Condensation type polyurethane fiber

Abstract

This invention provides a condensation polyurethane fiber comprising a condensation polyurethane resin, wherein the condensation polyurethane resin comprises: a plurality of first segments and a plurality of terminal groups, which are bonded to at least one of the first segments via R2; wherein R1 and R3 are independently and respectively comprising first organic groups from C2 to C20, and the first organic groups include hydrocarbon groups or groups containing carbon, hydrogen, and oxygen; wherein the first segments have the same or different R2, which are independently and respectively comprising second organic groups from C2 to C20, and the second organic groups include hydrocarbon groups or groups containing carbon, hydrogen, and oxygen; wherein the condensation polyurethane resin has an amine value in the range of not less than 10 meq / kg; and the coefficient of variation (CV value) of the condensation polyurethane fiber is not higher than 6.

Description

Technical Field

[0001] This invention relates to a condensation polyurethane fiber, and more particularly to a condensation non-isocyanate polyurethane fiber. Prior Technology

[0002] Spandex fiber has wide applications in sportswear, such as yoga wear. The raw material for producing Spandex fiber is polyurethane polyurea, such as patents TW200412352, US6916896B2, and US20250129522A1. Its structure contains a high content of urea bonds (>40 mol%), with strong hydrogen bonding. Therefore, solvent spinning is required during fiber production, and waste solvents must be treated afterward. Consequently, the industry hopes to switch to a green process like melt spinning. Common melt spinning raw materials are thermoplastic polyurethanes, such as US10875956B2, which mainly use isocyanates and polyols. Since isocyanates are toxic, non-isocyanate polyurethane (NIPU) processes have become a highly sought-after green process in the industry.

[0003] It is known that the green manufacturing process of non-isocyanate polyurethane can be divided into two methods: addition polymerization and polycondensation. The product structures of the two methods are not the same.

[0004] Addition polymerization, such as US 20230183423 A1, uses a compound containing multiple cyclic carbonate groups to add polymerize with a polyamine to prepare PU. The synthesized PU has OH functional groups on its side chains, hence it is called polyhydroxyurethane (PHU, as shown in the structure below).

[0005] Another more environmentally friendly green process is condensation polymerization. A commonly used starting material is a carbonate reacting with a diamine, followed by transesterification with a polyol to obtain a condensation-polymerized NIPU. The condensation-polymerized NIPU synthesized by condensation polymerization does not have OH functional side chains, and its structure differs from that of the addition polymerization product PHU. For example, CN 101696271 A, CN 103865059 A, CN 116355210 A, CN 112853531 A, and CN 104513393 B disclose the use of carbonate and diamine to first prepare a diurethane diol monomer (a type of diurethane), which is then polymerized with a polyol to obtain NIPU suitable for direct melt processing. However, the preparation of the diurethane diol monomer requires recrystallization purification using organic solvents, resulting in a large amount of waste liquid. The process is energy-intensive and environmentally unfriendly.

[0006] As mentioned above, although there are already green and environmentally friendly processes for preparing NIPU, the industry hopes to process green and environmentally friendly NIPU into fibers. It is worth noting that because the molecular structure of condensation-polymerized NIPU is linear, its molecular entanglement is insufficient (poor cohesion), leading to easy filament breakage or poor yarn uniformity during spinning, thus affecting the fiber's physical properties. For example, CN112853531A discloses a non-isocyanate method for preparing aliphatic polyurethane. This technology uses chain extenders to increase the molecular weight of NIPU to enable smooth spinning. However, in addition to considering molecular weight, the influence of molecular cohesion on the die swell ratio during high-temperature melt spinning also needs to be considered. Simply increasing the molecular weight cannot effectively control the die swell ratio, and filament breakage still occurs during spinning. Summary of the Invention

[0007] Therefore, the object of the present invention is to provide a condensation polyurethane fiber that can overcome the disadvantages of the prior art.

[0008] Therefore, the present invention provides a condensation polyurethane fiber comprising a condensation polyurethane resin, wherein the condensation polyurethane resin comprises: a plurality of first segments having a structure as shown in chemical formula (1): Chemical formula (1); and a plurality of terminal groups, which are R2-bonded to at least one of the first segments, and the terminal groups have the structure shown in chemical formula (2): Chemical formula (2); wherein R1 and R3 are independently composed of a first organic group from C2 to C20, and the first organic group includes a hydrocarbon group or a group containing carbon, hydrogen and oxygen, wherein the first segments have the same or different R2, which are independently composed of a second organic group from C2 to C20, and the second organic group includes a hydrocarbon group or a group containing carbon, hydrogen and oxygen, wherein the condensation polyurethane resin has an amine value of not less than 10 meq / kg; and the coefficient of variation (CV value) of the condensation polyurethane fiber is not higher than 6.

