• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    The present invention relates to a process for the preparation of oligomerization, polymerization or depolymerization of polyesters. The methods of the present invention include contacting a carbonyl compound with an alcohol in the presence of a particular composition. The catalyst formula M x Ti (III) Ti ( IV) and y O (x + 3 + 4y ) / 2 (M is an alkali metal, and Ti (III) is titanium in the oxidation state +3, Ti (IV) oxidation state is +4 titanium, x and y are any number greater than or equal to 0, and when x is 0, y is a number less than 1/2.
    公开号:KR20010108463A
    申请号:KR1020017012773
    申请日:2000-03-16
    公开日:2001-12-07
    发明作者:스티븐 레이먼드 러스팅；로버트 레이 버츠；유진 엠. 주니어. 맥크아론
    申请人:메리 이. 보울러；이 아이 듀폰 디 네모아 앤드 캄파니；
    IPC主号:
    专利说明:

    Catalysis with titanium oxide {Catalysis with Titanium Oxides}
    [2] Oxides of titanium are known in the art. In particular, Japanese Patent JP 51081896 of Nawata et al. Discloses the use of TiO 2 as a catalyst in the production of high molecular weight polyesters. Soviet patent SU765290 of Shtokoreva et al. Describes the use of Ti n O 2n-1 (n = 3-7). The composition formula Ti n O 2n-1 has the same meaning as TiO x [x = (2n-1 / n)] (x is 5/3 (n = 3) to 13/7 (n = 7) have. Titanium oxides have a variety of industrial applications.
    [3] Methods for preparing polyesters by polycondensation of diols and hydrocarbyl diacids are well known in the art and are described in Encyclopedia of Polymer Science and Engineering, 2nd ed., Volume 12, John Wiley and Sons, New York (1988) &Quot; The most common polyester produced by this method is poly (ethylene terephthalate) (hereinafter PET). Generally, PET is formed into a high molecular weight polyester by transesterification reaction of ethylene glycol and dimethyl terephthalate or esterification reaction with terephthalic acid to form a low molecular weight prepolymer and then polycondensation by ester exchange reaction. The transesterification reaction is generally catalyzed in the polycondensation step, because the reaction rate is slow and the reactants must be maintained at high temperature for a long period of time and consequently an additional thermal decomposition takes place.
    [4] However, there is a high demand for producing useful high molecular weight polyesters having low yellowing speed as fast as possible. The yellowness of the polyester is usually the result of polymer decomposition and side reactions occurring during the polymerization or downstream processing steps. Thus, the yellowness of synthetic polymers is an indication of their ability to be processed in the processing of the polymer as well as the quality of the polymer produced, as well as in processing forms (e.g., fibers, films and certain molded articles) in which color is important. Catalysts for the production of high molecular weight polyesters are well known, but are defective in conversion rates, ease of use, or quality of formed products.
    [5] Antimony-containing compounds having high reactivity and low coloration and having desired properties are widely used commercially as catalysts. However, due to the difficulties in dealing with antimony, known as toxic substances for cost and environmental reasons, there is a great need to find alternative catalysts for antimony.
    [1] The present invention relates to a method of using titanium oxide as a catalyst in an oligomerization process, a polymerization process, a depolymerization process, or a combination of two or more thereof.
    [6] The present invention provides methods that can be used for oligomerization, polymerization, depolymerization, or a combination of two or more thereof, for example, the production of polyesters. And the method of the invention a carbonyl compound with an alcohol compound of formula M x Ti (III) Ti ( IV) y O (x + 3 + 4y) / 2 (M is an alkali metal, Ti (III) is in the oxidation state +3 In the presence of a catalyst mixture comprising titanium, Ti (IV) is titanium oxide + 4, x and y are numbers greater than or equal to 0, and x is 0, y is less than 1/2. . The method of the present invention further comprises the step of recovering the product produced by this method.
    [7] The process of the present invention comprises, or consists essentially of, or consist of, a step of contacting the carbonyl compound under conditions sufficient to produce the polyester in the presence of the catalyst composition. Wherein the catalyst composition formula M x Ti (III) Ti ( IV) y O (x + 3 + 4y) / 2 (M is an alkali metal, Ti (III) is titanium in the oxidation state +3, Ti (IV) is X + y is a number greater than or equal to zero, and y is a number less than 1/2 when x is 0), or consist essentially of, or consist of, the titanium catalyst. The expression to be displayed with the same meaning as M x / (1 + y) TiO (x + 3 + 4y) / (2y + 2) to the M x Ti y + 1 O ( x + 3 + 4y) / 2 or as defined . The preferred titanium oxide of the present invention can be represented by TiO z (where z is the number of 1 to 1.67, preferably 1.4 to 1.6, most preferably 1.5). The most preferred titanium oxide is TiO 1.5 or Ti 2 O 3 .
