Polyetheramide copolymers, methods of making and using the same

Abstract

This invention relates to the field of polymer materials technology, and discloses a polyether amide copolymer, its preparation method, and its applications. The polyether amide copolymer includes hard segments and soft segments. The hard segments are polyamide 6-long-chain polyamide copolymers, comprising structural units provided by polyamide 6 and structural units provided by long-chain polyamides. Based on the total weight of the polyamide 6-long-chain polyamide copolymer, the content of the long-chain polyamide is 5-40 wt%. The soft segments are polyoxyolefin diols and / or amino-terminated polyoxyolefins. The polyether amide copolymers prepared by this invention all exhibit good elongation at break and good toughness.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a polyether amide copolymer, its preparation method, and its application. Background Technology

[0002] Polyether amide copolymers are a class of thermoplastic elastomers that have developed rapidly in recent years. They possess excellent low-temperature flexural properties, good corrosion resistance, mechanical properties, high elasticity, antistatic properties, and sound absorption effects, and are widely used in automobiles, sporting goods, medical devices, seals, and mechanical parts. The composition of the soft and hard segments in polyether amide copolymers has a significant impact on the elastomer's properties. Different compositions, ratios, and degrees of polymerization of the soft and hard segments will affect the copolymer's hardness, thermal stability, hygroscopicity, and elastic recovery.

[0003] Among commercially available polyether amides, the long-chain type, represented by PA12, is the most common. Long-chain polyether amides have good processability and excellent corrosion resistance, but due to their relatively high price, their application range is limited, typically found in high-end sporting goods and mid-to-high-end medical devices. PA6 type polyether amide, on the other hand, uses caprolactam as its hard segment raw material, which is widely available and relatively inexpensive. However, its elasticity and corrosion resistance are inferior.

[0004] Therefore, it is of great significance to research and develop a high-performance polyether amide copolymer. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of poor elasticity and toughness of PA6 type polyether amide in the prior art, and to provide a polyether amide copolymer, its preparation method and application, which can achieve a balance between strength and toughness.

[0006] To achieve the above objectives, a first aspect of the present invention provides a polyetheramide copolymer, wherein the polyetheramide copolymer comprises hard segments and soft segments, wherein the hard segments are polyamide 6-long-chain polyamide copolymers, the polyamide 6-long-chain polyamide copolymers comprising structural units provided by polyamide 6 and structural units provided by long-chain polyamides, and the content of long-chain polyamides is 5-40 wt% based on the total weight of the polyamide 6-long-chain polyamide copolymers; the soft segments are polyoxyolefin diols and / or amino-terminated polyoxyolefins.

[0007] A second aspect of the present invention provides a method for preparing the aforementioned polyether amide copolymer, wherein the preparation method comprises: performing a first polymerization of hard segments and soft segments under atmospheric pressure under stirring conditions, and then performing a second polymerization under vacuum to obtain the polyether amide copolymer.

[0008] A third aspect of the present invention provides the use of the aforementioned polyetheramide copolymer in the preparation of one or more engineering plastics, fibers, and films.

[0009] Compared with the prior art, the present invention has the following advantages through the above technical solution:

[0010] (1) Compared with existing polyether amide copolymers, the polyether amide copolymer provided by the present invention uses polyamide 6-long carbon chain polyamide copolymer as hard segment, which effectively overcomes the problem that long carbon chain polyamide raw materials are not easy to obtain and are expensive. The prepared polyether amide copolymer has the dual advantages of long carbon chain polyamide and polyether material, and can achieve a balance between strength and toughness.

[0011] (2) The polyether amide copolymer preparation method provided by the present invention is economical and environmentally friendly, and can be mass-produced on conventional polyamide 6 continuous polymerization equipment.

[0012] (3) The polyether amide copolymer raw material provided by the present invention is inexpensive, readily available, and has an excellent performance-price ratio. It can be widely used in the preparation of engineering plastics, fibers, films and other fields. Attached Figure Description

[0013] Figure 1 It is the polyetheramide copolymer prepared in Example 1 1 H-NMR spectrum. Detailed Implementation

[0014] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and 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.

