High-elasticity polyoxamide, its preparation method and application
By using polyether chains and oxamide structures to prepare highly elastic polyoxamide, the problem of highly toxic diisocyanate compounds in the preparation of spandex fibers has been solved, realizing the safe preparation and high-performance application of highly elastic fibers.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2023-05-12
- Publication Date
- 2026-06-30
AI Technical Summary
In the existing technology, the preparation process of spandex fiber uses highly toxic diisocyanate compounds, and the production is highly dangerous, making it difficult to achieve the safe preparation of high elastic fiber.
Highly elastic polyoxamyl is prepared by using polyether chains to provide soft segments and oxalamide structures to provide hard segments, through the reaction of oxalic acid and/or oxalate diesters with diamines, avoiding the use of highly toxic diisocyanate compounds, and utilizing the intermolecular hydrogen bonds and rigid six-membered rings in the oxalamide structure to form a highly elastic polymer.
The prepared high-elasticity polyoxamate has high elastic recovery rate, elongation at break and tensile strength, and the production process is safe and non-toxic, with high elastic recovery rate when applied to fibers.
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Figure CN118930849B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of chemical materials and relates to a highly elastic polyoxamid, its preparation method and application. Background Technology
[0002] Elastic fibers are generally linear block copolymers composed of soft and hard segments. The soft segments are stretchable and are interconnected by the hard segments. The alternation of soft and hard segments is equivalent to forming a series of small springs (such as...). Figure 1 (As shown). In the aggregate structure of multiple molecules in elastic fibers, the soft segments can move freely under stress at room temperature, and the intermolecular forces are very weak. The hard segments form entanglements and cross-links. The soft segments are like springs and can move. It is equivalent to weaving many small springs into a fishing net, which has both stretching and elasticity, and can also be pulled back and contracted by using the hard segments.
[0003] The hard segments in elastic fibers contain various polar groups, are crystalline, and can generate lateral cross-links between macromolecular chains. Under stress, these segments essentially do not deform, thus preventing intermolecular slippage. This provides the necessary node conditions for the significant elongation and resilience of the soft segments and endows the fiber with a certain strength. It is this coexistence of soft and hard segments that leads to the high elasticity of elastomers such as spandex fibers (Wang Jiazhao, Sun Zongxuan, Ji Yongling. Production and Application of Spandex Elastic Yarn, Beijing: Textile Industry Press, 1989).
[0004] To obtain ultra-high elasticity fibers, the soft segments must not easily enter the crystal lattice formed by the hard segments. This means the hard segments must have increased polarity, forming crystals through hydrogen bonds or strong polar bonds, while the soft segments must form an independent system with low polarity. The hard and soft segments are two independent systems that do not interfere with each other. To achieve this, both the hard and soft segments need to be sufficiently expanded, making the hard segments harder and the soft segments softer, each fulfilling its function, resulting in "separation." Since the crystalline and amorphous regions belong to the microstructure of the fiber, this is called "microphase separation." Microphase separation refers to the fact that at room temperature, the hard segment micro-regions are insoluble in the soft segments but are distributed within the soft segments, acting as cross-linking agents, which has a significant impact on the performance of polyurethane products. It is the key to spandex obtaining ultra-high elasticity (Tao Can, Microphase separation structure regulation, properties and applications of polyurethane, Anhui University, 2018; You Gexin, Chen Xiri, Yang Bo, Zhou Xiuwen. Influence of soft segment molecular weight on the degree of microphase separation and tensile properties of spandex, Engineering Plastics Application, 2017.12:88-92). P, Bagdi K, Molnár K, et al. Quantitative mapping of elastic moduli at the nanoscale in phase separated polyurethanes by AFM. European Polymer Journal, 2011, 47(4): 692-698).
[0005] The most widely used elastic fiber in current technology is spandex fiber. The "soft blocks" in the spandex molecular structure mainly come from polyethers, such as poly-1,4-butanediol (PTMEG), poly-1,2-propanediol, and even polyethylene glycol, as well as aliphatic polyesters, such as polybutylene succinate and polycaprolactone. The "hard blocks" in the spandex molecular structure rely on the strong intermolecular hydrogen bonds and rigidity provided by the isocyanate functional groups formed by toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) with alcohols, and the urea functional groups with organic amines.