[0009] The advantages of this invention are: by using the polycondensation polyurethane resin proposed in this case, without the need to add chain extenders, polycondensation polyurethane fibers can be smoothly processed by melt spinning, and polycondensation polyurethane fibers with good fiber uniformity can be obtained. Simple Explanation of the Diagram

[0010] none. Implementation

[0011] The present invention will now be described in detail.

[0012] The condensation-type polyurethane fiber of the present invention comprises a condensation-type polyurethane resin, wherein the condensation-type polyurethane resin comprises: a plurality of first segments having a structure as shown in chemical formula (1): Chemical formula (1); and a plurality of terminal groups, which are R2-bonded to at least one of the first segments, and the terminal groups have the structure shown in chemical formula (2): Chemical formula (2); wherein R1 and R3 are independently composed of a first organic group from C2 to C20, and the first organic group includes a hydrocarbon group or a group containing carbon, hydrogen and oxygen, wherein the first segments have the same or different R2, which are independently composed of a second organic group from C2 to C20, and the second organic group includes a hydrocarbon group or a group containing carbon, hydrogen and oxygen, wherein the condensation polyurethane resin has an amine value of not less than 10 meq / kg; and the coefficient of variation (CV value) of the condensation polyurethane fiber is not higher than 6.

[0013] Preferably, the hydrocarbon group refers to a group composed of carbon and hydrogen atoms, which can be alkyl, alkenyl, alkynyl, aromatic, etc.

[0014] Preferably, R1 and R3 each independently comprise a cyclic hydrocarbon group, an acyclic hydrocarbon group, or a combination thereof. The cyclic hydrocarbon group may be an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. More preferably, R1 and R3 independently comprise... , , One or a combination thereof, wherein n2 is 2 to 10 and n3 is 1 to 10.

[0015] Preferably, R2 includes , , , One or a combination thereof, wherein R21 and R22 are each C2~C20 hydrocarbon groups, and m is 1~250 for each.

[0016] Preferably, R2 is selected from , , , , , , , , One or a combination thereof, wherein n1 is 2 to 20 and m is 1 to 250. More preferably, m is 2 to 100.

[0017] Preferably, the amine value of the condensation polyurethane resin is in the range of 10~45 meq / kg.

[0018] Preferably, the condensation-type polyurethane resin also contains compounds containing urea groups.

[0019] Preferably, the total amount of the condensation-type polyurethane resin is 100 mol%, and the content of the urea-containing compound ranges from no more than 30 mol. More preferably, the content of the urea-containing compound ranges from 6 to 30 mol.

[0020] Preferably, the number average molecular weight (Mn) of the condensation-polymerized polyurethane resin is in the range of 1,000 to 300,000. More preferably, it is 10,000 to 200,000. Most preferably, it is 20,000 to 150,000.

[0021] The polycondensation-type polyurethane resin of the present invention as described above can be prepared by the following method, for example, comprising reacting a diamine compound as shown in Formula 3 with a carbonate compound to form a urethane mixture, the urethane mixture comprising an aminohydrocarbamate (a monourethane) and a hydrocarbon dicarbamate diester (a diurethane); and further reacting the urethane mixture with a diol compound as shown in Formula 4 to undergo an urethane exchange polycondensation reaction to form the polycondensation-type polyurethane resin. [Chemical Formula 3] H2N-R1-NH2 [Chemical Formula 4] HO-R2-H

[0022] In chemical formulas 3 and 4, R1 is a C2~C20 hydrocarbon group.

[0023] Preferably, R1 is selected from , , One or a combination thereof, wherein n2 is 2 to 10 and n3 is 1 to 10.

[0024] Preferably, R2 is selected from , , , One or a combination thereof, wherein R21 and R22 are each C2~C20 hydrocarbon groups, and m is 1~250 for each.

[0025] Preferably, R2 is selected from , , , , , , , , One or a combination thereof, wherein n1 is 2 to 20 and m is 1 to 250. More preferably, m is 2 to 100.

[0026] Preferably, the temperature range for the urethane esterification reaction is 30°C to 120°C, and the temperature range for the urethane exchange polycondensation reaction is 100°C to 200°C.

[0027] Preferably, the pressure of the urethane esterification reaction is about 760 torr, and the pressure of the urethane exchange polycondensation reaction is not higher than 30 torr.

[0028] Preferably, the molar ratio of the diamine compound to the carbonate compound is 1:2 to 1:10, and the molar ratio of the hydrocarbon dicarboxylate to the diol compound in the carbamate mixture is 1:0.01 to 1:2. More preferably, it is 1:0.2 to 1:1.

