TWI471355B - Titanium oxide composition and the application thereof on poly-esterification - Google Patents

Description

Titanium-containing composition and its application in polyester reaction

The present invention discloses a titanium-containing composition, and more particularly to a titanium-containing composition having a titanium-containing coprecipitate and its use in the reaction of a polyester.

Polyester-based compounds have a wide range of industrial applications. Taking PET (polyethylene terephthalate) as an example, it has excellent performance in terms of mechanical strength, heat resistance, transparency, and gas barrier properties, and is not only suitable for beverage filling such as juice, refreshing beverage, and carbonated beverage. The material of the container is also suitable for use in the production of films, sheets, fibers, and the like. Such polyester resins are usually formed by using an aliphatic diol such as terephthalic acid or an aliphatic diol such as ethylene glycol as a raw material to form a low polycondensate by an esterification reaction. Next, in the presence of a polycondensation catalyst, the low polycondensate is polymerized (liquid phase polycondensation) and polymerized to obtain a product. At present, the catalysts used in industrial production and research are mainly three series of compounds such as Sb, Ge and Ti. The ruthenium (Ge) catalyst can produce a brighter polyester, but the ruthenium catalyst is more expensive. The bismuth (Sb) catalyst will be reduced to cerium during the reaction, making the polyester foggy, and the hydrazine is toxic, causing pollution during the production process, resulting in an increase in post-treatment costs, resulting in an increase in PET production costs. A catalyst that is currently considered to be better is titanium (Ti). The use of titanium catalysts can solve the problem of heavy metal pollution. However, most titanium catalysts have problems with poor solubility. When the titanium catalyst is dispersed in ethylene glycol, usually only a suspension is formed, which tends to cause uneven reaction, resulting in unstable product quality.

In order to improve the problem of uneven reaction of the aforementioned titanium catalysts, many R&D units have proposed different solutions. For example, Lurgi Zimmer developed a supported titanium catalyst to prevent catalyst agglomeration; patent CN1403193 uses an organic modification method to prevent catalyst agglomeration; patent CN1644601 uses one of ethanol, isopropanol, toluene, mixed xylene or A solution of several kinds of solvents is used to prepare a liquid titanium catalyst; Japanese Patent Laid-Open No. 7-207010 utilizes an alkali metal compound to assist dissolution of a titanium catalyst; and patent CN1962723 utilizes a 2-hydroxycarboxylic acid compound to react with titanate first. Titanium compound, which is then reacted with a phosphorus compound to obtain a titanium-based catalyst having good photostability; Patent CN1809605 utilizes an aliphatic diol and a ternary polyol and water or a basic compound to obtain a titanium-containing solution; CN1630674 will be a titanium compound It is mixed with an alkali metal compound and a solubilizing acid such as glycerol or trimethylolpropane to increase the solubility of the titanium compound; CN1328072 is obtained by using nanometer-scale ethylene glycol titanium and an organic acid and a compound using a 1-4 valent metal ion. Titanium catalyst; CN1402653 is the addition of titanate to complexing agent (hydroxycarboxylic acid, alkanolamine, amino group) Acid or mixtures thereof), and water or an alcohol solvent to obtain a liquid catalyst hypophosphorous acid; CN1583823 is the use of a mixture of alkali metal hydroxide and ethylene glycol to dissolve the mixture of titanium dioxide and silicon dioxide and thus to obtain a liquid titanium-based catalyst.

Although the foregoing various solutions can improve the problem of uneven reaction to some extent, in the use of the catalyst, the aforementioned various solutions inevitably introduce many unnecessary impurities into the reaction system, resulting in the product. Quality decreases due to increased impurities. In addition, the second problem of the titanium-based catalyst is that titanium has high catalytic activity but poor thermal stability, which easily causes cracking of the polyester, resulting in a large amount of unnecessary by-products in the polycondensation process and the melt-forming process, and the polymerization. The ester hue is poor. However, if the phosphorus-based heat stabilizer is used to reduce the generation of by-products, the activity of the titanium catalyst in the prior art is suppressed, and the reactivity is lowered.

Therefore, how to improve the dispersibility of the titanium catalyst to make the polyester reaction uniform, while maintaining the reactivity of the titanium catalyst, and producing a polyester with no quality, has become a polyester product in the production process reform. Key technical issues that need to be addressed.

