WO2000061657A1 - Catalysis with titanium oxides - Google Patents
Catalysis with titanium oxides Download PDFInfo
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- WO2000061657A1 WO2000061657A1 PCT/US2000/006957 US0006957W WO0061657A1 WO 2000061657 A1 WO2000061657 A1 WO 2000061657A1 US 0006957 W US0006957 W US 0006957W WO 0061657 A1 WO0061657 A1 WO 0061657A1
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- acid
- titanium
- process according
- catalyst
- glycol
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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
Definitions
- This invention relates to a process using a titanium oxide as catalysts in an oligomerization process, polymerization process, depolymerization process, or combinations of two or more thereof.
- PET polyethylene terephthalate
- PET is generally formed into a low molecular weight prepolymer by transesterification of dimethyl terephthalate or esterification of terephthalic acid with ethylene glycol to form a bis(hydroxyalkyl)ester which is subsequently subject to polycondensation by transesterification to form a high molecular weight polyester. Because the transesterification is an inherently slow reaction, which requires holding the reactants at elevated temperatures for protracted periods with concomitant thermal degradation, the polycondensation step is generally catalyzed.
- Antimony-containing compounds are currently in widespread commercial use as catalysts which provide a desirable combination of high reaction rate and low color.
- there is considerable inducement to find a substitute for antimony because of the expense and difficulty of handling the known-to-be toxic antimony in an environmentally responsible manner.
- the present invention provides a process which can be used in oligomerization, polymerization, depolymerization, or combinations of two or more thereof such as, for example, the production of a polyester.
- the process comprises contacting a carbonyl compound with an alcohol compound in the presence of a catalyst mixture comprising a compound having the formula of M r Ti (m) Ti (IV yO (X+3+4 yy 2 wherein M is an alkali metal, Ti (m) is titanium in the +3 oxidation state, Ti (rv) is titanium in the +4 oxidation state, x and y are numbers greater than or equal to zero, and if x equals to zero, y is a number less than 1/2.
- the process can further comprise recovering the product produced by the process.
- the process can comprise, consist essentially of, or consist of contacting a carbonyl compound, in the presence of a catalyst composition and under a condition sufficient to effect the production of a polyester.
- the composition comprises, consists essentially of, or consists of a titanium catalyst having the formula of M ⁇ T ⁇ Ti ⁇ O ⁇ - ⁇ wherein M is an alkali metal, Ti (m) is titanium in the +3 oxidation state, Ti (IV) is titanium in the +4 oxidation state, x andy are numbers greater than or equal to zero, and if x equals to zero, y is a number less than 1/2.
- the aforementioned formula can be equivalently expressed M x Tiy+j ( x +s+4y)/2 or equivalently expressed as WL ⁇ /(l+y) iO( x +3+4y)/(2y+2)-
- the presently preferred titanium oxide can be expressed as TiO z in which z is a number between 1 and 1.67, preferably between 1.4 and 1.6, and most preferably 1.5.
- the presently most preferred titanium oxide is TiO, 5 or Ti 2 O 3 .
- any carbonyl compound which can react with an alcohol to produce an ester can be used.
- carbonyl compounds include, but are not limited to, acids, esters, amides, acid anhydrides, acid halides, oligomers or polymers having repeat units derived from an acid, or combinations of two or more thereof.
- the presently preferred acid is an organic acid.
- the presently preferred process is the polymerization of an acid and an alcohol for the production of a polyester.
- a preferred process for producing a polyester comprises, consists essentially of, or consists of contacting a polymerization mixture with a composition which comprises a titanium catalyst having the formula disclosed above.
- the polymerization mixture can comprise, consist essentially of, or consist of (1) either an organic acid or an ester thereof and an alcohol, or (2) an alcohol and an oligomer having repeat units derived from an organic acid or ester.