    [8] In the present invention, any carbonyl compound capable of reacting with an alcohol to form an ester can be used. Generally, such carbonyl compounds include, but are not limited to, oligomers or polymers having repeating units derived from acids, esters, amides, acid anhydrides, acid halides, acids, or combinations of two or more thereof. A preferred acid in the present invention is an organic acid. A preferred method in the present invention is a method of polymerizing an acid and an alcohol for producing a polyester.
    [9] Preferred polyester manufacturing methods comprise, or consist essentially of, or consist of contacting the polymerization mixture with a composition comprising a titanium stocking with the above-described formula. The polymerization mixture may comprise, consist essentially of, or consist of (1) an organic acid or ester thereof and an alcohol, or (2) an oligomer and alcohol having repeating units derived from an organic acid or ester.
    [10] The organic acid or ester thereof may be represented by the formula R 1 COOR 2 wherein R 1 and R 2 are the same or different and are (1) hydrogen, (2) a hydrocarboxyl group having a carboxylate end group, or (3) a hydrocarbyl group, May have from 1 to about 30 carbon atoms, preferably from about 3 to about 15, and may be an alkyl group, an alkenyl group, an aryl group, an alkaryl group, an aralkyl group, or a combination of two or more thereof. A preferred organic acid of the present invention is an organic acid having the formula HO 2 CACO 2 H (wherein A is an alkylene group, an arylene group, an alkenylene group, or a combination of two or more thereof). Each A has from about 2 to about 30 carbon atoms, preferably from about 3 to about 25, more preferably from about 4 to about 20, and most preferably from 4 to 15 carbon atoms. Examples of suitable organic acids include, but are not limited to, terephthalic acid, isophthalic acid, naphthalic acid, succinic acid, adipic acid, phthalic acid, glutaric acid, acrylic acid, oxalic acid, benzoic acid, maleic acid, propenoic acid, . The preferred organic acid of the present invention is terephthalic acid. Polyester made from terephthalic acid has a wide range of industrial applications. Examples of suitable esters include, but are not limited to, dimethyl adipate, dimethyl phthalate, methyl benzoate, dimethyl glutarate, and combinations of two or more thereof.
    [11] Any alcohol capable of esterifying with an acid to form a polyester can be used in the present invention. Preferred alcohols of the present invention are alcohols of the formula R 3 (OH) n, alkylene glycols of the formula (HO) nA (OH) n, polyalkylene glycols of the formula R 3 O [CH 2 CH (R 3 ) O] Or alkoxylated alcohol or a combination of two or more thereof, wherein R 3 is each the same or different and has 1 to about 10 carbon atoms, preferably 1 to about 8, most preferably 1 to 5 carbon atoms. Preferred R < 3 > s of the present invention are branched or straight chain alkyl groups. A is 2 to about 10, preferably 2 to about 7 and most preferably 2 to 4 carbon atoms per molecule. n are each the same or different and independently from 1 to about 10, preferably from 1 to about 7, and most preferably from 1 to 5. Examples of suitable solvents include alcohols such as ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, isopropylene glycol, butylene glycol, 1-methyl 1,2- propylene glycol, 1,3-propylene glycol, pentylene glycol, Glycol, triethylene glycol, 2-ethylhexanol, and combinations of two or more thereof. A preferred solvent of the present invention is ethylene glycol. Polyesters produced with ethylene glycol have a wide range of industrial applications.
    [12] A suitable catalyst in the present invention formula M x Ti (III) Ti ( IV) y O (x + 3 + 4y) / 2 (M is an alkali metal, and Ti (III) is titanium in the oxidation state +3, Ti (IV ) Is a titanium oxide having an oxidation number of +4, x and y are numbers greater than or equal to 0, and y is a number less than 1/2 when x is 0), or consist essentially of or consist of titanium oxide. Catalysts with x = 0 and y = 0 are most preferred. Preferred titanium-containing catalysts of the present invention are Ti 2 O 3 or TiO 1.5 .
