CN112135857B - Copolyester composition - Google Patents
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- CN112135857B CN112135857B CN201980029868.5A CN201980029868A CN112135857B CN 112135857 B CN112135857 B CN 112135857B CN 201980029868 A CN201980029868 A CN 201980029868A CN 112135857 B CN112135857 B CN 112135857B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
Abstract
The present invention relates to a copolyester composition containing a copolyester obtained from a dicarboxylic acid and/or an ester-forming derivative thereof and ethylene glycol, the copolyester composition having the following composition: the terephthalic acid and/or the ester-forming derivative component thereof is 40.0 mol% or more and 68.0 mol% or less with respect to the total acid components, the isophthalic acid containing a metal sulfonate group and/or the ester-forming derivative component thereof is 4.0 mol% or more and less than 10.0 mol% with respect to the total acid components, and the glass transition temperature of the copolyester composition as determined by differential scanning calorimetry is 50 ℃ or more and 75 ℃ or less.
Description
Technical Field
The present invention relates to a copolyester composition having a specific copolymerization composition and glass transition temperature and showing excellent water-absorbing swelling properties in hot water.
Background
Functional fibers are widely used not only for clothing applications but also for interior decoration, vehicle interior, industrial applications, and the like, and are extremely valuable industrially. On the other hand, the required characteristics are diversified, and there are cases where the single-component filaments made of a single-component polymer cannot cope with the diversified characteristics. Under such circumstances, development of composite fibers obtained by combining a plurality of polymers has been widely conducted.
In the composite fiber, it is known that a filament having a super-fine odd-shaped cross section obtained by splitting a sheath-core type composite fiber having an odd-shaped core formed of a two-component polymer is highly valuable as a high-density woven fabric having a smooth texture. In general, the method of shrinking, swelling, or dissolving out a single polymer component by a chemical agent is adopted for splitting of a composite fiber (patent documents 1 and 2). In addition, for the purpose of reducing costs without using chemical agents, the following proposals are made: a water-swellable polyether ester polymer which can be split into fibers by hot water treatment alone when applied to a profiled core-sheath composite fiber (patent document 3).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 61-108766
Patent document 2: international publication No. 2013/47051
Patent document 3: japanese patent laid-open publication No. 2005-200786
Disclosure of Invention
Problems to be solved by the invention
The deformed core-sheath type composite fibers described in patent documents 1 and 2 have a problem that the process is complicated and the cost is high because a chemical treatment process and a recovery process are required at the time of fiber cutting. Therefore, when the water-swellable polyether ester polymer proposed in patent document 3 for solving the problem is applied to a shaped core-sheath type composite fiber, a composite fiber having good splittability can be obtained by only hot water treatment when the composite ratio of the composition is 50%.
However, the following problems are judged to exist: if the compounding ratio of the composition is reduced to 65% or less for the purpose of improving the fiber strength or the like, the swelling performance in hot water is insufficient and the swelling ratio is only 43%, and therefore fiber cutting failure is likely to occur as compared with a chemical treatment application. Further, it was found that the following problems still remain: since 50% of polyethylene glycol is copolymerized in the composition, the heat resistance is poor at a usual spinning temperature of polyethylene terephthalate of 290 ℃.
The purpose of the present invention is to provide a copolyester composition that exhibits an excellent swelling ratio and a high viscosity retention rate. Specifically, the object is to provide a copolyester composition which exhibits an excellent swelling ratio of 60% or more in hot water at 90 ℃ and has a viscosity retention of 75% or more when molten and retained at 290 ℃ for 20 minutes.
Means for solving the problems
The above object can be achieved by a copolyester composition comprising a copolyester obtained from a dicarboxylic acid and/or an ester-forming derivative thereof and ethylene glycol, the copolyester composition having the following composition: the terephthalic acid and/or ester forming derivatives of terephthalic acid component relative to all acid components is more than 40.0 mol% and less than 68.0 mol%, containing metal sulfonate group of benzene two formic acid and/or ester forming derivatives of benzene two formic acid components relative to all acid components is more than 4.0 mol% and less than 10.0 mol%, and the copolymer polyester composition by differential scanning calorimetry analysis of the glass transition temperature of more than 50 ℃ and less than 75 ℃.