[0029] Preferably, the diamine compound is selected from cyclic diamines, acyclic diamines, or mixtures thereof. Alternatively, the diamine compound is selected from pentamethylenediamine, hexamethylenediamine, decanediamine, m-phenylenediamine, 1,3-bis(aminomethyl)cyclohexane, or mixtures thereof.

[0030] Preferably, the diol compound is selected from cyclic diols, acyclic diols, or mixtures thereof. More preferably, the diol compound is selected from ether diols (e.g., polyalkyl diols), ester diols (e.g., polyester diols), carbonate diols (e.g., polycarbonate diols), or alkylene diols. Alternatively, the diol compound is selected from polyethylene glycol (PEG), poly(tetramethylene ether) glycol (PTMEG), polypropylene glycol (PPG), polyethylene glycol-co-polypropylene glycol (PEG-co-PPG), polybutylene adipate (PBA), polyhexamethylene adipate (PHA), polyethylene adipate (PEA), polybutylene succinate (PBS), poly(ε-caprolactone) (PCL), bis(2-hydroxyethyl) terephthalate (BHET) oligomers, and poly(hexamethylene carbonate) glycol (PHC). The following are listed as one or a mixture thereof: diol, polyvinyl carbonate (PEC), polypropylene carbonate (PPC), ethylene glycol (EG), propylene glycol (PG), butanediol (BDO), neopentyl glycol (NPG), 2-methyl-1,3-propanediol (MPDO), diethylene glycol (DEG), triethylene glycol (TEG), bis(2-hydroxyethyl) terephthalate (BHET), 1,4-cyclohexanediol, isosorbide (ISOS), 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD).

[0031] Preferably, the number average molecular weight (Mn) of the diol compound is in the range of 60 to 10,000. More preferably, the Mn of the diol compound is in the range of 60 to 6,000.

[0032] Preferably, the diol compound is selected from a combination of at least two of the diols mentioned above.

[0033] Preferably, the carbonate compound is sourced from biomass, petroleum, recycled sources or carbon dioxide sources.

[0034] Preferably, the carbonate compound is obtained by reacting carbon dioxide with an epoxy compound.

[0035] Preferably, the carbonate compound is obtained by reacting carbon dioxide, an epoxy compound, and a diol.

[0036] Preferably, the carbonate compound is selected from cyclic carbonates, non-cyclic carbonates, polycarbonates, or mixtures thereof.

[0037] Alternatively, the cyclic carbonate is selected from ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, or mixtures thereof.

[0038] Alternatively, the acyclic carbonate is selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), diphenyl carbonate (DPC), substituted acyclic carbonates, or mixtures thereof. The substituted acyclic carbonate may be di(diethylene glycol) carbonate (DEGC).

[0039] Alternatively, the polycarbonate may be selected from polycarbonate diol, poly(ethylene carbonate), PEC, poly(propylene carbonate), PPC, or mixtures thereof.

[0040] Preferably, the amine value of the carbamate mixture is in the range of not less than 10 meq / kg. More preferably, the amine value of the carbamate mixture is in the range of 10 to 100 meq / kg.

[0041] Preferably, the carbonate compound is ethylene carbonate, and the carbamate mixture comprises di(2-hydroxyethyl) hydrocarbamate (a diamino ester) and 2-hydroxyethyl (aminohydrocarbyl)carbamate (a monoamino ester).

[0042] Preferably, the carbonate compound is dimethyl carbonate, and the carbamate mixture comprises methyl (aminohydrocarbyl)carbamate (a monoamino ester) and dimethyl hydrocarbyl carbamate (a diamino ester).

[0043] Preferably, the carbamate mixture is not purified prior to the transurethral polycondensation reaction. Preferably, the carbamate mixture is not recrystallized prior to the transurethral polycondensation reaction.

[0044] Preferably, the preparation method involves a urethane exchange polycondensation reaction in the presence of a catalyst to form the polycondensation-type polyurethane resin. Preferably, the catalyst is selected from dibutyltin oxide, tin oxide, stannous chloride, zinc oxide, zinc acetate, zinc chloride, aluminum acetate, magnesium acetate, aluminum chloride, tetrabutyl titanate, tetraisopropyl titanate, or mixtures thereof. More preferably, the total weight of the urethane mixture, the diol compound, and the catalyst is 100 wt%, and the weight proportion of the catalyst ranges from 0.0001 to 1 wt%.

[0045] The polycondensation-type polyurethane resin of the present invention can be spun using a conventional melt spinning process (without the need for additional solvents). For example, the polyurethane resin is melt-extruded by a screw extruder, then precisely metered by a metering pump, and fed into a spinning element. It is then ejected through a spinning die to form a filament bundle, which is then cooled, bundled, stretched, and wound to obtain the polycondensation-type polyurethane elastic fiber.