    [13] Titanium oxide M x Ti (III) Ti (IV) y O (x + 3 + 4y) / 2 can be prepared by any suitable method known to those skilled in the art. Alternatively, TiO 2 may be prepared by heating in a reducing atmosphere or Ti 2 O 3 in a slightly oxidizing atmosphere, or by adding trivalent or tetravalent titanium coordination compounds (such as titanium alkoxide). A preferred method of preparing M x Ti (III) Ti (IV) y O (x + 3 + 4y) / 2 is by reacting TiO 2 in a reducing atmosphere, for example with hydrogen or sodium borohydride, potassium borohydride, Boron compound or a combination of two or more thereof in the presence of other reducing agents. M x Ti (III) Ti ( IV) y O (x + 3 + 4y) / 2 containing catalysts the overall composition M x Ti (III) Ti ( IV) y O (x + 3 + 4y) / 2 expressed by May be a combination of each of the compound species.
    [14] M x Ti (III) Ti (IV) y O (x + 3 + 4y) / 2 where M is an alkali metal can be prepared by any suitable method known to those skilled in the art. It can also be prepared by reacting rutile TiO 2 with an excess of n-butyllithium in hexane at room temperature for 12 hours. This material is then heated to 500 < 0 > C in nitrogen.
    [15] Suitable catalysts may further comprise exchange compounds derived from transition metal hydrocarboxide or transition metal hydrocarboxide. The preferred transition metal compound of the present invention is titanium tetrahydrocarboxide and is easy to purchase and efficient. Suitable titanium-tetrahydro-carbalkoxy oxide compound has formula Ti (OR 4) z (z is a number from 0 to 4, R 4 are each a carbon atom number of from 1 to about 30, preferably from 1 to about 20 alkyl, cycloalkyl , Aryl, alkaryl and aralkyl hydrocarbon groups, and R < 4 > are each the same or different). Titanium tetrahydrocarbyloxide, which is a linear alkyl group having 1 to about 10 carbon atoms in the hydrocarboxyl group, is most preferred because it is easier to purchase and effective in solution formation. Suitable titanium tetrahydrocarboxide includes, but is not limited to, titanium tetramethoxide, titanium dimethoxydiethoxide, titanium tetraethoxide, titanium propoxide, titanium isopropoxide, titanium tetra-n-butoxide, Titanium tetrabutyloxide, titanium tetrabutyloxide, titanium tetrabutyloxide, titanium tetrabutyloxide, titanium tetrabutyloxide, titanium tetrabutyloxide, titanium tetrabutyloxide, titanium tetrabutyloxide, titanium tetrabutoxide, And combinations of two or more thereof.
    [16] Titanium tetraalkoxides are generally preferred among titanium tetrahydrocarboxide, and titanium tetra propoxide is particularly preferred in view of availability and cost.
    [17] The catalyst composition of the present invention may further comprise other compounds added to improve catalytic activity or reaction products. Examples of other compounds include, but are not limited to, cobalt / aluminum catalysts, antimony glycosides, antimony oxides, phosphoric acids, phosphinic acids, phosphoric acid esters, ethylene glycols, silicates, zirconates, titanium dioxide, no. The cobalt / aluminum catalyst comprises a cobalt salt and an aluminum compound in a molar ratio of aluminum to cobalt ranging from 0.25: 1 to 16: 1. Cobalt / aluminum catalysts are described in U.S. Patent No. 5,674,801, the disclosure of which is incorporated herein by reference.
    [18] The catalyst of the present invention may take any physical form such as solid phase powder, gel, colloidal suspension or solution. The catalyst particle size is preferably in the range of from about 0.001 to about 250, preferably from about 0.001 to about 100, and most preferably from 0.001 to 1 micron. M x Ti (III) Ti (IV) y O (x + 3 + 4y) / 2 can be determined by X-ray scattering, photoelectron spectroscopy, elemental analysis or weight loss method.
    [19] The contacting of the polymer components with the catalyst can be carried out by any suitable means. For example, each composition of the polymerization component may be combined prior to contacting the catalyst. In the present invention, however, the catalyst is first dispersed in an alkylene alcohol by any suitable means such as mechanical mixing or stirring to form a dispersion, which is then mixed with an organic dicarboxylic acid or an organic dicarboxylic acid and an oligomer of an alkylene glycol, or both It is preferable to add them under conditions sufficient to produce the polyester.