In view of the above background, in order to meet industrial requirements, the present invention provides a titanium-containing composition and its use in a polyesterification reaction.

It is an object of the present invention to provide a titanium-containing composition which is used by an organic acid to achieve uniform dispersion of a titanium-containing coprecipitate in a titanium-containing composition.

Another object of the present invention is to provide a method for catalyzing a polyester reaction by using a titanium-containing composition by using a titanium-containing composition according to the present specification to achieve an effect of improving the quality of the polyester product.

The present invention discloses a titanium-containing composition comprising a titanium-containing composition comprising titanium dioxide (TiO ₂ )/silica (SiO ₂ ) and/or titanium dioxide (TiO ₂ )/zirconia (ZrO ₂ ). Coprecipitates, organic acids, glycols, and water. The invention also discloses a method of catalyzing a polyester reaction with a titanium-containing composition. The method for catalyzing a polyester reaction by the titanium-containing composition includes a step of adding the titanium-containing composition to at least one of a raw material slurry preparation step, an esterification step, and a liquid phase polycondensation step.

The direction of the invention discussed herein is a titanium-containing esterification catalyst and its use. In order to thoroughly understand the present invention, detailed steps and compositions thereof will be set forth in the following description. Obviously, the practice of the invention is not limited to the specific details that are apparent to those skilled in the art. On the other hand, well-known components or steps are not described in detail to avoid unnecessarily limiting the invention. The preferred embodiments of the present invention are described in detail below, but the present invention may be widely practiced in other embodiments, and the scope of the present invention is not limited by the scope of the following patents. .

According to a preferred embodiment of the present specification, a titanium-containing composition is disclosed. The titanium-containing composition described above comprises a titanium-containing coprecipitate, an organic acid, a diol, and water. Wherein, the weight percentage of the titanium-containing coprecipitate is about 0.01 to 20% by weight based on the total amount of the titanium-containing composition, and the weight percentage of the organic acid is about 2 to 80%, and the weight percentage of the diol is about It is 0.1 to 95% by weight, and the weight percentage of water is about 0.1 to 99% by weight.

According to this embodiment, the titanium-containing coprecipitate contains a coprecipitate of titanium dioxide (TiO ₂ )/silica (SiO ₂ ) and/or a coprecipitate of titanium dioxide (TiO ₂ )/zirconia (ZrO ₂ ). Titanium compound. Wherein, in the above-mentioned titania/silica coprecipitate, TiO ₂ :SiO ₂ =90:10 to 20:80 mol/mol, in the coprecipitate of the above titanium dioxide/zirconia, TiO ₂ :ZrO ₂ =95: 5 to 70: 30 mol/mol.

The above organic acid may be one selected from the group consisting of formic acid, acetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tartaric acid, salicylic acid, citric acid, Lactic acid, malic acid, cinnamic acid, caffeic acid.

The above diol may be one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, and pentanediol.

In a preferred embodiment according to this embodiment, the above-described method of modulating the titanium-containing composition is as follows. After the titanium-containing coprecipitate, the organic acid, the ethylene glycol, and the water are mixed, they are stirred at normal temperature to obtain a uniform transparent solution. In another preferred embodiment of the present embodiment, the titanium-containing composition is prepared by mixing a titanium-containing coprecipitate, an organic acid, ethylene glycol, and water, and then performing a heating operation to obtain A uniform clear solution. The turbidity of the homogeneous clear solution of the above titanium-containing composition can be determined using a HunterLab COLORQUEST XE in accordance with the ASTM D 1003 method.

Example 1: Formulating a solution blank

Taking 99.5 g of a 50% aqueous solution of ethylene glycol, adding a coprecipitate of titanium dioxide/silica and/or a titanium compound C-94 (purchased from Sachtleben Chemie GmbH) having a composition of titanium dioxide/zirconia coprecipitate, 0.5 g, It was stirred at room temperature for 1 day to obtain a mixed solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine in accordance with the ASTM D 1003 method, and the turbidity of the above solution was found to be 95%.