- the organic acid or ester thereof can have the formula of R'COOR 2 in which R 1 and R 2 can be the same or different and can be (1) hydrogen, (2) hydrocarboxyl radical having a carboxylic acid group at the terminus, or (3) hydrocarbyl radical in which each radical has 1 to about 30, preferably about 3 to about 15 carbon atoms per radical which can be alkyl, alkenyl, aryl, alkaryl, aralkyl radical, or combinations of two or more thereof.
- the presently preferred organic acid is an organic acid having the formula of HO 2 CACO 2 H in which A is an alkylene group, an arylene group, alkenylene group, or combinations of two or more thereof.
- Each A has about 2 to about 30, preferably about 3 to about 25, more preferably about 4 to about 20, and most preferably 4 to 15 carbon atoms per group.
- suitable organic acids include, but are not limited to, terephthalic acid, isophthalic acid, napthalic acid, succinic acid, adipic acid, phthalic acid, glutaric acid, acrylic acid, oxalic acid, benzoic acid, maleic acid, propenoic acid, and combinations of two or more thereof.
- the presently preferred organic diacid is terephthalic acid because the polyesters produced therefrom have a wide range of industrial applications.
- suitable esters include, but are not limited to, dimethyl adipate, dimethyl phthalate, methyl benzoate, dimethyl glutarate, and combinations of two or more thereof.
- the presently preferred alcohol is having the formula of R 3 (OH) n , an alkylene glycol of the formula (HO) ⁇ A(OH) n , a polyalkylene glycol or alkoxylated alcohol having the formula of R 3 O[CH 2 CH(R 3 )O] n H, or combinations of two or more thereof in which each R 3 can be the same or different and is a hydrocarbyl radical having 1 to about 10, preferably 1 to about 8, and most preferably 1 to 5 carbon atoms per radical.
- the presently preferred R 3 is an alkyl radical, either branched or straight chain.
- A can have 2 to about 10, preferably 2 to about 7, and most preferably 2 to 4 carbon atoms per molecule.
- Each n can be the same or different and is independently a number in the range of from 1 about to about 10, preferably 1 to about 7, and most preferably 1 to 5.
- suitable solvents include, but are not limited to, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, isopropylene glycol, butylene glycol, 1 -methyl 1,2-propylene glycol, 1,3-propylene glycol, pentylene glycol, diethylene glycol, triethylene glycol, 2-ethyl hexanol, and combinations of two or more thereof.
- the presently preferred solvent is ethylene glycol for the polyester produced therefrom has a wide range of industrial applications.
- the presently preferred titanium-containing catalyst is Ti 2 O 3 or TiO, 5 .
- Titanium oxide M ⁇ Ti ( ⁇ ) Ti (n 0 ⁇ +3+4 ⁇ 2 can De produced by any suitable methods known to one skilled in the art. It can also be produced by heating TiO 2 in a reducing atmosphere, or Ti 2 O 3 in a slightly oxidizing atmosphere, or by combining three or four valent titanium coordination compounds such as, for example, a titanium alkoxide. It is presently preferred to produce M Ti (III) Ti (IV) y C ( x +3+4 2 by heating TiO 2 in a reducing atmosphere such as, for example, in the presence of hydrogen or other reducing agents such as sodium borohydride, potassium borohydride, carbon monoxide, an alkylboron compound, or combinations of two or more thereof.
- a reducing atmosphere such as, for example, in the presence of hydrogen or other reducing agents such as sodium borohydride, potassium borohydride, carbon monoxide, an alkylboron compound, or combinations of two or more thereof.
- the M ⁇ T ⁇ Ti ⁇ 0 ⁇ X+i+i ysj 2 -contairiing catalyst can also be a combination of individual species whose overall composition is given by the formula M x Ti ( ⁇ i) Ti (IV >y O ⁇ y ⁇ -
- M x Ti ( ⁇ I) Ti (IV) ⁇ ; O (X+3+4 y2 wherein M is an alkali metal can be produced by any suitable methods known tone skilled in the art. It can also be produced by reacting TiO 2 in the rutile crystalline state with an excess of n-butyl lithium in hexane at room temperature for twelve hours. This material can be subsequently heated to 500°C in nitrogen.