    [20] The oligomers of diacids and alkylene glycols generally have from about 1 to about 100, preferably from about 2 to about 10, total repeating units derived from diacids and alkylene oxides.
    [21] Suitable conditions for polyester production include temperatures in the range of from about 150 DEG C to about 500 DEG C, preferably from about 200 DEG C to about 400 DEG C, and most preferably from 250 DEG C to 300 DEG C, at a pressure of from about 0.001 to about 10 atmospheres, To about 20 hours, preferably from about 1 to about 15 hours, and most preferably from about 1 to about 10 hours. Solid phase polymerization diagram This condition can be used.
    [22] The molar ratio of the alcohol (or alkylene glycol) to the carbonyl compound (or organic acid or ester) may be any ratio as long as an ester or polyester can be produced. In general, the molar ratio may range from about 0.1: 1 to about 10: 1, preferably from about 0.5: 1 to about 5: 1, and most preferably from about 1: 1 to about 3: 1. The molar ratio of alcohol (or alkylene glycol) to carbonyl compound (or organic acid or ester) in the case of an oligomer having a repeating unit derived from a carbonyl compound (or an organic acid or ester) of a predetermined molar ratio to an alcohol (or alkylene glycol) q: (q-1). Wherein q is in the range of from about 2 to about 20, preferably from about 2 to 10, and most preferably from 2 to 5.
    [23] The catalyst may be present in the range of from about 0.0001 to about 30,000 parts per million by weight (ppmw), preferably from about 0.001 to about 1,000 ppmw, and most preferably from 0.001 to 100 ppmw per million parts by weight of the polymerization medium.
    [24] The present invention will be further described by way of the following examples. This embodiment should not be construed as limiting the scope of the invention.
    [25] In the examples, polyethylene terephthalate was produced under the conditions described above. The TiO 1.5 catalyst used in Examples 1 to 13 was obtained as Ti 2 O 3 from Alfa Aesar division of Johnson Matthey, Inc., Wood Hill, Mass.
    [26] ≪ Example 1 >
    [27] A 1-liter resin kiln was equipped with a Jeep mixer stirrer, heater, thermocouple, condenser and nitrogen sweep equipped with an electrocraft motomatic reflux controller. To this kiln was added 0.2 g of a TiO 1.5 catalyst, 115 ml of ethylene glycol, 6.23 l of concentrated H 3 PO 4 , 400 g of a low molecular weight ethylene terephthalate oligomer formed from 0.3 wt% passivated TiO 2 matting agent and ethylene glycol and terephthalic acid. The mixture was stirred for 120 minutes at 280 rpm under a vacuum of 60 rpm and 1 torr (133 Pa), during which time the supply voltage of the vessel agitator controller, which is an indicator of the torque applied to the agitator and the resulting viscosity of the reactant, , And then the polymer was poured into cold water to stop the polymerization reaction. The solid polymer was crystallized and micronized by annealing at 150 캜 for 12 hours, passed through a 2 mm filter, and chromaticity was measured using a Hunter colorimeter. The polymer colors were 69.48L, -0.9la, and 3.08b. The intrinsic viscosity of the polymer was 0.58 dL / g, the weight average molecular weight was 27,100, and the Z-average molecular weight was 41,500.
    [28] ≪ Example 2 >
    [29] Ti 2 O 3 (1.25 g) was mixed with 228 ml of ethylene glycol and 400 g of a low molecular weight ethylene terephthalate oligomer formed of ethylene glycol and terephthalic acid. The mixture was stirred in a resin kiln at 280 < 0 > C under a vacuum of 60 rpm and less than 1 torr as described in Example 1, and after stirring for 100 minutes, the limit voltage of the stirrer motor was reached. The polymer was quenched, annealed, finely pulverized and analyzed as described in Example 1. The polymer colors were 58.34 L, -0.80 a, 0.28 b. The intrinsic viscosity of the polymer was 0.58 dL / g, the weight average molecular weight was 26,000, and the Z-average molecular weight was 40,100.
