourless solution This product contained 1 09% Ti and 1 64% Ge by weight
  • Example 6 Monoethylene glycol (12 42 g, 0 2 mole) was added to titanium tetra-n-butoxide (1 7 g, 0 005 mole) in a beaker and stirred for 20 minutes 32% wt aqueous sodium hydroxide solution (0 60 g 0 005 mole) was added dropwise over 10 minutes followed by germanium citrate solution prepared as in Example 3 above (22 05 g, 0 015 mole Ge) over a further 10 minutes to yield a clear colourless solution This product contained 0 65% Ti and 2 96% Ge by weight
  • Germanium dioxide (3 986 g) was placed in a round- bottomed flask and suspended in water (14 0 g) After stirring for 15 minutes, oxalic acid (10 33 g, 0 115 moles) was added slowly over 20 minutes The resulting mixture was stirred for 90 minutes at room temperature then heated to 85° C over 240 minutes Finally it was allowed to cool to room temperature overnight The product was diluted with monoethylene glycol (15 6 g) to yield a clear solution having a Ge content of 6 31 % by weight
  • Monoethylene glycol (37 25 g, 0 60 mole) was added to titanium tetra-n-butoxide (5 10 g, 0 015 mole) in a beaker and stirred for 20 minutes 32% wt aqueous sodium hydroxide solution (1 80 g 0 015 mole) was added dropwise over 10 minutes followed by germanium oxalate solution prepared as above (5 75 g, 0 005 mole Ge) over a further 10 minutes to yield a clear colourless solution This product contained 1 44% Ti and 0 73% Ge by weight
  • Monoethylene glycol (12 42 g, 0 20 mole) was added to titanium tetra-n-butoxide (1 70 g, 0 005 mole) in a beaker and stirred for 20 minutes 32% wt aqueous sodium hydroxide solution (0 60 g 0 005 mole) was added dropwise over 10 minutes followed by germanium oxalate solution prepared as in Example 7 above (17 24 g, 0 015 mole Ge) over a further 10 minutes to yield a clear colourless solution This product contained 0 75% Ti and 3 40% Ge by weight
  • Citric acid monohydrate 132 5 g, 0 63 moles was dissolved in water (92 8 g)
  • titanium isopropoxide 72 0 g, 0 25 moles
  • This mixture was heated to reflux for 1 hour to yield a hazy solution
  • This solution stripped under vacuum to remove free water and isopropanoi
  • the product was cooled below 70°C and 32 %w/w aqueous sodium hydroxide (94 9 g, 0 76 moles) was added slowly to the stirred solution
  • the product was filtered, mixed with ethylene glycol (125 5 g, 2 0 moles) and heated under vacuum to remove free water/isopropanol
  • the product was a slightly hazy, very pale yellow liquid (Ti content 3 85 % by weight)
  • a polycondensation reaction was carried out in a mechanically-stirred 300 ml glass vessel fitted with side arm and cold trap for collection of monoethylene glycol
  • a thermostatically controlled ceramic heating element was used to provide heat and an oil vacuum pump was connected to the cold trap
  • A5 nitrogen blanket was provided via a connection to the cold trap
  • Polyethylene terephthalate was prepared from terephthalic acid-based prepolymer having a glycol acid ratio of 1 3 1 and a degree of polymerisation of 6 5 100 g of prepolymer was placed in the reaction flask under a nitrogen flow, followed by a dilute solution of catalyst component calculated on0 prepolymer weight to give the required level of metals, in monoethylene glycol This was heated to 250° C and stirred for 25 minutes, at which point a monoethylene glycol solution of stabiliser was added (phosphoric acid, calculated to produce the equivalent of 32 or 16 ppm P in the mixture) The nitrogen flow was stopped and vacuum applied steadily to 200 mbar After 25 minutes the temperature was increased steadily from 250° C to 290° C As the reaction progressed the current required to5 maintain a constant stirrer speed increased up to a value of 109 5 mA, at which point reaction was deemed to be complete If this current was not registered after 130 minutes, the reaction was stopped at that time The vacuum was then broken with nitrogen and the molten
