A sulfonate-containing polyether-polyester-polyamide block copolymer and a method for preparing the same

Abstract

The application discloses a sulfonate grafted polyether-polyester-polyamide block copolymer and a synthesis method thereof, and belongs to the field of materials. The application provides a block copolymer elastomer material with polycaprolactam as a hard segment, polyether and polyester as soft segments, and specific sulfonic acid groups are introduced to meet specific purposes. Caprolactam, 6-aminohexanoic acid, aliphatic dibasic acid, aliphatic diamine, polyether dihydric alcohol, sulfonate grafted polyester polyol BY-3305 and the like are used as raw materials, macromolecular sulfonate grafted polyester polyol BY-3305 is used as a sulfonate grafting agent, the sulfonate grafted polyester polyol BY-3305 has higher reaction efficiency and less reaction by-products than small molecule monomers containing sulfonic acid groups, and is beneficial to the smooth progress of polymerization. The sulfonate grafted polyether-polyester-polyamide block copolymer elastomer is obtained through one-step melt polymerization, and has the advantages of simple synthesis method, low production cost, high strength, adjustable performance and the like.

Description

Technical Field

[0001] This invention belongs to the field of materials, and particularly relates to a sulfonate-grafted polyether-polyester-polyamide block copolymer and its preparation method. Background Technology

[0002] Polyether block polyamide copolymer (PEBA) is a copolymer composed of hard segment polyamide that provides strength and soft segment polyether that provides elasticity. By controlling the different contents of hard and soft segments, a series of copolymer products with hardness and elasticity gradients can be obtained, making it applicable to different application scenarios.

[0003] Due to its unique structure, PEBA possesses many excellent properties, such as superior mechanical properties, resistance to mechanical fatigue, and ease of processing. In the composition of PEBA, the hard segment polyamide components include PA6 and PA12, while the soft segment polyether components include polyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran (PTMG), and polyetheramine (PO). The properties of PEBA obtained from the reaction of different types of polyamides with polyethers, such as mechanical properties, water absorption, and resistivity, vary significantly.

[0004] PEBA elastomers can be modified in various ways to meet different application requirements. For example, different groups can be added to the molecular chain to achieve purposes such as antistatic and antibacterial properties, or various additives can be directly doped into the polymer to make its performance more suitable for actual use. Among the currently disclosed synthesis methods of polyamide polymers containing sulfonic acid groups, patent CN105778445A discloses a method for synthesizing a polymeric antistatic agent containing sulfonic acid groups by stepwise polymerization of benzene rings with sulfonic acid and carboxyl groups (such as sodium isophthalic acid-5-sulfonate, potassium isophthalic acid-5-sulfonate) with caprolactam, polyethylene glycol, adipic acid, methanesulfonic acid, etc.; patent CN104610542A discloses a polyamide containing sulfonic acid groups and its preparation method. The process involves mixing monomers containing sulfonic acid groups (5-sulfosalicylic acid or 2-amino-5-sulfobenzoic acid) with polyamide monomers, catalysts, etc., and carrying out a melt polymerization reaction. The polyamide containing sulfonic acid groups prepared can be used for... It can be spun into fibers or processed into plastic products; Patent CN1327461A discloses a method for synthesizing an antistatic polyether polyamide copolymer using dicarboxylic acid sulfonate as a capping agent for polyamide blocks or together with diamine as monomers constituting polyamide blocks, and polyethylene oxide as polyether segments. The polyether polyamide copolymer obtained by this method has certain thermal stability; Patent CN116082634 discloses a method for preparing sulfonic acid-modified furanyl polyamide. This method uses 2,5-furandicarboxyl chloride, 4,4′-diaminodiphenyl ether, and 2,5-diaminobenzenesulfonic acid as polymerizing monomers to generate an environmentally friendly novel semi-bio-based polyamide through a polymerization reaction. The polyamide obtained by this method can be used to make electrode materials.