[0015] As previously stated, a first aspect of the present invention provides a polyetheramide copolymer, wherein the polyetheramide copolymer comprises hard segments and soft segments, wherein the hard segments are polyamide 6-long carbon chain polyamide copolymers, the polyamide 6-long carbon chain polyamide copolymers comprising structural units provided by polyamide 6 and structural units provided by long carbon chain polyamides, and the content of long carbon chain polyamides is 5-40 wt% based on the total weight of the polyamide 6-long carbon chain polyamide copolymers; the soft segments are polyoxyolefin diols and / or polyoxyolefins with terminal amino groups.

[0016] The inventors of this invention have discovered that a polyether amide copolymer prepared by using the polyamide 6-long carbon chain polyamide copolymer as the hard segment and polyoxyolefin diol and / or amino-terminated polyoxyolefin as the soft segment combines the advantages of both long carbon chain polyamide and polyether materials, and can achieve a balance between strength and toughness.

[0017] According to the present invention, preferably, the content of the long-chain polyamide is 5-30 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0018] According to the present invention, the long-chain polyamide is selected from one or more of polyamide 510, polyamide 512, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 1212 and polyamide 1214; more preferably, the long-chain polyamide is selected from one or more of polyamide 1012, polyamide 612, polyamide 512, polyamide 1010 and polyamide 610.

[0019] According to the present invention, based on the total weight of the polyether amide copolymer, the content of the hard segment is 30-95 wt% and the content of the soft segment is 5-70 wt%; preferably, based on the total weight of the polyether amide copolymer, the content of the hard segment is 40-90 wt% and the content of the soft segment is 10-60 wt%.

[0020] According to the present invention, the method for preparing the polyamide 6-long carbon chain polyamide copolymer includes:

[0021] In the presence of a catalyst and under nitrogen protection, caprolactam, long-chain polyamide, a molecular weight regulator, and water were subjected to a polymerization reaction to prepare polyamide 6-long-chain polyamide copolymer.

[0022] The inventors of this invention discovered that by utilizing the unique flexible segment structure of long-chain polyamides, a polyamide 6-long-chain polyamide copolymer was prepared through random copolymerization. The amide bond density of this polyamide 6-long-chain polyamide copolymer is reduced, and the hydrogen bonding effect is weakened, which improves the hydrolysis resistance, dimensional stability, solvent resistance, and wear resistance of polyamide 6.

[0023] According to the present invention, the oxygen in the reactor is removed by nitrogen purging 3-5 times in the reaction vessel; preferably, the temperature is first raised, and stirring is started when the temperature reaches 90-100°C, preferably 95°C, and the temperature is raised to the polymerization temperature to carry out the polymerization reaction; wherein, the polymerization reaction conditions include: polymerization at 210-250°C and pressure maintained at 0.1-0.5 MPa for 1-4 hours.

[0024] In addition, in this invention, after the polymerization reaction is completed, the pressure needs to be released to normal pressure within 0.5-1 hour, the temperature needs to be lowered to 180-200°C, and stirring needs to be stopped so that it can be used for the subsequent preparation of polyether amide copolymer.

[0025] According to the present invention, in a preferred embodiment, the preparation method of the polyamide 6-long carbon chain polyamide copolymer is carried out under stirring conditions. In the present invention, there are no particular limitations on the stirring, and it can be a conventional choice for those skilled in the art.

[0026] According to the present invention, the molecular weight regulator is selected from one or more of succinic acid, adipic acid, octanoic acid, sebacic acid, dodecanoic acid, terephthalic acid, and isophthalic acid; preferably, the molecular weight regulator is selected from one or more of adipic acid, sebacic acid, and terephthalic acid.

[0027] According to the present invention, the catalyst is selected from one or more of phosphoric acid, sodium hypophosphite, sodium dihydrogen phosphate, tetrabutyl titanate, antimony trioxide, and antimony glycolate; preferably, the catalyst is selected from one or more of sodium hypophosphite, tetrabutyl titanate, sodium hypophosphite, and antimony trioxide.

[0028] According to the present invention, the water is preferably deionized water.

[0029] According to the present invention, the polyoxyolefin diol is a linear or branched C2-C5 polyoxyolefin diol; preferably, the polyoxyolefin diol is selected from one or more of polyethylene glycol, polypropylene glycol, polyhexane glycol, polytetrahydrofuran glycol, and tetrahydrofuran-propylene oxide copolydiol; more preferably, the polyoxyolefin diol is polyethylene glycol and / or polypropylene glycol; even more preferably, the polyoxyolefin diol is selected from one or more of polyethylene glycol D800, polyethylene glycol D1000, polyethylene glycol D2000, and polypropylene glycol D1000.