Effects of the invention
According to the present invention, a copolyester composition having a high viscosity retention rate and an excellent swelling ratio can be obtained by setting the copolymerization composition and the glass transition temperature to specific ranges. Specifically, a copolyester composition exhibiting a swelling ratio of 60% or more in hot water and excellent in heat resistance at a melt spinning temperature of polyethylene terephthalate of 290 ℃ can be obtained.
Detailed Description
A copolyester composition according to an embodiment of the present invention comprises a copolyester obtained from a dicarboxylic acid and/or an ester-forming derivative thereof, and ethylene glycol, and has the following composition: the terephthalic acid and/or the ester-forming derivative component thereof is 40.0 mol% or more and 68.0 mol% or less with respect to the total acid components, the isophthalic acid containing a metal sulfonate group and/or the ester-forming derivative component thereof is 4.0 mol% or more and less than 10.0 mol% with respect to the total acid components, and the glass transition temperature of the copolyester composition as determined by differential scanning calorimetry is 50 ℃ or more and 75 ℃ or less.
The dicarboxylic acid may be terephthalic acid. The ester-forming derivatives of terephthalic acid include alkyl esters such as methyl ester (DMT, etc.) and ethyl ester thereof. For example, methyl ester is preferably used in view of excellent polycondensation reactivity.
The composition ratio of the terephthalic acid component to the total acid components is 40.0 mol% or more in view of the viscosity retention of 75% or more when the polyester composition is melted and retained at 290 ℃ for 20 minutes. On the other hand, the composition ratio of the terephthalic acid component is 68.0 mol% or less based on the total acid components, from the viewpoint that the crystal structure derived from the terephthalic acid component in the composition is relaxed, the intermolecular binding force is lowered, and the water-absorbing swelling property is exhibited.
In order to impart more excellent heat resistance, the composition ratio of the terephthalic acid component is preferably 50.0 mol% or more, and more preferably 55.0 mol% or more, based on the total acid components. In addition, from the viewpoint of obtaining excellent water absorption swelling properties, the composition ratio of the terephthalic acid component is preferably 65.0 mol% or less, and more preferably 60.0 mol% or less, with respect to the total acid components.
Examples of the isophthalic acid having a metal sulfonate group include sodium salt of 4-sulfoisophthalic acid, potassium salt of 4-sulfoisophthalic acid, sodium salt of 5-sulfoisophthalic acid, potassium salt of 5-sulfoisophthalic acid, and barium salt of 5-sulfoisophthalic acid. Among them, from the viewpoint of excellent polymerizability, a sodium salt of 5-sulfoisophthalic acid and a potassium salt of 5-sulfoisophthalic acid are preferable, and a sodium salt of 5-sulfoisophthalic acid is particularly preferable. In addition, these containing metal sulfonate group benzene two formic acid can use 1 kind of chemical structure, can also use a combination of 2 or more substances.
As the ester-forming derivative of isophthalic acid containing a metal sulfonate group, there may be mentioned: alkyl esters such as methyl esters (e.g., sodium dimethyl-5-sulfoisophthalate (SSIA)), ethyl esters thereof, and the like; acid halides such as acid chlorides and acid bromides; and isophthalic anhydride and the like. For example, from the viewpoint of excellent polycondensation reactivity, alkyl esters such as methyl ester and ethyl ester are preferred, and methyl ester is particularly preferred.
The composition ratio of the isophthalic acid component containing a metal sulfonate group is 4.0 mol% or more and less than 10.0 mol% with respect to the total acid components, from the viewpoint of imparting appropriate hydrophilicity and cationic crosslinking structure to the polyester composition and exhibiting water-absorbing swelling properties. When the amount is less than 4.0 mol%, the cationic crosslinked structure is not sufficiently formed, and the desired water-absorbing swelling property cannot be obtained. When the amount is 10.0 mol% or more, the hydrophilicity becomes excessive, and dissolution in hot water occurs earlier than swelling, so that the intended water absorption swelling performance cannot be obtained.
From the viewpoint of obtaining a polyester composition having more excellent swelling properties, the composition ratio of the isophthalic acid component containing a metal sulfonate group is preferably 9.5 mol% or less, more preferably 8.0 mol% or less, and further preferably 6.0 mol% or more and 8.0 mol% or less with respect to the total acid components.