[0005] Currently published methods for synthesizing polyether polyamide copolymers containing sulfonic acid groups all suffer from drawbacks to varying degrees, including complex reaction steps, lengthy reaction times, low monomer conversion efficiency, toxic reactants, and insufficient polymer mechanical properties, hindering large-scale industrial production. Furthermore, while block polyamide copolymer elastomers produced from caprolactam have low production costs and are conducive to commercial applications, their relatively low reactivity impedes their industrial production. Summary of the Invention

[0006] To address the aforementioned problems, this invention discloses a sulfonate-grafted polyether-polyester-polyamide block copolymer and its preparation method, which introduces specific sulfonate groups to meet specific applications. This invention employs a synthesis method involving the copolymerization of sulfonate-grafted polyester polyol BY-3305 with polyether polyol and polyamide, overcoming the drawbacks of previous methods. It exhibits higher reaction efficiency and fewer reaction byproducts compared to small molecule monomers containing sulfonate groups, and boasts advantages such as simple synthesis steps and high conversion rate. BY-3305, as a sulfonate-grafted polyester polyol, inherently possesses a certain degree of elasticity, and its addition at appropriate amounts will not affect the mechanical properties of the copolymer. The polyether-polyester-polyamide block copolymer of this invention is obtained through one-step melt polymerization, offering advantages such as simple synthesis method, low production cost, high strength, and adjustable properties.

[0007] To solve the technical problem of this invention, the proposed technical solution is: a method for preparing a sulfonate-containing polyether-polyester-polyamide block copolymer, wherein the polyether-polyester-polyamide block copolymer is prepared by melt polymerization of caprolactam, 6-aminohexanoic acid, aliphatic dicarboxylic acid, aliphatic diamine, polyether diol, and sulfonate-grafted polyester polyol BY-3305 as raw materials in the presence of a catalyst and an antioxidant;

[0008] The aliphatic dicarboxylic acid is 1,6-adipic acid, 1,10-decanoic acid, or 1,12-carbododecanoic acid; the aliphatic diamine is 1,6-hexanediamine, 1,10-decanediamine, or 1,12-carbododecanoic acid; the polyether diol is polytetrahydrofuran (PTMG) or polyethylene glycol (PEG) with a molecular weight of 250–2000; the catalyst is one or more of phosphoric acid, antimony trioxide, or antimony acetate; and the antioxidant is one or more of antioxidant 1010, antioxidant 1076, or triphenyl phosphite.

[0009] Preferably, the polyether-polyester-polyamide block copolymer is formed by melt polymerization of caprolactam, 6-aminohexanoic acid, adipic acid, sebacic acid, PTMG1000 or PEG, and sulfonate-grafted polyester polyol BY-3305 as raw materials in the presence of antimony acetate catalyst, phosphoric acid, antioxidant 1010, and triphenyl phosphite.

[0010] Preferably, the mass ratio of each raw material during synthesis is as follows: caprolactam: polyether diol: sulfonate-grafted polyester polyol BY-3305: aliphatic diamine: aliphatic diacid = 1:0.057-0.72:0-0.72:0.013-0.36:0.02-0.79; 6-aminohexanoic acid accounts for more than 5% of the total mass fraction of caprolactam and 6-aminohexanoic acid; the amount of catalyst is 0.01-1% of the polymer mass fraction; the amount of antioxidant is 0.05-1% of the polymer mass fraction; the molar number of the aliphatic diacid is equal to the sum of the molar numbers of polyether diol, aliphatic diamine, and sulfonate-grafted polyester polyol BY-3305.

[0011] The preferred optimal performance ratio that achieves the best balance between tensile strength and elongation at break is:

[0012] Caprolactam: 22.04 parts by weight; 6-Aminohexanoic acid: 2.45 parts by weight; Adipic acid: 4.06 parts by weight; Decanediamine: 3.45 parts by weight; PTMG1000: 7.50 parts by weight; BY-33056: 0.50 parts by weight; Antioxidant 1010: 0.20 parts by weight; Triphenyl phosphite: 0.10 parts by weight; Antimony acetate: 0.04 parts by weight; Phosphoric acid: 0.10 parts by weight.

[0013] The preferred optimal performance ratio that achieves the highest water absorption rate is:

[0014] Caprolactam: 22.04 parts by weight; 6-Aminohexanoic acid: 2.45 parts by weight; Adipic acid: 4.06 parts by weight; Decanediamine: 3.45 parts by weight; PEG1000: 7.50 parts by weight; BY-33056: 0.50 parts by weight; Antioxidant 1010: 0.20 parts by weight; Triphenyl phosphite: 0.10 parts by weight; Antimony acetate: 0.04 parts by weight; Phosphoric acid: 0.10 parts by weight.

