TWI717917B - Polyester and fiber - Google Patents

Abstract

A polyester is provided, which is formed by copolymerizing (a) diacid or diester and (b) diol, wherein (a) diacid or diester is (a1)

and (a2)

,

, or a combination thereof, and each of R¹ is independently H or C_1-10 alkyl group, wherein (b) diol is (b1) 1,6-hexanediol and (b2) 2,2,4,4-tetramethyl-1,3-cyclo butane diol, 1,4-cyclohexane dimethanol, tricyclo[5.2.1.0(2, 6)]decanedimethanol, or a combination thereof, and (b1) 1,6-hexanediol and (b2) 2,2,4,4-tetramethyl-1,3-cyclo butane diol, 1,4-cyclohexane dimethanol, tricyclo[5.2.1.0(2, 6)]decanedimethanol, or a combination thereof have a molar ratio (b1/b2) of 75:25 to 92:8.

Description

Polyester and fiber

This disclosure relates to polyester fibers, and more particularly to the composition and ratio of monomers forming polyester.

When the low-melting long-fiber fiber is knitting shoe uppers on a flat knitting machine, it must have sufficient fiber strength to meet the requirements of high-speed weaving and high productivity. The low-temperature hot-melt and solidified fiber can reduce the shrinkage rate of the woven upper, has good dimensional stability, can improve the overall product production efficiency and reduce the cost. Currently, the low-melting-point fibers used in the production of woven shoe uppers are mainly single-composition nylon filaments, whose melting point can be lower than 110˚C, but the raw materials of low-melting nylon are expensive and difficult to obtain.

The development of low-melting fiber applications with polyester materials can overcome the difficulty of obtaining nylon materials and recycling of woven shoe uppers, and can greatly increase the added value of polyester materials.

與(a2)

、

、或上述之組合,且R¹ 各自H或為C_1-10 的烷基;(b)二醇係(b1)己二醇與(b2)2,2,4,4-四甲基-1,3-環丁二醇、1,4-環己烷二甲醇、三環[5.2.1.0(2,6)]癸烷二甲醇、或上述之組合,且(b1)己二醇與(b2)2,2,4,4-四甲基-1,3-環丁二醇、1,4-環己烷二甲醇、三環[5.2.1.0(2,6)]癸烷二甲醇、或上述之組合的莫耳比例係75:25至92:8。The polyester provided by an embodiment of the present invention is formed by copolymerizing (a) a diacid or diester and (b) a diol, wherein (a) the diacid or diester is (a1)

And (a2)

,

, Or a combination of the above, and each of R ^{1 is} H or a C _1-10 alkyl group; (b) diol system (b1) hexanediol and (b2) 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 1,4-cyclohexanedimethanol, tricyclo[5.2.1.0(2,6)]decanedimethanol, or a combination of the above, and (b1) hexanediol and (b2 )2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol, tricyclo[5.2.1.0(2,6)]decanedimethanol, or The molar ratio of the above combination is 75:25 to 92:8.

係

,(a2)

、

、或上述之組合係

,且(a1)

與(a2)

的莫耳比為85:15至65:35。In one embodiment, (a1)

system

,(a2)

,

, Or a combination of the above

, And (a1)

And (a2)

The mol ratio is 85:15 to 65:35.

係

,(a2)

、

、或上述之組合係

,且(a1)

與(a2)

的莫耳比為85:15至15:85。In one embodiment, (a1)

system

,(a2)

,

, Or a combination of the above

, And (a1)

And (a2)

The mol ratio is 85:15 to 15:85.

In one example, the (b) diol does not contain ethylene glycol.

In one embodiment, the melting point of the polyester is 80°C to 115°C.

In one embodiment, the glass transition temperature of the polyester is 13°C to 25°C.

In one embodiment, the intrinsic viscosity of the polyester is greater than 0.85 dL/g and less than 1.2 dL/g.

The fiber provided by an embodiment of the present invention includes the above-mentioned polyester.

In one embodiment, the fiber strength of the fiber is greater than 0.9 gf/den and less than 5.0 gf/den.

In one embodiment, the elongation at break of the fiber is greater than 10% and less than 200%.

與(a2)

、

、或上述之組合,且R¹ 係各自為H或C_1-10 的烷基。舉例來說,R¹ 可為H,則

為對苯二甲酸,

為間苯二甲酸,而

為2,5-呋喃二甲酸。在另一實施例中,R¹ 可為甲基,則

為對苯二甲酸二甲酯(DMT),

為間苯二甲酸二甲酯(DMI),而

為2,5-呋喃二甲酸二甲酯(DmFDCA)。除此之外,亦可採用其他R¹ 而不限於上述例子。The polyester provided by an embodiment of the present invention is formed by copolymerizing (a) a diacid or diester and (b) a diol, wherein (a) the diacid or diester is (a1)

And (a2)

,

, Or a combination of the above, and R ¹ is each H or a C _1-10 alkyl group. For example, R ¹ can be H, then

Is terephthalic acid,

Is isophthalic acid, and

For 2,5-furandicarboxylic acid. In another embodiment, R ¹ can be methyl, then

Is dimethyl terephthalate (DMT),

Is dimethyl isophthalate (DMI), and

It is 2,5-dimethyl furandicarboxylate (DmFDCA). In addition, other R ¹ can also be used without being limited to the above examples.