In order to impart excellent water-absorbing swelling properties to the copolyester composition of the present invention, the glass transition temperature of the composition as determined by differential scanning calorimetry is 50 ℃ or higher. When the glass transition temperature of the copolyester composition of the present invention is less than 50 ℃, the copolyester composition softens in hot water and undergoes flow deformation and dissolution, and the intended water-absorbing swelling performance cannot be obtained. Further, since the pellets are melted and fused, the drying treatment at 60 ℃ or higher cannot be performed, and the drying time becomes long, which deteriorates the productivity.
On the other hand, when the glass transition temperature of the copolyester composition of the present invention is higher than 75 ℃, the molecular motion in hot water is suppressed and the water-swelling property is not exhibited, and from this point of view, the glass transition temperature is 75 ℃ or lower.
The glass transition temperature of the copolyester composition of the present invention is preferably 65 ℃ or lower from the viewpoint of excellent water-absorbing swelling properties, and more preferably 55 ℃ or higher, and even more preferably 60 ℃ or higher from the viewpoint of enabling drying at a higher temperature. The glass transition temperature of the copolyester composition can be set in a desired range by appropriately adjusting the composition of monomers such as dicarboxylic acid and ethylene glycol, polymerization reaction conditions, and the like.
The copolyester composition of the present invention comprises a terephthalic acid component, an isophthalic acid component having a metal sulfonate group, and a dicarboxylic acid component copolymerizable with these components. Examples of the other dicarboxylic acid component include, but are not limited to, alkyl esters of isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, and/or dimethyl isophthalate (DMI).
As the other dicarboxylic acid component, 1 kind of compound may be used, or 2 or more kinds may be combined, and the kind of compound may be selected so that the glass transition temperature of the copolyester composition does not deviate from the range of 50 ℃ to 75 ℃.
From the viewpoint of exhibiting excellent water-absorbing swelling properties, the copolyester composition of the present invention preferably contains 22.0 mol% or more of at least 1 selected from isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, and alkyl esters thereof, based on the total acid components. More preferably 25 mol% or more, and still more preferably 35 mol% or more. On the other hand, from the viewpoint of sufficiently securing the heat resistance, it is more preferably 56 mol% or less, and still more preferably 50 mol% or less.
In the copolyester composition of the present invention, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, and/or an alkyl ester thereof are more preferably used from the viewpoint of efficiently suppressing the formation of a crystal structure derived from a terephthalic acid component and obtaining excellent water-absorbing swelling properties, and isophthalic acid and/or an alkyl ester thereof are still more preferably used from the viewpoint of easily making the glass transition temperature 50 ℃ or higher and 75 ℃ or lower.
In the copolyester composition of the present invention, the heat of crystal fusion as determined by differential scanning calorimetry is preferably 10J/g or less, from the viewpoint of exhibiting excellent water-absorbing swelling properties. From the viewpoint of exhibiting more excellent water-absorbing swelling properties, the heat of crystal fusion is more preferably 5J/g or less, still more preferably 2J/g or less, and most preferably 0J/g (amorphous). The heat of crystal fusion of the copolyester composition can be set in a desired range by appropriately adjusting the composition of monomers such as dicarboxylic acid and ethylene glycol, polymerization reaction conditions, and the like.
The copolyester composition of the present invention may contain a polyalkylene oxide compound represented by the following chemical formula (1) and/or a one-side-capped polyalkylene oxide compound represented by the following chemical formula (2) within a range in which the glass transition temperature does not deviate from the range of 50 ℃ to 75 ℃ and the heat resistance at 290 ℃ is not impaired. The polyalkylene oxide compound contained may be copolymerized into the polyester or may be present in the polyester composition in an unreacted state. The polyester containing a polyalkylene oxide compound is excellent in molecular mobility and hydrophilicity, and can improve water-absorbing swelling properties.
H [ -O-R ] n-O-H formula (1)
H [ -O-R ] n-O-X formula (2)
In the above formulae (1) and (2), R is at least 1 selected from alkylene groups having 1 to 12 carbon atoms, preferably at least 1 selected from alkylene groups having 1 to 4 carbon atoms. Specific examples thereof include methylene, ethylene, propylene, trimethylene and tetramethylene groups, more preferably ethylene, propylene and tetramethylene groups, still more preferably ethylene, propylene and trimethylene groups, and particularly preferably ethylene.
The repeating structural units- (O-R) -in the above formulae (1) and (2) may be used alone or in combination of 2 or more. When 2 or more kinds are combined, random copolymerization, block copolymerization, or alternating copolymerization of repeating structural units may be used.