- Suitable catalyst can further comprise a transition metal hydrocarboxide or an exchange compound derivable from a transition metal hydrocarboxide.
- a titanium tetrahydrocarboxide is the presently preferred transition metal compound because they are readily available and effective.
- Suitable titanium tetrahydrocarboxide compounds include those expressed by the general formula Ti(OR 4 ) z wherein z is a number between 0 and 4 while each R 4 is individually selected from an alkyl, cycloalkyl, aryl, alkaryl, and aralkyl hydrocarbon radical containing from 1 to about 30, preferably 1 to about 20 carbon atoms per radical and each R 4 can be the same or different. Titanium tetrahydrocarbyloxides in which the hydrocarboxyl group contains from 1 to about 10 carbon atoms per radical which is a linear alkyl radical are most preferred because they are more readily available and are effective in forming the solution.
- Suitable titanium tetrahydrocarboxides include, but are not limited to, titanium tetramethoxide, titanium dimethoxydiethoxide, titanium tetraethoxide, titanium propoxide, titanium isopropoxide, titanium tetra-n-butoxide, titanium tetrahexyloxide, titanium tetradecyloxide, titanium tetraeicosyloxide, titanium tetracyclohexyloxide, titanium tetrabenzyloxide, titanium tetracyclohexyloxide, titanium tetrabenzyloxide, titanium tetratolyloxide, titanium tetraphenoxide, and combinations of any two or more thereof.
- titanium tetrahydrocarboxides titanium tetraalkoxides are generally preferred and titanium tetrapropoxide is particularly preferred because of its availability and cost.
- the catalyst composition can further comprise other compounds which may be added to either enhance the catalyst activity or reaction products.
- other compounds include, but not limited to, cobalt/aluminum catalyst, antimony glycoxide, antimony oxide, phosphoric acid, phosphinic acid, esters of phosphoric acid, ethylene glycol, silicates, zirconates, titanium dioxide, and combinations of two or more thereof.
- the cobalt/aluminum catalyst comprises a cobalt salt and an aluminum compound in which the mole ratio of aluminum to cobalt is in the range of from 0.25:1 to 16:1.
- the cobalt/aluminum catalyst is disclosed in the U.S. patent number 5,674,801, disclosure of which is incorporated herein by reference.
- the catalyst can be in any physical shape such as solid powder, gel, colloidal suspension or solution. It is presently preferred that the particle size of the catalyst is in the range of from about 0.001 to about 250, preferably about 0.001 to about 100, and most preferably 0.001 to 1 microns.
- M x Ti ⁇ ) Ti (n j ,- 0 (X+3+4 y y - can be determined by X-ray scattering, by photoelectron spectroscopy, by elemental analysis, or by weight loss method.
- the contacting of polymerization component with the catalyst can be carried out by any suitable means.
- the individual compositions of the polymerization component can be combined before being contacted with the catalyst.
- the catalyst be first dispersed in an alkylene glycol by any suitable means such as mechanical mixing or stirring to produce a dispersion followed by combining the dispersion with an organic diacid, an oligomer of an organic diacid and an alkylene glycol, or both under a condition sufficient to effect the production of a polyester.
- the oligomer of the diacid and alkylene glycol generally has a total of about 1 to about 100, preferably from about 2 to about 10 repeat units derived from the diacid and alkylene oxide.
- a suitable condition to effect the production of a polyester can include a temperature in the range of from about 150°C to about 500°C, preferably about 200°C to about 400°C, and most preferably 250°C to 300°C under a pressure in the range of from about 0.001 to about 10 atmospheres for a time period of from about 1 to about 20, preferably about 1 to about 15, and most preferably 1 to 10 hours.
- Such condition can also be used is solid state polymerization.
- the molar ratio of the alcohol (or alkylene glycol) to carbonyl compound (or organic acid or ester ) can be any ratio so long as the ratio can effect the production of an ester or polyester.