[0006]
[0007] While diisocyanate compounds can form "hard blocks" in spandex fiber molecules, the raw material diisocyanates are highly toxic and extremely sensitive, reacting strongly with water, amines, and other compounds. Furthermore, the preparation process requires the use of phosgene, a highly toxic compound, making production extremely dangerous. Therefore, there is an urgent need to develop a new type of highly elastic fiber. Summary of the Invention
[0008] To overcome the problems existing in the prior art, the present invention provides a highly elastic polyoxamid, its preparation method and application, wherein the highly elastic polyoxamid is formed by using a polyether chain to provide the "soft segment", an oxamid structure (i.e., obtained by reacting oxalic acid and / or oxalate diester with diamine) and a six-membered rigid ring to provide the "hard segment".
[0009] One objective of this invention is to provide a highly elastic polyoxinamide, the molecular structure of which contains polyether chain structural units and oxinamide structural units as shown in formula (I):
[0010]
[0011] Wherein, R' is a group containing a rigid six-membered ring.
[0012] In this process, the polyether chain is used as a soft segment, and the structural unit shown in formula (I) is used as a hard segment, forming a linear block copolymer composed of soft and hard segments.
[0013] The polyoxaamide described in this invention refers to polyethylene glycolamide obtained by polymerizing oxalic acid and / or oxalate diester with diamines. Due to the presence of two adjacent amide groups in its structure, polyoxaamide exhibits numerous intermolecular hydrogen bonds and extremely high cohesive energy density, resulting in exceptional rigidity, melting point, and solvent resistance. The hydrogen bonding between the functional groups of oxaamide is illustrated below:
[0014]
[0015] The oxamide structural unit of the present invention contains not only the rigid structure of oxamide, but also the rigid structure of R'. That is, the polyoxamide structure of the present invention contains a dioxamide structure formed by a rigid six-membered ring (such as an aromatic diamine or a cyclic dipeptide diamine compound). Compared with the ordinary aliphatic dioxamide structure, the present invention has better polarity and rigidity, and can better play the role of "hard block" in elastic macromolecular chains.
[0016] In a preferred embodiment, R' is a group containing a rigid six-membered ring, wherein the rigid six-membered ring is at least one of a cyclohexane ring, a benzene ring, and a 2,5-diketopiramate ring.
[0017] In a further preferred embodiment, R' is selected from one of the structures shown in formulas (I-1) to (I-6), and preferably from one of the structures shown in formulas (I-1) to (I-4):
[0018]
[0019] In formulas (I-1) to (I-4), R1 to R7 are each independently selected from hydrogen, alkyl or aryl, preferably from hydrogen, C1 to C10 alkyl or C6 to C10 aryl, more preferably from hydrogen or C1 to C6 alkyl; R8 to R9 are each independently selected from alkylene or arylene, preferably from C1 to C10 alkylene or C6 to C10 arylene, more preferably from C1 to C6 alkylene.
[0020] Wherein, C1 to C10 can be C1, C2, C4, C6, C8 or C10, C6 to C10 can be C6, C7, C8, C9 or C10, and C1 to C6 can be C1, C2, C3, C4, C5 or C6.
[0021] In a further preferred embodiment, R' is selected from one of the following structures:
[0022]
[0023] In a further preferred embodiment, R' is selected from one of the following structures:
[0024]
[0025] In a preferred embodiment, the molecular structure of the highly elastic polyoxazone contains repeating structural units as shown in formula (II):
[0026]
[0027] In equation (II), R' has the same definition as in equation (I). This indicates a polyether chain.
[0028] In formula (II), the soft segment is a polyether chain, and the hard segment is shown in the dashed box in the following formula:
[0029]
[0030] If the hard segment structure consists only of The hard segment structure has a small molecular weight, low polarity, rigidity, and weak intermolecular forces. Relying solely on it as a hard segment makes it difficult to form microphase separation within the polyether soft segments of polyetheramines. However, the hard segment structure provided by this invention (as shown in the dashed box in the above formula) uses a rigid structure R' to connect two... The connection forms a new hard segment structure with a large molecular weight, high polarity, rigidity and strong intermolecular forces, which makes it easier to crystallize and can produce lateral cross-linking between macromolecular chains, resulting in higher resilience.