On the other hand, (b) diol system (b1) hexanediol and (b2) 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO), 1,4-cyclohexane Alkane dimethanol, tricyclo[5.2.1.0(2,6)]decane dimethanol, or a combination of the above, and (b1) hexanediol and (b2) 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 1,4-cyclohexanedimethanol, tricyclo[5.2.1.0(2,6)]decanedimethanol, or a combination of the above molar ratio (b1/b2) is 75 : 25 to 92:8, such as 80:20 to 91:9, or 85:15 to 90:10. If the ratio of (b1) hexanediol is too high, the glass transition temperature will be too low, the fabric will be too soft after heat setting, and the melting point will be too high to reach the specification of melting point less than 110℃. If the ratio of (b1) hexanediol is too low, the crystallinity of the material will decrease, which will result in difficult spinning processing and low fiber strength.

與(a2)

的莫耳比(a1/a2)為85:15至65:35,例如80:20至70:30。若(a1)對苯二甲酸二甲酯的比例過高,則熔點無法降低至小於110℃以下。若(a1)對苯二甲酸二甲酯的比例過低,則材料結晶性低,紡絲加工不易,且纖維強度低。In one embodiment, (a1)

And (a2)

The molar ratio (a1/a2) is 85:15 to 65:35, for example 80:20 to 70:30. If the ratio of (a1) dimethyl terephthalate is too high, the melting point cannot be lowered to less than 110°C. If the ratio of (a1) dimethyl terephthalate is too low, the crystallinity of the material is low, the spinning process is not easy, and the fiber strength is low.

與(a2)

的莫耳比(a1/a2)為80:20至20:80。若(a1)對苯二甲酸二甲酯的比例過高,則熔點無法降低至110℃以下。若(a1)對苯二甲酸二甲酯的比例過低,則聚酯材料結晶性過低,紡絲加工不易,且纖維強度低。In one embodiment, (a1)

And (a2)

The molar ratio (a1/a2) is 80:20 to 20:80. If the ratio of (a1) dimethyl terephthalate is too high, the melting point cannot be lowered below 110°C. If the ratio of (a1) dimethyl terephthalate is too low, the crystallinity of the polyester material is too low, the spinning process is not easy, and the fiber strength is low.

It is worth noting that (b) glycol does not contain ethylene glycol. If (b) glycol contains ethylene glycol, which is a monomer commonly found in polyester, the melting point temperature of the formation is too high and the glass transition temperature is too low.

In one embodiment, take appropriate proportions of the above-mentioned (a) diacid or diester and (b) diol, mix with zinc acetate (catalyst amount), then pass in nitrogen, and heat to 190°C to 200°C for transesterification化反应。 Chemical reaction. After continuing the reaction for 2 hours to 3 hours, the heat stabilizer phosphoric acid and titanium catalyst are added for polycondensation reaction. Gradually reduce the pressure in the reaction system to 5 torr to 100 torr to remove excess hexanediol monomer, and then gradually heat the temperature to 270°C to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes To 180 minutes. Break the vacuum with nitrogen and stop heating and stirring to obtain polyester. In one embodiment, the melting point of the polyester is 80°C to 115°C. If the melting point of polyester is too high, the heat setting temperature required for the fabric is too high, it is difficult to use steam to heat the hot melt yarn to strengthen the fabric structure, and the size of the fabric shrinks seriously under high temperature conditions. If the melting point of polyester is too low, the fabric will easily deform when heated. In one embodiment, the glass transition temperature of the polyester is 13°C to 25°C. If the glass transition temperature of polyester is too high, the fabric lacks flexibility and comfort. If the glass transition temperature of the polyester is too low, the fabric will have poor stiffness and the shoe upper will easily deform. In one embodiment, the intrinsic viscosity of the polyester is greater than 0.85 dL/g and less than 1.20 dL/g, for example: greater than 0.9 dL/g and less than 1.20 dL/g. If the intrinsic viscosity of polyester is too high, the fluidity after hot melting will be poor and the adhesion will be low. If the intrinsic viscosity of the polyester is too low, the spinning process is not easy, the filament breakage is easy to occur, and the yield of the hot melt spinning process is poor. Spinning the above-mentioned polyester, the spinning temperature is 200 to 250 ℃, the spinning rate is 1,000 m/min to 3,000 m/min, the yarn contains 24 fibers to obtain polyester fiber, and the temperature is The post-stretching process is carried out at a temperature of 60°C, and the stretching ratio is between 1.1 and 1.6 to fully stretch the polyester fiber. In one embodiment, the fiber strength of the fiber is greater than 0.9 gf/den and less than 5.0 gf/den, for example: greater than 0.9 gf/den and less than 4.0 gf/den, or greater than 0.9 gf/den and less than 3.0 gf/den. If the fiber strength of the fiber is too low, wire breakage is likely to occur during the weaving of the upper. In one embodiment, the elongation at break of the fiber is greater than 10% and less than 200%, for example: greater than 10% and less than 150%. If the breaking elongation of the fiber is too low, the extensibility is low, and it is easy to produce broken filaments.