[0046] Preferably, the melt temperature of the screw extruder is 130~150℃ and the spinning speed is 50~2000 m / min.

[0047] Preferably, the die expansion ratio of the spinning die is 1.1 to 1.7. More preferably, it is 1.2 to 1.5.

[0048] The morphology of the polyurethane condensation fiber of the present invention is not limited, such as monofilament, multifilament, staple fiber, elastic fiber, sheath-core fiber, side-by-side fiber, and sea-island fiber.

[0049] Preferably, the denier number of the condensation-type polyurethane elastic fiber of the present invention is 1 to 200 denier.

[0050] Preferably, the coefficient of variation (CV value) of the polycondensation-type polyurethane fiber is not higher than 6, and more preferably, it is 2 to 6.

[0051] The condensation-polymerized polyurethane fiber of this invention can be further applied to the production of various fabrics, such as woven fabrics, knitted fabrics, non-woven fabrics, etc. Furthermore, it can be applied to the production of sportswear, such as yoga wear.

[0052] The present invention will be further described with reference to the following embodiments, but it should be understood that these embodiments are for illustrative purposes only and should not be construed as limiting the implementation of the present invention.

[0053] [[] [Condensation Polyurethane Resin] []]

[0054] [Example] [1 (E1)] [>]

[0055] In a 1 L stainless steel reactor, 1,6-hexanediamine (HMDA, purchased from Huafeng Chemical) (as a diamine compound), ethylene carbonate (EC, purchased from Donglian Chemical) (as a carbonate compound), and polyethylene glycol 1000 (PEG1000, purchased from Donglian Chemical) (as a glycol compound) were mixed in a molar ratio of 1:2.1:0.26 and subjected to a carbamate esterification reaction at 75 °C with stirring for 5 h to obtain the carbamate mixture of Example 1 (containing 2-hydroxyethyl aminohexylcarbamate, di-2-hydroxyethyl hexanedicarbamate, and PEG1000; the amine value of the carbamate mixture of E1 was measured to be 61.6 meq / kg using ASTM D2074).

[0056] SnCl2 (as a catalyst) was added to the reactor described above, and an urethane exchange polycondensation reaction was carried out at 180°C and a pressure below 30 torr for 1 h. Subsequently, the pressure was reduced to 3 torr until the viscosity of the product no longer increased, so as to obtain the polycondensation type polyurethane resin of Example 1, which has a number average molecular weight (Mn) of 48,000.

[0057] [Example] [2 (E2)] [>]

[0058] The preparation of the condensation polyurethane resin in Example 2 was similar to that in Example 1, except that PEG1000 was replaced with poly(tetramethylene ether) glycol 1000 (PTMEG1000, purchased from Formosa Plastics Group). HMDA, EC, and PTMEG1000 were mixed in a molar ratio of 1:2.1:0.26 (the amine value of the urethane mixture of E2 was 49.8 meq / kg) to obtain the condensation polyurethane resin of E2 with a Mn of 50,000.

[0059] [Example] [3 (E3)] [>]

[0060] The preparation of the condensation polyurethane resin in Example 3 was similar to that in Example 1, except that PEG1000 was replaced with polybutylene adipate 1000 (PBA1000, purchased from Risheng Chemical), and HMDA, EC, and PBA1000 were mixed in a molar ratio of 1:2.1:0.26 (the amine value of the E3 urethane mixture was 48.1 meq / kg) to obtain the E3 condensation polyurethane resin with a Mn of 51,000.

[0061] [Example] [4 (E4)] [>]

[0062] The preparation of the condensation polyurethane resin in Example 4 was similar to that in Example 1, except that PEG1000 was replaced with poly(ε-caprolactone) 2000 (PCL2000, purchased from Huafeng Chemical), and HMDA, EC, and PCL2000 were mixed in a molar ratio of 1:2.1:0.13 (the amine value of the E4 urethane mixture was 75.2 meq / kg) to obtain the E4 condensation polyurethane resin with a Mn of 49,000.

[0063] [Example] [5 (E5)] [>]

[0064] The preparation of the condensation polyurethane resin in Example 5 was similar to that in Example 1, except that PEG1000 was replaced with poly(hexamethylene carbonate) diol 1000 (PHC diol 1000, purchased from Tosoh Corporation, Japan, model Nippollan 981), and HMDA, EC, and PHC diol 1000 were mixed in a molar ratio of 1:2.1:0.26 (the amine value of the E5 urethane mixture was 10.6 meq / kg) to obtain the E5 condensation polyurethane resin with a Mn of 101,000.