Example 2: Preparing Solution 1-1

59.7 g of a 50% aqueous solution of ethylene glycol, adding 39.8 g of tartaric acid, stirring and dissolving, adding a coprecipitate of titanium dioxide/silica and or a titanium compound C-94 composed of a titania/zirconia coprecipitate (purchased 0.5 g from Sachtleben Chemie GmbH) was stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine in accordance with the ASTM D 1003 method, and the haze of the solution was measured to be 1.7%.

Example 3: Preparing Solution 1-2

79.6 g of a 50% aqueous solution of ethylene glycol was added to 19.9 g of tartaric acid, stirred and dissolved, and then a titanium dioxide/silica coprecipitate and a titanium compound C-94 composed of a titania/zirconia coprecipitate (purchased from Sachtleben) were added. Chemie GmbH) 0.5 g, stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine in accordance with the ASTM D 1003 method, and the haze of the solution was measured to be 1.8%.

Example 4: Preparing Solution 1-3

94.5 g of a 50% aqueous solution of ethylene glycol was added to 5 g of tartaric acid, and after stirring and dissolved, a coprecipitate of titanium dioxide/silica and a titanium compound C-94 composed of a titania/zirconia coprecipitate (purchased from Sachtleben) were added. Chemie GmbH) 0.5 g, stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured in accordance with ASTM D 1003 using a HunterLab COLORQUEST XE machine, and the haze of the solution was measured to be 1.8%.

Example 5: Preparing Solution 2-1

59.7 g of a 50% aqueous solution of ethylene glycol was added to 39.8 g of salicylic acid, stirred and dissolved, and then a titanium dioxide/silica coprecipitate and a titanium compound C-94 composed of a titania/zirconia coprecipitate were added. 0.5 g from Sachtleben Chemie GmbH) was stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured in accordance with ASTM D 1003 using a HunterLab COLORQUEST XE machine, and the haze of the solution was measured to be 1.5%.

Example 6: Formulation Solution 2-2

79.6 g of a 50% aqueous solution of ethylene glycol was added to 19.9 g of salicylic acid, stirred and dissolved, and then a titanium dioxide/silica coprecipitate and a titanium compound C-94 composed of a titania/zirconia coprecipitate were added. 0.5 g from Sachtleben Chemie GmbH) was stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured according to the ASTM D 1003 method using a HunterLab COLORQUEST XE machine, and the haze of the solution was measured to be 1.5%.

Example 7: Preparing Solution 2-3

Add 94.5 g of 50% aqueous solution of ethylene glycol to 5 g of salicylic acid, stir to dissolve, then add a coprecipitate of titanium dioxide/silica and or a titanium compound C-94 composed of a titania/zirconia coprecipitate (purchased from 0.5 g of Sachtleben Chemie GmbH) was stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured in accordance with ASTM D 1003 using a HunterLab COLORQUEST XE machine, and the haze of the solution was measured to be 1.6%.

Example 8: Preparing Solution 3-1

Take 59.7 g of a 50% aqueous solution of ethylene glycol, add 39.8 g of succinic acid, stir to dissolve, then add a coprecipitate of titanium dioxide/silica and or a titanium compound C-94 composed of a titania/zirconia coprecipitate (purchased 0.5 g from Sachtleben Chemie GmbH) was stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine in accordance with the ASTM D 1003 method, and the haze of the solution was measured to be 1.3%.

Example 9: Formulation Solution 3-2

Take 79.6 g of a 50% aqueous solution of ethylene glycol, add 19.9 g of succinic acid, stir to dissolve, then add a coprecipitate of titanium dioxide/silica and or a titanium compound C-94 composed of a titania/zirconia coprecipitate (purchased 0.5 g from Sachtleben Chemie GmbH) was stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine in accordance with the ASTM D 1003 method, and the haze of the solution was measured to be 1.3%.

Example 10: Formulation Solution 3-3

Take 94.5 g of 50% aqueous solution of ethylene glycol, add 5 g of succinic acid, stir to dissolve, then add a coprecipitate of titanium dioxide/silica and or a titanium compound C-94 composed of a titania/zirconia coprecipitate (purchased from 0.5 g of Sachtleben Chemie GmbH) was stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine in accordance with the ASTM D 1003 method, and the haze of the solution was measured to be 1.4%.