[0030] According to the present invention, the amino-terminated polyoxyolefin is a linear or branched C2-C5 amino-terminated polyoxyolefin; preferably, the amino-terminated polyoxyolefin is selected from one or more of amino-terminated polyethylene oxide, amino-terminated propylene oxide, and amino-terminated polytetrahydrofuran; more preferably, the amino-terminated polyoxyolefin is a polyetheramine with a molecular weight of 400-2000 g / mol; even more preferably, the amino-terminated polyoxyolefin is selected from one or more of polyetheramine D500, polyetheramine D1000, and polyetheramine D2000.

[0031] According to the present invention, the relative viscosity of the polyether amide copolymer is 1.0-2.1, preferably 1.12-2.1.

[0032] The second aspect of this invention provides a method for preparing the aforementioned polyetheramide copolymer, wherein the method comprises: performing a first polymerization of hard segments and soft segments under atmospheric pressure under stirring conditions, and then performing a second polymerization under vacuum to obtain the polyetheramide copolymer.

[0033] According to the present invention, the hard segment and the soft segment are subjected to a first polymerization under normal pressure. The conditions for the first polymerization include: a temperature of 220-260°C and a polymerization time of 2-5 h; preferably, the temperature is 220-250°C and the polymerization time is 2-4 h.

[0034] According to the present invention, the hard segment and the soft segment are first polymerized under normal pressure, and then a second polymerization is carried out under vacuum. The conditions for the second polymerization include: a temperature of 240-265°C and a polymerization time of 1-5 hours; preferably, the temperature is 250-260°C and the polymerization time is 1-5 hours.

[0035] According to the present invention, preferably, the polyether amide copolymer (elastomer) can be extracted according to the application scenario to remove oligomers and small molecules of the copolymer.

[0036] A third aspect of this invention provides the use of the aforementioned polyetheramide copolymer in the preparation of one or more engineering plastics, fibers, and films.

[0037] Compared with existing technologies, the polyether amide copolymer preparation method provided by this invention is economical and environmentally friendly, and can be mass-produced on conventional polyamide 6 continuous polymerization equipment. The polyether amide copolymer raw materials provided by this invention are inexpensive, readily available, and offer excellent performance-price ratio, making them widely applicable in the preparation of engineering plastics, fibers, films, and other fields.

[0038] The present invention will be described in detail below through embodiments.

[0039] In the following examples and comparative examples:

[0040] Tensile testing was conducted according to national standard GB / T 1040.1-2018, notched impact strength was conducted according to GB / T1843-2008, relative viscosity was tested using an Ubbelohde viscometer, and fluidity was tested using 98% concentrated sulfuric acid.

[0041] Unless otherwise specified, all raw materials are commercially available products.

[0042] Example 1

[0043] This embodiment is intended to illustrate the polyether amide copolymer prepared according to the present invention.

[0044] Preparation of polyamide 6-long carbon chain polyamide copolymer:

[0045] (a) Place 126 kg caprolactam, 14 kg polyamide 1012 (salt), 4.4 kg adipic acid, 0.2 kg sodium hypophosphite, and 2.8 kg deionized water into a reaction vessel and purge with nitrogen three times to remove oxygen from the reactor.

[0046] (b) Start heating up to 95°C, turn on stirring, and after the temperature rises to 210°C, polymerize under pressure at 0.4 MPa for 3 hours;

[0047] (c) Depressurize to atmospheric pressure within 0.5 hours, cool to 180°C, and stop stirring.

[0048] As a result, a polyamide 6-long carbon chain polyamide copolymer was prepared.

[0049] The content of the long-chain polyamide is 10 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0050] (d) Using the polyamide 6-long carbon chain polyamide copolymer as the hard segment, add 60 kg of polyetheramine D2000 as the soft segment, heat to 250 °C and polymerize under normal pressure for 4 h, then vacuum polymerize at 250 °C for 1 h.

[0051] As a result, a polyether amide copolymer was prepared.

[0052] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 70 wt%, and the content of the soft segment is 30 wt%.