- the ratio can be in the range of from about 0.1:1 to about 10:1, preferably about 0.5:1 to about 5:1, and most preferably about 1 :1 to about 3:1.
- the molar ratio of the alcohol (or alkylene glycol) to carbonyl compound (or organic acid or ester) for the oligomer having repeat units derived from the carbonyl compound (or organic acid or ester) to alcohol (or alkylene glycol) can have the same ratio of q:(q-l) in which q can be in the range of from about 2 to about 20, preferably about 2 to 10, and most preferably 2 to 5.
- the catalyst can be present in the range of about 0.0001 to about 30,000 parts per million by weight (ppmw) of the polymerization medium, preferably about 0.001 to about 1,000 ppmw, and most preferably 0.001 to 100 ppmw.
- polyethylene terephthalate was made under the conditions specified.
- the TiO t 5 catalyst used in Examples 1-13 was obtained as Ti.O. from the Alfa Aesar division of Johnson Matthey, Inc., Wood Hill, Massachusetts.
- Example 1
- a 1 -liter resin kettle was provided with a Jiffy Mixer stirring agitator with an Electro-Craft Motomatic constant speed controller, a heater, a thermocouple, condenser and nitrogen sweep.
- To this kettle was added 0.2g of the TiO j . catalyst, 115ml of ethylene glycol, 6.23 ⁇ l of concentrated H3PO4 5 0.3wt% passivated TiO 2 delusterant and 400g of a low molecular weight ethylene terephthalate oligomer formed from ethylene glycol and terephthalic acid.
- the mixture was stirred at 280°C at 60rpm and vacuum of less than 1 torr (133 Pa) for 120 minutes at which time the supply voltage to the vessel's agitator control, an indication of the torque applied to the agitator and therefore of the viscosity of the reactants, reached a limiting value of 150mv, upon which the polymer was poured into cold water to quench the polymerization.
- the polymer solid was annealed for crystallization at 150°C for 12 hours and ground to pass through a 2mm filter screen for color measurement using a Hunter colorimeter.
- the polymer color numbers were 69.48L, -0.91a, 3.08b.
- Example 2 Ti .O. (1.25g) was mixed with 228ml of ethylene glycol and 400g of a low molecular weight ethylene terephthalate oligomer formed from ethylene glycol and terephthalic acid. The mixture was stirred in a resin kettle as described in Example 1 at 280°C at 60rpm and vacuum of less than 1 torr and the limiting voltage on the agitator motor was achieved after 100 minutes of stirring. The polymer was quenched, annealed, ground and analyzed as described in Example 1.
- Example 3 The ⁇ 2O3 titania catalyst was used with 150g of the ethylene terephthalate oligomer described in Example 1, lOg ethylene glycol with 76ppm by weight titania catalyst. The mixture was stirred in a resin kettle as described in Example 1 at 50rpm and vacuum of less than 1 torr for 60 minutes as the supply voltage to the vessel's agitator control reached a value of 120mv. The polymer was quenched, annealed, ground and analyzed as described in Example 1.
- the polymer color numbers were 72.9L, -0.76a, 4.25b.
- the polymer weight average molecular weight is 48,200 and the Z-average molecular weight is 73,900.
- Example 4 Ti2 ⁇ 3 of previous examples hereinabove disclosed was ground to a finer particle size distribution such that 90% of the particles were less than 10 microns.
- Poly(ethylene terephthalate) was prepared using 0.8g of the ground ⁇ 2O3 catalyst, 115ml ethylene glycol and 400g of a low molecular weight oligomer from Example 1 of ethylene glycol and terephthalic acid.
- Example 5 The mixture was stirred in a resin kettle as described in Example 1 at 60rpm and vacuum of less than 1 torr for 45 minutes at which time the supply voltage to the vessel's agitator motor reached a limiting value of 150mv.
- the polymer was quenched, annealed, ground and analyzed as described in Example 1.
- the polymer color numbers were 42J3L, -0.95a, -1.89b.