Example 11: Preparing Solution 4-1

59.7 g of a 50% aqueous solution of ethylene glycol, adding 39.8 g of oxalic acid, stirring and dissolving, adding a coprecipitate of titanium dioxide/silica and or a titanium compound C-94 composed of a titania/zirconia coprecipitate (purchased 0.5 g from Sachtleben Chemie GmbH) was stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine in accordance with the ASTM D 1003 method, and the haze of the solution was measured to be 1.0%.

Example 12: Formulation Solution 4-2

Taking 79.6 g of 50% aqueous solution of ethylene glycol, adding 19.9 g of oxalic acid, stirring and dissolving, adding a coprecipitate of titanium dioxide/silica and or a titanium compound C-94 composed of a titania/zirconia coprecipitate (purchased from 0.5 g of Sachtleben Chemie GmbH) was stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine in accordance with the ASTM D 1003 method, and the haze of the solution was measured to be 1.1%.

Example 13: Formulation Solution 4-3

Take 94.5 g of a 50% aqueous solution of ethylene glycol, add 5 g of oxalic acid, stir to dissolve, then add a coprecipitate of titanium dioxide/silica and or a titanium compound C-94 composed of a titania/zirconia coprecipitate (purchased from Sachtleben). Chemie GmbH) 0.5 g, stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured in accordance with ASTM D 1003 using a HunterLab COLORQUEST XE machine, and the haze of the solution was measured to be 1.0%.

The results of the foregoing Examples 1 to 13 are organized as shown in Table 1 below.

According to another embodiment of the present specification, a method of catalyzing a polyesterification reaction with a titanium-containing composition is disclosed. The above polyesterification reaction comprises a copolyesterification reaction. The above method for catalyzing a polyesterification reaction with a titanium-containing composition comprises a transesterification reaction in which a titanium-containing composition is added to a dicarboxylic acid ester, or a polycondensation reaction of a dicarboxylic acid and an excess amount of a glycol. Wherein, the titanium-containing composition described above comprises a titanium-containing coprecipitate, an organic acid, a diol, and water. Wherein, the weight percentage of the titanium-containing coprecipitate is about 0.01 to 20% by weight based on the total amount of the titanium-containing composition, and the weight percentage of the above organic acid is about 2 to 80%, and the weight percentage of the glycol It is about 0.1 to 95% by weight, and the weight percentage of water is about 0.1 to 99% by weight.

According to this embodiment, the titanium-containing coprecipitate contains a coprecipitate of titanium dioxide (TiO ₂ )/silica (SiO ₂ ) and/or a coprecipitate of titanium dioxide (TiO ₂ )/zirconia (ZrO ₂ ). Titanium compound. Wherein, in the above-mentioned titania/silica coprecipitate, TiO ₂ :SiO ₂ =90:10 to 20:80 mol/mol, in the coprecipitate of the above titanium dioxide/zirconia, TiO ₂ :ZrO ₂ =95: 5 to 70: 30 mol/mol.

The above organic acid may be one selected from the group consisting of formic acid, acetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tartaric acid, salicylic acid, citric acid, Lactic acid, malic acid, cinnamic acid, caffeic acid.

The above diol may be one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, and pentanediol.

In a preferred embodiment according to this embodiment, the above-described method of modulating the titanium-containing composition is as follows. After the titanium-containing coprecipitate, the organic acid, the diol, and water are mixed, they are stirred at normal temperature to obtain a uniform transparent solution. In another preferred embodiment of the present embodiment, the titanium-containing composition is prepared by mixing a titanium-containing coprecipitate, an organic acid, ethylene glycol, and water, and then performing a heating operation to obtain A uniform clear solution.

It is well known to those skilled in the art that different titanium catalysts generally require different dissolution modes to achieve optimum dispersion. According to the present embodiment, the catalyst dissolved in the glycol is completely dispersed by the use of an organic acid to completely solve the problem of uneven dispersion of the catalyst, thereby improving the quality of the polyester product and lowering the Lb value of the polyester chip.