[0015] The preferred optimal performance ratio that achieves the lowest surface resistivity is:

[0016] Caprolactam: 22.18 parts by weight; 6-Aminohexanoic acid: 2.47 parts by weight; Adipic acid: 3.90 parts by weight; Decanediamine: 3.45 parts by weight; PEG1000: 4.00 parts by weight; BY-33056: 4.00 parts by weight; Antioxidant 1010: 0.20 parts by weight; Triphenyl phosphite: 0.10 parts by weight; Antimony acetate: 0.04 parts by weight; Phosphoric acid: 0.10 parts by weight.

[0017] Preferably, it includes the following steps:

[0018] (1) Add the required caprolactam, 6-aminohexanoic acid, aliphatic dicarboxylic acid, aliphatic diamine, polyether diol, sulfonate-grafted polyester polyol BY-3305, antioxidant, and catalyst to a three-necked flask and purge with nitrogen for 5 to 20 minutes.

[0019] (2) The three-necked flask is heated to 210-265℃ under nitrogen protection and the reaction is maintained at this condition for 3-5 hours. The small molecules produced by the reaction are distilled out by the condenser of the distillation head.

[0020] (3) The three-necked flask is kept at a constant temperature of 210-265℃ and continuously evacuated for 1.5-3.5 hours to obtain the product.

[0021] To solve the technical problem of this invention, the proposed technical solution is as follows: the polyether-polyester-polyamide block copolymer prepared according to any of the above methods is characterized in that: the sulfonate-grafted polyether-polyester-polyamide block copolymer has the following structural formula:

[0022]

[0023] In the formula, a = 4-10, b = 6-12, c = 2-4, x = 10-150, y = 2-10, m = 3-50, and PET represents sulfonate-grafted polyester BY-3305.

[0024] The sulfonate-grafted polyether-polyester-polyamide block copolymer is obtained by one-step polymerization of caprolactam, 6-aminohexanoic acid, aliphatic diacid, aliphatic diamine, polyether diol, and sulfonate-grafted polyester polyol BY-3305 as raw materials in the presence of a polymerization catalyst. This polyether-polyester-polyamide block copolymer material has excellent mechanical properties, and its mechanical properties, surface resistivity, and water absorption can be adjusted within a certain range. It also possesses certain antistatic properties and can be used in various applications such as electronic product components and sporting goods.

[0025] Specifically, the aliphatic dicarboxylic acid is a saturated aliphatic dicarboxylic acid with six or more carbon atoms, such as adipic acid, sebacic acid, and dodecanoic acid; the aliphatic diamine is a saturated aliphatic diamine with six or more carbon atoms, such as hexamethylenediamine, decanediamine, and dodecanodiamine.

[0026] The polyether diol is polyethylene glycol and polytetrahydrofuran glycol, with a molecular weight in the range of 250-2000. Polypropylene glycol ethers with a molecular weight in the range of 250-2000 are also suitable for this invention.

[0027] The sulfonate-grafted polyester polyol BY-3305 was purchased from Beijing Baiyuan Chemical Co., Ltd., and its model number is BY-3305. According to the company's public information, its molecular weight is approximately 1500, its hydroxyl value is 70.08, and its sulfonic acid group content is 0.38 mol / Kg.

[0028] The polymerization catalyst is one or more commonly used catalysts in polyamide and polyester polymerization, such as titanate, phosphoric acid, antimony trioxide, antimony acetate, etc.

[0029] Since the reaction is carried out at a high temperature of around 250°C, a certain amount of antioxidant needs to be added to the material to prevent oxidation. The antioxidants are commonly used antioxidants in polyester and polyamide polymerization reactions, such as antioxidant 1010, antioxidant 1076, triphenyl phosphite, etc., or one or more of these.

[0030] The mass ratio of each raw material in the synthesis of the above-mentioned sulfonate-grafted polyether-polyester-polyamide block copolymer elastomer is as follows:

[0031] Caprolactam: Polyether: Sulfonate grafted polyester polyol BY-3305: Diamine: Diacid = 1: 0.057~0.72: 0~0.72: 0.013~0.36: 0.02~0.79.

[0032] To increase the polymerization rate, the 6-amino acid accounts for more than 5% of the total mass fraction of 6-aminohexanoic acid and caprolactam;

[0033] To improve the conversion rate of reactants and obtain high molecular weight polymers, the following conditions must be met: the number of carboxyl groups in aliphatic dicarboxylic acids is equal to or approximately equal to the sum of the number of hydroxyl groups in polyether diols, amino groups in aliphatic diamines, and hydroxyl groups in sulfonate-grafted polyester polyols.

