JP4000867B2 - Method for producing polyester composition - Google Patents

Description

【００４８】
【発明の効果】
本発明のポリエステル組成物は色調に優れ、かつ繊維用、フィルム用、ボトル用などの成形体の製造において口金汚れなどの問題を解消される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a polyester composition.
[0002]
[Prior art]
Polyesters are widely used in various fields including fibers, films and bottles because of their excellent properties. Among these, polyethylene terephthalate is excellent in mechanical strength, chemical characteristics, dimensional stability and the like and is preferably used.
[0003]
In general, polyethylene terephthalate is produced from terephthalic acid or an ester-forming derivative thereof and ethylene glycol. In a commercial process for producing a high molecular weight polymer, an antimony compound is widely used as a polycondensation catalyst. However, polymers containing antimony compounds have some undesirable properties as described below.
[0004]
For example, it is known that when a polyester obtained using an antimony catalyst is melt-spun into a fiber, a residue of the antimony catalyst is deposited around the die hole. As this deposition progresses, it becomes a cause of defects in the filament, so that it needs to be removed in a timely manner. The deposition of the antimony catalyst residue is considered to be due to the antimony compound in the polymer being transformed in the vicinity of the die and partially vaporizing and dissipating, and then a component mainly composed of antimony remains in the die.
[0005]
In addition, the antimony catalyst residue in the polymer tends to be relatively large particles, and it becomes a foreign substance, causing an increase in the filtration pressure of the filter during molding, causing yarn breakage during spinning or film tearing during film formation, etc. It has undesirable properties.
[0006]
In view of the above background, there is a demand for polyesters that contain little or no antimony.
[0007]
From this background, titanium compounds and germanium compounds are known when the role of the polycondensation catalyst is required for compounds other than antimony compounds, but germanium compounds are very expensive and difficult to use for general purposes. On the other hand, the use of a titanium compound having a relatively low cost and high activity has been studied, but this compound has a problem of lowering the color tone and heat resistance of the polymer.
[0008]
Furthermore, as a method for improving the color tone and heat resistance of such a titanium compound, for example, WO95 / 18839 proposes a method using a composite oxide composed of titanium and silicon as a catalyst. However, the effect of improving the color tone and heat resistance was still insufficient.
[0009]
Further, as a problem common to titanium-based polymerization catalysts, there has been a problem that the addition of titanium oxide particles used as a matting agent in clothing fibers or the like significantly reduces the polymerization reaction rate and decreases productivity. Although the mechanism of deactivation by the titanium oxide particles is not clear, for example, in order not to significantly reduce the polymerization reaction rate, just adding a large amount of titanium-based polymerization catalyst, the thermal decomposition of the polymer proceeds remarkably during remelting, Eventually, a polymer having good color tone and heat resistance cannot be obtained.
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide a polyester composition containing particles having a low content of antimony and germanium compounds, good color tone and heat resistance, and a method for producing the same.
[0011]
[Means for Solving the Problems]
The object of the present invention is to add at least one compound selected from the group consisting of a manganese compound, a magnesium compound, and a calcium compound, and titanium oxide particles, and then add a titanium complex as a polycondensation catalyst to perform a polycondensation reaction. it features a performing, by adding this time manganese compound, magnesium compound, at least one compound selected from the group consisting of calcium compound, and the content of the titanium oxide particles in Suyo satisfy formula 1 or formula 2, titanium complexes der below 20ppm each content of the antimony compound was characterized by adding so as to 0.5~150ppm in terms of titanium atom and germanium compounds in terms of metal atom relative to the polyester composition obtained by Lupo Riesuteru This is achieved by a method for producing the composition.
[0012]
20 ≦ TI / MN ≦ 3000 (Formula 1)
20 ≦ TI / (MN + MG + CA) ≦ 3000 (Formula 2)
[TI is the content (ppm) of titanium oxide particles in the polyester composition, and MN, MG, and CA are the contents (ppm) in terms of each metal atom of the manganese compound, magnesium compound, and calcium compound in the polyester composition, respectively. . ]
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The polyester of the present invention is a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, and particularly if it can be used as a molded article such as a fiber, a film, or a bottle. There is no limitation.