[0031] In a preferred embodiment, the polyether chain is a polyether chain with a molecular weight of 300 to 3000, preferably a polyether chain with a molecular weight of 600 to 2000, such as a polyether chain with a molecular weight of 300, 500, 700, 800, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800 or 3000.
[0032] In a further preferred embodiment, the polyether in the polyether chain is at least one of the following: a homopolymer of polyoxyethylene, polyoxypropylene, and polytetrahydrofuran, a copolymer of two of them, or a copolymer of three of them, for example, at least one of polyoxyethylene, polyoxypropylene, a polyoxyethylene-polyoxypropylene copolymer, or polytetrahydrofuran.
[0033] In a preferred embodiment, the highly elastic polyoxamid is selected from at least one polymer of formula (III):
[0034]
[0035] In equation (III), R' has the same definition as in equation (I). The term represents a polyether chain. In the above formula, n is 2 to 100, for example, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100.
[0036] In this invention, the polyoxamate has soft segments and hard segments, such as... Figure 1 As shown, where, This represents the soft block, i.e., the polyether segment. This represents the hard block, i.e., the oxalamide chain segment, thus forming a linear structure with interlocking soft and hard components, giving the polyoxalamide high elasticity.
[0037] In a preferred embodiment, the highly elastic polyoxamid is prepared from raw materials including polyetheramine, oxalic acid and / or oxalate diester, and small molecule diamine compounds.
[0038] The preparation process does not involve the use of highly toxic diisocyanate compounds.
[0039] The second objective of this invention is to provide a method for preparing highly elastic polyoxazone, preferably for preparing the highly elastic polyoxazone described in the first objective of this invention. The preparation method includes reacting raw materials including polyetheramine, oxalic acid and / or oxalate diester, and a small molecule diamine compound.
[0040] In a preferred embodiment, the polyetheramine has a molecular weight of 300 to 3000, preferably 600 to 2000, for example 300, 500, 800, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800 or 3000.
[0041] In a further preferred embodiment, the polyetheramine is a polyetheramine with terminal dual functionality, wherein the polyether is at least one of the homopolymers, copolymers of two or three of polyoxyethylene, polyoxypropylene, and polytetrahydrofuran, for example, at least one of polyoxyethylene, polyoxypropylene, polyoxyethylene-polyoxypropylene copolymer, or polytetrahydrofuran.
[0042] In a further preferred embodiment, the polyetheramine may be: CAED-600, CAED-900, CAD-2000, or CAED-2003 produced by Yangzhou Chenhua New Materials Co., Ltd., or produced by Huntsman Corporation. D-230 D-400 D-2000 D-4000 ED-600 ED-900 ED-2003 refers to at least one of MA-223, MA-240, MA-2200, and MA-2203ED from Akoli Technology Co., Ltd.
[0043] In a preferred embodiment, the oxalate diester is selected from dialkyl oxalates, preferably from at least one of diethyl oxalate, dimethyl oxalate, dipropyl oxalate, dibutyl oxalate, and diisopropyl oxalate.
[0044] In a preferred embodiment, the small molecule diamine compound is selected from at least one of NH2-R'-NH2, wherein R' is a group containing a rigid six-membered ring.
[0045] In this process, the rigid group R' in the small molecule diamine compound can combine with oxalamide to form a hard segment. If the preparation process does not use a small molecule diamine compound with a rigid structure, or if the small molecule diamine compound is an aliphatic diamine, then the hard segment is entirely provided by oxalamide. In this case, the hard segment structure is small and the rigidity is also small, and it cannot perform "microphase separation" well in the polyether segment-soft segment "soft block", and cannot provide enough "crosslinking points".
[0046] In a further preferred embodiment, R' is selected from one of the structures shown in formulas (I-1) to (I-6), and preferably from one of the structures shown in formulas (I-1) to (I-4):
[0047]
[0048] In formulas (I-1) to (I-4), R1 to R7 are each independently selected from hydrogen, alkyl or aryl, preferably from hydrogen, C1 to C10 alkyl or C6 to C10 aryl, more preferably from hydrogen or C1 to C6 alkyl; R8 to R9 are each independently selected from alkylene or arylene, preferably from C1 to C10 alkylene or C6 to C10 arylene, more preferably from C1 to C6 alkylene.