In order to make the above content and other purposes, features, and advantages of this disclosure more obvious and understandable, the following specifically enumerates preferred embodiments, and in conjunction with the accompanying drawings, detailed descriptions are as follows: [ Examples ]

Example 1 Combine 300 grams (1.545 mol) of DMT, 75 grams (0.386 mol) of DMI, 34.8 grams (0.241 mol) of CBDO, 320 grams (2.7 mol) of hexanediol, and 200 ppm (based on theoretical product weight) The zinc acetate is added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. Nuclear magnetic resonance spectrometer (NMR) was used to confirm the molar ratio of DMT to DMI (80:20) in the diester copolymerized to form the polyester product, and the molar ratio of hexylene glycol and CBDO to the glycol copolymerized to form the polyester product. Ratio (90:10). The intrinsic viscosity of the above polyester is 0.971 dL/g (ASTM D4603-2003), the melting point is 111.3°C (ASTM D3418-15), the glass transition temperature is 14.7°C (ASTM D3418-15), and the crystallinity is 20.3J/g (ASTM D3418-15). Spinning the above-mentioned polyester, the spinning temperature is 220 ℃, the spinning speed is 1,000 m/min, the yarn contains 24 fibers to obtain polyester fiber, and the post-stretching process is performed at a temperature of 45 ℃. The magnification is 1.4 to fully extend the polyester fiber. The fiber strength before stretching is 1.55 gf/den (ASTM D3822-2007), and the elongation at break is 134.2% (ASTM D3822-2007). The fully extended fiber strength is 2.23 gf/den (ASTM D3822-2007), and the elongation at break is 47.1% (ASTM D3822-2007).

Example 2 Combine 300 grams (1.545 mol) of DMT, 75 grams (0.386 mol) of DMI, 41.7 grams (0.29 mol) of CBDO, 320 grams (2.7 mol) of hexanediol, and 200 ppm (based on theoretical product weight) The zinc acetate is added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DMI (80:20) in the diester copolymerized to form the polyester product, and the molar ratio of hexanediol to CBDO (87:13) in the diol copolymerized to form the polyester product. ). The intrinsic viscosity of the above polyester is 0.960 dL/g (ASTM D4603-2003), the melting point is 107.5°C (ASTM D3418-15), the glass transition temperature is 15.4°C (ASTM D3418-15), and the crystallinity is 18.9J/g (ASTM D3418-15). The polyester is processed by spinning, the spinning temperature is 220°C, the spinning speed is 1,000 m/min, and the yarn contains 24 fibers to obtain polyester fiber. The fiber strength is 2.20 gf/den (ASTM D3822-2007), and the elongation at break is 59.1% (ASTM D3822-2007). In this embodiment, the fiber strength can reach 2.0 gf/den without post-stretching processing.

Example 3 Combine 75 grams (0.386 mol) of DMT, 284.3 grams (1.545 mol) of DmFDCA, 55.6 grams (0.386 mol) of CBDO, 320 grams (2.7 mol) of hexanediol, and 200 ppm (based on theoretical product weight) The zinc acetate is added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DmFDCA (20:80) in the diester copolymerized to form the polyester product, and the molar ratio of hexylene glycol to CBDO (85:15) in the diol copolymerized to form the polyester product. ). The intrinsic viscosity of the above polyester is 0.940 dL/g (ASTM D4603-2003), the melting point is 106.7°C (ASTM D3418-15), the glass transition temperature is 17.6°C (ASTM D3418-15), and the crystallinity is 23.9 J/g (ASTM D3418-15). Spinning the above-mentioned polyester, the spinning temperature is 220 ℃, the spinning speed is 1,000 m/min, the yarn contains 24 fibers to obtain polyester fiber, and the post-stretching process is performed at a temperature of 45 ℃. The magnification is 1.4 to fully extend the polyester fiber. The fiber strength before stretching is 0.92 gf/den (ASTM D3822-2007), and the elongation at break is 147.4% (ASTM D3822-2007). The fully extended fiber strength is 1.50 gf/den (ASTM D3822-2007), and the elongation at break is 32.3% (ASTM D3822-2007).