- the polymer inherent viscosity is 0.73 dL/g, the weight average molecular weight was 28J 00 and the Z-average molecular weight was 43,300.
- the polymer of this example was prepared by mixing 0J6g of the ⁇ 2O3 of Example 4 with 0.3 wt% passivated Ti ⁇ 2 delusterant, 115ml ethylene glycol and 400g of the low molecular weight oligomer of ethylene glycol and terephthalic acid described in Example 1. The mixture was stirred in a resin kettle as described in Example 1 at 60rpm and vacuum of less than 1 torr for 55 minutes at which time the supply voltage to the vessel's agitator motor reached a limiting value of 150mv. The polymer was quenched, annealed, ground and analyzed as described in Example 1. The polymer color numbers were 54.85L, -1.25a, -1.21b. The polymer inherent viscosity was 0.56 dL/g, the weight average molecular weight was 25,000 and the Z-average molecular weight was 37,900.
- the polymer of this example was prepared by mixing 0.08g of the ⁇ 2O3 of Example 4 with 0.3 wt% passivated TiO 2 delusterant, 115ml ethylene glycol and 400g of the low molecular weight oligomer of ethylene glycol and terephthalic acid as described in Example 1. The mixture was stirred in a resin kettle as described in Example 1 at 60rpm and vacuum of less than 1 torr for 115 minutes at which time the supply voltage to the vessel's agitator motor reached a limiting value of 150mv. The polymer was quenched, annealed, ground and analyzed as described in Example 1. The polymer color numbers were 59.84L, -1.34a, 0.60b. The polymer inherent viscosity is 0.57 dL/g, the weight average molecular weight is 22,800 and the Z-average molecular weight is 35.500.
- the Ti2 ⁇ 3 ground as in Example 4 was further ground so that 90% of the particles were smaller than 1 ⁇ m.
- Poly(ethylene terephthalate) was prepared by mixing 0.08g of the so-ground Ti-0. with 0.3 wt% passivated TiO 2 delusterant, 115ml ethylene glycol and 400g of the low molecular weight oligomer of ethylene glycol and terephthalic acid as described in Example 1. The mixture was stirred in a resin kettle as described in Example 1 at 60rpm and vacuum of less than 1 torr for 75 minutes at which time the supply voltage to the vessel's agitator motor reached a limiting value of 150mv. The polymer was quenched, annealed, ground and analyzed as described in Example 1. The polymer color numbers were
- Poly(ethylene terephthalate) was prepared using 0J g of the lithium titania catalyst, 228ml ethylene glycol and 400g of the low molecular weight oligomer of ethylene glycol and terephthalic acid as described in Example 1.
- the mixture was stirred at 60rpm and vacuum of less than 1 torr for 100 minutes as the supply voltage to the vessel's agitator control reached a value of 150mv.
- the polymer was quenched, annealed, ground and analyzed as described in Example 1.
- the polymer color numbers were 71.85L, -1.17a, 6.71b.
- the polymer inherent viscosity is 0.58 dL/g, the weight average molecular weight is 26,800 and the Z-average molecular weight is 41,500.
- Example 9 The lithium titania catalyst was prepared as described in Example 8.
- Poly(ethylene terephthalate) was prepared using 150g of oligomer described in Example 1, lOg ethylene glycol and 76ppm lithium titania catalyst. The mixture was stirred in a resin kettle as described in Example 1 at 50rpm and vacuum of less than 1 torr for 75 minutes as the supply voltage to the vessel's agitator control reached a value of 120mv. The polymer was quenched, annealed, ground and analyzed as described in Example 1. The polymer color numbers were 75J7L, - 0.88a, 6.9b. The polymer inherent viscosity is 1.02 dL/g, the weight average molecular weight is 53,100 and the Z-average molecular weight is 82,000.
- Example 10 Example 10
- Polyethylene terephthalate was prepared using 150g of prepolymer described in Example 1, lOg ethylene glycol and 76ppm titania catalyst.