[0065] [Example] [6 (E6)] [>]

[0066] The preparation of the condensation polyurethane resin in Example 6 was similar to that in Example 5, except that EC was replaced with dimethyl carbonate (DMC, purchased from DiYi Chemical) and PHC diol 1000 was replaced with PTMEG 1000. HMDA, DMC, and PTMEG 1000 were mixed in a molar ratio of 1:10:1 (the amine value of the urethane mixture of E6 was 55.1 meq / kg). After adding SnCl2, the mixture was refluxed at 85°C for 16 h, and then subjected to urethane exchange polycondensation to obtain the condensation polyurethane resin of E6 with a Mn of 44,000.

[0067] [Example] [7 (E7)] [>]

[0068] The preparation of the condensation polyurethane resin in Example 7 was similar to that in Example 5, except that EC was replaced with diphenyl carbonate (DPC, purchased from Tei-Yi Chemical), and HMDA, DPC, and PHC diol 1000 were mixed in a molar ratio of 1:4:1 (the amine value of the urethane mixture of E7 was 15.3 meq / kg) to obtain the condensation polyurethane resin of E7 with a Mn of 41,000.

[0069] [Example] [8 (E8)] [>]

[0070] The preparation of the condensation polyurethane resin in Example 8 was similar to that in Example 5, except that EC was replaced with di(diethylene glycol) carbonate [DEGC, purchased from Donglian Chemical], and HMDA, DEGC, and PHC diol 1000 were mixed in a molar ratio of 1:4:1 (the amine value of the carbamate mixture of E8 was 32.3 meq / kg) to obtain the condensation polyurethane resin of E8 with a Mn of 46,000.

[0071] < [Example] [9 (E9)] [>]

[0072] The preparation of the condensation polyurethane resin in Example 9 was similar to that in Example 5, except that HMDA was replaced with m-phenylenediamine (MXDA, purchased from Mitsubishi Chemical), and MXDA, EC, and PHC diol 1000 were mixed in a molar ratio of 1:2.1:0.26 (the amine value of the urethane mixture of E9 was 49.6 meq / kg) to obtain the condensation polyurethane resin of E9 with a Mn of 81,000.

[0073] [Example] [10 (E10)] [>]

[0074] The preparation of the condensation polyurethane resin in Example 10 was similar to that in Example 5, except that HMDA was replaced with 1,3-bis(aminomethyl)cyclohexane (1,3-BAC, purchased from Mitsubishi Chemical), and 1,3-BAC, EC, and PHC diol 1000 were mixed in a molar ratio of 1:2.1:0.26 (the amine value of the E10 urethane mixture was 50.9 meq / kg) to obtain the E10 condensation polyurethane resin with a Mn of 94,000.

[0075] [Example] [11 (E11)] [>]

[0076] The preparation of the condensation polyurethane resin in Example 11 was similar to that in Example 5, except that HMDA was replaced with decanediamine (DMDA, purchased from Mitsubishi Chemical), and DMDA, EC, and PHC diol 1000 were mixed in a molar ratio of 1:2.1:0.26 (the amine value of the urethane mixture of E11 was 25.1 meq / kg) to obtain the condensation polyurethane resin of E11 with a Mn of 76,000.

[0077] [Example] [12 (E12)] [>]

[0078] The preparation of the condensation polyurethane resin in Example 12 was similar to that in Example 1, except that PEG1000 was replaced with PEG2000 (purchased from Donglian Chemical), and HMDA, EC, and PEG2000 were mixed in a molar ratio of 1:2.1:0.26 (the amine value of the urethane mixture of E12 was 11.2 meq / kg) to obtain the condensation polyurethane resin of E12 with a Mn of 89,300.

[0079] [Example] [13 (E13)] [>]

[0080] The preparation of the condensation polyurethane resin in Example 13 was similar to that in Example 12, except that PEG2000 was replaced with PEG2000 and PTMEG1000 (purchased from Formosa Plastics Elastic Fiber), and HMDA, EC, PEG2000:PTMEG1000 were mixed in a molar ratio of 1:2.1:0.13:0.13 (the amine value of the urethane mixture of E13 was 12.1 meq / kg) to obtain the condensation polyurethane resin of E13 with a Mn of 83,000.

[0081] [Example] [14 (E14)] [>]

[0082] The preparation of the condensation polyurethane resin in Example 14 was similar to that in Example 12, except that PEG2000 was replaced with PEG2000 and 1,2-propylene glycol (purchased from Tei-Yi Chemical), and HMDA, EC, 1,2-propylene glycol:PEG2000 were mixed in a molar ratio of 1:2.1:0.13:0.13 (the amine value of the urethane mixture of E14 was 12.1 meq / kg) to obtain the condensation polyurethane resin of E14 with a Mn of 35,000.