[0053] Figure 1 It is the polyetheramide copolymer prepared in Example 1 1 H-NMR spectrum, from Figure 1 It can be seen that: Figure 1As can be seen, peak a (δ = 1.21) corresponds to the H on the methyl group in polyetheramine; peak b (δ = 1.36) corresponds to the H on the methylene group in the long-chain PA1012 segment, two methylene groups away from the two ends of the amide group; peak c (δ = 1.42) corresponds to the H on the middle methylene group in the PA6 segment; peak d (δ = 1.67) corresponds to the H on the second methylene group next to the -CO- group of the amide group; peak e (δ = 1.75) corresponds to the H on the second methylene group next to the -NH- group of the amide group; and peak f (δ = 2.42) corresponds to the H on the end-capped adipic acid structure. The H on the methylene group connected to the amide group and the H on the methylene group adjacent to the -CO- group; the peak at g (δ = 3.48) corresponds to the H on the methylene group adjacent to the -NH- group of the amide group; the peak at h (δ = 3.71) corresponds to the H on the methylene group adjacent to the -O- group within the polyetheramine segment; the peak at i (δ = 3.86) corresponds to the H on the C on the side methyl group within the polyetheramine segment; the peak at j (δ = 4.27) corresponds to the H on the C on the amide group adjacent to the PA segment within the polyetheramine segment; the protons in the product structure formula correspond one-to-one with the peaks in the NMR spectrum, indicating that the synthesized polymer is the target product.

[0054] Example 2

[0055] This embodiment is intended to illustrate the polyether amide copolymer prepared according to the present invention.

[0056] Preparation of polyamide 6-long carbon chain polyamide copolymer:

[0057] (a) Place 72 kg of caprolactam, 8 kg of polyamide 1012 salt, 8.8 kg of adipic acid, 0.2 kg of sodium hypophosphite, and 2.8 kg of deionized water into a reaction vessel, and purge the reactor with nitrogen three times to remove oxygen.

[0058] (b) Start heating up to 95°C, turn on stirring, and after the temperature rises to 210°C, polymerize under pressure at 0.2 MPa for 3 hours;

[0059] (c) Depressurize to atmospheric pressure within 0.5 hours, cool to 180°C, and stop stirring.

[0060] As a result, a polyamide 6-long carbon chain polyamide copolymer was prepared.

[0061] The content of the long-chain polyamide is 10 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0062] (d) Using the polyamide 6-long carbon chain polyamide copolymer as the hard segment, add 120 kg of polyetheramine D2000 as the soft segment, heat to 250 °C and polymerize under normal pressure for 4 h, then vacuum polymerize at 250 °C for 1 h.

[0063] As a result, a polyether amide copolymer was prepared.

[0064] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 40 wt%, and the content of the soft segment is 60 wt%.

[0065] Example 3

[0066] This embodiment is intended to illustrate the polyether amide copolymer prepared according to the present invention.

[0067] Preparation of polyamide 6-long carbon chain polyamide copolymer:

[0068] (a) Place 126 kg caprolactam, 14 kg polyamide 1012 salt, 4.4 kg adipic acid, 0.1 kg tetrabutyl titanate, and 2.8 kg deionized water into a reaction vessel and purge with nitrogen three times to remove oxygen from the reactor.

[0069] (b) Start heating up to 95°C, turn on stirring, and after the temperature rises to 210°C, polymerize under pressure at 0.3 MPa for 3 hours;

[0070] (c) Depressurize to atmospheric pressure within 0.5 hours, cool to 180°C, and stop stirring.

[0071] As a result, a polyamide 6-long carbon chain polyamide copolymer was prepared.

[0072] The content of the long-chain polyamide is 10 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0073] (d) Using the polyamide 6-long carbon chain polyamide copolymer as the hard segment, add 60 kg of polyethylene glycol D2000 as the soft segment, heat to 240°C and polymerize under normal pressure for 3 h, then vacuum polymerize at 250°C for 4 h.

[0074] As a result, a polyether amide copolymer was prepared.

[0075] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 70 wt%, and the content of the soft segment is 30 wt%.

[0076] Example 4

[0077] This embodiment is intended to illustrate the polyether amide copolymer prepared according to the present invention.

[0078] Prepared polyamide 6-long carbon chain polyamide copolymer:

[0079] (a) Place 126 kg caprolactam, 14 kg polyamide 612 salt, 8.8 kg adipic acid, 0.1 kg tetrabutyl titanate, and 2.8 kg deionized water into a reaction vessel and purge with nitrogen three times to remove oxygen from the reactor.