- Example 11 The mixture was stirred in a resin kettle as described in Example 1 at 50rpm and vacuum of less than 1 torr for 60 minutes as the supply voltage to the vessel's agitator control reached a value of 120mv.
- the polymer was quenched, annealed, ground and analyzed as described in Example 1.
- the polymer color numbers were 78.73L, -0.67a, 8J2b.
- the polymer inherent viscosity is 0.84 dL/g, the weight average molecular weight is 52,900 and the Z-average molecular weight is 81 ,500.
- Example 11 The polymer color numbers were 78.73L, -0.67a, 8J2b.
- the polymer inherent viscosity is 0.84 dL/g
- the weight average molecular weight is 52,900
- the Z-average molecular weight is 81 ,500.
- the lithium titania catalyst was prepared as described in Example 10.
- Poly(ethylene terephthalate) was prepared using 150g of prepolymer described in Example 1, lOg ethylene glycol, 60ppm H3PO 4 , and 76ppm titania catalyst. The mixture was stirred in a resin kettle as described in Example 1 at 50rpm and vacuum of less than 1 torr for 300 rninutes as the supply voltage to the vessel's agitator control reached a value of 120mv.
- the polymer was quenched, annealed, ground and analyzed as described in Example 1.
- the polymer color numbers were 78L, 0.12a, 7.36b.
- the polymer inherent viscosity is 0.85 dL/g, the weight average molecular weight is 27,200 and the Z-average molecular weight is 44,000.
- Li x TiO 2 was blue/black in color.
- Poly(ethylene terephthalate) was prepared using 150g of prepolymer described in Example 1, lOg ethylene glycol, 60ppm H3PO 4 , and 76ppm lithium titania catalyst.
- Example 13 The mixture was stirred in a resin kettle as described in Example 1 at 50rpm and vacuum of less than 1 torr for 180 minutes as the supply voltage to the vessel's agitator control reached a value of 120mv.
- the polymer was quenched, annealed, ground and analyzed as described in Example 1.
- the polymer color numbers were 80.4L, -0J3a, 6.08b.
- the polymer inherent viscosity is 0.85dL/g, the weight average molecular weight is 40,900 and the Z-average molecular weight is 63,000.
- Prepolymer was prepared in a 600 liter reactor by combining 34J kg dimethyl terephthalate, 23.0 kg ethylene glycol, and 4.80g zinc acetate dihydrate, heating to 200°C with agitation while methanol was distilled from the reaction mixture. After the methanol distillation was completed, the prepolymer was removed and used as a master batch for subsequent polymerizations. Its color numbers are 85.6L, -0.45a, +5.07b.
- Polyethylene terephthalate was prepared using 150g of the prepolymer so made, 10 g ethylene glycol and 76ppm by weight of the same Ti.O. used in Example 1 • The mixture was stirred in a resin kettle as described in Example 1 at 50rpm and vacuum of less than 1 torr for 60 minutes at which time the supply voltage to the vessel's agitator motor reached a limiting value of 120 mv. The polymer was quenched, annealed, ground and analyzed as described in Example 1. The polymer color numbers were 72.9L, -0.76a, 4.25b. The polymer weight average molecular weight was 48,200 and the Z-average molecular weight was 73,900. Examples 14-30
- a master batch of oligo(trimethylene terephthalate) was prepared in a 600 liter reactor by combining 34J kg dimethyl terephthalate, 23.0 kg ethylene glycol, and 4.80g zinc acetate dihydrate, heating to 200°C with agitation while methanol was distilled from the reaction mixture. After the methanol distillation was completed, the prepolymer was quenched in cold water, removed and dried. Each of the following polycondensations runs were carried out starting from the same, master batch of oligo(trimethylene terephthalate).
- Tyzor TE® comprising titanium trietiianolarninato ispropoxide was obtained from DuPont. About 20ml of this product was sealed in glass tube and placed underneath a broad-band ultraviolet lamp for about one week until the solution color became a steady, dark bluish-purple which indicates the presence of titanium in the oxidation state Ti(III).