Example 4 Combine 300 grams (1.545 mol) of DMT, 75 grams (0.386 mol) of DMI, 41.8 grams (0.29 mol) of 1,4-cyclohexane dimethanol (CHDM), 320 grams (2.7 mol) of hexylene glycol and 200 ppm (based on the theoretical product weight) of zinc acetate are added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DMI (80:20) in the diester copolymerized to form the polyester product, and the molar ratio of hexanediol to CHDM (85:15) in the glycol copolymerized to form the polyester product. ). The intrinsic viscosity of the above polyester is 0.993 dL/g (ASTM D4603-2003), the melting point is 112.8°C (ASTM D3418-15), the glass transition temperature is 16.6°C (ASTM D3418-15), and the crystallinity is 22.0J/g (ASTM D3418-15). Spinning the above-mentioned polyester, the spinning temperature is 230 ℃, the spinning speed is 1,000 m/min, the yarn contains 24 fibers to obtain the polyester fiber, and the post-stretching process is carried out at a temperature of 45 ℃. The magnification is 1.45 to fully extend the polyester fiber. The fiber strength before stretching is 2.4 gf/den (ASTM D3822-2007), and the elongation at break is 71.2% (ASTM D3822-2007). The fiber strength after fully extended is 3.7 gf/den (ASTM D3822-2007), and the elongation at break is 21% (ASTM D3822-2007).

Example 5 300 grams (1.545 mol) of DMT, 75 grams (0.386 mol) of DMI, 37.9 grams (0.193mol) of tricyclo[5.2.1.0(2,6)]decane dimethanol (Tricyclo[5.2.1.0(2 ,6)] decanedimethanol, TDD), 320 grams (2.7 mol) of hexanediol, and 200 ppm (based on the theoretical product weight) of zinc acetate are added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DMI (80:20) in the diester copolymerized to form the polyester product, and the molar ratio of hexanediol to TDD (90:10) in the diol copolymerized to form the polyester product. ). The intrinsic viscosity of the above polyester is 0.925 dL/g (ASTM D4603-2003), the melting point is 105.7°C (ASTM D3418-15), the glass transition temperature is 17.1°C (ASTM D3418-15), and the crystallinity is 19.3 J/g (ASTM D3418-15). Spinning the above-mentioned polyester, the spinning temperature is 220 ℃, the spinning speed is 1,000 m/min, the yarn contains 24 fibers to obtain the polyester fiber, and the post-stretching process is carried out at a temperature of 45 ℃. The magnification is 1.45 to fully extend the polyester fiber. The fiber strength before stretching is 2.4 gf/den (ASTM D3822-2007), and the elongation at break is 75.5% (ASTM D3822-2007). The fully extended fiber strength is 3.2 gf/den (ASTM D3822-2007), and the elongation at break is 20% (ASTM D3822-2007).

Example 6 Mix 263 grams (1.351 mol) of DMT, 112 grams (0.579 mol) of DMI, 41.8 grams (0.29 mol) of 1,4-cyclohexane dimethanol (CHDM), 320 grams (2.7 mol) of hexylene glycol and 200 ppm (based on the theoretical product weight) of zinc acetate are added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DMI (70:30) in the diester copolymerized to form the polyester product, and the molar ratio of hexylene glycol to CHDM (85:15) in the diol copolymerized to form the polyester product. ). The intrinsic viscosity of the above polyester is 0.988 dL/g (ASTM D4603-2003), the melting point is 96.5°C (ASTM D3418-15), the glass transition temperature is 16.6°C (ASTM D3418-15), and the crystallinity is 22.0 J/g (ASTM D3418-15). Spinning the above-mentioned polyester, the spinning temperature is 230 ℃, the spinning speed is 1,000 m/min, the yarn contains 24 fibers to obtain the polyester fiber, and the post-stretching process is carried out at a temperature of 45 ℃. The magnification is 1.4 to fully extend the polyester fiber. The fiber strength before stretching is 1.86 gf/den (ASTM D3822-2007), and the elongation at break is 85.3% (ASTM D3822-2007). The fully extended fiber strength is 2.8 gf/den (ASTM D3822-2007), and the elongation at break is 26.3% (ASTM D3822-2007).

The monomer ratio and fiber properties used in the polyesters of Examples 1 to 6 are shown in Table 1. It can be seen from Examples 1-6 that the use of appropriate cyclic diol monomers can reduce the melting point of polyester to less than 115°C, with a certain degree of crystallinity, and viscosity> 0.9 dL/g. In addition, the glass transition temperature of polyester increases with the addition of cyclic glycol monomer. The polyesters of Examples 1-6 have good spinnability and characteristics similar to nylon low-melting-point fibers.

Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Diester (mol%) DMT 80 80 20 80 80 70 DMI 20 20 0 20 20 30 DmFDCA 0 0 80 0 0 0 Diol (mol%) Hexanediol 90 87 85 85 90 85 CBDO 10 13 15 0 0 0 CHDM 0 0 0 15 0 15 TDD 0 0 0 0 10 0 Intrinsic viscosity (dL/g) 0.971 0.960 0.940 0.993 0.925 0.988 Melting point (˚C) 111.3 107.5 106.7 112.8 105.7 96.5 Tg (˚C) 14.7 15.4 17.6 16.6 17.1 15.7 Crystallinity (J/g) 20.3 18.9 23.9 22.0 19.3 17.8 Fiber before drawing Fiber strength (gf/den) 1.55 2.20 0.92 2.0 2.4 1.86 Elongation at break (%) 134.2 59.1 147.4 71.2 75.5 85.3 Stretched fiber Fiber strength 2.23 NA 1.50 3.7 3.2 2.8 Elongation at break (%) 47.1 NA 32.3 twenty one 20 26.3

Comparative example 1 300 grams (1.545 mol) of DMT, 71 grams (0.386 mol) of DmFDCA, 320 grams (2.7 mol) of hexanediol, and 200 ppm (based on the theoretical product weight) of zinc acetate were added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. The molar ratio of DMT to DmFDCA (80:20) in the diester copolymerized to form the polyester product was confirmed by NMR. The intrinsic viscosity of the above polyester is 0.80 dL/g (ASTM D4603-2003), the melting point is 125°C (ASTM D3418-15), the glass transition temperature is 7.5°C (ASTM D3418-15), and the crystallinity is 29.2 J/g (ASTM D3418-15). The melting point of the above polyester is too high, not suitable for low-temperature heat setting processing, and the glass transition temperature is too low, which is unfavorable for spinning processing. After spinning and winding, the yarn stability is poor, the yarn is sticky, and the strength and elongation cannot be achieved. Characteristic analysis.

Comparative example 2 75 grams (0.386 mol) of DMT, 284.3 grams (1.545 mol) of DmFDCA, 320 grams (2.7 mol) of hexanediol, and 200 ppm (based on the theoretical product weight) of zinc acetate were added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. The molar ratio of DMT to DmFDCA (20:80) in the diester copolymerized to form the polyester product was confirmed by NMR. The intrinsic viscosity of the above polyester is 0.81 dL/g (ASTM D4603-2003), the melting point is 126.2°C (ASTM D3418-15), the glass transition temperature is 10.2°C (ASTM D3418-15), and the crystallinity is 33.7J/g (ASTM D3418-15). The melting point of the above-mentioned polyester is too high, not suitable for low-temperature heat setting processing, unfavorable for spinning processing, the yarn stability after spinning and winding is poor, the yarn is sticky, and the strength and elongation characteristics cannot be analyzed.

Comparative example 3 Combine 300 grams (1.545 mol) of DMT, 75 grams (0.386 mol) of DMI, 25.9 grams (0.405 mol) of ethylene glycol (EG), 320 grams (2.7 mol) of ethylene glycol, and 200 ppm (Based on the theoretical product weight) zinc acetate is added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DMI (80:20) in the diester copolymerized to form the polyester product, and the molar ratio of hexanediol to EG (85:15) in the diol copolymerized to form the polyester product. ). The intrinsic viscosity of the above polyester is 0.950 dL/g (ASTM D4603-2003), the melting point is 118.1°C (ASTM D3418-15), the glass transition temperature is 10.2°C (ASTM D3418-15), and the crystallinity is 23.8J/g (ASTM D3418-15). Spinning the above-mentioned polyester, the spinning temperature is 220 ℃, the spinning speed is 1,000 m/min, the yarn contains 24 fibers to obtain polyester fiber, and the post-stretching process is performed at a temperature of 45 ℃. The magnification is 1.5 to fully extend the polyester fiber. The fiber strength before stretching was 2.42 gf/den (ASTM D3822-2007), and the elongation at break was 92.6% (ASTM D3822-2007). The fully extended fiber strength is 3.28 gf/den (ASTM D3822-2007), and the elongation at break is 28.3% (ASTM D3822-2007). The diol copolymerized to form polyester contains EG instead of the appropriate cyclic diol, which will cause the glass transition temperature to be too low. It is used in woven shoe uppers with low stiffness and easy deformation, and the melting point temperature is too high. The use of steam for shaping is time-consuming and energy-consuming .

Comparative example 4 Combine 300 grams (1.545 mol) of DMT, 75 grams (0.386 mol) of DMI, 28.2 grams (0.193 mol) of isosorbide, 320 grams (2.7 mol) of hexylene glycol, and 200 ppm (in theory) Based on the product weight) zinc acetate is added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DMI (80:20) in the diester copolymerized to form the polyester product, and the molar ratio of hexanediol to isosorbide (99 :1). The intrinsic viscosity of the above polyester is 0.958 dL/g (ASTM D4603-2003), the melting point is 120.4°C (ASTM D3418-15), the glass transition temperature is 9.3°C (ASTM D3418-15), and the crystallinity is 22.4 J/g (ASTM D3418-15). Due to the poor reactivity of isosorbide, the glass transition temperature of polyester is too low, the yarn stability after spinning and winding is poor, the yarn is sticky, and the strength and elongation characteristics cannot be analyzed, and it is not suitable for forming high strength. fiber.