[0049] Wherein, C1 to C10 can be C1, C2, C4, C6, C8 or C10, C6 to C10 can be C6, C7, C8, C9 or C10, and C1 to C6 can be C1, C2, C3, C4, C5 or C6.
[0050] Preferably, R' is selected from one of the following structures:
[0051]
[0052] In a further preferred embodiment, the small molecule diamine compound is selected from at least one of p-phenylenediamine, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylmethane, lysine cyclic dipeptide (also known as: 6-bis(4-aminobutyl)piperazine-2,5-dione), 4,4'-biphenyldiamine, 1,3-cyclohexanedimethylamine, and 1,4-cyclohexanedimethylamine.
[0053] The structures of the above-mentioned small molecule diamine compounds are as follows:
[0054]
[0055] In a preferred embodiment, the preparation method includes: (1) mixing polyetheramine, oxalic acid, and / or oxalate diester, followed by reaction and post-treatment to obtain an oxalamide-terminated polyether compound; (2) reacting the oxalamide-terminated polyether compound with a small molecule diamine compound to obtain the polyoxamide. The specific reaction process is shown below:
[0056]
[0057]
[0058] In a preferred embodiment, in step (1), the molar amount of oxalic acid and / or oxalate diester is greater than the molar amount of polyetheramine.
[0059] In a further preferred embodiment, in step (1), the molar ratio of the oxalic acid and / or oxalate diester to the molar ratio of the polyetheramine is greater than or equal to 2:1.
[0060] In a further preferred embodiment, in step (1), the molar ratio of the oxalic acid and / or oxalate diester to the molar ratio of the polyetheramine is (3-8):1, preferably (4-6):1, for example 3:1, 4:1, 5:1, 6:1, 7:1 or 8:1.
[0061] In a preferred embodiment, in step (1), the temperature of the reaction is 50 to 120°C, and / or the reaction time is 2 to 8 hours, and / or the reaction is carried out at atmospheric pressure.
[0062] For example, the reaction temperature is 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C, and / or the reaction time is 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours.
[0063] In a preferred embodiment, in step (1), the post-treatment includes: (preferably at 80-100°C, if the reaction temperature is below 80°C, it needs to be heated to 80-100°C first) vacuum filtration to remove unreacted oxalic acid and / or oxalate diester and other small molecule products (e.g., alcohols, water, etc.).
[0064] In a further preferred embodiment, in the post-processing of step (1), the pressure of the vacuum filtration is -0.01 to -0.1 MPa, for example -0.01 MPa, -0.02 MPa, -0.04 MPa, -0.06 MPa, -0.08 MPa or -0.1 MPa.
[0065] In a preferred embodiment, in step (2), the molar ratio of the oxalamide ester-terminated polyether compound or the polyether amine to the small molecule diamine compound is 1:(0.9 to 1.1), for example, 1:0.9, 1:1 or 1:1.1.
[0066] In a preferred embodiment, in step (2), the temperature of the reaction is 50-120°C (preferably 50-100°C), and / or the reaction time is 2-8 hours.
[0067] For example, the reaction temperature is 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C, and / or the reaction time is 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours.
[0068] The oxalamide ester-terminated polyether compound has a very low melting point, below 100°C, due to the presence of a high proportion of polyether segments in its structure (the oxalamide structure has a low weight ratio). Therefore, when proceeding to the next step of chain extension with a small molecule diamine compound, the reaction temperature is also low (preferably not higher than 100°C).
[0069] In a preferred embodiment, in step (2), a vacuum pump can be used to remove small molecule byproducts generated during the reaction (such as small molecule methanol, ethanol, isobutanol or butanol).
[0070] In this invention, the highly elastic polyoxamid is prepared using polyetheramine, oxalic acid and / or oxalate diester, and small molecule diamine compounds. The reaction does not require solvents, does not use diisocyanate compounds such as TDI and MDI, and the entire preparation process does not require high temperature.