[0083] [Example] [15 (E15)] [>]

[0084] The preparation of the condensation polyurethane resin in Example 15 was similar to that in Example 12, except that PEG2000 was replaced with PEG2000 and neopentyl glycol (purchased from Tei-Yi Chemical), and HMDA, EC, neopentyl glycol:PEG2000 were mixed in a molar ratio of 1:2.1:0.13:0.13 (the amine value of the urethane mixture of E15 was 12.1 meq / kg) to obtain the condensation polyurethane resin of E15 with a Mn of 124,000.

[0085] [Example] [16 (E16)] [>]

[0086] The preparation of the condensation polyurethane resin in Example 16 was similar to that in Example 12, except that PEG2000 was replaced with PEG2000 and PPG1000 (purchased from Donglian Chemical), and HMDA, EC, PPG1000:PEG2000 were mixed in a molar ratio of 1:2.1:0.13:0.13 (the amine value of the urethane mixture of E16 was 12.1 meq / kg) to obtain the condensation polyurethane resin of E16 with a Mn of 37,000.

[0087] [Example] [17 (E17)] [>]

[0088] The preparation of the condensation polyurethane resin in Example 17 was similar to that in Example 12, except that PEG2000 was replaced with PEG2000 and BHET (purchased from Shuye Environmental Protection), and HMDA, EC, BHET:PEG2000 were mixed in a molar ratio of 1:2.1:0.13:0.13 (the amine value of the urethane mixture of E17 was 12.1 meq / kg) to obtain the condensation polyurethane resin of E17 with a Mn of 131,000.

[0089] [Comparative Example] [1 (CE1)] [>]

[0090] The preparation of the condensation polyurethane resin in Comparative Example 1 was similar to that in Example 1, except that HMDA, EC, and PEG1000 were subjected to a urethane esterification reaction at 130°C for 5 h (the amine value of the urethane esterification product was measured to be 375.6 meq / kg using ASTM D2074), followed by an urethane exchange condensation reaction to obtain the condensation polyurethane resin CE1 with a Mn of 25,000.

[0091] [Comparative Example] [2 (CE2)] [>]

[0092] In a 1 L stainless steel reactor, HMDA and EC were mixed at a molar ratio of 1:2.1 and subjected to a carbamate esterification reaction at 75 °C for 5 h to obtain the carbamate mixture of Comparative Example 2. The obtained carbamate mixture was washed, filtered, and recrystallized to obtain an intermediate product of di-2-hydroxyethyl hexamethylenedicarbamate (solid) (the amine value of the intermediate product was measured to be 1.8 meq / kg using ASTM D2074). Subsequently, the above intermediate product was mixed with PEG1000 at a molar ratio of 1:0.26 and subjected to a urethane exchange polycondensation reaction using the same preparation steps as in Example 1 to obtain a condensation-type polyurethane resin of CE2 with a Mn of 210,000.

[0093] [Comparative Example] [3 (CE3)] [>]

[0094] The polyurethane resin in Comparative Example 3 was TPU granules (model ER-80AML) purchased from Kao Ding Precision Materials [prepared by reacting PBA with diphenylmethane diisocyanate (MDI)], with a Mn of 130,000.

[0095] [Comparative Example] [4 (CE4)] [>]

[0096] The polyurethane resin in Comparative Example 4 was TPU granules (model BE-5038E) purchased from Kao Ding Precision Materials (prepared by reacting PTMEG and MDI), with a Mn of 170,000.

[0097] [Comparative Example] [5 (CE5)] [>]

[0098] The polyurethane resin in Comparative Example 5 was TPU granules (model WHTA9011) purchased from Wanhua Chemical [obtained by reacting PCL with hexamethylene diisocyanate (HMDI)], with a Mn of 200,000.

[0099] [Comparative Example] [6 (CE6)] [>]

[0100] The preparation of the condensation-type polyurethane resin in Comparative Example 6 was similar to that in Example 6, except that hexamethylene dicarboxylate was used, along with PTMEG1000 and 1,6-hexanediol (HDO, purchased from Teiichi Chemical). The molar ratio of hexamethylene dicarboxylate, HDO, and PTMEG1000 was 1:0.6:0.4. The polyurethane exchange condensation reaction was carried out at 100°C and a pressure below 600 torr for 2 h, followed by a polyurethane exchange condensation reaction at 260°C and a pressure below 150 torr for 4 h to obtain the condensation-type polyurethane resin of Comparative Example 6, with a Mn of 116,000.