In the formula (2), X is an alkyl group having 1 to 10 carbon atoms in order to efficiently improve molecular mobility. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. More preferably methyl group, ethyl group, butyl group, and decyl group, and still more preferably methyl group and decyl group.
From the viewpoint of efficiently improving the molecular mobility and hydrophilicity, the average number n of repeating units of the polyalkylene oxide compounds represented by the above formulae (1) and (2) is in the range of 19 or more and 455 or less, preferably 90 or more and 188 or less.
In the case where the polyalkylene oxide compound is contained in the present invention, the content of the polyalkylene oxide compound is preferably 1% by weight or more, more preferably 5% by weight or more, based on the obtained copolyester composition, from the viewpoint of efficiently improving the water absorption swelling property. On the other hand, in order to prevent deterioration of heat resistance, it is preferably 15% by weight or less, and more preferably 10% by weight or less. The content described herein can be determined by NMR measurement.
Examples of the polyalkylene oxide compound include polyethylene glycol, polyethylene glycol capped with a single methyl group, polyethylene glycol capped with a single decyl group, and the like.
The weight average molecular weight of the copolyester composition of the present invention measured by gel permeation chromatography is preferably 30000 or more in terms of improving the morphological stability at the time of swelling treatment, and is preferably 80000 or less in terms of good processability at the time of spinning and thermoforming.
The copolyester composition of the present invention may contain particles for the purpose of reducing friction with various guides (guide) and rollers in the molding process, improving process passability, and adjusting the color tone of the product. The kind of the particles to be included is arbitrary. Specific examples of the inorganic particles include inorganic particles such as silica, titania, calcium carbonate, barium sulfate, alumina, and zirconia, and organic polymer particles such as crosslinked polystyrene. Among these particles, titanium dioxide particles are preferred because they are excellent in dispersibility in polymers and low in cost.
The copolyester composition of the present invention can be synthesized by any method. For example, the same procedure as in the following general method for synthesizing polyethylene terephthalate can be used.
Polyethylene terephthalate can be synthesized by a first-stage reaction in which a glycol ester of terephthalic acid or its oligomer is produced by an esterification reaction between terephthalic acid and ethylene glycol or an ester exchange reaction between a lower alkyl ester of terephthalic acid represented by dimethyl terephthalate and ethylene glycol, and a second-stage reaction in which a polycondensation reaction is carried out by heating the reaction product of the first stage under reduced pressure in the presence of a polymerization catalyst until a desired degree of polymerization is achieved.
In the present invention, a copolymerization component is added in any of the above-mentioned steps or between the steps. The timing of adding the copolymerization component may be any timing before the esterification reaction, or during the transesterification reaction, from the end of the transesterification reaction to the start of the polycondensation reaction, or to the substantial end of the polycondensation reaction.
With respect to the esterification, the reaction proceeds even in the absence of a catalyst. In the transesterification reaction, it is usually carried out by using a lithium compound such as lithium acetate dihydrate (LAH), a manganese compound such as manganese acetate tetrahydrate (MN), a calcium compound, a magnesium compound, a zinc compound, or the like as a catalyst, and after the transesterification reaction is substantially completed, a phosphorus compound such as Phosphoric Acid (PA) is added for the purpose of deactivating the catalyst used in the reaction. As the polycondensation catalyst, antimony compounds such as antimony trioxide, titanium compounds, germanium compounds, and the like can be used.
The copolyester composition of the present invention can be used as a constituent of a conjugate fiber. The composite fiber described herein means that 2 or more polymers are separately present in 1 fiber.
Examples
The present invention will be specifically described below with reference to examples. These examples are illustrative, and the present invention is not limited thereto.
< compositional analysis of copolyester composition >
The copolymerization amount of the isophthalic acid containing a metal sulfonate group and/or the ester-forming derivative component thereof, the copolymerization-forming dicarboxylic acid and/or the ester-forming derivative component thereof, and the polyalkylene oxide component in the copolyester composition is analyzed by using a nuclear magnetic resonance apparatus (NMR).
The device comprises the following steps: AL-400 manufactured by Nippon electronics Co Ltd
Deuterated solvents: deuterated HFIP
Cumulative number of times: 128 times
Sample concentration: determination sample 50 mg/deuterated solvent 1mL
< analysis of thermal Properties of copolyester composition >
The glass transition temperature and the heat of crystal fusion of the copolyester composition were analyzed by a differential scanning calorimeter.