[0014]
Specific examples of such polyesters include polyethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polyethylene-1,2-bis (2-chloro Phenoxy) ethane-4,4′-dicarboxylate, polypropylene terephthalate and the like. The present invention is particularly suitable for the most commonly used polyethylene terephthalate or polyester copolymers mainly composed of polyethylene terephthalate.
[0015]
In addition to diethylene glycol, these polyesters include dicarboxylic acids such as adipic acid, isophthalic acid, sebacic acid, phthalic acid, and 4,4′-diphenyldicarboxylic acid and ester-forming derivatives thereof, polyethylene glycol, Dioxy compounds such as methylene glycol, neopentyl glycol and polypropylene glycol, oxycarboxylic acids such as p- (β-oxyethoxy) benzoic acid and ester-forming derivatives thereof may be copolymerized.
[0016]
The polyester composition of the present invention contains titanium oxide particles, and further contains at least one compound selected from the group consisting of a manganese compound, a magnesium compound and a calcium compound in a range satisfying Formula 1 or Formula 2. When the polyester composition is polymerized within a range satisfying this relationship, a good polymerization activity is obtained without causing a decrease in the activity of the polymerization catalyst used, and a polymer having a good color tone is obtained. Further, the obtained polymer has good heat resistance, and there is little thermal deterioration even when melted and held at a high temperature in a molding process or the like.
[0017]
20 ≦ TI / MN ≦ 3000 (Formula 1)
20 ≦ TI / (MN + MG + CA) ≦ 3000 (Formula 2)
[TI is the content (ppm) of titanium oxide particles in the polyester composition, and MN, MG, and CA are the contents (ppm) in terms of each metal atom of the manganese compound, magnesium compound, and calcium compound in the polyester composition, respectively. . ]
Furthermore, the value of TI / (MN + MG + CA) is preferably 50 to 2000, and particularly preferably 80 to 1000 from the viewpoint of the heat resistance of the polymer.
[0018]
Here, the content of the titanium oxide particles is preferably 0.01 to 10% by weight because the process passability during the molding process is improved, and more preferably 0.05 to 7% by weight. Moreover, it is preferable that an average particle diameter is 0.1-3 micrometers. The titanium oxide particles referred to here are particles generally used for improving process passability in the yarn-making process or film-forming process or adjusting the color tone of the product, and are polyester polymerization catalysts. This function is substantially not provided.
[0019]
Further, it is preferable that the content of each of the manganese compound, the magnesium compound, and the calcium compound is 1 to 100 ppm in terms of each metal atom, since the color tone of the obtained polymer and the heat resistance of the polymer are particularly good. More preferably, it is 3 to 50 ppm. In particular, it is preferable to use a manganese compound because the generation of foreign matter is reduced.
[0020]
The manganese compound of the present invention is specifically manganese acetate, manganese benzoate, manganese chloride, etc., the magnesium compound is specifically magnesium acetate, magnesium oxide, magnesium hydroxide, etc., and the calcium compound is specifically calcium acetate, calcium hydroxide. Etc.
[0021]
In the polyester composition of the present invention, the content of the antimony compound and the germanium compound must be 20 ppm or less in terms of metal atoms. By setting the amount within this range, it is possible to obtain a relatively inexpensive polymer with little occurrence of base stains during molding. More preferably, the content of each compound is 10 ppm or less, and it is particularly preferable that the content is not substantially contained.
[0022]
The polyester composition of the present invention is obtained by adding titanium oxide as particles and at least one compound selected from the group consisting of a manganese compound, a magnesium compound, and a calcium compound at any stage in a series of reactions for producing a polyester. Then, a titanium complex is added as a polycondensation catalyst to perform polycondensation. When a titanium complex as a polycondensation catalyst is added after adding the titanium oxide particles, the catalytic activity of the titanium complex decreases, the polycondensation reaction rate decreases, the productivity decreases, and the color tone of the polymer deteriorates. However, before adding the titanium complex as the polycondensation catalyst, by adding at least one compound selected from the group consisting of titanium oxide particles and manganese compounds, magnesium compounds, calcium compounds, Even if a certain titanium complex is added, the catalytic activity is hardly lowered and a sufficient polycondensation reaction rate can be obtained. In particular, it is preferable to add at least one compound selected from the group consisting of a manganese compound, a magnesium compound, and a calcium compound after adding titanium oxide particles so that the catalytic activity is hardly lowered.