In a preferred embodiment according to this embodiment, the above method for catalyzing a polyesterification reaction with a titanium-containing composition may further comprise a transesterification reaction of adding a phosphide to the above dicarboxylic acid ester or a dicarboxylic acid and an excess amount of two The polycondensation reaction of the alcohol. The above phosphide can exert the effect of a thermal stabilizer in the above polyesterification reaction. The above phosphide may be selected from the group consisting of phosphoric acid, phosphorous acid, trimethyl phosphate TMP, triethyl phosphate TEP, tripropyl phosphate, triphenyl phosphate TPP, triisopropyl phosphate, tributyl phosphate TBP, phenyl Phosphorous acid, alkyl phenyl phosphate, aromatic acid phosphate, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, diisopropyl phosphite, dibutyl phosphite, diphenyl phosphite A phosphorus compound or a salt of each of the foregoing phosphides. Among them, phosphoric acid, triethyl phosphate, trimethyl phosphate, and the like are preferable. The amount of the phosphorus compound to be used is usually about 1 to 30 ppm based on the phosphorus atom relative to the obtained polyester resin. According to the present example, the phosphorus compounds may be used singly or in combination of two or more.

In another preferred embodiment according to this embodiment, the above method for catalyzing the polyesterification reaction with the titanium-containing composition may further comprise adding a co-catalyst to the transesterification reaction of the above dicarboxylic acid ester or dicarboxylic acid and excess In the polycondensation reaction of glycols. The above common catalyst is used to enhance the activity of the titanium-containing composition. The above common catalyst may be an acetate, a carbonate, a chloride, a sulfate or a nitrate selected from the group consisting of manganese, zinc, cobalt, magnesium, aluminum, calcium, barium, iron, gallium, copper, nickel, tin, and the like. Or a metal compound such as a metal oxide. According to the present example, in the above method of catalyzing the polyesterification reaction with the titanium-containing composition, the total amount of all metal atoms is preferably less than 50 ppm, more preferably 30 ppm or less.

In another preferred embodiment according to this embodiment, the above-described method of catalyzing a polyesterification reaction with a titanium-containing composition is used to prepare a thermoplastic polymer. The above thermoplastic polymer is a polyester composed of a repeating unit A derived from a diacid component and at least one repeating unit B derived from a monodiol component. The above diacid component may be an aliphatic dicarboxylic acid selected from C2 to C16, an aromatic dicarboxylic acid of C8 to C16, or a combination thereof. Optionally, the C8-C16 aromatic dicarboxylic acid is terephthalic acid. More preferably, the above thermoplastic polymer is polyethylene terephthalate or a copolyester of polyterephthalic acid. And preferably, terephthalic acid accounts for at least 60 mol% of the diacid component based on the total number of moles of the diacid component, and based on the total number of moles of the glycol component, The alcohol is at least 60 mol% of the diol component.

According to the present example, optionally, the above diacid component comprises two C8-C16 aromatic dicarboxylic acids. In one embodiment of the present example, the two C8-C16 aromatic dicarboxylic acids are respectively benzene. Dicarboxylic acid and isophthalic acid. More preferably, the diacid component comprises 96 to 99 mol% of terephthalic acid and 4 to 1% by mol of phthalic acid.

According to this example, optionally, the above diol component comprises at least one C2 to C10 diol. More preferably, the diol component comprises at least one C2 to C5 diol, and during the polymerization, part of the ethylene glycol is dehydrated to form diethylene glycol (DEG), so the copolymerization of the polymerization product Repeating unit B derived from diethylene glycol will be present in the ester. Preferably, in the polyester, the repeating unit B derived from ethylene glycol is 95 to 99 mol%, based on the total number of moles of the repeating unit B, and the repeating unit B derived from diethylene glycol is 5~1mol%.

Hereinafter, a process of polycondensing an aromatic dicarboxylic acid or a corresponding ester thereof and an aliphatic diol or a corresponding ester thereof to prepare a polyester resin will be exemplified as an exemplary embodiment of the present embodiment. . However, the description should not be limited to the content described in this example, and should be based on the scope of the patent application that follows.

< Method for producing polyester resin > < Esterification process >

First, when producing a polyester resin, an aromatic dicarboxylic acid or a corresponding ester thereof and an aliphatic diol or a corresponding ester thereof are prepared into a slurry, and then continuously supplied to an esterification reaction step. By the esterification step, a low polycondensate which is an esterification reaction of an aromatic dicarboxylic acid and an aliphatic diol is obtained, and its number average molecular weight is about 500 to 5,000. The low polycondensate is then supplied to a liquid phase polycondensation process.