The device comprises the following steps: q-2000 manufactured by TA Instruments
Sample preparation: vacuum drying at 150 deg.C for 24 hr
Temperature rise rate: 16 deg.C/min, from 20 deg.C to 280 deg.C
< determination of molecular weight of copolyester composition >
The molecular weight of the copolyester composition was determined by Gel Permeation Chromatography (GPC).
The device comprises the following steps: waters-e2695 manufactured by Waters corporation
A detector: differential refractive index detector RI manufactured by Waters corporation (Waters-2414, sensitivity 128 x)
And (3) chromatographic column: shodex HFIP806M manufactured by Showa Denko (2-root connection)
Column temperature: 30 deg.C
Solvent: hexafluoroisopropanol (addition of 0.01N sodium trifluoroacetate)
Flow rate: 1.0mL/min
Sample introduction amount: 0.10mL
Standard sample: standard polymethyl methacrylate
< measurement of dryable temperature of copolyester composition >
2kg of pellets were put into a pot having a length of 400mm, a width of 400mm and a height of 5mm, and heated in a vacuum dryer under a reduced pressure of 0.1KPa or less for 24 hours, and the upper limit temperature at which pellets were not fused together was set as a dryable temperature.
< measurement of viscosity holding ratio of copolyester composition at 290 ℃ for 20 minutes >
The melt viscosity of the copolyester composition was measured using a capillary rheometer. The viscosity immediately after the pellets were melted and the viscosity after the pellets were retained for 20 minutes after melting were measured at 290 ℃ under the following conditions, and the viscosity retention at 290 ℃ for 20 minutes was calculated.
The device comprises the following steps: capillograph 1B, manufactured by Toyo Seiki Seisaku-Sho
Inner diameter of capillary: 1.0mm
The length of the capillary tube is as follows: 40.0mm
Measuring temperature: 290 deg.C
Shearing speed: 243/sec
Viscosity maintenance ratio (%) = (B/A). Times.100 at 290 ℃ for 20 minutes
A is the viscosity of the pellets immediately after melting, B is the viscosity after melting and staying for 20 minutes
< Hot Water swelling ratio of copolyester composition >
The hot water swelling ratio of the copolyester composition was measured by the following procedure. The pellets of the copolyester composition are dried at a drying temperature until the water content is 300ppm or less by a vacuum dryer which reduces the pressure to 0.1KPa or less. Then, the bath ratio expressed by the weight of ion-exchanged water to the weight of the polyester composition was 1:100, ion-exchanged water was added thereto, and the temperature was raised from room temperature to 90 ℃ at 4 ℃/min, followed by hot water treatment at 90 ℃ for 60 minutes. The volume of the pellets was measured every 5 minutes from the start of temperature rise, and the hot water swelling ratio of the copolyester was calculated from the maximum volume appearing before the end of hot water treatment.
Hot water swelling ratio (%) = { (D-C)/C }. Times.100
C is the volume (mm) of the copolyester composition before hot water treatment 3 )
D is the maximum volume (mm) of the copolymerized polyester composition in the hot water treatment 3 )
< evaluation of Hot Water Release Property of copolyester composition >
The copolyester composition of the present invention was evaluated for hot water peelability (which is an index of fiber cuttability when applied to a profiled core-sheath type composite fiber) relative to a polyethylene terephthalate composition according to the following method. The copolyester composition and polyethylene terephthalate (inherent viscosity: 0.67 dL/g) each 0.5g were press-processed at 290 ℃ and 2MPa for 60 seconds. The resulting film-shaped articles were laminated, and further subjected to press processing at 290 ℃ and 2MPa for 5 seconds to obtain a copolyester composition/polyethylene terephthalate adhesive film. The adhesive film was cut into strips of 50mm × 1mm at a bath ratio of 1:100, ion-exchanged water was added, the temperature was raised from room temperature to 90 ℃ at 4 ℃/min, and then hot water treatment was performed at 90 ℃ for 60 minutes to determine the peelability of the adhesive film.
Very good: the adhesive film is completely peeled off from the beginning of temperature rise to 90 DEG C
Good: the adhesive film was completely peeled off until the hot water treatment was completed.
And (delta): the adhesive film was partially peeled off until the hot water treatment was completed. Or the copolyester composition is dissolved in a state where peeling is not generated at all.
X: at the end of the hot water treatment, the adhesive film was not peeled off at all, and the copolyester composition was not dissolved.
