TW201823300A - Catalyst preparation method, catalyst prepared thereby and applications thereof providing polyester having a good hue through chemical modification of Ruthenium compound - Google Patents

Abstract

A process for preparing a catalyst comprises heating a mixture to carry out a chemical reaction so as to obtain a product containing a portion of a compound, wherein R represents a divalent organic group, and the mixture consists essentially of an organic dibasic acid diglycol ester and Ruthenium (III) compound. The present invention also provides a composition for preparing a polyester comprising the catalyst prepared by the above process, an organic polybasic acid, an anhydride thereof or an ester thereof and a glycol. The catalyst prepared by the process of the present invention can be used for the polycondensation reaction of preparing a polyester, and a polyester product having good hue.

Description

Catalyst manufacturing method, catalyst prepared by the method and application of preparing polyester

The invention relates to a catalyst manufacturing method and a catalyst prepared by the catalyst. The catalyst is mainly used for preparing polyester.

In the existing processes of polyester products [such as polyethylene terephthalate (PET)], antimony (III) compounds [such as antimony (III) acetate, antimony (III) oxide, or ethylene glycol are mostly used. Antimony (III)] is used as a catalyst for polycondensation reaction. However, the use of the above-mentioned antimony (III) compounds tends to cause the hue of catalyst solutions or polyester products to be dull and yellowish. Therefore, additional stabilizers or co-catalysts are required. (cocatalyst) (eg US 3,844,976 and US 8,648,166B2).

CN 1255478A discloses a method for preparing a polyester catalyst (ie, ethylene glycol antimony), which removes impurities and unreacted (or excess) reactants (ethylene glycol and Sb ₂ O ₃ ) through a multi-stage separation step. The hue of polyester products still has room for improvement.

CN 103435793A discloses a homogeneous liquid polyester catalyst at normal temperature, which mainly mixes an antimony compound with a binary organic acid, lactic acid, and ethylene glycol, and heats and dissolves to form a normal temperature homogeneous solution (a uniform liquid at normal temperature, (It will not crystallize out). The liquid polyester catalyst can be used in the polyester synthesis, the feeding process is more convenient, however, it is only physical blending, the chemical structure of the antimony compound has not changed, so this catalyst is used When the polymerization reaction is carried out, there is still a problem that the hue of the polyester product is not good.

Therefore, it is an object of the present invention to provide a catalyst manufacturing method by which the antimony compound is chemically modified to improve the problem of poor hue of polyester caused by the aforementioned antimony (III) compound.

Therefore, the method for preparing the catalyst of the present invention includes heating a mixture to perform a chemical reaction to obtain a A product of a partial compound, wherein R represents a divalent organic group, and the mixture is substantially composed of an organic dibasic acid didiol and an antimony (III) compound.

Therefore, another object of the present invention is to provide a catalyst, which is produced by the manufacturing method as described above.

Therefore, another object of the present invention is to provide a composition for preparing a polyester, comprising the catalyst as described above; an organic polyacid, an acid anhydride or an ester thereof; and a diol.

Therefore, another object of the present invention is to provide a method for preparing a polyester, which comprises heating a mixture for a chemical reaction to obtain Catalysts for some compounds, in which R represents a divalent organic group, and the mixture consists essentially of an organic dibasic acid didiol ester and an antimony (III) compound; and an organic polybasic acid, an anhydride thereof, or an ester thereof And a glycol undergoes a polycondensation reaction in contact with the catalyst to obtain the polyester.

The effect of the present invention lies in that the catalyst prepared through the production method of the present invention can be used in the polycondensation reaction for preparing polyester without adding additional stabilizers or using a co-catalyst, and a polyester product with a good hue can be obtained.

The following will describe the content of the present invention in detail:

The method for preparing the catalyst of the invention comprises heating a mixture to perform a chemical reaction to obtain a A product of a partial compound, wherein R represents a divalent organic group, and the mixture is substantially composed of an organic dibasic acid didiol and an antimony (III) compound.