[0080] (b) Start heating up to 95°C, turn on stirring, and after the temperature rises to 230°C, polymerize under pressure at 0.4 MPa for 3 hours;

[0081] (c) Depressurize to atmospheric pressure within 0.5 hours, cool to 200°C, and stop stirring.

[0082] As a result, a polyamide 6-long carbon chain polyamide copolymer was prepared.

[0083] The content of the long-chain polyamide is 10 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0084] (d) Using the polyamide 6-long carbon chain polyamide copolymer as the hard segment, add 60 kg of polyethylene glycol D1000 as the soft segment, heat to 220°C and polymerize under normal pressure for 2 h, then vacuum polymerize at 250°C for 3.5 h.

[0085] As a result, a polyether amide copolymer was prepared.

[0086] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 70 wt%, and the content of the soft segment is 30 wt%.

[0087] Example 5

[0088] This embodiment is intended to illustrate the polyether amide copolymer prepared according to the present invention.

[0089] Prepared polyamide 6-long carbon chain polyamide copolymer:

[0090] (a) Place 112 kg caprolactam, 28 kg polyamide 512 salt, 8.1 kg sebacic acid, 0.1 kg tetrabutyl titanate, and 2.8 kg deionized water into a reaction vessel and purge with nitrogen three times to remove oxygen from the reactor.

[0091] (b) Start heating up to 95°C, turn on stirring, and after the temperature rises to 240°C, polymerize under pressure at 0.5 MPa for 2.5 h;

[0092] (c) Depressurize to atmospheric pressure within 1 hour, cool to 210°C, and stop stirring.

[0093] As a result, a polyamide 6-long carbon chain polyamide copolymer was prepared.

[0094] The content of the long-chain polyamide is 20 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0095] (d) Using the polyamide 6-long carbon chain polyamide copolymer as the hard segment, add 40 kg of polypropylene glycol D1000 as the soft segment, heat to 240 °C and polymerize under normal pressure for 4 h; then vacuum polymerize at 250 °C for 5 h.

[0096] As a result, a polyether amide copolymer was prepared.

[0097] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 80 wt%, and the content of the soft segment is 20 wt%.

[0098] Example 6

[0099] This embodiment is intended to illustrate the polyether amide copolymer prepared according to the present invention.

[0100] Prepared polyamide 6-long carbon chain polyamide copolymer:

[0101] (a) Place 119 kg caprolactam, 51 kg polyamide 1010 salt, 6 kg sebacic acid, 0.2 kg sodium hypophosphite, and 2.8 kg deionized water into a reaction vessel and purge with nitrogen three times to remove oxygen from the reactor.

[0102] (b) Start heating up to 95°C, turn on stirring, and after the temperature rises to 230°C, polymerize under pressure at 0.4 MPa for 3 hours;

[0103] (c) Depressurize to atmospheric pressure within 0.5 h, cool to 185°C, and stop stirring.

[0104] As a result, a polyamide 6-long carbon chain polyamide copolymer was prepared.

[0105] The content of the long-chain polyamide is 30 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0106] (d) Using the polyamide 6-long carbon chain polyamide copolymer as the hard segment, add 30 kg of polyetheramine D1000 as the soft segment, heat to 245°C and polymerize under normal pressure for 4 h, then vacuum polymerize at 250°C for 1 h.

[0107] As a result, a polyether amide copolymer was prepared.

[0108] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 85 wt%, and the content of the soft segment is 15 wt%.

[0109] Example 7

[0110] This embodiment is intended to illustrate the polyether amide copolymer prepared according to the present invention.

[0111] Prepared polyamide 6-long carbon chain polyamide copolymer:

[0112] (a) Place 132.5 kg caprolactam, 7.5 kg polyamide 1012 salt, 16.6 kg terephthalic acid, 0.2 kg sodium hypophosphite, and 2.8 kg deionized water into a reaction vessel and purge with nitrogen three times to remove oxygen from the reactor.

[0113] (b) Start heating up to 90°C, turn on stirring, and after the temperature rises to 240°C, polymerize under pressure at 0.4 MPa for 3 hours;

[0114] (c) Depressurize to atmospheric pressure within 0.5 hours, cool to 180°C, and stop stirring.