[0023]
That is, the present invention has a problem in that when a polyester composition containing titanium oxide particles is produced using a titanium-based polycondensation catalyst, the catalytic activity is lowered, which has not been observed with conventional antimony-based polymerization catalysts. On the other hand, a new method for avoiding this problem has been found.
[0024]
In the present invention, a phosphorus compound may be used for the purpose of improving the color tone of the polymer during the polymerization reaction or improving the heat resistance of the resulting polymer, but the titanium complex as the polycondensation catalyst is easily deactivated. Further, it may be added so as to be 10 ppm or less in terms of phosphorus atom with respect to the obtained polymer, but preferably it is not substantially added. In addition, it is preferable to add a titanium complex as a polycondensation catalyst after adding a phosphorus compound because the delay in polymerization time is reduced. Here, the phosphorus compound is not particularly limited, such as phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid or esters thereof.
[0026]
The titanium complex as the polycondensation catalyst of the present invention is a titanium complex containing a chelating agent capable of coordinating with a titanium atom, and is not particularly limited. Among them, a titanium chelate complex of a polyvalent carboxylic acid is used. And the resulting polymer has a good color tone and is less likely to produce foreign matter. In particular, a titanium chelate of hydroxy polyvalent carboxylic acid or nitrogen-containing polyvalent carboxylic acid is preferable. Examples of chelating agents that form such titanium complexes include polyvalent carboxylic acids such as phthalic acid, trimellitic acid, trimesic acid, hemimellitic acid and pyromellitic acid, hydroxy polyvalent carboxylic acids such as malic acid and citric acid, Examples thereof include nitrogen-containing polyvalent carboxylic acids such as ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, diethylenetriaminepentaacetic acid, and triethylenetetraminehexaacetic acid.
[0029]
When the titanium complex as a polycondensation catalyst in the present invention is added in an amount of 0.5 to 150 ppm in terms of Ti atom to the obtained polyester, the polymerization activity is high, and the color tone and heat resistance of the resulting polymer are also preferable. More preferably, it is 1-100 ppm, More preferably, it is 3-50 ppm.
[0030]
The production method of the present invention will be described using polyethylene terephthalate as an example.
[0031]
High molecular weight polyethylene terephthalate used for fibers, films and the like is usually produced by one of the following processes. (1) A process of obtaining low molecular weight polyethylene terephthalate or oligomer by direct esterification reaction using terephthalic acid and ethylene glycol as raw materials, and further obtaining a high molecular weight polymer by subsequent polycondensation reaction, (2) dimethyl terephthalate and ethylene In this process, a glycol is used as a raw material, a low molecular weight product is obtained by an ester exchange reaction, and a high molecular weight polymer is obtained by a subsequent polycondensation reaction. Here, the reaction proceeds even without a catalyst, but the transesterification usually proceeds using a compound such as manganese, calcium, magnesium, zinc, or lithium as a catalyst, and the transesterification is substantially carried out. After completion, a phosphorus compound is added for the purpose of inactivating the catalyst used in the reaction.
[0032]
In the production method of the present invention, the low polymer obtained in any stage of the series of reactions (1) or (2), preferably in the first half of the series of reactions (1) or (2), is oxidized as particles. After adding at least one compound selected from the group consisting of titanium, manganese compounds, magnesium compounds and calcium compounds, a titanium complex is added as a polycondensation catalyst and polycondensation is performed to obtain a high molecular weight polyethylene terephthalate. . However, when adding a manganese compound, magnesium compound, or calcium compound as a transesterification catalyst before the transesterification reaction starts, add the manganese compound, magnesium compound, or calcium compound again after the esterification reaction is completed. It is not always necessary to do.