[0034] The catalyst is 0.01 wt% to 1 wt% of the total polymer mass.

[0035] Antioxidant content: 0.05 wt% to 1 wt% of the total polymer mass.

[0036] The present invention further discloses a method for preparing the above-mentioned sulfonate-grafted polyether-polyester-polyamide block copolymer elastomer as follows:

[0037] Add the required components for the reaction, such as caprolactam, 6-aminocaproic acid, aliphatic dicarboxylic acid, aliphatic diamine, polyether diol, sulfonate-grafted polyester polyol BY-3305, antioxidant, and catalyst, into the reactor, and then purge with high-purity nitrogen for 5–20 minutes.

[0038] Under nitrogen protection and mechanical stirring, the reactants were heated to approximately 250°C and maintained at this condition for 3–5 hours. Small molecule compounds such as water released during the reaction were distilled off through the condenser of the distillation head.

[0039] Then reduce the nitrogen flow rate and connect the reaction to a vacuum system. Control the reaction conditions at a residual pressure of 5-20 mmHg and an internal temperature of around 250°C. Continue the reaction under these conditions for 1.5-3.5 hours. Once the reaction is complete, remove the product.

[0040] It should be noted that the sulfonate-grafted polyether-polyester-polyamide block copolymer elastomer described above can be obtained at a reaction temperature range of 210-265℃. Within this temperature range, a lower temperature requires a longer reaction time, while a higher temperature allows for a shorter reaction time.

[0041] Beneficial effects:

[0042] 1. This invention uses macromolecular sulfonate-grafted polyester polyol BY-3305 as a sulfonate grafting agent, which has higher reaction efficiency and fewer reaction byproducts than small molecule monomers containing sulfonic acid groups, which is conducive to the smooth progress of the polymerization reaction and obtains sulfonate-grafted polyether-polyester-polyamide block copolymer elastomer.

[0043] 2. This invention employs a one-step method to prepare sulfonate-grafted polyether-polyester polyamide block copolymer elastomers. The process involves a single feeding, requiring only temperature and vacuum control according to process requirements to directly synthesize the product. This invention features a simple synthesis method and excellent copolymer mechanical properties, and is expected to have wide applications in antistatic polymer materials, water-absorbing fiber materials, and solid-state battery electrolytes in the future.

[0044] 3. This invention introduces macromolecular sulfonate grafted polyester polyol comonomer, introducing sulfonic acid groups into the product structure while also introducing polyester segments into the elastomer.

[0045] This invention allows for the adjustment of the ratio of macromolecular sulfonate-grafted polyester polyol comonomers to polyethers such as PTMG and PEG, resulting in sulfonate-grafted polyether-polyester polyamide block copolymer elastomers with adjustable water absorption, surface resistance, and mechanical properties to suit different application scenarios. Attached Figure Description

[0046] Figure 1 This is the infrared FTIR spectrum of Example 4.

[0047] Figure 2 This is the infrared FTIR spectrum of Example 5. Detailed Implementation

[0048] The present invention will be further described below with reference to the embodiments and the technical solutions in the embodiments. The described embodiments are only some embodiments of the present invention and do not constitute a limitation on other rights of the present invention.

[0049] For ease of comparison, the aliphatic dicarboxylic acid in the embodiments is adipic acid, the aliphatic dicarboxylic acid is decanediamine, and the amount of decanediamine used is the same; the polyether diol in the embodiments is polyethylene glycol and polytetrahydrofuran diol, with a molecular weight in the range of 250-2000; a composite catalyst of antimony acetate and phosphoric acid is used in the embodiments; antioxidant 1010 and triphenyl phosphite are used as a composite antioxidant in the embodiments.

[0050] The raw materials used in the embodiments of the present invention are as follows:

[0051] Caprolactam, AR, selected from Aladdin Reagent Co., Ltd.;

[0052] 6-Aminocaproic acid, CP, is selected from Shanghai Bid Pharmaceutical Technology Co., Ltd.;

[0053] Sulfonate-grafted polyester polyol, industrial grade, model BY-3305 (molecular weight approximately 1500, hydroxyl value 70.08, sulfonic acid group content 0.38mol / Kg), selected from Beijing Baiyuan Chemical Co., Ltd.

[0054] 1,6-Adipic acid, AR, selected from Aladdin Reagent Co., Ltd.;

[0055] 1,10-Cephalodiamine, CP, selected from Shanghai Myriel Biochemical Technology Co., Ltd.;

[0056] Antimony acetate, CP, was selected from Shanghai Myriel Biochemical Technology Co., Ltd.