Preferably, the method for preparing the catalyst of the present invention includes heating the mixture to perform a chemical reaction to obtain The products of some compounds, 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 diacid didiol ester is an aromatic diacid didiol ester. More preferably, the aromatic dibasic acid didiol is a bis (2-hydroxyethyl) terephthalate, BHET monomer, the structure of which is shown in Chemical Formula 1 below. In the present invention, bis-2-hydroxyethyl terephthalate can be a commercially available test grade chemical, a product obtained by alcoholysis of PET by ethylene glycol, and a reaction of terephthalic acid and ethylene oxide. The product obtained, but excludes the polymer or oligomer obtained by the polymerization reaction of terephthalic acid and ethylene glycol. [Chemical Formula 1]

Preferably, in the catalyst manufacturing method of the present invention, the antimony (III) compound is selected from antimony (III) acetate or antimony (III) oxide (ie, Sb ₂ O ₃ ).

In a specific embodiment of the present invention, the mixture is composed of an organic dibasic acid didiol and an antimony (III) compound.

Preferably, in the catalyst manufacturing method of the present invention, in the mixture, the molar ratio of the organic dibasic acid didiol ester to the antimony (III) compound ranges from 1.5 to 3.2, more preferably, The molar ratio of the organic dibasic acid didiol to the antimony (III) compound ranges from 2.2 to 3.2. In a specific embodiment of the present invention, the molar ratio of the organic dibasic acid didiol to the antimony (III) compound is 2.5.

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

Preferably, in the preparation method of the catalyst of the present invention, the mixture is chemically reacted by heating in an environment free of ethylene glycol.

Preferably, in the composition for preparing polyester of the present invention, the organic polyacid is selected from the group consisting of an aromatic dibasic acid (such as terephthalic acid or isophthalic acid), and an aliphatic dibasic acid (such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, adipic acid or sebacic acid), aliphatic tribasic acid or tetrabasic acid (e.g. 1,1,2- Ethanetricarboxylic acid, 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid), aromatic tribasic acid or tetrabasic acid (e.g. benzene, tetracarboxylic acid) Acid, 1,2,4- trimellitic acid, 1,3,5- trimellitic acid or 3,3 ', 4,4'-biphenyltetracarboxylic acid) or a combination thereof. In a specific 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-ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 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. In a specific embodiment of the present invention, the glycol is ethylene glycol.

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

Preferably, in the method for preparing a polyester of the present invention, R represents -C ₂ H _4- , the organic dibasic acid didiol is bis 2-hydroxyethyl terephthalate, and the organic polybasic acid is Phthalic acid, the glycol is ethylene glycol.

Preferably, in the method for preparing a polyester according to the present invention, the mixture is chemically reacted by heating in an environment free of ethylene glycol, and the catalyst and the diol are in two phases.

The composition for preparing polyester of the present invention may further contain any other known polymers, stabilizers, antioxidants, antistatic agents, antifoaming agents, dyeing aids, dyes, pigments, delustering agents, fluorescent agents Light brightener or other additives.

The composition for preparing a polyester of the present invention can be further subjected to a polycondensation reaction through a conventional method to obtain a polyester product.

The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limiting the implementation of the present invention.