[0071] The third objective of this invention is to provide the application of the high-elasticity polyoxamid described in the first objective of this invention or the high-elasticity polyoxamid obtained by the preparation method described in the second objective of this invention in elastic fibers.
[0072] In a preferred embodiment, the highly elastic polyoxoamide is used to prepare elastic fibers by melt spinning.
[0073] The fiber can be obtained, but is not limited to, by cutting and drying the highly elastic polyoxamid, then heating and melting it in a screw extrusion spinning machine, extruding it, and then conveying it to a spinneret for spinning.
[0074] The endpoints and any values of the ranges disclosed in this invention are not limited to the precise ranges or values; these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In the following, various technical solutions can, in principle, be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.
[0075] Compared with the prior art, the present invention has the following beneficial effects:
[0076] (1) In this invention, the polyoxamate has soft segments and hard segments, such as Figure 1 As shown, where, This represents the soft block, i.e., the polyether segment. This represents the hard block, i.e., the oxalamide chain segment, thus forming a linear structure with interlocking soft and hard components, giving the polyoxalamide high elasticity.
[0077] (2) The preparation process of the high elasticity polyoxamid described in this invention is simple, the raw material source is stable, and no highly toxic diisocyanate compounds are used in the production. At the same time, due to the rigid and highly polar aromatic diamine dioxamid and cyclic dipeptide diamine dioxamid structures introduced into the molecular backbone as the "hard block" of the elastic polyoxamid, the prepared elastic polyoxamid has a high elastic recovery rate when applied to fibers.
[0078] (3) The fibers prepared using the high elasticity polyoxamid have high elongation at break, high breaking strength, high 200% stress and excellent elastic recovery rate (e.g., 200% elastic recovery rate). Attached Figure Description
[0079] Figure 1 A schematic diagram showing the structure of elastic fibers under tension or in a solvent is provided.
[0080] Figure 2 This diagram shows the structural schematics of the soft and hard segments in the highly elastic polyoxoamide of the present invention.
[0081] Figures 3-4 The DSC diagrams of the highly elastic polyoxazones obtained in Examples 1 and 2 are shown respectively;
[0082] Figure 5 The TG curve of the highly elastic polyoxazone obtained in Example 1 is shown. Detailed Implementation
[0083] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.
[0084] It should also be noted that the various specific technical features described in the following embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations will not be described separately in this invention.
[0085] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.
[0086] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.
[0087]
Example 1
[0088] In a dry, anhydrous 5L four-necked flask, 1417.06 g (12 mol, produced by Sinopharm Group) of dimethyl oxalate was added and heated to 50°C to melt. While stirring, 1800 g (2 mol, produced by Yangzhou Chenhua New Materials Co., Ltd., molecular weight 900) of polyetheramine CAED900 was rapidly added, and the reaction was maintained at 50°C for 8 hours. The temperature was then raised to 100°C, and the negative pressure was reduced to -0.05 MPa. Excess dimethyl oxalate and methanol generated in the reaction were removed from the system. The reaction was stopped when no more liquid was removed from the system, yielding an oxamide-terminated polyether compound.
[0089] 216.28 g (2 mol) of p-phenylenediamine was added to the above reaction system, the temperature was raised to 100°C, and the methanol generated in the reaction was removed by a vacuum pump. The chain extension reaction was carried out for 2 hours to obtain highly elastic polyoxazone. Product number 1#. GPC testing was performed on the product, and the GPC results are as follows:
[0090]
[0091]
Example 2
[0092] In a dry, anhydrous 10L four-necked flask, 1315.3g (9mol, produced by Sinopharm Group) of diethyl oxalate was added. The mixture was heated to 50°C, and while stirring, 6000g (3mol, produced by Yangzhou Chenhua New Materials Co., Ltd., molecular weight 2000) of polyetheramine CAD2000 was rapidly added. The temperature was then raised to 100°C and maintained at 100°C for 2 hours. The system was then subjected to a negative pressure of -0.1 MPa, and excess diethyl oxalate and the ethanol produced in the reaction were removed. The reaction was stopped when no more liquid was removed from the system, yielding an oxalamide-terminated polyether compound.