  • the polymer intrinsic viscosities (I V s) were measured by glass capillary viscometry using 60/405 phenol/1 , 1 , 2, 2-tetrachlorethane as solvent
  • the polymers were examined by 1 H NMR spectroscopy to determine the amount of diethylene glycol (DEG) residues present in the polymer chain (expressed as weight per cent of polymer), the proportion of hydroxyl (OH) end groups present (expressed as number of end groups per 100 polymer repeating units) and the proportion of vinyl end groups (VEG) present (expressed as number of end groups per 100 polymer repeating units)
  • DEG diethylene glycol
  • OH hydroxyl
  • VEG vinyl end groups
  • the number average molecular weight and molecular weight distribution were determined by gel permeation chromatography (GPC)of the polymer dissolved in orthochlorophenol
  • the catalysts were used to prepare polyethylene terephthalate (PET) in a larger reactor Ethylene glycol (2 04 kg) and terephthalic acid (4 55 kg) were charged to a stirred jacketed reactor The catalyst and other additives were added and the reactor heated to 226 - 252 °C at a pressure of 40 psi to initiate the first stage direct esterification (DE) process Water was removed as it was formed with recirculation of the ethylene glycol On completion of the DE reaction the contents of the reactor were allowed to reach atmospheric pressure before a vacuum was steadily applied The stabilisers were added and the mixture heated to 290 ⁇ 2 °C under vacuum to remove ethylene glycol and yield polyethylene terephthalate The final polyester was discharged once a constant torque had been reached which indicated an IV of around 0 62 The properties of the polymers were measured as described in Example 11 and are reported in Table 3
  • Example 3 and Example 4 show standard recrystalhsation enthalpies on cooling
  • the germanium solution and Examples 5 and 6 show reduced crystalhnity levels and relatively low recrystalhsation temps (Tc and Tco) This reduction in overall crystalhnity indicates clean polymers
  • Tc and Tco recrystalhsation temperatures
  • the titanium - germanium mixed catalyst compositions of the invention have the advantage of requiring considerably less germanium metal than is usually used for making polyesters which has considerable economic benefit because germanium is a very expensive metal in comparison with titanium or antimony
  • the Examples demonstrate that titanium - germanium catalysts usually produce polyester with improved colour compared with the polyester produced using the titanium only catalyst with similar hgand chemistry prepared in Example 9 These catalysts also unexpectedly usually produce polyester at faster rates than polyester produced using the titanium only catalysts with similar hgand chemistry in Example 9
  • the titanium - antimony catalysts have the advantage of requiring considerably less antimony metal
  • the high levels of antimony required in conventional polyester reactions using antimony only catalysts leave considerable residues in the polyester which can cause blockages in downstream processing equipment such as spinnerets, cause unsightly haze in bottles and also cause crystallisation problems in the finished polymer
  • the titanium - antimony catalysts shown in Example 10 produces polyester with improved colour compared with the polyester produced using titanium only catalysts with similar hgand chemistry in Example 9
  • the titanium - antimony catalysts shown Example 10 also unexpectedly produces polyester at a faster rate than polyester produced using titanium only catalyst in Example 9 Table 1
  • Tg polymer glass transition temperature
  • Tn 0 onset of crystallisation (heating)
  • Tp melting point
  • Tc crystallisation (cooling)