[ example 1]
4.1kg (42.0 mol% based on the total acid components) of dimethyl terephthalate (DMT), 1.2kg (8.0 mol% based on the total acid components) of sodium dimethyl-5-sulfoisophthalate (SSIA), 4.9kg (50.0 mol% based on the total acid components) of dimethyl isophthalate (DMI), 5.8kg of Ethylene Glycol (EG), 3.0g of manganese acetate tetrahydrate (MN), 50.0g of lithium acetate dihydrate (LAH), and 2.5g of antimony trioxide (AO) were added, and an ester Exchange (EI) reaction was carried out while distilling off methanol at 140 to 230 ℃ and 1.0g of Phosphoric Acid (PA) was added after 210 minutes. Further, 25.0g of [ pentaerythritol-tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenol) propionate ] ("Irganox (registered trademark.: the same applies hereinafter)" manufactured by BASF) and 10.0g of silicone oil ("TSF 433" manufactured by Momentive Performance Materials) were added thereto, and then, the pressure and temperature were reduced and increased to start the polycondensation reaction. The pressure was gradually reduced to 0.1kPa or less, the temperature was increased to 290 ℃, and 120 minutes after the start of polymerization, the reaction system was purged with nitrogen, returned to normal pressure, the polycondensation reaction was stopped, and the polymer was extruded from a nozzle in a strand form, cooled in a water tank, and pelletized to obtain pellets.
The polymer characteristics of the resulting copolyester composition are shown in Table 1.
[ examples 2 to 5]
A copolyester composition was obtained in the same manner as in example 1, except that the molar contents of DMT and dimethyl isophthalate used in example 1 were changed as shown in table 1.
[ examples 6 to 8]
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT, SSIA and dimethyl isophthalate used in example 1 were changed as shown in Table 1.
[ Table 1]
[ examples 9 to 13]
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT, SSIA and dimethyl isophthalate used in example 1 were changed as shown in Table 2, and polyethylene glycol shown in Table 2 was added before the polycondensation reaction.
[ example 14]
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT, SSIA and dimethyl isophthalate used in example 1 were changed as shown in Table 2 and that one-side methyl terminated polyethylene glycol shown in Table 2 was added before the polycondensation reaction.
[ example 15]
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT, SSIA and dimethyl isophthalate used in example 1 were changed as shown in Table 2 and that a single-sided decyl terminated polyethylene glycol shown in Table 2 was added before the polycondensation reaction.
[ example 16]
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT and SSIA used in example 1 were changed as shown in Table 2, dimethyl isophthalate was changed to dimethyl naphthalenedicarboxylate as shown in Table 2, and polyethylene glycol shown in Table 2 was added before the polycondensation reaction.
[ example 17]
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT and SSIA used in example 1 were changed as shown in Table 2, and dimethyl isophthalate was changed to dimethyl cyclohexanedicarboxylate as shown in Table 2.
[ example 18]
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT and SSIA used in example 1 were changed as shown in Table 2, and a part of dimethyl isophthalate added was changed to dimethyl adipate as shown in Table 2.
[ example 19]
A copolyester composition was obtained in the same manner as in example 1, except that the molar contents of DMT and SSIA used in example 1 were changed as shown in table 2, and a part of dimethyl isophthalate added was changed to dimethyl sebacate as shown in table 2.
[ Table 2]
Comparative examples 1 and 2
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT, SSIA and dimethyl isophthalate used in example 1 were changed as shown in Table 3.
In the composition obtained in comparative example 1, since the molar content of DMT was too large, a strong crystal structure was formed in the composition, and thus the water-absorbing swelling property was not exhibited.
The composition obtained in comparative example 2 had a small molar content of DMT and water-absorbing and swelling properties, but the viscosity retention at 290 ℃ when molten and retained for 20 minutes was less than 75%.
Comparative example 3
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT, SSIA and dimethyl isophthalate used in example 1 were changed as shown in Table 3.
The composition obtained in comparative example 3 had insufficient SSIA molar content, and therefore, had insufficient water-absorbing swelling properties. The hot water swelling ratio was only 20%, and the releasability from the polyethylene terephthalate composition was not exhibited.
Comparative example 4
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT, SSIA and dimethyl isophthalate used in example 1 were changed as shown in Table 3 and polyethylene glycol was added as shown in Table 3 before the polycondensation reaction.