[0115] As a result, a polyamide 6-long carbon chain polyamide copolymer was prepared.

[0116] The content of the long-chain polyamide is 5 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0117] (d) The polyamide 6-long carbon chain polyamide copolymer was used as the hard segment, and 50 kg of polyetheramine D500 was added as the soft segment. The mixture was heated to 250 °C and polymerized under normal pressure for 3.5 h. Then, vacuum polymerization was carried out at 250 °C for 2 h.

[0118] As a result, a polyether amide copolymer was prepared.

[0119] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 75 wt%, and the content of the soft segment is 25 wt%.

[0120] Example 8

[0121] This embodiment is intended to illustrate the polyether amide copolymer prepared according to the present invention.

[0122] Prepared polyamide 6-long carbon chain polyamide copolymer:

[0123] (a) Place 162 kg caprolactam, 18 kg polyamide 610 salt, 4.4 kg adipic acid, 0.1 kg antimony trioxide, and 2.8 kg deionized water into a reaction vessel and purge with nitrogen three times to remove oxygen from the reactor.

[0124] (b) Start heating up to 93°C, turn on stirring, and after the temperature rises to 240°C, polymerize under pressure at 0.5 MPa for 4 hours;

[0125] (c) Depressurize to atmospheric pressure within 0.5 hours, cool to 180°C, and stop stirring.

[0126] As a result, a polyamide 6-long carbon chain polyamide copolymer was prepared.

[0127] The content of the long-chain polyamide is 10 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0128] (d) Using the polyamide 6-long carbon chain polyamide copolymer as the hard segment, add 20 kg of polyethylene glycol D800 as the soft segment, heat to 240 °C and polymerize under normal pressure for 2.5 h, then vacuum polymerize at 250 °C for 3.5 h.

[0129] As a result, a polyether amide copolymer was prepared.

[0130] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 90 wt% and the content of the soft segment is 10 wt%.

[0131] Example 9

[0132] This embodiment is intended to illustrate the polyamide 6-long carbon chain polyamide copolymer and polyether amide copolymer prepared according to the present invention.

[0133] The polyamide 6-long carbon chain polyamide copolymer was prepared in the same manner as in Example 1, except that in step (a), “126 kg caprolactam, 14 kg polyamide 1012 (salt), 4.4 kg adipic acid” was replaced with “119 kg caprolactam, 21 kg polyamide 1012 (salt), 4.4 kg adipic acid”.

[0134] As a result, a polyamide 6-long carbon chain polyamide copolymer was prepared.

[0135] The content of the long-chain polyamide is 15 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0136] Using the polyamide 6-long carbon chain polyamide copolymer prepared above, a polyether amide copolymer was prepared in the same manner as in Example 1.

[0137] As a result, a polyether amide copolymer was prepared.

[0138] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 70 wt%, and the content of the soft segment is 30 wt%.

[0139] Example 10

[0140] This embodiment is intended to illustrate the polyamide 6-long carbon chain polyamide copolymer and polyether amide copolymer prepared according to the present invention.

[0141] Polyamide 6-long carbon chain polyamide copolymer was prepared according to the same method as in Example 1, and a polyamide 6-long carbon chain polyamide copolymer was obtained; wherein, based on the total weight of the polyamide 6-long carbon chain polyamide copolymer, the content of the long carbon chain polyamide was 10 wt%.

[0142] Using the polyamide 6-long carbon chain polyamide copolymer prepared above, a polyether amide copolymer was prepared in the same manner as in Example 1, except that "140 kg of polyether amine D2000 was added".

[0143] As a result, a polyether amide copolymer was prepared.

[0144] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 50 wt%, and the content of the soft segment is 50 wt%.

[0145] Comparative Example 1

[0146] (a) Place 140 kg caprolactam, 4.4 kg adipic acid, 0.2 kg sodium hypophosphite and 2.8 kg deionized water into a reaction vessel and purge with nitrogen three times to remove oxygen from the reactor.

[0147] (b) Start heating up to 95°C, turn on stirring, and after the temperature rises to 210°C, polymerize under pressure at 0.4 MPa for 3 hours;

[0148] (c) Depressurize to atmospheric pressure within 0.5 hours, cool to 180°C, and stop stirring.