[0033]
Moreover, although said reaction is implemented by formats, such as a batch type, a semibatch type, or a continuous type, the manufacturing method of this invention can be applied to all the formats.
[0034]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical-property value in an Example was measured by the method described below.
(1) Intrinsic viscosity of polymer [η]
Measurement was performed at 25 ° C. using orthochlorophenol as a solvent.
(2) Color tone of polymer Suga Test Instruments Co., Ltd. color difference meter (SM color computer model SM-3) was used to measure as a Hunter value (L, a, b value).
(3) Content of each element of titanium, manganese, magnesium, calcium, silicon and phosphorus in the polyester composition X-ray fluorescence (X-ray fluorescence analyzer 3270 manufactured by Rigaku Corporation) or ICP (inductively coupled plasma) ) Determination by luminescence analysis (SPS4000 manufactured by Seiko Instruments Inc.). In addition, in order to remove the influence of the titanium dioxide particle, the silicon oxide particle, etc. in the polyester composition used as needed, after carrying out the following pretreatment, the fluorescent X ray or ICP emission analysis was performed as needed. That is, the polyester composition is dissolved in orthochlorophenol, the viscosity of the polymer solution is adjusted with chloroform as necessary, and then the particles are precipitated with a centrifuge. Thereafter, only the supernatant liquid is collected by a gradient method, and the polymer is reprecipitated by adding acetone, filtered and washed to obtain a polymer from which particles are removed. Metal analysis was performed on the polymer from which the particles obtained by the above pretreatment were removed.
[0035]
Comparative Example 1
A catalyst-free oligomer produced from high-purity terephthalic acid and ethylene glycol according to a conventional method was melted and stirred at 250 ° C., and 0.3% by weight was added to the melt with respect to the polyester capable of obtaining titanium oxide particles. After stirring for 5 minutes, it was added so as to be 30 ppm in terms of manganese atom with respect to the polyester from which manganese acetate was obtained. Further, after stirring for 5 minutes, titanium tetraisopropoxide (TPT) (manufactured by Wako Pure Chemical Industries, Ltd.) is added to the polyester to obtain 10 ppm in terms of titanium atom, and then the low polymer is added at 30 rpm. While stirring, the reaction system was gradually heated from 250 ° C. to 285 ° C. and the pressure was reduced to 40 Pa. The time to reach the final temperature and final pressure was both 60 minutes. When the predetermined stirring torque was reached, the reaction system was purged with nitrogen, returned to normal pressure, the polycondensation reaction was stopped, discharged into cold water in a strand form, and immediately cut to obtain polyester pellets. The time from the start of decompression to the arrival of the predetermined stirring torque was 3 hours.
[0036]
The intrinsic viscosity of the obtained polymer was 0.66, and the color tone of the polymer was L = 75 and b = 3.0. Moreover, it confirmed that content of the titanium atom derived from the titanium catalyst measured from the polymer, and manganese atom was 10 ppm and 30 ppm, respectively.
[0037]
After drying this pellet, it was supplied to an extruder type spinning machine and melt-spun at a spinning temperature of 295 ° C. At this time, a metal nonwoven fabric having an absolute filtration accuracy of 10 μm was used as a filter, and a 0.6 mmφ round hole was used as the base. The yarn discharged from the die was gradually cooled with a heating cylinder having a length of 30 cm, an inner diameter of 25 cmφ and a temperature of 300 ° C., then cooled and solidified by applying chimney cooling air, and then taken up at a take-up speed of 550 m / min. The undrawn yarn was drawn at a drawing temperature of 95 ° C. while appropriately changing the draw ratio so that the drawn yarn has an elongation of 14 to 15%, and then heat-treated at a heat treatment temperature of 220 ° C. and a relaxation rate of 2.0%. I got a thread.
[0038]
In the melt spinning process, filtering pressure rise during spinning had little physician. Yarn breakage during the stretching was Tsu or almost.