In the case of the composition obtained in comparative example 4, since the SSIA molar content was too large and dissolution in hot water occurred earlier than swelling, the water-absorbing swelling property was not exhibited.
Comparative example 5
A copolyester composition was obtained in the same manner as in example 1, except that the molar contents of DMT and SSIA used in example 1 were changed as shown in Table 3, and that one-side methyl-terminated polyethylene glycol was added as shown in Table 3 before the polycondensation reaction.
The composition obtained in comparative example 5 used a large amount of one-side methyl-terminated polyethylene glycol (average number of repeating units n: 90) having a large effect of lowering the glass transition temperature, and the resulting copolyester composition had a glass transition temperature of less than 50 ℃ and flow deformation and dissolution occurred earlier than swelling in hot water, and thus the intended water-absorbing swelling performance could not be obtained. The hot water swelling ratio was only 40%, and the releasability from the polyethylene terephthalate composition was also insufficient. In addition, the drying temperature is low (55 ℃), and the viscosity retention rate is less than 75% when the glass is melted and retained at 290 ℃ for 20 minutes.
Comparative example 6
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT and SSIA used in example 1 were changed as shown in Table 3, and a part of dimethyl isophthalate added was changed to dimethyl naphthalenedicarboxylate as shown in Table 3.
The composition obtained in comparative example 6 had the effect that the naphthalenedicarboxylic acid component having a large effect of increasing the glass transition temperature was not used in combination with the polyalkylene oxide compound, and the resulting copolyester composition had a glass transition temperature of more than 75 ℃ and the molecular motion in hot water was suppressed, so that the intended water-absorbing swelling performance could not be obtained. The hot water swelling ratio was only 10%, and the releasability from the polyethylene terephthalate composition was not exhibited.
Comparative example 7
A copolyester composition was obtained in the same manner as in example 1 except that the molar contents of DMT and SSIA used in example 1 were changed as shown in Table 3, a part of dimethyl isophthalate added was changed to dimethyl adipate as shown in Table 3, and polyethylene glycol shown in Table 3 was added before the polycondensation reaction.
The composition obtained in comparative example 7 had an excessive amount of SSIA by mole and used a large amount of an adipic acid component having a large effect of lowering the glass transition temperature, and therefore, due to this effect, flow deformation and dissolution occurred in hot water before swelling, and the intended water-absorbing swelling performance could not be obtained. The hot water swelling ratio was only 30%, and the releasability from the polyethylene terephthalate composition was also insufficient. In addition, the drying temperature is low (40 ℃), and the viscosity retention rate is less than 75% when the product is melted and retained at 290 ℃ for 20 minutes.
Comparative example 8
2.5kg of DMT (95.0 mol% based on the total acid components), 0.3kg of SSIA (5.0 mol% based on the total acid components), 5.0kg of polyethylene glycol having an average number of repeating units n of 90 (50 mass% based on the obtained copolyester composition), 3.7kg of 1, 4-Butanediol (BG), and 9.0g of titanium tetra-n-butoxide were added, and EI reaction was carried out while distilling off methanol at 140 to 200 ℃. After 210 minutes, 25.0g of Irganox1010 was added, the temperature was raised to 250 ℃ and the pressure was reduced. The pressure was gradually reduced to 0.1kPa or less, and 120 minutes after the start of the polymerization, the reaction system was purged with nitrogen, returned to normal pressure, the polycondensation reaction was stopped, extruded from a nozzle in the form of strands, cooled in a water tank, and pelletized to obtain pellets, thereby obtaining a copolyester composition.
Since the terephthalic acid component is excessive, the polyester composition forms a firm crystal structure and does not exhibit the intended water-absorbing swelling property. The hot water swelling ratio was only 30%, and the releasability from the polyethylene terephthalate composition was also insufficient.
Comparative example 9
The same procedure as in example 1 was repeated except that the molar contents of DMT and SSIA used in example 1 were changed as shown in Table 3 and dimethyl isophthalate (a copolymerization-forming dicarboxylic acid component) was not added, and the resulting copolyester composition was post-kneaded with polyethylene glycol as shown in Table 3 to obtain a copolymerized/kneaded polyester.
Since the terephthalic acid component is excessive, the polyester composition forms a firm crystal structure and does not exhibit the intended water-absorbing swelling property. The hot water swelling ratio was only 40%, and the releasability from the polyethylene terephthalate composition was also insufficient.