[0057] Antioxidant 1010, AR, is selected from Shanghai Myriel Biochemical Technology Co., Ltd.;

[0058] Triphenyl phosphite, CP, selected from Aladdin Reagent Co., Ltd.;

[0059] Polytetrahydrofuran, CP, with molecular weights of 250, 1000, and 2000, was selected from Shanghai Mairui Biochemical Technology Co., Ltd.

[0060] Polyethylene glycol, CP, molecular weight 600, 1000, selected from Sinopharm Chemical Reagent Co., Ltd.;

[0061] Phosphoric acid, CP, content >85%, selected from Shanghai Lingfeng Chemical Reagent Co., Ltd.

[0062] Example 1

[0063] This embodiment describes a method for synthesizing a polyether-polyester-polyamide block copolymer, comprising the following steps:

[0064] Add each raw material according to the ingredient list in Table 1, Example 1, and purge the air in the reaction flask with high-purity nitrogen for 10 minutes.

[0065] The material was heated to 250°C in an oil bath under continuous nitrogen purging and held for 4 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 15 mmHg for 2.5 hours to obtain a polyether-polyester-polyamide block copolymer.

[0066]

[0067] The product structure of this embodiment is as follows:

[0068] Where x = 10~150, y = 13~15, z = 2~10, and PET represents sulfonate-grafted polyester polyol BY-3305.

[0069] Example 2

[0070] This embodiment describes a method for synthesizing a polyether-polyester-polyamide block copolymer, comprising the following steps:

[0071] Add each raw material according to the ingredient list in Table 1, Example 2, and purge the air in the reaction flask with high-purity nitrogen for 10 minutes.

[0072] The material was heated to 250°C in an oil bath under continuous nitrogen purging and held for 4 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 10 mmHg for 2 hours to obtain a polyether-polyester-polyamide block copolymer.

[0073] Example 3

[0074] The present embodiment of a method for synthesizing a polyether-polyester-polyamide block copolymer includes the following steps:

[0075] Add each raw material according to the ingredient list in Table 1, Example 3, and purge the air in the reaction flask with high-purity nitrogen for 10 minutes.

[0076] The material was heated to 250°C in an oil bath under continuous nitrogen purging and maintained for 5 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 10 mmHg for 2 hours to obtain a polyether-polyester-polyamide block copolymer.

[0077]

[0078] Where x = 10~150, y = 13~15, z = 2~10, and PET represents sulfonate-grafted polyester BY-3305.

[0079] Example 4

[0080] This embodiment describes a method for synthesizing a polyether-polyester-polyamide block copolymer, comprising the following steps:

[0081] Add each raw material according to the ingredient list in Table 1, Example 4, and purge the air in the reaction flask with high-purity nitrogen for 10 minutes.

[0082] The material was heated to 250°C in an oil bath under continuous nitrogen purging and maintained for 5 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 10 mmHg for 2 hours to obtain a polyether-polyester-polyamide block copolymer.

[0083] The structural formula of this embodiment is as follows:

[0084]

[0085] Where x = 10~150, y = 13~15, z = 2~10, and PET represents sulfonate-grafted polyester BY-3305.

[0086] Specifically, the following steps are included:

[0087] (1) Add the required caprolactam, 6-aminohexanoic acid, adipic acid, decanediamine, polyether diol, sulfonate-grafted polyester polyol BY-3305, antioxidant, and catalyst to a three-necked flask and purge with nitrogen for 5 to 20 minutes.

[0088] (2) The three-necked flask is heated to 250°C under nitrogen protection and the reaction is maintained under these conditions for 5 hours. The small molecules produced by the reaction are distilled out through the condenser of the distillation head.

[0089] (3) The three-necked flask was kept at a constant temperature of 250°C and evacuated for 2 hours to obtain the product.