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

Abstract

L'invention concerne une composition de catalyseur pouvant servir de catalyseur dans la préparation d'un ester, y compris d'un polyester, qui contient un composé organométallique. Ce composé organométallique est un complexe d'un premier métal sélectionné dans le groupe comprenant titane et zirconium ; d'un deuxième métal sélectionné dans le groupe comprenant germanium, antimoine et étain ; et d'acide carboxylique, de préférence en présence d'un alcool possédant au moins deux groupes hydroxy et une base. La composition de catalyseur peut contenir en outre un alcool dihydrique et une base.
PCT/GB2001/000001 2000-02-01 2001-01-03 Compositions de catalyseur d'esterification WO2001056694A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001223831A AU2001223831A1 (en) 2000-02-01 2001-01-03 Esterification catalyst compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0002156.8A GB0002156D0 (en) 2000-02-01 2000-02-01 Esterification catalyst compositions
GB0002156.8 2000-02-01

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AR (1) AR026841A1 (fr)
AU (1) AU2001223831A1 (fr)
CO (1) CO5231193A1 (fr)
GB (1) GB0002156D0 (fr)
UY (1) UY26572A1 (fr)
WO (1) WO2001056694A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003080705A1 (fr) * 2002-03-20 2003-10-02 Cyclics Corporation Systemes catalytiques
US6713601B2 (en) 2000-09-12 2004-03-30 Cyclics Corporation Species modification in macrocyclic polyester oligomers, and compositions prepared thereby
US6787632B2 (en) 2001-10-09 2004-09-07 Cyclics Corporation Organo-titanate catalysts for preparing pure macrocyclic oligoesters
US6831138B2 (en) 2002-01-07 2004-12-14 Cyclics Corporation Polymer-containing organo-metal catalysts
US6841505B2 (en) 2002-07-26 2005-01-11 E..I. Du Pont De Nemours And Company Titanium-zirconium catalyst compositions and use thereof
WO2005035622A1 (fr) * 2003-10-07 2005-04-21 Johnson Matthey Plc Catalyseur pour la fabrication d'esters
US6953768B2 (en) 2002-11-26 2005-10-11 Teck Cominco Metals Ltd. Multi-component catalyst system for the polycondensation manufacture of polyesters
EP1602679A1 (fr) * 2003-03-07 2005-12-07 Mitsubishi Chemical Corporation Catalyseur de polymerisation de polyester, son procede de production et procede pour la production de polyester au moyen d'un tel catalyseur
WO2011114348A1 (fr) 2010-03-17 2011-09-22 Reliance Industries Limited Système de catalyseur et procédé de préparation de résines, fibres, filaments et fils polyester à l'aide dudit système de catalyseur
EP2765150A1 (fr) * 2013-02-06 2014-08-13 Lotte Chemical Corporation Composition de résine pour la fabrication de résine de polyester thermoplastique obtenue par l'utilisation de catalyseur vert
CN113896869A (zh) * 2021-12-10 2022-01-07 江苏新视界先进功能纤维创新中心有限公司 在连续聚合装置上制备色相品质良好的环保pet聚酯的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3346541A (en) * 1961-03-09 1967-10-10 Ici Ltd Process for manufacturing linear fiber and film forming polyesters by polycondensation in the presence of a titanium alkoxide catalyst and a germanium compound
US4131601A (en) * 1976-10-05 1978-12-26 Teijin Limited Process for the preparation of polyesters
US5385773A (en) * 1993-04-27 1995-01-31 Eastman Chemical Company Copolyester of cyclohexanenedimethanol and process for producing such polyester
WO1998056848A1 (fr) * 1997-06-10 1998-12-17 Akzo Nobel N.V. Procede de production de polyesters et de copolyesters
WO2000071252A1 (fr) * 1999-05-25 2000-11-30 Acma Limited Catalyseurs d'esterification

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3346541A (en) * 1961-03-09 1967-10-10 Ici Ltd Process for manufacturing linear fiber and film forming polyesters by polycondensation in the presence of a titanium alkoxide catalyst and a germanium compound
US4131601A (en) * 1976-10-05 1978-12-26 Teijin Limited Process for the preparation of polyesters
US5385773A (en) * 1993-04-27 1995-01-31 Eastman Chemical Company Copolyester of cyclohexanenedimethanol and process for producing such polyester
WO1998056848A1 (fr) * 1997-06-10 1998-12-17 Akzo Nobel N.V. Procede de production de polyesters et de copolyesters
WO2000071252A1 (fr) * 1999-05-25 2000-11-30 Acma Limited Catalyseurs d'esterification