- Tyzor LA® comprising titanium lactate in water was obtained from DuPont (Wilmington, Delaware). About 20ml of this product was sealed in glass tube and placed underneath a broad-band ultraviolet lamp for about one week until the solution color became a steady, dark bluish-purple which indicated the presence of titanium in the oxidation state Ti(III).
- Titanium(IV) proxide in propanol was obtained from Aldrich Chemicals (Milwaukee, Wisconsin). About 20ml of an equichoric mixture of titanium proxide and ethylene glycol was sealed in glass tube and placed underneath a broad-band ultraviolet lamp for about one week until the solution color became a steady, dark violet which indicates the presence of titanium in the oxidation state Ti(III).
- Titanium(III) trioxide (titanium (III) sesquioxide) was purchased from Aldrich Chemicals, suspended in ethylene glycol and ground in a ball mill so that 90% of the particles were smaller than 1 micron in diameter. The suspension was dried by evaporating the glycol in a vacuum oven at 250°C.
- Example number The Example number, the catalyst systems used to polymerize the oligo(trimethylene terephthalate) master batch, and the polymer products' Hunter L,a,b color numbers and weight-average molecular weight are described in the following Table 1. Table 1
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA01010084A MXPA01010084A (en) | 1999-04-08 | 2000-03-16 | Catalysis with titanium oxides. |
EP00918018A EP1171504B1 (en) | 1999-04-08 | 2000-03-16 | Catalysis with titanium oxides |
JP2000611594A JP2002542323A (en) | 1999-04-08 | 2000-03-16 | Catalyst containing titanium oxide |
DE60000480T DE60000480T2 (en) | 1999-04-08 | 2000-03-16 | CATALYSIS WITH TITANOXYDES |
AT00918018T ATE224416T1 (en) | 1999-04-08 | 2000-03-16 | CATALYSIS WITH TITANIUM OXIDES |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/288,371 | 1999-04-08 | ||
US09/288,371 US6034203A (en) | 1999-04-08 | 1999-04-08 | Catalysis with titanium oxides |
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WO2000061657A1 true WO2000061657A1 (en) | 2000-10-19 |
Family
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PCT/US2000/006957 WO2000061657A1 (en) | 1999-04-08 | 2000-03-16 | Catalysis with titanium oxides |
Country Status (12)
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US (1) | US6034203A (en) |
EP (1) | EP1171504B1 (en) |
JP (1) | JP2002542323A (en) |
KR (1) | KR100567702B1 (en) |
CN (1) | CN1117788C (en) |
AT (1) | ATE224416T1 (en) |
DE (1) | DE60000480T2 (en) |
ES (1) | ES2181650T3 (en) |
MX (1) | MXPA01010084A (en) |
MY (1) | MY127013A (en) |
TW (1) | TW514651B (en) |
WO (1) | WO2000061657A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7759270B2 (en) | 2005-05-12 | 2010-07-20 | Fuji Titanium Industry Co., Ltd. | Titanium oxide sol and process for producing polyalkylene terephthalate therewith |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US6372879B1 (en) | 2000-01-07 | 2002-04-16 | Atofina Chemicals, Inc. | Polyester polycondensation with catalyst and a catalyst enhancer |
WO2007066446A1 (en) * | 2005-12-09 | 2007-06-14 | Kumamoto Technology And Industry Foundation | Method of depolymerizing polyester and unsaturated polyester and method of recovering polyester monomer with the depolymerization method |
TW201100460A (en) | 2009-03-18 | 2011-01-01 | Saudi Basic Ind Corp | Process for making thermoplastic polyesters |
MX349068B (en) | 2012-06-21 | 2017-06-28 | Inst Mexicano Del Petróleo | Nanostructured titania semiconductor material and its production process. |