[0093] 611.1 g (2.7 mol) of 2,2-bis(4-aminophenyl)propane was added to the above reaction system, the temperature was raised to 100 °C, and the ethanol generated in the reaction was evaporated. The chain extension reaction was carried out for 3 hours to obtain highly elastic polyoxamid.
[0094] Product number 2#. GPC testing was performed on the product, and the GPC results are as follows:
[0095]
[0096]
Example 3
[0097] In a dry, anhydrous 5L four-necked flask, 2922.8g of diethyl oxalate (20mol, produced by Sinopharm Group) was added. The mixture was heated to 50°C, and while stirring, 6000g of polyetheramine CAED600 (10mol, produced by Yangzhou Chenhua New Materials Co., Ltd., molecular weight 600) was rapidly added. The reaction was maintained at 50°C for 8 hours, then the temperature was raised to 100°C and the negative pressure was reduced to -0.1 MPa. Excess diethyl oxalate and the ethanol produced in the reaction were removed from the system. The reaction was stopped when no more liquid was removed from the system, yielding an oxalamide-terminated polyether compound.
[0098] 1981.2 g (10 mol) of 4,4'-diaminodiphenylmethane was added to the above reaction system, the temperature was raised to 50 °C, and the ethanol generated in the reaction was evaporated. The chain extension reaction was carried out for 8 hours to obtain highly elastic polyoxamid.
[0099] Product number 3#. GPC testing was performed on the product, and the GPC results are as follows:
[0100]
[0101]
Example 4
[0102] In a dry, anhydrous 5L four-necked flask, 857.4 g (7.2 mol, produced by Sinopharm Group) of dimethyl oxalate was added and heated to 60°C to melt. While stirring, 3600 g (1.8 mol, produced by Yangzhou Chenhua New Materials Co., Ltd., molecular weight 2000) of polyetheramine CAED 2003 was rapidly added, and the reaction was maintained at 60°C for 6 hours. The temperature was then raised to 100°C, and the negative pressure was reduced to -0.05 MPa. Excess dimethyl oxalate and methanol generated in the reaction were removed from the system. The reaction was stopped when no more liquid was removed from the system, yielding an oxamide-terminated polyether compound.
[0103] 297.4 g (1.5 mol) of 4,4'-diaminodiphenylmethane and 76.86 g (0.3 mol, Maclean's Reagent Company) of lysine cyclic dipeptide were added to the above reaction system. The mixture was heated to 100 °C while simultaneously evaporating the methanol produced in the reaction. The chain extension reaction was carried out for 2 hours to obtain highly elastic polyoxazone. Product number 4#. GPC testing was performed on the product, and the GPC results are as follows:
[0104]
[0105]
Example 5
[0106] In a dry, anhydrous 10L four-necked flask, add 1096.1g of diethyl oxalate (7.5mol, produced by Sinopharm Group), heat to 50°C, and while stirring, rapidly add 6000g of polyetheramine (1.5mol, produced by Huntsman, molecular weight 4000). D 4000, heated to 90℃ and maintained at 90℃ for 3 hours, then the pressure was reduced to -0.1 MPa, and excess diethyl oxalate and ethanol produced in the reaction were removed from the system. The reaction was stopped when no more liquid was removed from the system, yielding an oxalamide-terminated polyetheramine compound;
[0107] 226.15 g (1 mol) of 2,2-bis(4-aminophenyl)propane and 72.12 g (0.364 mol) of 4,4'-diaminodiphenylmethane were added to the above reaction system. The temperature was raised to 50 °C, and the ethanol generated in the reaction was evaporated simultaneously. The chain extension reaction was carried out for 8 hours to obtain highly elastic polyoxazone. Product number 5#. GPC testing was performed on the product, and the GPC results are as follows:
[0108]
[0109]
Example 6
[0110] In a dry, anhydrous 10L four-necked flask, 2630.52g (18mol, produced by Sinopharm Group) of diethyl oxalate was added. The mixture was heated to 50°C, and while stirring, 6000g (3mol, produced by Akoli Technology Co., Ltd., molecular weight 2000) of polyetheramine MA-2200 was rapidly added. The temperature was raised to 80°C and maintained at 80°C for 6 hours. Then, the pressure was reduced to -0.1 MPa, and excess diethyl oxalate and ethanol produced in the reaction were removed from the system. The reaction was stopped when no more liquid was removed from the system, yielding an oxalamide-terminated polyetheramine compound.