    [30] ≪ Example 3 >
    [31] A Ti 2 O 3 titania catalyst was used with 150 g of the ethylene terephthalate oligomer described in Example 1, 10 g of ethylene glycol and 76 ppm of a titania catalyst. The mixture was stirred in a resin kiln for 60 minutes under a vacuum of 50 rpm and less than 1 torr as described in Example 1 and the supply voltage of the vessel's stirrer controller reached a value of 120 mv. The polymer was quenched, annealed, finely pulverized and analyzed as described in Example 1. The polymer color number was 72.9 L, -0.76 a, 4.25 b. The polymer had a weight average molecular weight of 48,200 and a Z-average molecular weight of 73,900.
    [32] <Example 4>
    [33] Milling the above-described Examples 1 to 3 of Ti 2 O 3 and 90% of the particles are made into a fine particle size less than 10 microns. Poly (ethylene terephthalate) was prepared using 0.8 g of a Ti 2 O 3 fine particle catalyst, 115 ml of ethylene glycol, and 400 g of the low molecular weight oligomer of Example 1 prepared from ethylene glycol and terephthalic acid. The mixture was stirred in a resin kiln for 45 minutes under a vacuum of less than 60 rpm and less than 1 torr as described in Example 1 and during this time the supply voltage of the vessel's agitator motor reached a limit of 150 mv. The polymer was quenched, annealed, finely pulverized and analyzed as described in Example 1. The polymer colors were 42.13 L, -0.95 a, -1.89 b. The intrinsic viscosity of the polymer was 0.73 dL / g, the weight average molecular weight was 28,100, and the Z-average molecular weight was 43,300.
    [34] &Lt; Example 5 >
    [35] The polymer of this example was prepared by mixing 0.16 g of Ti 2 O 3 of Example 4 containing 0.3% by weight passivated TiO 2 matting agent, 115 ml of ethylene glycol, and 400 g of the low molecular weight oligomer of terephthalic acid with ethylene glycol of Example 1 . The mixture was stirred in a resin kiln as described in Example 1 at 60 rpm and under vacuum of less than 1 torr for 55 minutes during which the supply voltage of the vessel agitator motor reached a limit of 150 mv. The polymer was quenched, annealed, finely pulverized and analyzed as described in Example 1. The polymer colors were 54.85 L, -1.25 a, -1.21 b. The intrinsic viscosity of the polymer was 0.56 dL / g, the weight average molecular weight of the polymer was 25,000, and the Z-average molecular weight was 37,900.
    [36] &Lt; Example 6 >
    [37] The polymer of this example was prepared by mixing 0.08 g of Ti 2 O 3 of Example 4 containing 0.3 wt% passivated TiO 2 matting agent, 115 ml of ethylene glycol and 400 g of the ethylene glycol of Example 1 and 400 g of a low molecular weight oligomer of terephthalic acid . The mixture was stirred in a resin kiln as described in Example 1 at 60 rpm and under a vacuum of less than 1 torr for 115 minutes during which the supply voltage of the vessel agitator motor reached a limit of 150 mv. The polymer was quenched, annealed, finely pulverized and analyzed as described in Example 1. The polymer color number was 59.84 L, -1.34 a, 0.60 b. The intrinsic viscosity of the polymer was 0.57 dL / g, the weight average molecular weight of the polymer was 22,800, and the Z-average molecular weight was 35,500.
    [38] &Lt; Example 7 >
    [39] The fine powder Ti 2 O 3 of Example 4 was further pulverized so that 90% of the particles were less than 1 탆. 0.08 g of the finely pulverized Ti 2 O 3 containing 0.3 wt% passivated TiO 2 matting agent, 115 ml of ethylene glycol, and 400 g of the low molecular weight oligomer of terephthalic acid and ethylene glycol of Example 1 were mixed to prepare a poly (ethylene terephthalate ). The mixture was stirred in a resin kiln as described in Example 1 at 60 rpm and under a vacuum of less than 1 torr for 75 minutes during which the supply voltage of the vessel agitator motor reached a limit of 150 mv. The polymer was quenched, annealed, finely pulverized and analyzed as described in Example 1. The polymer colors were 60.42 L, -1.99 a, 0.58 b. The intrinsic viscosity of the polymer was 0.69 dL / g, the weight average molecular weight of the polymer was 28,800, and the Z-average molecular weight was 43,700.