Comparative example 5 Combine 300 grams (1.545 mol) of DMT, 75 grams (0.386 mol) of DMI, 92.8 grams (0.386 mol) of hydrogenated bisphenol A (HBPA), 320 grams (2.7 mol) of hexanediol, and 200 ppm (based on the theoretical product weight) of zinc acetate is added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DMI (80:20) in the diester copolymerized to form the polyester product, and the molar ratio of hexanediol to HBPA (80:20) in the diol copolymerized to form the polyester product. ). The intrinsic viscosity of the above polyester is 0.529 dL/g (ASTM D4603-2003), the melting point is 108.3°C (ASTM D3418-15), the glass transition temperature is 20.2°C (ASTM D3418-15), and the crystallinity is 22.6 J/g (ASTM D3418-15). Due to the poor thermal stability of HBPA, thermal degradation occurs during the process of increasing the intrinsic viscosity by high temperature polymerization at 280°C. The intrinsic viscosity first increases and then decreases. The intrinsic viscosity of polyester is too low and is not suitable for spinning and forming high-strength fibers.

Comparative example 6 Combine 300 grams (1.545 mol) of DMT, 75 grams (0.386 mol) of DMI, 19.1 grams (0.0965 mol) of 4,4'-bicyclohexanol (4,4'-bicyclohexanol), 320 grams (2.7mol) The hexamethylene glycol and 200 ppm (based on the theoretical product weight) of zinc acetate are added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. Use NMR to confirm the molar ratio of DMT to DMI (80:20) in the diester copolymerized to form the polyester product, and among the diols copolymerized to form the polyester product, hexanediol and 4,4'-bicyclohexanol The molar ratio (96:4). The intrinsic viscosity of the above polyester is 0.905 dL/g (ASTM D4603-2003), the melting point is 120.0°C (ASTM D3418-15), the glass transition temperature is 15.8°C (ASTM D3418-15), and the crystallinity is 24.4J/g (ASTM D3418-15). Spinning the above-mentioned polyester, the spinning temperature is 220 ℃, the spinning speed is 1,000 m/min, the yarn contains 24 fibers to obtain polyester fiber, and the post-stretching process is performed at a temperature of 45 ℃. The magnification is 1.4 to fully extend the polyester fiber. The fiber strength before stretching is 2.0 gf/den (ASTM D3822-2007), and the elongation at break is 65% (ASTM D3822-2007). The fully extended fiber strength is 2.6 gf/den (ASTM D3822-2007), and the elongation at break is 25.1% (ASTM D3822-2007). The diol copolymerized to form polyester contains 4,4'-bicyclohexanol instead of appropriate cyclic diols, and the melting point is low, the structure is rigid, and the reactivity is poor, increasing the copolymerization ratio of 4,4'-bicyclohexanol It is difficult to increase the viscosity characteristics of the copolyester to above 0.90 dL/g. It can be seen from the above that not all cyclic diols are suitable for collocation with hexanediol to form polyesters with low melting point and high strength.

Comparative example 7 Combine 300 g (1.545 mol) of DMT, 75 g (0.386 mol) of DMI, 62 g (0.204mol) of 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4 ,8,10-tetraoxaspiro[5.5]undecane(3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4, 8,10-tetraoxaspiro[5.5]undecane,SPG), 320 grams (2.7 mol) of hexanediol and 200 ppm (based on the theoretical product weight) of zinc acetate are added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DMI (80:20) in the diester copolymerized to form the polyester product, and the molar ratio of hexanediol to SPG (90:10) in the diol copolymerized to form the polyester product. ). The intrinsic viscosity of the above polyester is 0.659 dL/g (ASTM D4603-2003), the melting point is 115.7°C (ASTM D3418-15), the glass transition temperature is 10.4°C (ASTM D3418-15), and the crystallinity is 30.2J/g (ASTM D3418-15). Spinning the above-mentioned polyester, the spinning temperature is 220 ℃, the spinning speed is 1,000 m/min, the yarn contains 24 fibers to obtain polyester fiber, and the fiber strength is 1.14 gf/den (ASTM D3822-2007) , And the elongation at break is 20.5% (ASTM D3822-2007). The elongation at break of this fiber is too low to be stretched, which may be caused by the partial cross-linking reaction of SPG during the polymerization process.