MX360196B (en) | 2013-09-25 | 2018-10-11 | Mexicano Inst Petrol | Nanostructured titania catalyst with stabilized acidity and process thereof. |
EP3000835B1 (en) * | 2014-09-24 | 2020-11-25 | Clariant International Ltd | Catalyst composition for a polyester manufacturing process |
CN109575253B (en) * | 2018-11-09 | 2020-07-31 | 中原工学院 | Preparation method of PTT-based low-melting-point copolyester |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US3870688A (en) * | 1971-05-12 | 1975-03-11 | Toyo Boseki | Titanium tartrate catalyzed polyesterification |
SU765290A1 (en) * | 1977-08-01 | 1980-09-23 | Институт химии Уральского научного центра АН СССР | Method of preparing polyesters |
EP0859020A2 (en) * | 1997-02-12 | 1998-08-19 | Zimmer Aktiengesellschaft | Process for the production of polypropylene terephthalate |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4912286A (en) * | 1988-08-16 | 1990-03-27 | Ebonex Technologies Inc. | Electrical conductors formed of sub-oxides of titanium |
US5596069A (en) * | 1995-06-08 | 1997-01-21 | E. I. Du Pont De Nemours And Company | Catalyst and process for producing catalyst |
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1999
- 1999-04-08 US US09/288,371 patent/US6034203A/en not_active Expired - Fee Related
-
2000
- 2000-03-16 MX MXPA01010084A patent/MXPA01010084A/en unknown
- 2000-03-16 EP EP00918018A patent/EP1171504B1/en not_active Expired - Lifetime
- 2000-03-16 CN CN00808435A patent/CN1117788C/en not_active Expired - Fee Related
- 2000-03-16 AT AT00918018T patent/ATE224416T1/en not_active IP Right Cessation
- 2000-03-16 ES ES00918018T patent/ES2181650T3/en not_active Expired - Lifetime
- 2000-03-16 DE DE60000480T patent/DE60000480T2/en not_active Expired - Fee Related
- 2000-03-16 WO PCT/US2000/006957 patent/WO2000061657A1/en active IP Right Grant
- 2000-03-16 KR KR1020017012773A patent/KR100567702B1/en not_active IP Right Cessation
- 2000-03-16 JP JP2000611594A patent/JP2002542323A/en not_active Withdrawn
- 2000-03-20 TW TW089105047A patent/TW514651B/en not_active IP Right Cessation
- 2000-04-07 MY MYPI20001450A patent/MY127013A/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3870688A (en) * | 1971-05-12 | 1975-03-11 | Toyo Boseki | Titanium tartrate catalyzed polyesterification |
SU765290A1 (en) * | 1977-08-01 | 1980-09-23 | Институт химии Уральского научного центра АН СССР | Method of preparing polyesters |
EP0859020A2 (en) * | 1997-02-12 | 1998-08-19 | Zimmer Aktiengesellschaft | Process for the production of polypropylene terephthalate |
Non-Patent Citations (1)
Title |
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DATABASE WPI Section Ch Week 198124, Derwent World Patents Index; Class A23, AN 1981-43411D, XP002142340 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7759270B2 (en) | 2005-05-12 | 2010-07-20 | Fuji Titanium Industry Co., Ltd. | Titanium oxide sol and process for producing polyalkylene terephthalate therewith |
Also Published As
Publication number | Publication date |
---|---|
ATE224416T1 (en) | 2002-10-15 |
US6034203A (en) | 2000-03-07 |
DE60000480D1 (en) | 2002-10-24 |
JP2002542323A (en) | 2002-12-10 |
CN1117788C (en) | 2003-08-13 |
DE60000480T2 (en) | 2003-04-30 |
TW514651B (en) | 2002-12-21 |
EP1171504A1 (en) | 2002-01-16 |
ES2181650T3 (en) | 2003-03-01 |
MXPA01010084A (en) | 2002-04-24 |
KR100567702B1 (en) | 2006-04-05 |
KR20010108463A (en) | 2001-12-07 |
CN1353731A (en) | 2002-06-12 |
MY127013A (en) | 2006-11-30 |
EP1171504B1 (en) | 2002-09-18 |
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