[0101] [[] [Condensation Polyurethane Fiber] []]

[0102] Spinning was performed using a USTER® Tensorapid spinning machine. The polyurethane resins of Examples 1-17 and Comparative Examples 1-6 were melted and extruded through a screw extruder, then precisely metered by a metering pump and fed into the spinning element. The resins were then extruded through a spinneret to form filament bundles, which were subsequently cooled, bundled, stretched, and wound to obtain the polyurethane elastic fibers. The melt temperature of the screw extruder was 150°C, and the spinning speed was 200 m / min. The die sizing ratio and fiber denier number in the spinning process can be found in Table 1.

[0103] [[] [Amine Value Measurement] []]

[0104] The amine values ​​of the condensation polyurethane resin, polyurethane resin, urethane mixture and intermediate product of Examples 1-17 and Comparative Examples 1-6 were measured using ASTM D2074, and the results are shown in Table 1 below.

[0105] [[] [Polyurethane molecular weight] []]

[0106] The number average molecular weight (Mn) of the condensation polyurethane resins of Examples 1-17 and Comparative Examples 1-6 was measured using ASTM D3536, and the results are shown in Table 1 below.

[0107] [[] [Urea bond content in condensation polyurethane] []]

[0108] The nuclear magnetic resonance spectra of the polyurethane resins of Examples 1-17 and Comparative Examples 1-6 were measured by 1H NMR (DMSO-d6). The integral area (A1) with a chemical shift (δ) between 5.6 and 5.8 ppm and the integral area (A2) with a chemical shift between 6.7 and 7.3 ppm were calculated. The urea-containing segment content (mol%) of the polyurethane resin was defined as [A1 / (A1+A2)]×100%. The results are shown in Table 1.

[0109] [[] [Spinning process die swell ratio] []]

[0110] The die swell ratio is defined as: the diameter of the extruder after exiting the spinning die (D, extrudate) / the diameter of the spinning die (D, die).

[0111] [[] [Fiber Variation Coefficient] []]

[0112] The coefficient of variation (CV) is used to measure fiber uniformity, and its formula is as follows: Wherein, the standard deviation (σ) is the dispersion of the fiber denier; the mean (μ) is the average denier of the fiber. Take ten fibers and calculate their average denier. [Table 1] Amine value of polyurethane resin (meq / kg) Urea content (mol%) spinning process Diode swell ratio fiber Coefficient of variation (CV) fiber Dani number Denier E1 31.3 29.7 1.1 1.9 151 E2 22.4 23.5 1.2 2.6 110 E3 28.8 26.3 1.1 1.3 211 E4 26.9 25.1 1.1 3.4 105 E5 14.6 18.5 1.2 4.2 twenty one E6 22.9 23.7 1.1 3.2 106 E7 18.5 20.6 1.3 4.9 99 E8 19.7 21.3 1.2 3.7 89 E9 12.4 16.4 1.4 5.1 74 E10 10.6 7.9 1.4 5.2 71 E11 15.6 19.2 1.5 5.3 74 E12 11.2 10.1 1.4 5.2 72 E13 12.1 8.7 1.4 5.1 101 E14 23.8 24.3 1.1 3.5 104 E15 22.4 23.1 1.2 3.6 103 E16 12.6 19.5 1.4 5.4 79 E17 21.5 22.9 1.1 3.7 101 CE1 45.2 32.1 1.0 6.2 73 CE2 6.4 5.6 2.2 7.9 104 CE3 5.3 1.3 2.0 6.8 114 CE4 6.5 2.4 2.1 7.3 128 CE5 5.3 1.7 2.2 7.6 107 CE6 8.6 4.5 1.9 6.6 93

[0113] As shown in Table 1, the amine values ​​of the condensation-type polyurethane resins in Examples 1-17 ranged from 10.6 to 31.3 meq / kg, exhibiting appropriate hydrogen bond cohesion. Their spinning expansion ratio was controlled between 1.1 and 1.5, and the coefficient of variation of the resulting fibers was all below 6. In contrast, the amine value of the resin in Comparative Example 1 was 45.2 meq / kg, and its spinning expansion ratio was 1, resulting in necking and easy fiber breakage. Furthermore, the coefficient of variation of the spun fibers was greater than 6. The amine value of the resin in Comparative Example 2 was 5.6. The amine value of the polyurethane resin is 2.2, and the sizing ratio during spinning is 2.2. In addition, Comparative Examples 3 to 5 are polyurethanes made from isocyanate. Because isocyanate reacts very quickly, its amine value is low, only 5.3 to 6.5 meq / kg. The amine value of the polyurethanes in Comparative Examples 2 and 3 to 5 is all below 10 meq / kg, and the sizing ratio is greater than 1.7, resulting in poor spinning stability and a fiber variation coefficient greater than 6. It can be seen that the amine value of polyurethane resin will affect the sizing ratio during spinning, and thus affect the fiber variation coefficient after spinning.