[0149] As a result, a polyamide 6 homopolymer was prepared.

[0150] (d) The polyamide 6 homopolymer prepared above was used as the hard segment, and 60 kg of polyetheramine D2000 was added as the soft segment. The mixture was heated to 250 °C and polymerized under normal pressure for 4 h. Then, vacuum polymerization was carried out at 250 °C for 1 h.

[0151] As a result, a polyether amide copolymer was prepared.

[0152] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 70 wt%, and the content of the soft segment is 30 wt%.

[0153] Comparative Example 2

[0154] (a) Place 140 kg caprolactam, 8.8 kg adipic acid, 0.1 kg tetrabutyl titanate and 2.8 kg deionized water into a reaction vessel and purge with nitrogen three times to remove oxygen from the reactor.

[0155] (b) Start heating up to 95°C, turn on stirring, and after the temperature rises to 230°C, polymerize under pressure at 0.4 MPa for 3 hours;

[0156] (c) Depressurize to atmospheric pressure within 0.5 hours, cool to 200°C, and stop stirring.

[0157] As a result, a polyamide 6 homopolymer was prepared.

[0158] (d) The polyamide 6 homopolymer prepared above was used as the hard segment, and 60 kg of polyethylene glycol D1000 was added as the soft segment. The mixture was heated to 220°C and polymerized under normal pressure for 2 h. Then, vacuum polymerization was carried out at 250°C for 3.5 h.

[0159] As a result, a polyether amide copolymer was prepared.

[0160] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 70 wt%, and the content of the soft segment is 30 wt%.

[0161] Comparative Example 3

[0162] The polyamide 6-long carbon chain polyamide copolymer was prepared in the same manner as in Example 1, except that in step (a), “126 kg caprolactam, 14 kg polyamide 1012 (salt), 4.4 kg adipic acid” was replaced with “45 kg caprolactam, 5 kg polyamide 1012 (salt), 10.5 kg adipic acid”.

[0163] As a result, a polyamide 6-long carbon chain polyamide copolymer was prepared.

[0164] The content of the long-chain polyamide is 10 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0165] Using the polyamide 6-long carbon chain polyamide copolymer prepared above as the hard segment, 150 kg of polyetheramine D2000 was added as the soft segment, and the polyetheramide copolymer was prepared in the same way as in Example 1.

[0166] As a result, a polyether amide copolymer was prepared.

[0167] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 25 wt%, and the content of the soft segment is 75 wt%.

[0168] Comparative Example 4

[0169] The polyamide 6-long carbon chain polyamide copolymer was prepared in the same manner as in Example 1, except that in step (a), “126 kg caprolactam, 14 kg polyamide 1012 (salt), 4.4 kg adipic acid” was replaced with “70 kg caprolactam, 70 kg polyamide 1012 (salt), 4.4 kg adipic acid”.

[0170] As a result, a polyamide 6-long carbon chain polyamide copolymer was prepared.

[0171] The content of the long-chain polyamide is 50 wt%, based on the total weight of the polyamide 6-long-chain polyamide copolymer.

[0172] Using the polyamide 6-long carbon chain polyamide copolymer prepared above, a polyether amide copolymer was prepared in the same manner as in Example 1.

[0173] As a result, a polyether amide copolymer was prepared.

[0174] Based on the total weight of the polyether amide copolymer, the content of the hard segment is 70 wt%, and the content of the soft segment is 30 wt%.

[0175] Test case

[0176] The performance of Examples 1-10 and Comparative Examples 1-4 was tested. The relative viscosity of the prepared polyether amide copolymer was measured, the prepared polyether amide copolymer was injection molded, and the tensile strength and elongation at break were tested. The data are shown in Table 1.

[0177] Table 1

[0178]

[0179]

[0180] Note: NB indicates that the spline did not break during the notch impact strength test.

[0181] As shown in the table above, the polyether amide copolymers prepared in the embodiments of the present invention all exhibit good elongation at break, and the elongation at break gradually increases with the increase of soft segment content, indicating improved toughness. However, the tensile strength decreases with the increase of soft segment content. The polyether amide copolymers provided by the present invention can be formulated by adjusting the process according to actual application scenarios to achieve a balance between strength and toughness. The comparative data show that in the embodiments of the present invention, after the hard segments of the polyether amide copolymers are modified by long-chain random copolymerization, their tensile strength decreases slightly, but their elongation at break increases significantly, indicating that increased flexibility of the hard segments is beneficial for further improving the toughness of polyether amide copolymerization.