[0111] 646.12 g (2.857 mol) of 2,2-bis(4-aminophenyl)propane was added to the above reaction system, and the temperature was raised to 70 °C. Simultaneously, the ethanol generated in the reaction was evaporated, and the chain extension reaction was carried out for 7 hours to obtain highly elastic polyoxazone. Product number 6#. GPC testing was performed on the product, and the GPC results are as follows:
[0112]
[0113] Comparative Example 1
[0114] Repeat the process of Example 1, except that equimolar amounts of ethylenediamine are used to replace p-phenylenediamine, while other conditions remain unchanged.
[0115] [Performance Test 1]
[0116] The polyoxamid polymer sample prepared in the examples was shredded, dried, and then heated, melted, and extruded in a screw extrusion spinning mill. The extruded fiber was then fed to a spinneret for spinning at a speed of 450 m / min, a screw speed of 50 r / min, a spinning head temperature of 220°C, and a screw pressure of 8.6 MPa. The resulting fiber had a specification of 237 dtx / 36f, a draw ratio of 6, a draw temperature of 25°C, and a heat setting temperature of 150°C. The performance test results of the obtained fiber are as follows:
[0117] Elastic recovery rate / %: FZ / T 50007-2012;
[0118] Elongation at break (ELO) / %: FZ / T 50006-2013;
[0119] Fracture strength (TEN) / cN tex-1: FZ / T 50006-2013;
[0120] 200% stress / cN: FZ / T 50006-2013.
[0121] Table 1. Performance tests of fibers prepared by melt spinning of the elastic polymers in the examples.
[0122] Sample number TEN(cN) ELO (%) Strength at 200% elongation (cN) 200% elastic recovery rate / % 1# 122.31 200.72 163.4 89.5 2# 126.34 224.73 165.2 92.5 3# 117.63 167.39 182.1 -- 4# 136.47 265.73 154.32 98.3 5# 116.13 304.39 102.35 86.4 6# 143.08 285.06 141.84 98.2 7# 97.21 138.4 87.12 --
[0123] As shown in Table 1, the fibers of the 1 to 6# elastic polymers prepared in the examples all have good elastic recovery rates after melt spinning, with 200% elastic recovery rates all above 85% (except for sample 3#, because its ELO (%) is only 167%, and there is no 200% recovery). The 200% deformation is all above 100cN.
[0124] However, the elongation at break, tensile strength, and 200% stress of the fibers prepared by Comparative Example 1 after melt spinning were all lower than those of the Example.
[0125] [Performance Test 2]
[0126] The highly elastic polyoxazone obtained in Examples 1 and 2 were subjected to DSC analysis, and the results are as follows: Figures 3-4 As shown; the high-elasticity polyoxazone obtained in Example 1 was subjected to TG detection, and the results are as follows. Figure 5 As shown. By Figures 3-5 It can be seen that the high-elasticity polyoxamid obtained by this invention has good thermal properties.
[0127] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.
Claims
1. A highly elastic polyoxazone, the molecular structure of which is composed of polyether chain structural units and oxazone structural units as shown in formula (I): Formula (I); Wherein, R' is selected from one of the structures shown in equations (I-1) to (I-3) and (I-5) to (I-6). In formulas (I-1) to (I-3), R1 to R7 are each independently selected from hydrogen, alkyl or aryl.
2. The highly elastic polyoxamide of claim 1, wherein, In formulas (I-1) to (I-3), R1 to R7 are each independently selected from hydrogen, C1 to C10 alkyl groups, or C6 to C10 aryl groups.
3. The highly elastic polyoxamide of claim 1, wherein, In formulas (I-1) to (I-3), R1 to R7 are each independently selected from hydrogen or C1 to C6 alkyl groups.
4. The highly elastic polyoxamide of claim 1, wherein, R' is selected from one of the structures shown in equations (I-1) to (I-3).
5. The highly elastic polyoxamide of claim 1, wherein, The molecular structure of the highly elastic polyoxazone contains repeating structural units as shown in formula (II): Formula (II) In equation (II), R' has the same definition as in equation (I). This indicates a polyether chain.