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6713601B2 (en) 2000-09-12 2004-03-30 Cyclics Corporation Species modification in macrocyclic polyester oligomers, and compositions prepared thereby
US6787632B2 (en) 2001-10-09 2004-09-07 Cyclics Corporation Organo-titanate catalysts for preparing pure macrocyclic oligoesters
US6831138B2 (en) 2002-01-07 2004-12-14 Cyclics Corporation Polymer-containing organo-metal catalysts
WO2003080705A1 (fr) * 2002-03-20 2003-10-02 Cyclics Corporation Systemes catalytiques
US6841505B2 (en) 2002-07-26 2005-01-11 E..I. Du Pont De Nemours And Company Titanium-zirconium catalyst compositions and use thereof
EP1562704A4 (fr) * 2002-07-26 2009-08-12 Du Pont Compositions de catalyseur titane-zirconium et utilisation de celles-ci
EP1562704A1 (fr) * 2002-07-26 2005-08-17 E.I. Du Pont De Nemours And Company Compositions de catalyseur titane-zirconium et utilisation de celles-ci
US7153811B2 (en) 2002-11-26 2006-12-26 Teck Cominco Metals Ltd Multi-component catalyst system for the polycondensation manufacture of polyesters
US6953768B2 (en) 2002-11-26 2005-10-11 Teck Cominco Metals Ltd. Multi-component catalyst system for the polycondensation manufacture of polyesters
EP1602679A4 (fr) * 2003-03-07 2007-02-28 Mitsubishi Chem Corp Catalyseur de polymerisation de polyester, son procede de production et procede pour la production de polyester au moyen d'un tel catalyseur
EP1602679A1 (fr) * 2003-03-07 2005-12-07 Mitsubishi Chemical Corporation Catalyseur de polymerisation de polyester, son procede de production et procede pour la production de polyester au moyen d'un tel catalyseur
US7332564B2 (en) 2003-03-07 2008-02-19 Mitsubishi Chemical Corporation Polymerization catalyst for polyester, method for producing it and process for producing polyester using it
EP1964870A1 (fr) * 2003-03-07 2008-09-03 Mitsubishi Chemical Corporation Procédé de production de polyester
US7834128B2 (en) 2003-03-07 2010-11-16 Mitsubishi Chemical Corporation Polymerization catalyst for polyester, method for producing it and process for producing polyester using it
CN100413908C (zh) * 2003-10-07 2008-08-27 约翰森·马瑟公开有限公司 用于制造酯的催化剂
EA011171B1 (ru) * 2003-10-07 2009-02-27 Джонсон Мэтти Плс Катализатор для получения сложных эфиров, способ получения сложного эфира и способ получения сложного полиэфира с участием такого катализатора
WO2005035622A1 (fr) * 2003-10-07 2005-04-21 Johnson Matthey Plc Catalyseur pour la fabrication d'esters
WO2011114348A1 (fr) 2010-03-17 2011-09-22 Reliance Industries Limited Système de catalyseur et procédé de préparation de résines, fibres, filaments et fils polyester à l'aide dudit système de catalyseur
EP2765150A1 (fr) * 2013-02-06 2014-08-13 Lotte Chemical Corporation Composition de résine pour la fabrication de résine de polyester thermoplastique obtenue par l'utilisation de catalyseur vert
CN113896869A (zh) * 2021-12-10 2022-01-07 江苏新视界先进功能纤维创新中心有限公司 在连续聚合装置上制备色相品质良好的环保pet聚酯的方法

Also Published As

Publication number Publication date
AU2001223831A1 (en) 2001-08-14
UY26572A1 (es) 2001-04-30
AR026841A1 (es) 2003-02-26
GB0002156D0 (en) 2000-03-22
CO5231193A1 (es) 2002-12-27

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