[0182] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A polyetheramide copolymer characterized by, The polyetheramide copolymer comprises hard segments and soft segments, wherein the hard segments are polyamide 6-long-chain polyamide copolymers, the polyamide 6-long-chain polyamide copolymers comprising structural units provided by polyamide 6 and structural units provided by long-chain polyamides, and the content of long-chain polyamides is 5-40 wt% based on the total weight of the polyamide 6-long-chain polyamide copolymers; the soft segments are polyoxyolefin diols and / or polyoxyolefins with terminal amino groups.

2. The polyetheramide copolymer of claim 1, wherein, Based on the total weight of the polyamide 6-long carbon chain polyamide copolymer, the content of the long carbon chain polyamide is 5-30 wt%. And / or, the long carbon chain polyamide is selected from one or more of polyamide 510, polyamide 512, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 1212 and polyamide 1214.

3. The polyetheramide copolymer according to claim 1 or 2, wherein, Based on the total weight of the polyether amide copolymer, the content of the hard segment is 30-95 wt%, and the content of the soft segment is 5-70 wt%. Preferably, based on the total weight of the polyether amide copolymer, the content of the hard segment is 40-90 wt%, and the content of the soft segment is 10-60 wt%.

4. The polyetheramide copolymer according to any one of claims 1-3, wherein, The preparation method of the polyamide 6-long carbon chain polyamide copolymer includes: In the presence of a catalyst and under nitrogen protection, caprolactam, long-chain polyamide, a molecular weight regulator, and water were subjected to a polymerization reaction to prepare polyamide 6-long-chain polyamide copolymer.

5. The polyetheramide copolymer according to claim 4, wherein the polymerization reaction conditions include: Polymerize at 210-250℃ under pressure of 0.1-0.5 MPa for 1-4 hours.

6. The polyetheramide copolymer according to claim 4 or 5, wherein, The molecular weight regulator is selected from one or more of succinic acid, adipic acid, octanoic acid, sebacic acid, dodecanoic acid, terephthalic acid, and isophthalic acid; And / or, the catalyst is selected from one or more of phosphoric acid, sodium hypophosphite, sodium dihydrogen phosphate, tetrabutyl titanate, antimony trioxide, and antimony glycolate.

7. The polyetheramide copolymer according to claim 1, wherein, The polyoxyolefin diol is a linear or branched C2-C5 polyoxyolefin diol; Preferably, the polyoxyolefin diol is selected from one or more of polyethylene glycol, polypropylene glycol, polyhexane glycol, polytetrahydrofuran glycol, and tetrahydrofuran-propylene oxide copolydiol; More preferably, the polyoxyolefin diol is polyethylene glycol and / or polypropylene glycol.

8. The polyetheramide copolymer according to claim 1, wherein, The terminal amino polyoxyolefin is a linear or branched C2-C5 terminal amino polyoxyolefin. Preferably, the amino-terminated polyoxyolefin is selected from one or more of amino-terminated polyethylene oxide, amino-terminated polypropylene oxide, and amino-terminated polytetrahydrofuran. More preferably, the amino-terminated polyoxyolefin is a polyetheramine with a molecular weight of 400-2000 g / mol; More preferably, the terminal amino polyoxyolefin is selected from one or more of polyetheramine D500, polyetheramine D1000 and polyetheramine D2000.

9. The polyetheramide copolymer according to any one of claims 1-8, wherein, The relative viscosity of the polyether amide copolymer is 1-2.

1.

10. A method for preparing the polyether amide copolymer according to any one of claims 1-9, characterized in that, The preparation method includes: under stirring conditions, performing a first polymerization of hard segments and soft segments at atmospheric pressure, and then performing a second polymerization under vacuum to obtain a polyether amide copolymer.

11. The preparation method according to claim 10, wherein, The conditions for the first polymerization include: a temperature of 220-260℃ and a polymerization time of 2-5 hours; And / or, the conditions for the second polymerization include: a temperature of 240-265°C and a polymerization time of 1-5 h.

12. The use of a polyether amide copolymer according to any one of claims 1-9 in the preparation of one or more engineering plastics, fibers and films.

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