[ Table 3]
While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. The present application is based on japanese patent application filed on 28/6/2018 (japanese patent application No. 2018-122846), and the entire contents thereof are incorporated herein.
Claims (3)
1. A copolyester composition comprising a copolyester obtained from a dicarboxylic acid and/or an ester-forming derivative thereof and ethylene glycol, the copolyester composition having the following composition: the copolymer polyester composition comprises 40.0 to 60.0 mol% of terephthalic acid and/or ester-forming derivative component thereof with respect to the total acid component, 35.0 to 56.0 mol% of at least 1 selected from isophthalic acid, naphthalenedicarboxylic acid, and/or alkyl esters thereof with respect to the total acid component, 4.0 to less than 10.0 mol% of m-benzenedicarboxylic acid containing a metal sulfonate group and/or ester-forming derivative component thereof with respect to the total acid component, and has a weight average molecular weight of 30000 to 80000 as measured by gel permeation chromatography, and a glass transition temperature of 50 to 75 ℃ as measured by differential scanning calorimetry.
2. The copolyester composition according to claim 1, wherein the heat of crystal fusion is 10J/g or less as determined by differential scanning calorimetry.
3. The copolyester composition according to claim 1 or 2, which comprises at least 1 of the polyalkylene oxide compound represented by the following chemical formula (1) and the one-side-capped polyalkylene oxide compound represented by the following chemical formula (2) in a total amount of 1 to 15% by weight based on the polyester,
h [ -O-R ] n-O-H formula (1)
H [ -O-R ] n-O-X formula (2)
In the chemical formulas (1) and (2), R is at least 1 selected from alkylene groups having 1 to 12 carbon atoms, X is at least 1 selected from alkyl groups having 1 to 10 carbon atoms, and the average number of repeating units n is an integer of 19 to 455.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2018-122846 | 2018-06-28 | ||
| JP2018122846 | 2018-06-28 | ||
| PCT/JP2019/025014 WO2020004350A1 (en) | 2018-06-28 | 2019-06-24 | Copolyester composition |
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| JP (1) | JP7380220B2 (en) |
| CN (1) | CN112135857B (en) |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03265624A (en) * | 1990-03-15 | 1991-11-26 | Kanebo Ltd | Polyester copolymer and polyester film or photograhic material containing undercoat comprising same copolymer |
| KR20160079346A (en) * | 2014-12-26 | 2016-07-06 | 도레이케미칼 주식회사 | Water-soluble polyester with improved heat resistance, method for manufacturing thereof and Complex fiber comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6335824A (en) * | 1986-07-29 | 1988-02-16 | Teijin Ltd | Soil release polyester fiber |
| KR940000794B1 (en) * | 1991-02-11 | 1994-01-31 | 제일합섬 주식회사 | Surface treated and biaxially oriented polyester film |
| JPH04283279A (en) * | 1991-03-08 | 1992-10-08 | Toyobo Co Ltd | Coating composition |
| JP2002020472A (en) * | 2000-07-05 | 2002-01-23 | Teijin Ltd | Thermoplastic polyester |
| JP3526855B2 (en) * | 2001-11-16 | 2004-05-17 | 日本合成化学工業株式会社 | Sulfonic acid group-containing polyester and aqueous polyester solution using the same |
| US20130045912A1 (en) * | 2010-03-27 | 2013-02-21 | Clariant Finance (Bvi) Limited | Colored Polyester |
| JP2016180092A (en) * | 2015-03-24 | 2016-10-13 | ユニチカ株式会社 | Polyester-based laminated film |
| JPWO2017022569A1 (en) * | 2015-07-31 | 2018-05-17 | 東レ株式会社 | Polyethylene terephthalate fiber and polyester resin |
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- 2019-06-24 WO PCT/JP2019/025014 patent/WO2020004350A1/en active Application Filing
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03265624A (en) * | 1990-03-15 | 1991-11-26 | Kanebo Ltd | Polyester copolymer and polyester film or photograhic material containing undercoat comprising same copolymer |
| KR20160079346A (en) * | 2014-12-26 | 2016-07-06 | 도레이케미칼 주식회사 | Water-soluble polyester with improved heat resistance, method for manufacturing thereof and Complex fiber comprising the same |
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| JPWO2020004350A1 (en) | 2021-05-13 |
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| JP7380220B2 (en) | 2023-11-15 |
| TW202006006A (en) | 2020-02-01 |
| WO2020004350A1 (en) | 2020-01-02 |
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