    [40] &Lt; Example 8 >
    [41] About 2 g of a lithium-reducing titania catalyst was prepared by reacting white Degussa P25 TiO 2 in excess of n-butyllithium and hexane at room temperature for about 12 hours to form a blue / black anatase system LixTiO 2 (x = about 0.5) . This material was then converted to the deep blue spinel LiTi 2 O 4 was heated to 500 ℃ under nitrogen. Formation of this spinel was confirmed by X-ray diffraction. Poly (ethylene terephthalate) was prepared using 0.1 g of lithium titania catalyst, 228 ml of ethylene glycol, and 400 g of ethylene glycol and terephthalic acid low molecular weight oligomer of Example 1. The mixture was stirred for 100 minutes under a vacuum of 60 rpm and less than 1 torr during which the supply voltage of the vessel agitator controller reached a limit of 150 mv. The polymer was quenched, annealed, finely pulverized and analyzed as described in Example 1. The polymer colors were 71.85 L, -1.17 a, 6.71 b. The intrinsic viscosity of the polymer was 0.58 dL / g, the weight average molecular weight of the polymer was 26,800, and the Z-average molecular weight was 41,500.
    [42] &Lt; Example 9 >
    [43] A lithium titania catalyst was prepared as described in Example 8. Poly (ethylene terephthalate) was prepared using 150 g of the oligomer described in Example 1, 10 g of ethylene glycol, and 76 ppm of a lithium titania catalyst. The mixture was stirred in a resin kiln as described in Example 1 at 50 rpm and under a vacuum of less than 1 torr for 75 minutes during which the supply voltage of the vessel agitator controller reached a value of 120 mv. The polymer was quenched, annealed, finely pulverized and analyzed as described in Example 1. The polymer colors were 75.17 L, -0.88 a, 6.9 b. The intrinsic viscosity of the polymer was 1.02 dL / g, the weight average molecular weight of the polymer was 53,100, and the Z-average molecular weight was 82,000.
    [44] &Lt; Example 10 >
    [45] White Degussa P25 TiO 2 (preheated to 900 ° C and completely converted to rutile) was reacted in excess n-butyllithium and hexane at room temperature for about 12 hours to produce about 2 g of a lithium-reduced titania catalyst. The color of the formed LixTiO 2 was light blue. As a result of X-ray diffraction, the main phase was rutile type LixTiO 2 (x = about 0.025). Poly (ethylene terephthalate) was prepared using 150 g of the prepolymer described in Example 1, 10 g of ethylene glycol, and 76 ppm of a titania catalyst. This mixture was stirred in a resin kiln as described in Example 1 at 50 rpm and under vacuum of less than 1 torr for 60 minutes during which the supply voltage of the vessel agitator controller reached a value of 120 mv. The polymer was quenched, annealed, finely pulverized and analyzed as described in Example 1. The polymer color number was 78.73 L, -0.67 a, 8.12 b. The intrinsic viscosity of the polymer was 0.84 dL / g, the weight average molecular weight of the polymer was 52,900, and the Z-average molecular weight was 81,500.
    [46] &Lt; Example 11 >
    [47] A lithium titania catalyst was prepared as described in Example 10. Poly (ethylene terephthalate) was prepared using 150 g of the prepolymer described in Example 1, 10 g of ethylene glycol, 60 ppm of H 3 PO 4 and 76 ppm of titania catalyst. The mixture was stirred in a resin kiln as described in Example 1 under a vacuum of 50 rpm and less than 1 torr for 300 minutes during which the supply voltage of the vessel agitator controller reached a value of 120 mv. The polymer was quenched, annealed, finely pulverized and analyzed as described in Example 1. The polymer colors were 78L, 0.12a, 7.36b. The intrinsic viscosity of the polymer was 0.85 dL / g, the weight average molecular weight of the polymer was 27,200, and the Z-average molecular weight was 44,000.
    [48] &Lt; Example 12 >
    [49] White Degussa P25 TiO 2 was reacted in an excess amount of n-butyllithium and hexane at room temperature for 12 hours to prepare about 2 g of a lithium-reduced titania catalyst. The color of the formed LixTiO 2 was blue / black. As a result of X-ray diffraction, the main phase was anatase-based Li x TiO 2 (x = about 0.5). Poly (ethylene terephthalate) was prepared using 150 g of the prepolymer described in Example 1, 10 g of ethylene glycol, 60 ppm of H 3 PO 4 and 76 ppm of a lithium titania catalyst. This mixture was stirred in a resin kiln as described in Example 1 under a vacuum of 50 rpm and less than 1 torr for 180 minutes during which the supply voltage of the vessel agitator controller reached a value of 120 mv. The polymer was quenched, annealed, finely pulverized and analyzed as described in Example 1. The intrinsic viscosity of the polymer was 0.85 dL / g, the weight average molecular weight of the polymer was 40,900, and the Z-average molecular weight was 63,000.