[0114] Comparative Example 2 is similar to CN 104513393 B. As shown in Table 2, the amine value of the purified condensation polyurethane resin in Comparative Example 2 is lower than that in Example 2, at only 6.4 meq / kg. Specifically, since Comparative Example 2 removed impurities through recrystallization purification, the purified intermediate product consisted only of diurethane. However, Example 2 in this case did not undergo purification and directly carried out the next polymerization step with the intermediate product. Therefore, the intermediate product of Example 2 in this case is a mixture of urethanes, including diurethane and monourethane, which is different from the reactants in the urethane exchange condensation reaction of Comparative Example 2. After polymerization, the amine value of the product in Comparative Example 2 was too low, which affected the spinning die expansion ratio, and the coefficient of variation of the obtained fiber was 7.9 (poor). The differences in the condensation polyurethane resin processing of Comparative Example 2 and Example 2 are shown in Table 2. [Table 2] Amine value of polyurethane resin (meq / kg) spinning process Diode swell ratio fiber Coefficient of variation (CV) Denier fiber number E2 22.4 1.2 2.6 110 CE2 6.4 2.2 7.9 104

[0115] Comparative Example 6 is similar to CN112853531A. As can be seen from Table 3, the amine value of the condensation-type polyurethane resin in Comparative Example 6 is lower than that in Example 6, at only 8.6 meq / kg (amine value is too low), and the fiber coefficient of variation is 6.6 (relatively high). Specifically, since Comparative Example 6 increased its molecular weight by adding a chain extender (1,6-hexanediol), its amine value was too low, the mold expansion ratio was 1.9, and the coefficient of variation of the resulting fiber was 6.6 (poor). [Table 3] Amine value of polyurethane resin (meq / kg) spinning process Diode swell ratio fiber Coefficient of variation (CV) fiber Dani number Denier E6 22.9 1.1 3.2 106 CE6 8.6 1.9 6.6 93

[0116] In summary, the polycondensation-type polyurethane resin of the present invention has an amine value of not less than 10 meq / kg, can be successfully melt-spun, and the resulting polyurethane fibers have a coefficient of variation of not more than 6, thus effectively achieving the purpose of the present invention.

[0117] However, the above description is merely an embodiment of the present invention and should not be construed as limiting the scope of the present invention. Any simple equivalent changes and modifications made in accordance with the scope of the patent application and the contents of the patent specification shall still fall within the scope of the patent of the present invention.

[0118] none

[0119] Domestic storage information (please note in order of storage institution, date, and number) none Overseas storage information (please note in the order of storage country, institution, date, and number) none

Claims

1. A condensation polyurethane fiber comprising a condensation polyurethane resin, wherein the condensation polyurethane resin comprises: a plurality of first segments having a structure as shown in chemical formula (1): Chemical formula (1); a urea-containing segment comprising 100 mol% of the total amount of the condensation polyurethane resin, wherein the content of the urea-containing segment is not greater than 30 mol%; and a plurality of terminal groups having R2 bonds to at least one of the first segments, wherein the terminal groups have a structure as shown in chemical formula (2): Chemical formula (2); wherein R1 and R3 are independently each comprising a first organic group from C2 to C20, and the first organic group comprises a hydrocarbon group or a group containing carbon, hydrogen and oxygen, wherein, These first segments have the same or different R2, each independently containing a second organic group from C2 to C20, and the second organic group contains a hydrocarbon group or a group containing carbon, hydrogen and oxygen, wherein the condensation polyurethane resin has an amine value of not less than 10 meq / kg; and the coefficient of variation (CV value) of the condensation polyurethane fiber is not higher than 6.

2. The condensation polyurethane fiber as claimed in claim 1, wherein R1 and R3 independently comprise, , or combinations thereof, wherein, n2 is 2~10 for each, and n3 is 1~10 for each.

3. The condensation-type polyurethane fiber as claimed in claim 1, wherein R2 is selected from, one of, or a combination thereof, wherein, R21 and R22 are each independently C2~C20 hydrocarbon groups, and m is 1~250 for each.

4. The condensation polyurethane fiber as claimed in claim 1, wherein R2 is selected from one or a combination of , ... n1 is 2~20 for each, and m is 1~250 for each.

5. The polycondensation polyurethane fiber as claimed in claim 1, wherein the monoamine valence of the polycondensation polyurethane fiber is in the range of 10 to 45 meq / kg.

6. The polycondensation polyurethane fiber as claimed in claim 1, wherein the monoamine valence of the polycondensation polyurethane fiber is in the range of 20 to 45 meq / kg.

7. The polycondensation polyurethane fiber as claimed in claim 1, wherein the coefficient of variation (CV value) of the polycondensation polyurethane fiber is 2 to 6.

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