TWI596135B - Preparation of catalyst, catalyst obtained and and the preparation of polyester applications - Google Patents

Description

Catalyst preparation method, catalyst prepared therefrom and application thereof for preparing polyester

The present invention relates to a process for preparing a catalyst and a catalyst produced therefrom, which is mainly used for the preparation of polyester.

In the existing processes of polyester products [eg polyethylene terephthalate (PET)], most of them are cerium (III) compounds [eg cerium (III) acetate, cerium (III) oxide or ethylene glycol).锑(III)] as a catalyst for the polycondensation reaction, however, the use of the above ruthenium (III) compound tends to cause the hue of the catalyst solution or the polyester product to be dull and yellowish, thus requiring the addition of a stabilizer or the use of a co-catalyst. (cocatalyst) (eg US 3,844,976 and US 8,648,166 B2).

CN 1255478A discloses a method for preparing a polyester catalyst (ie, ethylene glycol ruthenium) by removing impurities and unreacted (or excess) reactants (ethylene glycol and Sb ₂ O ₃ ) through a plurality of separation steps, but preparing the same. The hue of the polyester product still has room for improvement.

CN 103435793A discloses a normal temperature homogeneous liquid polyester catalyst, which mainly comprises mixing a cerium compound with a dibasic organic acid, lactic acid and ethylene glycol, and heating and dissolving to form a normal temperature homogeneous solution (a uniform liquid state at normal temperature, The liquid polyester catalyst can be more conveniently used in the synthesis of the polyester. However, it is only physically mixed, and the chemical structure of the ruthenium compound is not changed, so the catalyst is used. When the polymerization is carried out, there is still a problem that the polyester product has a poor hue.

Accordingly, it is an object of the present invention to provide a process for the preparation of a catalyst by chemically modifying a ruthenium compound to improve the hue of the polyester of the ruthenium (III) compound.

Thus, the process of the catalyst of the present invention comprises heating a mixture to carry out a chemical reaction to obtain a A product of a compound of the formula wherein R represents a divalent organic group consisting essentially of an organic dibasic acid dibasic ester and a ruthenium (III) compound.

Therefore, another object of the present invention, that is, to provide a catalyst, is produced by the above-described method.

Accordingly, it is still another object of the present invention to provide a composition for preparing a polyester comprising the catalyst as described above; an organic polybasic acid, an anhydride thereof or an ester thereof; and a glycol.

Accordingly, it is still another object of the present invention to provide a method of preparing a polyester comprising heating a mixture to carry out a chemical reaction to obtain a a catalyst for a part of a compound, wherein R represents a divalent organic group, the mixture consists essentially of an organic dibasic acid dibasic ester and a ruthenium (III) compound; and an organic polybasic acid, an anhydride thereof or an ester thereof And the diol is subjected to a polycondensation reaction in contact with the catalyst to obtain the polyester.

The effect of the present invention is that the catalyst prepared by the process of the present invention can be used for the polycondensation reaction of preparing a polyester without additionally adding a stabilizer or using a co-catalyst, and a polyester product having a good hue can be obtained.

The contents of the present invention will be described in detail below:

The method for preparing a catalyst according to the invention comprises heating a mixture to carry out a chemical reaction to obtain a A product of a compound of the formula wherein R represents a divalent organic group consisting essentially of an organic dibasic acid dibasic ester and a ruthenium (III) compound.

Preferably, in the method of preparing the catalyst of the present invention, the mixture is heated to carry out a chemical reaction to obtain a A product of a partial compound, wherein Ar represents a divalent aromatic group and R represents a divalent organic group. More preferably, Ar represents 1,4-phenylene and R represents -C ₂ H ₄ -.

Preferably, the organic dibasic acid didiol ester is an aromatic dibasic acid didiol ester. More preferably, the aromatic dibasic acid didiol ester is a bis(2-hydroxyethyl) terephthalate, BHET monomer having the structure shown in the following Chemical Formula 1. In the present invention, bis 2-hydroxyethyl terephthalate may be a commercially available reagent-grade chemical, a product obtained by alcoholysis of PET with ethylene glycol, and reacted with terephthalic acid and ethylene oxide. The resulting product, but excludes polymers or oligomers obtained by the polymerization of terephthalic acid and ethylene glycol. [Chemical Formula 1]

Preferably, in the process of the catalyst of the present invention, the ruthenium (III) compound is selected from the group consisting of ruthenium (III) acetate or ruthenium (III) oxide (i.e., Sb ₂ O ₃ ).

In a particular embodiment of the invention, the mixture is comprised of an organic dibasic acid didiol ester and a ruthenium (III) compound.