Comparative example 8 Combine 79.1 g (0.408 mol) DMT, 300 g (1.63 mol) DmFDCA, 62 grams (0.204 mol) of SPG, 320 grams (2.7 mol) of hexanediol, and 200 ppm (based on the theoretical product weight) of zinc acetate were added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DmFDCA (20:80) in the diester copolymerized to form the polyester product, and the molar ratio of hexanediol to SPG (90:10) in the diol copolymerized to form the polyester product. ). The intrinsic viscosity of the above polyester is 0.744 dL/g (ASTM D4603-2003), the melting point is 108.5°C (ASTM D3418-15), the glass transition temperature is 19.4°C (ASTM D3418-15), and the crystallinity is 24.5J/g (ASTM D3418-15). Spinning the above-mentioned polyester, the spinning temperature is 220 ℃, the spinning speed is 1,000 m/min, the yarn contains 24 fibers to obtain the polyester fiber, and the post-stretching process is carried out at a temperature of 45 ℃. The magnification is 1.3 to fully extend the polyester fiber. The fiber strength before stretching is 1.10 gf/den (ASTM D3822-2007), and the elongation at break is 81.2% (ASTM D3822-2007). The fully extended fiber strength is 1.87 gf/den (ASTM D3822-2007), and the elongation at break is 7.80% (ASTM D3822-2007). The low elongation at break of this fiber after processing and extension may be caused by the partial cross-linking reaction of SPG during the polymerization process.

Comparative example 9 Combine 225 grams (1.158 mol) of DMT, 150 grams (0.772 mol) of DMI, 41.8 grams (0.29 mol) of 1,4-cyclohexane dimethanol (CHDM), 320 grams (2.7 mol) of hexylene glycol and 200 ppm (based on the theoretical product weight) of zinc acetate are added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DMI (60:40) in the diester copolymerized to form the polyester product, and the molar ratio of hexanediol to CHDM (85:15) in the diol copolymerized to form the polyester product. ). The intrinsic viscosity of the above polyester is 0.950 dL/g (ASTM D4603-2003), and the melting point (ASTM D3418-15) cannot be measured. The glass transition temperature is 15.1℃ (ASTM D3418-15). The material is amorphous and cannot be measured. The crystallinity (ASTM D3418-15) is obtained, so it cannot be processed by spinning.

Comparative example 10 Combine 300 grams (1.545 mol) of DMT, 75 grams (0.386 mol) of DMI, 27.8 grams (0.193 mol) of CBDO, 320 grams (2.7 mol) of hexanediol, and 200 ppm (based on theoretical product weight) The zinc acetate is added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of the thermal stabilizer phosphoric acid (the same molar number as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product Weight based). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 180 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DMI (80:20) in the diester copolymerized to form the polyester product, and the molar ratio of hexylene glycol to CBDO (92.5:7.5) in the glycol copolymerized to form the polyester product. The intrinsic viscosity of the above polyester is 0.996 dL/g (ASTM D4603-2003), the melting point is 116.7°C (ASTM D3418-15), the glass transition temperature is 11.4°C (ASTM D3418-15), and the crystallinity is 31.0J/g (ASTM D3418-15). Spinning the above-mentioned polyester, the spinning temperature is 220 ℃, the spinning speed is 1,000 m/min, the yarn contains 24 fibers to obtain polyester fiber, and the post-stretching process is performed at a temperature of 45 ℃. The magnification is 1.4 to fully extend the polyester fiber. The fiber strength before stretching is 1.34 gf/den (ASTM D3822-2007), and the elongation at break is 145.1% (ASTM D3822-2007). The fully extended fiber strength is 2.31 gf/den (ASTM D3822-2007), and the elongation at break is 19% (ASTM D3822-2007). Although this composition can obtain fibrous materials with strength greater than 2.0 gf/den, its melting point is higher than 115°C and the glass transition temperature is less than 13°C.

Comparative example 11 Combine 75 grams (0.386 mol) of DMT, 284.3 grams (1.545 mol) of dimethyl 2,5-furandicarboxylate (DmFDCA), 27.8 grams (0.193 mol) of CBDO, and 320 grams ( 2.7 mol) of hexanediol and 200 ppm (based on the theoretical product weight) of zinc acetate were added to the reaction tank. Blow in nitrogen, heat to 200°C, and stir at 150 rpm for transesterification reaction. After continuing the reaction for three hours, remove the condensed methanol and add 0.055 g of heat stabilizer phosphoric acid (the same molar amount as zinc acetate) and 0.0778 g of C-94 titanium catalyst (150 ppm, based on the theoretical product weight) ). Gradually reduce the pressure in the reaction system to 50 torr within 30 minutes to remove excess hexanediol monomer. Gradually heat the temperature to 280°C and gradually reduce the reaction pressure to below 1 torr, and continue the reaction for 120 minutes. Finally, break the vacuum with nitrogen, stop heating and stirring, and take out the polyester product. NMR was used to confirm the molar ratio of DMT to DmFDCA (20:80) in the diester copolymerized to form the polyester product, and the molar ratio of hexanediol to CBDO (92.5:7.5) in the diol copolymerized to form the polyester product. ). The intrinsic viscosity of the above polyester is 0.959 dL/g (ASTM D4603-2003), the melting point is 117.1°C (ASTM D3418-15), the glass transition temperature is 14.3°C (ASTM D3418-15), and the crystallinity is 30.1 J/g (ASTM D3418-15). The polyester is processed by spinning, the spinning temperature is 220°C, the spinning speed is 1,000 m/min, and the yarn contains 24 fibers to obtain polyester fiber. The fibers spun formed by this composition are slackened immediately after being collected in the bobbin, and the characteristics of the obtained fibers cannot be measured smoothly, nor can they be post-stretched.