<Synthesis example> BHET Monomer synthesis catalyst C _E

In a 250 mL glass bottle, put 106.22 g (0.42 mol) of bis-2-hydroxyethyl terephthalate (BHET monomer) and heat to 120 ° C, then add 50 g (0.17 mol) of antimony (III) acetate, and heat up A chemical reaction was performed at 130 ° C for 4 hours. Finally, a white powder product (catalyst C _E ) was obtained after distillation under reduced pressure. From its HMBC (heteronuclear multiple-bond correlation) spectrum, it can be known that the BHET monomer and antimony (III) acetate The reaction produces a product with long-range coupling of H-6 (δ = 4.37), C-4 (δ = 164.8), and C-7 (δ = 171.5) (shown in Chemical Formula 2 below). The compound is indeed contain Part (in this synthesis example, 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 at 250 ° C. under a pressure of 2 kg / cm ² N ₂ for 280 minutes. 15.6 BHET oligomer ( M _p = 3016), with PDI = 1.18 ( = 4341, = 5122), indicating 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 bottle and heated to 230 ° C. Then 11.4 g (0.038 mol) of antimony (III) acetate was added, and the temperature was raised to 260 ° C for 4 hours. Finally, vacuum distillation was performed to obtain a yellow-brown powder product (catalyst C _C ).

＜ Hue measurement ＞

The color difference meter (model NE4000) of Japan NIPPON DENSHOKU company was used to measure 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, and the results are shown in Table 1 below. . 【Table 1】

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 smaller and the CIE a * value and the CIE b * value are more than 0, indicating that Its lightness is lower (the color is darker) and it is more tan (the color is more off-white), so the hue is poor. In addition, the process of the comparative synthesis example needs to be heated to 230-260 ° C. to react to obtain its product catalyst C _C , while the process of the synthesis example only needs to be heated to 120-130 ° C. to obtain its product catalyst C _E.

<Example> Polyester PET _E

[ Formulation of composition for preparing polyester ]

First, 2161.5 g of terephthalic acid and 1009.1 g of ethylene glycol were placed in a 5 L reactor, and the pre-polymerization reaction was performed at 250 ° C. and a pressure of 2 kg / cm ² N ₂ for 285 min. The molar ratio of terephthalic acid is 0.00015: 1) and the catalyst C _E powder of the above synthesis example (the amount is equivalent to causing 0.0133 g of antimony per 100 g of polyester product obtained subsequently). The medium C _E and ethylene glycol are in two phases.

[ Synthetic polyester ]

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

＜ Comparative example 1 ＞ Polyester PET _C1

Comparative Example 1 is roughly the same as the above example, 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 every 100 g The ester product contains 0.0133 g of antimony). Subsequently, a polycondensation reaction is performed, and the reaction is discharged after 350 minutes to obtain a polyester product (polyester PET _C1 ).

＜ Comparative example 2 ＞ Polyester PET _C2

Comparative Example 2 is roughly the same as the above example, except that the catalyst C _E powder of the above synthesis example is changed to antimony (III) acetate powder (the amount is equivalent to the content of 100 g of polyester product obtained subsequently. 0.0133 g of antimony). Subsequently, a polycondensation reaction is performed, and the product is discharged after 415 minutes to obtain a polyester product (polyester PET _C2 ).

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

Comparative Examples 3 and 4 were roughly the same as the above examples, except that the catalyst C _E powder of the above synthesis example was changed to antimony (III) oxide powder (the amount is equivalent to 100 g of polyester subsequently obtained The products contained 0.0133 g and 0.0250 g of antimony, respectively. Subsequently, a polycondensation reaction is performed, and the materials are discharged after 380 minutes and 305 minutes of reaction to obtain polyester products (polyester PET _C3 , PET _C4 ).

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

Comparative Examples 5 and 6 are roughly the same as the above examples, except that the catalyst C _E powder of the above synthesis example is changed to ethylene glycol antimony (III) powder (the amount is equivalent to 100 g The polyester products contained 0.0133 g and 0.0180 g of antimony, respectively. Subsequently, a polycondensation reaction is performed, and the materials are discharged after 355 minutes and 245 minutes of reaction, respectively, to obtain polyester products (polyester PET _C5 , PET _C6 ).

＜ Hue measurement ＞

The color difference meter (model NE4000) of Japan NIPPON DENSHOKU company was used to measure the CIE L * value, a * value, and b * value of the polyester PET _E and PET _C1 to PET _C6 of the above examples and comparative examples 1 to 6, respectively. As shown in Table 2 below.