< Liquid polymerization process >

In the liquid polymerization step, the low polycondensate obtained in the esterification step is subjected to polycondensation under reduced pressure and by heating to a temperature equal to or higher than the melting point of the polyester resin (usually 250 to 280 □). In the polycondensation reaction, it is desirable to remove the unreacted aliphatic diol to carry out the above polycondensation reaction. After the liquid phase polycondensation resin having an intrinsic viscosity IV of 0.4 to 0.8 dl/g is obtained by a liquid polymerization step, the pellet is converted into a liquid polymerized ester particle.

According to the present embodiment, the titanium-containing composition and other additives which are added as needed, for example, a co-catalyst containing a metal compound, and a thermal stabilizer containing a phosphorus compound, may be present at the time of the polycondensation reaction. Therefore, the addition of the titanium-containing composition and the additive may be added in any of the steps of the raw material slurry preparation step, the esterification step, and the liquid phase polycondensation step. Furthermore, according to the present embodiment, when the titanium-containing composition and the additive are used, the amount may be added at a time, or may be added in several steps to one step or several different steps.

< Solid polymerization process >

The liquid polymeric resin in the solid phase polymerization step is first heated to a temperature lower than the temperature at which the solid phase polymerization is carried out to carry out a precrystallization treatment, and then supplied to the solid polycondensation step. The solid state polymerization step may be carried out at 190 to 240 ° C under a nitrogen atmosphere. After the solid state polymerization process, a solid polymerized polyester having an intrinsic viscosity IV of 0.4 to 1.5 dl/g can be obtained.

According to the present embodiment, the production process of the polyester resin in the above-described esterification step and polycondensation step can be carried out by any one of a batch type, a semi-continuous type, and a continuous type. The polyester resin obtained by the method disclosed in the present embodiment can be used as a material of various molded bodies, for example, melt-molded and used for hollow molded articles such as bottles, films, fibers, and the like.

Example 14: Comparative Example 1 Titanium Powder

38.1 KG of terephthalic acid (TPA), and 0.81 KG of phthalic acid (IPA), and 18.16 KG of ethylene glycol (EG) were placed in a stirred tank and stirred to form a paste. The paste was then poured into an esterification tank and heated to 255 ° C for esterification reaction for a reaction time of about 6.5 hours. When the esterification rate is more than 95%, an esterified product can be obtained. The esterified product was transferred to a polymerization tank, and the titanium catalyst solution prepared by the formulation blank of Example 1 was added with 30 ppm (titanium atom relative to PET), thermal stabilizer 35 ppm, and toner cobalt acetate 35 ppm. The polycondensation reaction was then carried out at about 280 ° C under 1 Torr. It is polymerized to an intrinsic viscosity of about 0.6 dL/g. It is then diced to obtain liquid polymerized ester granules of PET. Next, the liquid polymerized ester particles were poured into a solid polymerization reactor, and the obtained liquid polymerized ester particles were precrystallized at 150 ° C for 2 hours. The mixture was heated at 235 ° C under 2 Torr for 4 hours to obtain a solid phase polycondensate polyethylene terephthalate ester pellet. The physical properties measured by the above ester granules are shown in Table 2 .

Example 15: Tartaric acid

38.1 KG of terephthalic acid (TPA), and 0.81 KG of phthalic acid (IPA), and 18.16 KG of ethylene glycol (EG) were placed in a stirred tank and stirred to form a paste. The paste was then poured into an esterification tank and heated to 255 ° C for esterification reaction for a reaction time of about 6.5 hours. When the esterification rate is more than 95%, an esterified product can be obtained. The esterified product was transferred to a polymerization tank, and a titanium catalyst solution prepared by Formulations 1-3 of Example 4 was added with 30 ppm (titanium atom relative to PET), thermal stabilizer 35 ppm, and toner cobalt acetate 35 ppm. The polycondensation reaction was then carried out at about 280 ° C under 1 Torr. It is polymerized to an intrinsic viscosity of about 0.6 dL/g. It is then diced to obtain liquid polymerized ester granules of PET. Next, the liquid polymerized ester particles were poured into a solid polymerization reactor, and the obtained liquid polymerized ester particles were precrystallized at 150 ° C for 2 hours. The mixture was heated at 235 ° C under 2 Torr for 4 hours to obtain a solid phase polycondensate polyethylene terephthalate ester pellet. The physical properties measured by the above ester granules are shown in Table 2 .