Table 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Diester (mol%) DMT 80 20 80 80 DMI 0 20 20 DmFDCA 20 80 0 0 Diol (mol%) Hexanediol 100 85 99 80 96 EG 0 15 0 CBDO 0 Isosorbide 0 1 0 0 HBPA 0 0 20 0 Bihexanol 0 0 0 4 SPG 0 CHDM 0 Intrinsic viscosity (dL/g) 0.80 0.81 0.950 0.958 0.529 0.905 Melting point (˚C) 125 126.2 118.1 120.4 108.3 120.0 Tg (˚C) 7.5 10.2 10.2 9.3 20.2 15.8 Crystallinity (J/g) 29.2 33.7 23.8 22.4 22.6 24.4 Fiber before stretching Fiber strength (gf/den) NA NA 2.42 NA NA 2.0 Elongation at break (%) NA NA 92.6 NA NA 65.3 After stretching fiber Fiber strength NA NA 3.28 NA NA 2.6 Elongation at break (%) NA NA 28.3 NA NA 25.1

table 3 Comparative example 7 Comparative example 8 Comparative example 9 Comparative example 10 Comparative example 11 Diester (mol%) DMT 80 20 60 80 20 DMI 20 0 40 20 0 DmFDCA 0 80 0 0 80 Diol (mol%) Hexanediol 90 85 92.5 EG 0 0 0 CBDO 0 7.5 Isosorbide 0 HBPA 0 Bihexanol 0 SPG 10 0 CHDM 0 15 0 Intrinsic viscosity (dL/g) 0.659 0.744 0.950 0.996 0.959 Melting point (˚C) 115.7 108.5 NA 116.7 117.1 Tg (˚C) 10.4 19.4 15.1 11.4 14.3 Crystallinity (J/g) 30.2 24.5 NA 31.0 30.1 Fiber before drawing Fiber strength (gf/den) 1.14 1.10 NA 1.34 NA Elongation at break (%) 20.5 81.2 145.1 Stretched fiber Fiber strength 1.87 2.31 Elongation at break (%) 7.80 19

To sum up, take a suitable ratio of appropriate cyclic diol and hexanediol as the diol, and react with aromatic diacids or diesters such as (a1) DMT and (a2) DMI or DmFDCA to obtain high strength and Low melting point polyester fiber.

Although this disclosure has been disclosed in several preferred embodiments as above, it is not intended to limit this disclosure. Anyone with ordinary knowledge in the relevant technical field can make arbitrary changes without departing from the spirit and scope of this disclosure. Therefore, the scope of protection of this disclosure shall be subject to the scope of the attached patent application.

no.

no.

no.

Claims (10)

A polyester that is made by copolymerizing (a) diacids or diesters and (b) diols, where (a) diacids or diesters (a1)

And (a2)

,

, Or a combination of the above, and R ^{1 is} each H or a C _1-10 alkyl group; (b) diol system (b1) hexanediol and (b2) 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 1,4-cyclohexanedimethanol, tricyclo[5.2.1.0(2,6)]decanedimethanol, or a combination of the above, and (b1) hexanediol and (b2 )2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol, tricyclo[5.2.1.0(2,6)]decanedimethanol, or The molar ratio of the above combination is 75:25 to 92:8. The polyester described in item 1 of the scope of patent application, where (a1)

system

,(a2)

,

, Or a combination of the above

, And (a1)

And (a2)

The mol ratio is 85:15 to 65:35. The polyester described in item 1 of the scope of patent application, where (a1)

system

,(a2)

,

, Or a combination of the above

, And (a1)

And (a2)

The mol ratio is 85:15 to 15:85. The polyester described in item 1 of the scope of patent application, wherein (b) diol does not contain ethylene glycol. The polyester described in item 1 of the scope of patent application has a melting point of 80°C to 115°C. The polyester described in item 1 of the scope of patent application has a glass transition temperature of 13°C to 25°C. The polyester described in item 1 of the scope of patent application has an intrinsic viscosity greater than 0.85 dL/g and less than 1.20 dL/g. A fiber including the polyester described in item 1 of the scope of patent application. The fiber described in item 8 of the scope of patent application has a fiber strength greater than 0.9 gf/den and less than 5.0 gf/den. The fiber described in item 8 of the scope of patent application has a breaking elongation greater than 10% and less than 200%.