＜ Viscosity measurement ＞

Take 0.1 g of polyester PET _E and PET _C1 to PET _{C6 of the} above examples and comparative examples 1 to 6, respectively, and dissolve them in a mixed solvent of 25 mL of phenol / tetrachloroethane (weight ratio of 3: 2) at 30 ° C. Using an Ubbelohde viscometer to measure its intrinsic viscosity (IV, [η]), all IV values were greater than 0.56 dL / g. 【Table 2】

For polyester products, the hue of the polyester product is required to be as large as possible, and the CIE b * value is as close to 0 as possible (preferably not greater than 2). It can be clearly seen from Table 2 that the CIE b * values of the polyesters PET _C1 to PET _C6 of Comparative Examples 1 to 6 are all 2.7 or more, while the CIE L * values of the polyester PET _E of the examples are sufficiently large and CIE b * The value is closer to 0, showing that the brightness is high enough and whiter, so the hue is better.

In summary, the catalyst preparation method and the prepared catalyst of the present invention can effectively improve the problem of poor hue of polyester caused by antimony (III) compounds during the polycondensation reaction for preparing polyester, so it can be achieved. Object of the invention.

However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited in this way, any simple equivalent changes and modifications made in accordance with the scope of the patent application and the content of the patent specification of the present invention are still Within the scope of the invention patent.

Claims (14)

A catalyst manufacturing method includes heating a mixture for a chemical reaction to obtain a Some of the compounds are products in which R represents a divalent organic group, and the mixture is substantially composed of an organic dibasic acid didiol and an antimony (III) compound. The method for producing a catalyst according to claim 1, wherein in the mixture, the molar ratio of the organic dibasic acid didiol ester to the antimony (III) compound ranges from 1.5 to 3.2. The method for producing a catalyst according to claim 1, wherein the mixture is subjected to a chemical reaction by heating in an environment free of ethylene glycol. The method for preparing a catalyst according to claim 1, comprising heating the mixture to perform a chemical reaction to obtain a catalyst containing The products of some compounds, 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 catalyst production method according to claim 4, wherein Ar represents 1,4-phenylene, R represents -C ₂ H _4- , and the aromatic dibasic acid didiol is terephthalic acid bis 2 -Hydroxyethyl. The method for producing a catalyst according to claim 1, wherein the antimony (III) compound is selected from antimony (III) acetate or antimony (III) oxide. A catalyst is produced by the manufacturing method according to any one of claims 1 to 6. A composition for preparing a polyester, comprising: the catalyst according to claim 7; an organic polyacid, an anhydride thereof, or an ester thereof; and a diol. The composition for preparing a polyester according to claim 8, wherein the organic polyacid is selected from terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 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 Formic acid, 1,2,4,5- trimellitic acid, 1,2,4- trimellitic acid, 1,3,5- trimellitic acid or 3,3 ', 4,4'-biphenyltetracarboxylic acid or its combination. The composition for producing a polyester according to claim 8, wherein the glycol is selected from the group consisting of 1,2-ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1 2,2-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 and the diol are in two phases. A method for preparing a polyester, comprising: heating a mixture to perform a chemical reaction to obtain a mixture containing Catalysts for some compounds, in which R represents a divalent organic group, and the mixture consists essentially of an organic dibasic acid didiol ester and an antimony (III) compound; and an organic polybasic acid, an anhydride thereof, or an ester thereof And a glycol undergoes a polycondensation reaction in contact with the catalyst to obtain the polyester. The method for preparing a polyester according to claim 12, wherein R represents -C ₂ H _4- , the organic dibasic acid didiol is bis 2-hydroxyethyl terephthalate, and the organic polybasic acid is For terephthalic acid, the glycol is ethylene glycol. The method for preparing a polyester according to claim 12, wherein the mixture is chemically reacted by heating in an environment free of ethylene glycol, and the catalyst and the glycol are in two phases.