Preferably, in the process of the catalyst of the present invention, the molar ratio of the organic dibasic acid diglyceride to the ruthenium (III) compound in the mixture ranges from 1.5 to 3.2, more preferably, The molar ratio of the organic dibasic acid diglyceride to the ruthenium (III) compound ranges from 2.2 to 3.2. In a particular embodiment of the invention, the molar ratio of the organic dibasic acid diglyceride to the ruthenium (III) compound is 2.5.

Preferably, in the process of the catalyst of the present invention, the mixture is subjected to a chemical reaction at 120 to 170 °C. More preferably, the mixture is subjected to a chemical reaction at 120 to 140 °C. In a particular embodiment of the invention, the mixture is subjected to a chemical reaction at 120 to 130 °C.

Preferably, in the process of the catalyst of the present invention, the mixture is heated to carry out a chemical reaction in an environment free of ethylene glycol.

Preferably, in the composition for preparing a polyester of the present invention, the organic polybasic acid is selected from an aromatic dibasic acid (for example, terephthalic acid or isophthalic acid) or an aliphatic dibasic acid (for example). 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, adipic acid or sebacic acid), an aliphatic tribasic acid or a tetrabasic acid (for example, 1,1,2- Ethane tricarboxylic acid, 1,2,3-propane tricarboxylic acid or 1,2,3,4-butane tetracarboxylic acid), an aromatic tribasic acid or a tetrabasic acid (for example, 1,2,4,5-benzene IV) Acid, trimellitic acid, trimellitic acid or 3,3',4,4'-biphenyltetracarboxylic acid) or a combination thereof. In a particular embodiment of the invention, the organic polyacid is terephthalic acid.

Preferably, in the composition for preparing a polyester of the present invention, the diol is selected from the group consisting of 1,2-ethanediol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, and , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, isosorbide or a combination thereof. In a particular embodiment of the invention, the glycol is 1,2-ethylene glycol.

Preferably, in the composition for preparing a polyester of the present invention, the catalyst and the diol are in two distinct phases.

Preferably, in the method for producing a polyester of the present invention, R represents -C ₂ H ₄ -, and the organic dibasic acid dibasic ester is bis 2-hydroxyethyl terephthalate, and the organic polybasic acid is Terephthalic acid, the glycol is ethylene glycol.

Preferably, in the method of preparing a polyester of the present invention, the mixture is heated in a glycol-free environment for chemical reaction, and the catalyst is in two phases with the diol.

The composition for preparing a polyester of the present invention may further contain any other known polymer, stabilizer, antioxidant, antistatic agent, antifoaming agent, dyeing auxiliary, dye, pigment, delustering agent, firefly Light whitening agent or other additives.

The composition for producing a polyester of the present invention can be further subjected to a polycondensation reaction by a generally existing method to obtain a polyester product.

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

<synthesis example> BHET Monomer synthesis catalyst C _E

106.22 g (0.42 mol) of bis 2-hydroxyethyl terephthalate (BHET monomer) was placed in a 250 mL glass vial and heated to 120 ° C, followed by 50 g (0.17 mol) of cerium (III) acetate. The chemical reaction was carried out at 130 ° C for 4 hours, and finally distilled under reduced pressure to obtain a white powder product (catalyst C _E ). From the HMBC (heteronuclear multiple-bond correlation) spectrum, the BHET monomer and cerium (III) acetate were known. The reaction produces a product having a long-range coupling of H-6 (δ = 4.37) and C-4 (δ = 164.8) and C-7 (δ = 171.5) (shown in the following Chemical Formula 2), the compound of which is indeed contain Part (in the present synthesis, R represents -C ₂ H ₄ -). [Chemical Formula 2]

<Comparative Synthesis Example> BHET Oligomer synthesis catalyst C _C

[ preparation BHET Oligomer ]

First, 345.8 g of terephthalic acid and 161.5 g of ethylene glycol were placed in a 1 L reactor, and the reaction was carried out under a pressure of 250 ° C and 2 kg/cm ² N ₂ for 280 min, and the average degree of polymerization was obtained after distilling off water. BHET oligomer of 15.6 ( M _p = 3016) with PDI = 1.18 ( =4341, = 5122), showing that the molecular weight distribution of the BHET oligomer is quite concentrated.

[ Synthetic catalyst ]

Next, 253.3 g (0.084 mol) of the above BHET oligomer was placed in a 200 mL glass vial and heated to 230 ° C, followed by the addition of 11.4 g (0.038 mol) of cerium (III) acetate, and the temperature was raised to 260 ° C for 4 hours. Finally, distillation under reduced pressure gave a yellow-brown powder product (catalyst C _C ).