6. The highly elastic polyoxamide of claim 1, wherein, The polyether chain is a polyether chain with a molecular weight of 300 to 3000.
7. The highly elastic polyoxamide of claim 1, wherein, The polyether chain is a polyether chain with a molecular weight of 600 to 2000.
8. The highly elastic polyoxamide of claim 1, wherein, The polyether in the polyether chain is at least one of the following: homopolymer of polyoxyethylene, polyoxypropylene, and polytetrahydrofuran, copolymer of two of them, or copolymer of three of them.
9. The highly elastic polyoxamide of claim 1, wherein, The highly elastic polyoxazone is selected from at least one of the polymers shown in formula (III): Equation (III) In formula (III), R' has the same definition as formula (I), represents a polyether chain.
10. A process for the preparation of a high-elasticity polyoxamide for the preparation of a high-elasticity polyoxamide according to any one of claims 1 to 9, said process comprising: (1) A polyetheramine, oxalic acid and / or oxalate diester are mixed, and after reaction and post-treatment, an oxalamide ester-terminated polyether compound is obtained, wherein the molar ratio of the oxalic acid and / or oxalate diester to the polyetheramine is greater than or equal to 2:1, and the post-treatment includes: vacuum filtration; (2) The oxalamide ester-terminated polyether compound is reacted with a small molecule diamine compound to obtain the polyoxamide; wherein the small molecule diamine compound is selected from at least one of NH2-R'-NH2, and R' is selected from one of the structures shown in formulas (I-1) to (I-3) and (I-5) to (I-6): In formulas (I-1) to (I-3), R1 to R7 are each independently selected from hydrogen, alkyl or aryl.
11. The method of claim 10, wherein, The molecular weight of the polyetheramine is 300-3000.
12. The method of claim 10, wherein, The molecular weight of the polyetheramine is 600-2000.
13. The method of claim 10, wherein, The polyetheramine is a polyetheramine with terminal dual functionality, wherein the polyether is at least one of the following: homopolymer of polyoxyethylene, polyoxypropylene, polytetrahydrofuran, copolymer of two, or copolymer of three.
14. The method of claim 10, wherein, The oxalate diester is selected from dialkyl oxalate esters.
15. The preparation method according to claim 10, characterized in that, The oxalate diester is selected from at least one of diethyl oxalate, dimethyl oxalate, dipropyl oxalate, dibutyl oxalate, and diisopropyl oxalate.
16. The method of claim 10, wherein, R' is selected from one of the structures shown in equations (I-1) to (I-3): In formulas (I-1) to (I-3), R1 to R7 are each independently selected from hydrogen, C1 to C10 alkyl groups, or C6 to C10 aryl groups.
17. The method of claim 10, wherein, In formulas (I-1) to (I-3), R1 to R7 are each independently selected from hydrogen or C1 to C6 alkyl groups.
18. The method of claim 10, wherein, The small molecule diamine compound is selected from at least one of p-phenylenediamine, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylmethane, lysine cyclic dipeptide, 4,4'-biphenyldiamine, 1,3-cyclohexanedimethylamine, and 1,4-cyclohexanedimethylamine.
19. The method of claim 16, wherein, The preparation method includes: the molar ratio of the oxalic acid and / or oxalate diester to the molar ratio of the polyetheramine is (3~8):
1.
20. The method of claim 16, wherein, In step (2), the molar ratio of the oxalamide ester-terminated polyether compound or the polyether amine to the small molecule diamine compound is 1:(0.9~1.1).
21. The preparation method according to claim 19, characterized in that, In step (1), the reaction temperature is 50~120℃, and / or the reaction time is 2~8 hours; and / or, In step (2), the temperature of the reaction is 50-120°C, and / or the reaction time is 2-8 hours.
22. The use of the high-elasticity polyoxamid according to any one of claims 1 to 9 or the high-elasticity polyoxamid obtained by the preparation method according to any one of claims 10 to 21 in elastic fibers.
23. The use according to claim 22, characterized in that, Elastic fibers are prepared by melt spinning using the highly elastic polyoxoamide.