[0090] The infrared spectrum of Example 4 is shown below. Figure 1 The characteristic peak shown in the figure is as follows: 3300 cm⁻¹ -1 The peak at 2929 cm⁻¹ represents the stretching vibration peak of the NH bond in the amide bond of the block polymer. -1 and 2859cm -1 The peaks for the symmetric and asymmetric stretching vibrations of CH are at 1733 cm⁻¹. -1 The peak at 1635 cm⁻¹ represents the stretching vibration of the carbonyl group. -1 The peak at 1097 cm⁻¹ represents the NH bending vibration of secondary amides. -1 The peak at this point represents the symmetric stretching vibration of the ester group -COO-, with a wavelength of 687 cm⁻¹. -1 The peak at this point is the characteristic peak of in-plane rocking of the CC plane caused by CC stretching vibration. Due to the wavelength of 3487 cm⁻¹... -1 The disappearance of the nearby free -OH peaks indicates that both PEG and BY-3305 have undergone complete block copolymerization with the PA6 hard segment.

[0091] Example 5

[0092] This embodiment describes a method for synthesizing a polyether-polyester-polyamide block copolymer, comprising the following steps:

[0093] According to the ingredient list in Example 5 of Table 2, add the following raw materials: 22.04g caprolactam, 2.45g 6-aminocaproic acid, 4.06g adipic acid, 3.45g decanediamine, 7.5g PTMG1000, and 0.5g BY-3305 to a 250ml three-necked flask. Also add 0.20g antioxidant 1010, 0.10g triphenyl phosphite, 0.04g antimony acetate catalyst, and 0.10g phosphoric acid. Purge the air in the reaction flask with high-purity nitrogen for 5 minutes.

[0094] The material was heated to 250°C in an oil bath under continuous nitrogen purging and held for 3.5 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 15 mmHg for 2.5 hours to obtain a polyether-polyester-polyamide block copolymer.

[0095] The structural formula of this embodiment is as follows:

[0096]

[0097] Where x = 10~150, y = 13~15, z = 2~10, and PET represents sulfonate-grafted polyester polyol BY-3305.

[0098] Specifically, the following steps are included:

[0099] (1) Add the required caprolactam, 6-aminohexanoic acid, adipic acid, decanediamine, polyether diol, sulfonate-grafted polyester polyol BY-3305, antioxidant, and catalyst to a three-necked flask and purge with nitrogen for 5 to 20 minutes.

[0100] (2) The three-necked flask is heated to 250°C under nitrogen protection and the reaction is maintained at this condition for 3.5 hours. The small molecules produced by the reaction are distilled out through the condenser of the distillation head.

[0101] (3) The three-necked flask was kept at a constant temperature of 250°C and evacuated for 2.5 hours to obtain the product.

[0102] The FTIR spectrum of Example 5 is shown below. Figure 2 The characteristic peak shown in the figure is as follows: 3300 cm⁻¹ -1 The peak at 2930 cm⁻¹ represents the stretching vibration peak of the NH bond in the amide bond of the block polymer. -1 and 2856cm -1 The peaks for the symmetric and asymmetric stretching vibrations of CH are at 1733 cm⁻¹. -1 The peak at 1635 cm⁻¹ represents the stretching vibration of the carbonyl group.-1 The peak at 1107 cm⁻¹ represents the NH bending vibration of secondary amides. -1 The peak at this point represents the symmetric stretching vibration of the ester group -COO-, with a wavelength of 685 cm⁻¹. -1 The peak at this point is the characteristic peak of in-plane rocking of the CC plane caused by CC stretching vibration. Due to the wavelength of 3487 cm⁻¹... -1 The disappearance of the nearby free -OH peaks indicates that PTMG and BY-3305 have completely reacted with the PA6 hard segment.

[0103] Example 6

[0104] This embodiment describes a method for synthesizing a polyether-polyester-polyamide block copolymer, comprising the following steps:

[0105] Add each raw material according to the ingredient list in Table 2, Example 6, and purge the air in the reaction flask with high-purity nitrogen for 15 minutes.

[0106] The material was heated to 250°C in an oil bath under continuous nitrogen purging and held for 3.5 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 20 mmHg for 3 hours to obtain a polyether-polyester-polyamide block copolymer.

[0107] The structural formula of this embodiment is as follows:

[0108]

[0109] Where x = 10~150, y = 13~15, z = 2~10, and PET represents sulfonate-grafted polyester BY-3305.

[0110] Specifically, the following steps are included:

[0111] (1) Add the required caprolactam, 6-aminohexanoic acid, adipic acid, decanediamine, polyether diol, sulfonate-grafted polyester polyol BY-3305, antioxidant, and catalyst to a three-necked flask and purge with nitrogen for 5 to 20 minutes.

[0112] (2) The three-necked flask is heated to 250°C under nitrogen protection and the reaction is maintained at this condition for 3.5 hours. The small molecules produced by the reaction are distilled out through the condenser of the distillation head.