<Hue measurement>

The CIE L* value, a* value and b* value of the catalysts C _E and C _C of the above synthesis examples and comparative synthesis examples were respectively measured by a color difference meter (model NE4000) of Japan NIPPON DENSHOKU Co., Ltd., and the results are shown in Table 1 below. . [Table 1] <TABLE border="1"borderColor="#000000"width="_0009"><TBODY><tr><td></td><td> CIE L* value</td><td> CIE a* value</td><td> CIE b* value</td></tr><tr><td> Catalyst C_E</td><td> 91.70 </ Td><td> -0.49 </td><td> 6.60 </td></tr><tr><td> Catalyst C_C</td><td> 65.11 </ Td><td> 4.70 </td><td> 16.73 </td></tr></TBODY></TABLE>

It can be clearly seen from Table 1 that compared with the catalyst C _E of the synthesis example, the CIE L* value of the catalyst C _C of the comparative synthesis example is small and the CIE a* value and the CIE b* value are more than 0, showing Its brightness is lower (the color is darker) and it is more yellowish brown (the color is more deviated from white), so the hue is poor. In addition, the process of the comparative synthesis method needs to be heated to 230~260 °C to obtain the catalyst C _{C of} the product, and the process of the synthesis example only needs to be heated to 120-130 ° C to obtain the catalyst C _{E of} the product.

<Examples> Polyester PET _E

[ Formulating a composition for preparing a polyester ]

First, 2161.5 g of terephthalic acid and 1009.1 g of ethylene glycol were placed in a 5 L reactor, and prepolymerization was carried out at 250 ° C under a pressure of 2 kg/cm ² N ₂ for 285 min, followed by the addition of phosphoric acid (amount relative to The molar ratio of terephthalic acid is 0.00015:1) and the catalyst C _E powder of the above synthesis example (the amount equivalent to causing 0.0133 g of lanthanum element per 100 g of the polyester product obtained later) The medium C _E and the ethylene glycol are in two phases.

[ Synthetic polyester ]

Subsequently, the above composition for preparing a polyester was subjected to a polycondensation reaction at 270 to 275 ° C, and discharged after 345 minutes of reaction to obtain a polyester product (polyester PET _E ).

<Comparative example 1 >polyester PET _C1

Comparative Example 1 is substantially the same as the above embodiment except that the catalyst C _E powder of the above synthesis example is changed to the catalyst C _C powder of the above comparative synthesis example (the amount is equivalent to each subsequent 100 g of poly The ester product contains 0.0133 g of lanthanum). Subsequently, a polycondensation reaction was carried out and discharged after 350 minutes of reaction to obtain a polyester product (polyester PET _C1 ).

<Comparative example 2 >polyester PET _C2

Comparative Example 2 is substantially the same as the above embodiment except that the catalyst C _E powder of the above synthesis example was changed to cerium (III) acetate powder (the amount corresponding to the subsequent obtained per 100 g of the polyester product) 0.0133 g锑 element). Subsequently, a polycondensation reaction was carried out, and after the reaction was carried out for 415 min, a polyester product (polyester PET _C2 ) was obtained.

<Comparative example 3 , 4 >polyester PET _C3 , PET _C4

Comparative Examples 3 and 4 are substantially the same as the above examples, except that the catalyst C _E powder of the above synthesis example is changed to cerium (III) oxide powder (the amount corresponding to each subsequent 100 g of polyester obtained) The product contained 0.0133 g and 0.0250 g of lanthanum, respectively. Subsequently, the polycondensation reaction was carried out, and the mixture was discharged after 380 min and 305 min, respectively, to obtain a polyester product (polyester PET _C3 , PET _C4 ).

<Comparative example 5 , 6 >polyester PET _C5 , PET _C6

Comparative Examples 5 and 6 are substantially the same as the above examples, except that the catalyst C _E powder of the above synthesis example is changed to ethylene glycol ruthenium (III) powder (the amount equivalent to each subsequent 100 g obtained) The polyester product contained 0.0133 g and 0.0180 g of lanthanum, respectively. Subsequently, the polycondensation reaction was carried out, and the mixture was discharged after 355 min and 245 min, respectively, to obtain a polyester product (polyester PET _C5 , PET _C6 ).

<Hue measurement>

The CIE L* value, a* value and b* value of the polyester PET _E and PET _C1 ~ PET _C6 of the above Examples and Comparative Examples 1 to 6 were respectively measured by a color difference meter (model NE4000) of Japan NIPPON DENSHOKU Co., Ltd., and the results were respectively measured. As shown in Table 2 below.