[0041]
Examples 1 and 2
Titanium tetraisopropoxide (TPT) a Chitan'nitoriro 3 acetate, except for changing the respective switch Tanringo acid in the same manner as in Comparative Example 1 by polymerizing a polymer were melt-spun.
[0043]
Comparative Example 2
Polymerization was carried out in the same manner as in Example 1 except that manganese acetate was not added, but the reaction did not proceed and no polymer was obtained.
[0044]
Comparative Example 3
A polymer was polymerized and melt-spun in the same manner as in Example 1 except that antimony trioxide was used as the catalyst.
[0045]
The results of Examples 1 and 2 and Comparative Examples 1 to 3 are shown in Table 1. Those within the scope of the present invention had good polymerization reactivity, and polymer properties and yarn-making properties were good. However, those outside the scope of claims of the present invention were inferior in polymerization reactivity and color tone. In addition, those using antimony trioxide showed good polymerization reactivity and color tone, but the base was soiled during spinning, resulting in frequent yarn breakage.
[0046]
[Table 1]

[0048]
【The invention's effect】
The polyester composition of the present invention is excellent in color tone, and solves problems such as die contamination in the production of molded articles for fibers, films and bottles.

Claims (7)

In a method for producing a polyester containing particles by polycondensing a product obtained by an esterification reaction or an ester exchange reaction with an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, After adding at least one compound selected from the group consisting of a manganese compound, a magnesium compound, and a calcium compound, and titanium oxide particles, a polycondensation reaction is performed by adding a titanium complex as a polycondensation catalyst. and wherein the content of the manganese compound and titanium oxide particles are added to Suyo satisfy equation 1, it is added to a 0.5~150ppm in terms of titanium atom relative to the polyester composition obtained titanium complex metal atom conversion content of the antimony compound and germanium compound In the manufacturing method of each 20ppm or less der Lupo Riesuteru composition.
20 ≦ TI / MN ≦ 3000 (Formula 1)
[TI represents the content (ppm) of titanium oxide particles in the polyester composition, and MN represents the content (ppm) of the manganese compound in terms of metal atoms in the polyester composition. ] In a method for producing a polyester containing particles by polycondensing a product obtained by an esterification reaction or an ester exchange reaction with an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, After adding at least one compound selected from the group consisting of a manganese compound, a magnesium compound, and a calcium compound, and titanium oxide particles, a polycondensation reaction is performed by adding a titanium complex as a polycondensation catalyst. manganese compound, magnesium compound, at least one compound selected from the group consisting of calcium compound, and the content of the titanium oxide particles are added to Suyo satisfy equation 2, a titanium atom relative to the polyester composition obtained titanium complex so as to be 0.5~150ppm in terms of Method for producing antimony compound was characterized and germanium compound, and 20ppm or less der Lupo Riesuteru composition content of metal atoms in terms of adding.
20 ≦ TI / (MN + MG + CA) ≦ 3000 (Formula 2)
[TI is the content (ppm) of titanium oxide particles in the polyester composition, and MN, MG, and CA are the contents (ppm) in terms of each metal atom of the manganese compound, magnesium compound, and calcium compound in the polyester composition, respectively. . ] Method for producing a content polyester composition of 10ppm der Ru請 Motomeko 1 or 2, wherein less in terms of phosphorus atom of the phosphorus compound. The polyester composition according to any one of claims 1 to 3 , wherein after adding the titanium oxide particles, at least one compound selected from the group consisting of a manganese compound, a magnesium compound and a calcium compound is added. Manufacturing method. Furthermore, after adding a phosphorus compound, a titanium complex is added as a polycondensation catalyst, The manufacturing method of the polyester composition of any one of Claims 1-4 characterized by the above-mentioned. The method for producing a polyester composition according to any one of claims 1 to 5 , wherein the chelating agent for the titanium complex is a polyvalent carboxylic acid. The method for producing a polyester composition according to claim 6 , wherein the chelating agent of the titanium complex is a hydroxy polyvalent carboxylic acid or a nitrogen-containing polyvalent carboxylic acid.