    [50] &Lt; Example 13 >
    [51] 34.1 kg of dimethyl terephthalate, 23.0 kg of ethylene glycol, and 4.80 g of zinc acetate dihydrate were added to a 600-liter reactor, and the mixture was heated to 200 캜 with stirring to remove methanol from the reaction mixture to prepare a prepolymer. After the methanol distillation was completed, the prepolymer was taken out and used as a master batch in subsequent polymerization steps. The number of colors was 85.6 L, -0.45 a, and + 5.07 b.
    [52] Polyethylene terephthalate was prepared using 150 g of the prepared prepolymer, 10 g of ethylene glycol, and 76 ppmw of the same Ti 2 O 3 used in Example 1. The mixture was stirred in a resin kiln as described in Example 1 for 60 minutes under a vacuum of 50 rpm and less than about 1 torr during which time the supply voltage of the stirring motor of the vessel reached a limit of 120 mv. The polymer was quenched as described in Example 1, annealed and pulverized and analyzed. The polymer color number was 72.9 L, -0.76 a, 4.25 b. The polymer had a weight average molecular weight of 48,200 and a Z-average molecular weight of 73,900.
    [53] &Lt; Examples 14 to 30 &
    [54] Trimethylene terephthalate oligomer
    [55] 34.1 kg of dimethyl terephthalate, 23.0 kg of ethylene glycol and 4.80 g of diethyl acetate dihydrate were combined in a 600-liter reactor, and the mixture was heated to 200 ° C with stirring to distill off methanol from the reaction mixture to obtain a master batch of oligo (trimethylene terephthalate) . After completion of methanol distillation, the prepolymer was quenched with cold water, taken out and dried. Each of the following polycondensation operations was carried out using this oligo (trimethylene terephthalate) master batch as a raw material. All the polycondensation reactions were carried out in the same three-necked flask equipped with a condenser, a stirrer motor controller equipped with a torque sensor, and a condenser, using a same trimethylene glycol batch and a molar ratio of glycol to oligomer of 2 . One flask was used for each of the polymerization reactions before the reaction. Specifically, 70 g of oligomer was added to the upper gas space to reduce glycol reflux, high purity nitrogen blanket to reduce oxygen contamination, constant speed stirring to stabilize the rate of melt surface formation, and vacuum level to 2 torr to reduce oligomer sublimation And combined with 48.8 ml of additional glycol using a facility capable of rapid heating and quenching of the melt after the heat treatment. The conversion of all products was checked in terms of weight average molecular weight (using size scale chromatography) and color after complete crystallization and milled to a uniform powder. All polycondensation reactions were carried out at 250 ° C for 150 minutes only, with the same heating and evacuation times.
    [56] Titanium triethanolaminate isopropoxide (TiTe-III) to ultraviolet ray synthesis of Ti (III)
    [57] Tyzor TE (TM) containing titanium triethanolaminate isopropoxide was obtained from DuPont. Approximately 20 ml of this product was sealed in a glass tube and placed under a broadband ultraviolet lamp for about a week until the color of the solution became a constant dark blue color indicating the presence of Ti (III) oxide.
    [58] Ultraviolet ray synthesis of Ti (III) from titanium lactate (TiLa-III)
    [59] Tyzor LA (TM) containing titanium lactate in water was obtained from DuPont (Wilmington, Del.). Approximately 20 ml of this product was sealed in a glass tube and placed under a broadband ultraviolet lamp for about a week until the color of the solution became a constant dark blue color indicating the presence of Ti (III) oxide.
    [60] Ultraviolet ray synthesis of Ti (III) from titanium propoxide (TiPr-III)
    [61] Titanium (IV) propoxide in propanol was obtained from Aldrich Chemicals (Milwaukee, Wis.). Approximately 20 ml of a mixture of titanium propoxide and ethylene glycol is sealed in a glass tube and the solution is incubated under a broadband ultraviolet lamp for approximately one week until the color of the solution becomes a constant dark blue color indicating the presence of titanium oxide Ti (III) I have.