<Viscocity measurement>

The PET PET _E and the PET _C1 ~ PET _C6 0.1 g of the above examples and Comparative Examples 1 to 6 were respectively dissolved in a mixed solvent of 25 mL of phenol/tetrachloroethane (3:2 by weight) at 30 ° C. The intrinsic viscosity (IV, [η]) was measured by a Ubbelohde viscometer, and all IV values were greater than 0.56 dL/g. [Table 2] <TABLE border="1"borderColor="#000000"width="_0010"><TBODY><tr><td></td><td> CIE L* value</td><td> CIE a* value</td><td> CIE b* value</td></tr><tr><td> polyester PET_E</td><td> 70.8 </ Td><td> 0.9 </td><td> 1.5 </td></tr><tr><td> polyester PET_C1</td><td> 71.0 </td ><td> -1.2 </td><td> 5.6 </td></tr><tr><td> Polyester PET_C2</td><td> 70.4 </td ><td> -0.9 </td><td> 6.3 </td></tr><tr><td> Polyester PET_C3</td><td> 62.9 </td ><td> -0.2 </td><td> 14.2 </td></tr><tr><td> Polyester PET_C4</td><td> 59.6 </td ><td> -1.6 </td><td> 2.7 </td></tr><tr><td> Polyester PET_C5</td><td> 68.8 </td ><td> -1.6 </td><td> 5.2 </td></tr><tr><td> Polyester PET_C6</td><td> 66.6 </td ><td> -0.1 </td><td> 3.8 </td></tr></TBODY></TABLE>

For polyester products, the hue requirement for the polyester product is such that the CIE L* value is as large as possible and the CIE b* value is as close as possible to zero (preferably no greater than 2). As is apparent from Table 2, the CIE b* values of the polyester PET _C1 ~ PET _C6 of Comparative Examples 1 to 6 were all 2.7 or more, and the CIE L* value of the polyester PET _E of the example was sufficiently large and CIE b* The value is closer to 0, indicating that the brightness is sufficiently high and whiter, so the hue is better.

In summary, the method for preparing the catalyst of the present invention and the prepared catalyst are used for the polycondensation reaction of preparing a polyester to effectively improve the problem that the ruthenium (III) compound causes a poor hue of the polyester, so that it can be achieved. The object of the invention.

However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the equivalent equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still The scope of the invention is covered.

Claims (14)

A catalyst preparation method comprising heating a mixture to carry out a chemical reaction to obtain a A product of a portion of a compound wherein R represents a divalent organic group consisting essentially of an organic dibasic acid didiol ester and a ruthenium (III) compound. The method of preparing a catalyst according to claim 1, wherein in the mixture, the molar ratio of the organic dibasic acid diglyceride to the ruthenium (III) compound ranges from 1.5 to 3.2. The method of producing a catalyst according to claim 1, wherein the mixture is heated in a solvent-free environment for chemical reaction. The method for preparing a catalyst according to claim 1, comprising heating the mixture to carry out a chemical reaction to obtain a A product of a part of the compound, wherein Ar represents a divalent aromatic group, R represents a divalent organic group, and the organic dibasic acid didiol ester is an aromatic dibasic acid didiol ester. The method of preparing a catalyst according to claim 4, wherein Ar represents 1,4-phenylene, R represents -C ₂ H ₄ -, and the aromatic dibasic acid diglyceride is terephthalic acid double 2 - hydroxyethyl ester. The method of preparing a catalyst according to claim 1, wherein the ruthenium (III) compound is selected from the group consisting of ruthenium (III) acetate or ruthenium (III) oxide. A catalyst produced by the method according to any one of claims 1 to 6. A composition for producing a polyester, comprising: the catalyst according to claim 7; an organic polybasic acid, an anhydride thereof or an ester thereof; and a glycol. The composition for preparing a polyester according to claim 8, wherein the organic polybasic acid is selected from the group consisting of terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3- Cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, 1,1,2-ethanetricarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butane IV Formic acid, pyromellitic acid, trimellitic acid, trimellitic acid or 3,3',4,4'-biphenyltetracarboxylic acid or its combination. The composition for preparing a polyester according to claim 8, wherein the diol is selected from the group consisting of 1,2-ethanediol, triethylene glycol, 1,2-propanediol, and 1,3-propanediol. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, isosorbide or a combination thereof. The composition for preparing a polyester according to claim 8, wherein the catalyst is in two phases with the diol. A method of preparing a polyester comprising: heating a mixture to carry out a chemical reaction to obtain a a catalyst for a part of a compound, wherein R represents a divalent organic group, the mixture consists essentially of an organic dibasic acid dibasic ester and a ruthenium (III) compound; and an organic polybasic acid, an anhydride thereof or an ester thereof And the diol is subjected to a polycondensation reaction in contact with the catalyst to obtain the polyester. The method for producing a polyester according to claim 12, wherein R represents -C ₂ H ₄ -, the organic dibasic acid di diol is bis 2-hydroxyethyl terephthalate, and the organic polybasic acid is Terephthalic acid, the glycol is ethylene glycol. The method for producing a polyester according to claim 12, wherein the mixture is heated in a solvent-free environment to carry out a chemical reaction, and the catalyst is in two phases with the diol.