Example 16: Succinic acid

38.1 KG of terephthalic acid (TPA), and 0.81 KG of phthalic acid (IPA), and 18.16 KG of ethylene glycol (EG) were placed in a stirred tank and stirred to form a paste. The paste was then poured into an esterification tank and heated to 255 ° C for esterification reaction for a reaction time of about 6.5 hours. When the esterification rate is more than 95%, an esterified product can be obtained. The esterified product was transferred to a polymerization tank, and a titanium catalyst solution prepared by Formulation 2-3 of Example 7 was added with 30 ppm (titanium atom relative to PET), thermal stabilizer 35 ppm, and toner cobalt acetate 35 ppm. The polycondensation reaction was then carried out at about 280 ° C under 1 Torr. It is polymerized to an intrinsic viscosity of about 0.6 dL/g. It is then diced to obtain liquid polymerized ester granules of PET. Next, the liquid polymerized ester particles were poured into a solid polymerization reactor, and the obtained liquid polymerized ester particles were precrystallized at 150 ° C for 2 hours. The mixture was heated at 235 ° C under 2 Torr for 4 hours to obtain a solid phase polycondensate polyethylene terephthalate ester pellet. The physical properties measured by the above ester granules are shown in Table 2 .

Example 17: Salicylic acid

38.1 KG of terephthalic acid (TPA), and 0.81 KG of phthalic acid (IPA), and 18.16 KG of ethylene glycol (EG) were placed in a stirred tank and stirred to form a paste. The paste was then poured into an esterification tank and heated to 255 ° C for esterification reaction for a reaction time of about 6.5 hours. When the esterification rate is more than 95%, an esterified product can be obtained. The esterified product was transferred to a polymerization tank, and a titanium catalyst solution prepared by Formulation 3-3 of Example 10 was added with 30 ppm (titanium atom relative to PET), thermal stabilizer 35 ppm, and toner cobalt acetate 35 ppm. The polycondensation reaction was then carried out at about 280 ° C under 1 Torr. It is polymerized to an intrinsic viscosity of about 0.6 dL/g. It is then diced to obtain liquid polymerized ester granules of PET. Next, the liquid polymerized ester particles were poured into a solid polymerization reactor, and the obtained liquid polymerized ester particles were precrystallized at 150 ° C for 2 hours. The mixture was heated at 235 ° C under 2 Torr for 4 hours to obtain a solid phase polycondensate polyethylene terephthalate ester pellet. The physical properties measured by the above ester granules are shown in Table 2 .

Example 18: Oxalic acid

38.1 KG of terephthalic acid (TPA), and 0.81 KG of phthalic acid (IPA), and 18.16 KG of ethylene glycol (EG) were placed in a stirred tank and stirred to form a paste. The paste was then poured into an esterification tank and heated to 255 ° C for esterification reaction for a reaction time of about 6.5 hours. When the esterification rate is more than 97%, an esterified product can be obtained. The esterified product was transferred to a polymerization tank, and a titanium catalyst solution prepared by Formulation 4-3 of Example 13 was added with 30 ppm (titanium atom relative to PET), thermal stabilizer 35 ppm, and toner cobalt acetate 35 ppm. The polycondensation reaction was then carried out at about 280 ° C under 1 Torr. It is polymerized to an intrinsic viscosity of about 0.6 dL/g. It is then diced to obtain liquid polymerized ester granules of PET. Next, the liquid polymerized ester particles were poured into a solid polymerization reactor, and the obtained liquid polymerized ester particles were precrystallized at 150 ° C for 2 hours. The mixture was heated at 235 ° C under 2 Torr for 4 hours to obtain a solid phase polycondensate polyethylene terephthalate ester pellet. The physical properties measured by the above ester granules are shown in Table 2 .

*IV-MSP: Viscosity of liquid polymeric ester particles

*IV-SSP: viscosity of ester particles after solidification

* Viscosity values are tested using Ubbelohde viscosity and the test method is in accordance with ASTM D 4603.

The values of *L, Lb, and La were tested using a Nippon Denshoku ZE2000 color difference meter in accordance with ASTM D 1925. The larger the L value, the higher the brightness; a>0 means the color is reddish, a<0 means the color is greenish, b>0 means the color is yellowish, and b<0 means the color is blue.