    [62] Fine (below micron size) Ti 2O 3(μTi 2O 3)
    [63] Titanium (III) trioxide (titanium (III) sesquioxide) was purchased from Aldrich Chemicals, suspended in ethylene glycol and finely ground such that 90% of the particles by ball mill were less than 1 micron in diameter. The suspension was dried by evaporating the glycol in a vacuum oven at 250 &lt; 0 &gt; C.
    [64] The number of catalysts used in the polymerization of the oligo (trimethylene terephthalate) master batch and the Hunter L, a, b color number and weight average molecular weight of the polymer product are shown in Table 1 below.
    [65]
    [66] The examples described herein demonstrate that high molecular weight and low yellowness polyesters are produced through the highly reduced titania oxide catalyst system. This catalyst system may also be used together with other catalysts and additives.
    权利要求:
    Claims (10)
    [1" claim-type="Currently amended] The carbonyl compound and alcohol compound, formula M x Ti (III) Ti ( IV) y O (x + 3 + 4y) / 2 (M is an alkali metal, and Ti (III) is titanium in the +3 oxidation state, Ti (IV) is an oxidation number of +4 titanium, x and y are each a number greater than or equal to 0, and when x is 0, y is less than 1/2) in the presence of a catalyst comprising a titanium containing compound How to.
    [2" claim-type="Currently amended] Wherein each R is selected from the group consisting of hydrogen, a hydrocarboxyl group, a hydrocarbyl group and combinations of two or more thereof, each of which has 1 to about 30 carbon atoms, (Wherein A is selected from the group consisting of an alkylene group, an arylene group, an alkenylene group, and a combination of two or more thereof), wherein the alcohol is selected from the group consisting of an alkyl group, aryl group, alkaryl group, aralkyl group, alkenyl group and a combination of two or more thereof. Lt; / RTI &gt;
    [3" claim-type="Currently amended] The process according to claim 1 or 2, wherein the alcohol is selected from the group consisting of ethylene glycol, propylene glycol, isopropylene glycol, butylene glycol, 1-methylpropylene glycol, pentylene glycol and combinations of two or more thereof.
    [4" claim-type="Currently amended] 4. The process according to any one of claims 1 to 3, wherein the alcohol is ethylene glycol.
    [5" claim-type="Currently amended] The method according to any one of claims 1 to 4, wherein the carbonyl compound is selected from the group consisting of terephthalic acid, dimethyl terephthalate, isophthalic acid, naphthalic acid, succinic acid, adipic acid, phthalic acid, glutaric acid, acrylic acid, oxalic acid, Acid, propene acid, and combinations of two or more thereof.
    [6" claim-type="Currently amended] 6. The method of claim 5, wherein the carbonyl compound is terephthalic acid.
    [7" claim-type="Currently amended] 7. The method according to any one of claims 1 to 6, wherein M is lithium.
    [8" claim-type="Currently amended] 8. The method according to any one of claims 1 to 7, wherein x is zero.
    [9" claim-type="Currently amended] 9. The method according to any one of claims 1 to 8, wherein y is 0.
    [10" claim-type="Currently amended] 10. The process according to any one of claims 1 to 9, wherein x is 0, y is 0, and the catalyst is Ti 2 O 3 or TiO 1.5 .
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    同族专利:
    公开号 | 公开日
    EP1171504A1|2002-01-16|
    US6034203A|2000-03-07|
    DE60000480T2|2003-04-30|
    KR100567702B1|2006-04-05|
    JP2002542323A|2002-12-10|
    ES2181650T3|2003-03-01|
    WO2000061657A1|2000-10-19|
    MXPA01010084A|2002-04-24|
    EP1171504B1|2002-09-18|
    DE60000480D1|2002-10-24|
    CN1117788C|2003-08-13|
    CN1353731A|2002-06-12|
    TW514651B|2002-12-21|
    AT224416T|2002-10-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-04-08|Priority to US09/288,371
    1999-04-08|Priority to US09/288,371
    2000-03-16|Application filed by 메리 이. 보울러, 이 아이 듀폰 디 네모아 앤드 캄파니
    2001-12-07|Publication of KR20010108463A
    2006-04-05|Application granted
    2006-04-05|Publication of KR100567702B1
    优先权:
    申请号 | 申请日 | 专利标题
    US09/288,371|US6034203A|1999-04-08|1999-04-08|Catalysis with titanium oxides|
    US09/288,371|1999-04-08|
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