* Haze: Detected in accordance with ASTM D 1003 using HunterLab's COLORQUEST XE.

In summary, the present specification discloses a titanium-containing composition and its use in a polyester/copolyester process. The titanium-containing composition described above comprises a titanium-containing coprecipitate, an organic acid, a glycol, and water. Wherein the titanium-containing coprecipitate is a titanium compound containing a coprecipitate of titanium dioxide (TiO ₂ )/silica (SiO ₂ ) and/or a coprecipitate of titanium dioxide (TiO ₂ )/zirconia (ZrO ₂ ) . When the titanium-containing composition is applied to a catalyst in a polyester/copolyester process, the effect of completely dispersing and dissolving the titanium-containing catalyst in the diol can be achieved by using an organic acid, thereby improving the polyester product. quality. The titanium-containing composition may be added to any of the steps of a raw material slurry preparation step, an esterification step, and a liquid phase polycondensation step. Further, the titanium-containing composition may be added to one or more of the above steps in a single addition or multiple additions.

Obviously, many modifications and differences may be made to the invention in light of the above description. It is therefore to be understood that within the scope of the appended claims, the invention may be The above are only the preferred embodiments of the present invention, and are not intended to limit the scope of the claims of the present invention; all other equivalent changes or modifications which are not departing from the spirit of the present invention should be included in the following claims. Within the scope.

Claims (6)

A titanium-containing composition comprising: a titanium-containing coprecipitate having a weight percentage of the titanium-containing coprecipitate of 0.5% by weight, wherein the titanium-containing coprecipitate comprises a coprecipitate of titanium dioxide/silica and/or a titanium dioxide/zirconia coprecipitate; an organic acid having a weight percentage of the organic acid of 2 to 45 wt%, wherein the organic acid is one selected from the group consisting of oxalic acid, succinic acid, tartaric acid, and salicylic acid. The weight percentage of the diol, the diol is 27 to 49% by weight; and the weight percentage of water and water is 27 to 49% by weight. The titanium-containing composition according to claim 1, wherein the titanium-containing coprecipitate comprises a coprecipitate of titanium oxide (TiO ₂ )/silica (SiO ₂ ) and/or titanium dioxide (TiO ₂ )/dioxide a titanium compound of a zirconium (ZrO ₂ ) coprecipitate, wherein the above titanium oxide/silica coprecipitate has a total of TiO ₂ :SiO ₂ = 90:10 to 20:80 mol/mol, and the above titanium oxide/zirconia In the precipitate, TiO ₂ :ZrO ₂ = 95:5 to 70:30 mol/mol. The titanium-containing composition according to claim 1, wherein the above-mentioned glycol is selected from one of the group consisting of ethylene glycol, propylene glycol, and butylene glycol. A method for catalyzing a polyesterification reaction with a titanium-containing composition, comprising: adding a titanium-containing composition to a polymerization reaction of a dicarboxylic acid and a glycol, wherein the titanium-containing composition comprises: a titanium-containing coprecipitate The titanium-containing coprecipitate is 0.5 wt%, wherein the titanium-containing coprecipitate comprises a titania/silica coprecipitate and/or a titania/zirconia coprecipitate; an organic acid, the organic The weight percentage of the acid is 2 to 45 wt%, wherein the above organic acid is selected from one of the group consisting of oxalic acid, succinic acid, tartaric acid, salicylic acid; diol, and the weight percentage of the above diol is 27 ~49 wt%; and water, the weight percentage of the above water is 27 to 49 wt%. A method for catalyzing a polyesterification reaction with a titanium-containing composition according to the fourth aspect of the patent application, wherein the dicarboxylic acid is selected from the group consisting of C2 to C6 aliphatic dicarboxylic acid and C3 to C5 aromatics. An aromatic dicarboxylic acid, or a combination thereof, wherein the diol comprises at least one C2 to C4 diol. A method for catalyzing a polyesterification reaction by a titanium-containing composition according to the fourth aspect of the patent application, wherein the titanium-containing composition is added to a raw material slurry preparation step, an esterification step, and a liquid phase polycondensation step in a polyesterification reaction In at least one of the processes.