[0113] (3) The three-necked flask was kept at a constant temperature of 250°C and evacuated for 3 hours to obtain the product.

[0114] Since Example 6 and Example 4 have the same structural formula and infrared spectrum, it also indicates that the PEG segment and BY-3305 segment in Example 6 both underwent copolymerization with the PA6 segment.

[0115] Example 7

[0116] This embodiment describes a method for synthesizing a polyether-polyester-polyamide block copolymer, comprising the following steps:

[0117] Add each raw material according to the ingredient list in Table 2, Example 7, and purge the air in the reaction flask with high-purity nitrogen for 20 minutes.

[0118] The material was heated to 250°C in an oil bath under continuous nitrogen purging and held for 3 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 20 mmHg for 3 hours to obtain a polyether-polyester-polyamide block copolymer.

[0119] Example 8

[0120] This embodiment describes a method for synthesizing a polyether-polyester-polyamide block copolymer, comprising the following steps:

[0121] Add each raw material according to the ingredient list in Table 2, Example 8, and purge the air in the reaction flask with high-purity nitrogen for 10 minutes.

[0122] The material was heated to 250°C in an oil bath under continuous nitrogen purging and held for 4 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 5 mmHg for 1.5 hours to obtain a polyether-polyester-polyamide block copolymer.

[0123] Example 9

[0124] This embodiment describes a method for synthesizing a polyether-polyester-polyamide block copolymer, comprising the following steps:

[0125] Add each raw material according to the ingredient list in Example 9 of Table 2, and purge the air in the reaction bottle with high-purity nitrogen for 10 minutes.

[0126] The material was heated to 250°C in an oil bath under continuous nitrogen purging and held for 3.5 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 10 mmHg for 2 hours to obtain a polyether-polyester-polyamide block copolymer.

[0127] Comparative Example 1

[0128] The comparative example describes a method for synthesizing a polyether-polyamide block copolymer, comprising the following steps:

[0129] 22.01 g (0.1945 mol) caprolactam, 2.45 g (0.0187 mol) 6-aminohexanoic acid, 4.09 g (0.0280 mol) adipic acid, 3.45 g (0.0200 mol) decanediamine, and 8 g (0.0080 mol) PTMG1000 were added to a 250 ml three-necked flask. Separately, 0.20 g of antioxidant 1010, 0.10 g of triphenyl phosphite, 0.04 g of antimony acetate catalyst, and 0.10 g of phosphoric acid were added. High-purity nitrogen was bubbled through the flask to purge the air from the reaction vessel for 10 minutes.

[0130] The material was heated to 250°C in an oil bath under continuous nitrogen purging and maintained for 5 hours. Then, a vacuum was applied at 250°C until the system residual pressure was 10 mmHg for 2 hours to obtain a polyether-polyamide block copolymer.

[0131] The structural formula of the comparative product is as follows:

[0132]

[0133] Where x = 10 to 150, y = 13 to 15.

[0134] Comparative Example 2

[0135] The comparative example describes a method for synthesizing a polyether-polyamide block copolymer, comprising the following steps:

[0136] Add each raw material according to the ingredient list in Table 3 (Comparative Example 2), and purge the air in the reaction flask with high-purity nitrogen for 10 minutes.

[0137] The material was heated to 250°C in an oil bath under continuous nitrogen purging and held for 3.5 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 20 mmHg for 3.5 hours to obtain the polyether-polyamide block copolymer.

[0138] The structural formula of the comparative product is as follows:

[0139]

[0140] Where x = 10 to 150, y = 13 to 15.

[0141] Comparative Example 3

[0142] The method for synthesizing a polyester-polyamide block copolymer according to the comparative example includes the following steps:

[0143] Add each raw material according to the ingredient list in Table 3 (Comparative Example 3), and purge the air in the reaction flask with high-purity nitrogen for 10 minutes.

[0144] The material was heated to 250°C in an oil bath under continuous nitrogen purging and held for 4 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 10 mmHg for 2 hours to obtain the polyether-polyamide block copolymer.

[0145] The theoretical structural formula for the comparative product is as follows:

[0146]

[0147] Where x = 10 to 150.

[0148] The experiment revealed that the comparative ratio showed almost no reaction, and the product, once extracted, was a blocky solid with a hard, inelastic texture, which did not meet the characteristics of block polymer elastomers.

[0149] Comparative Example 4

[0150] This embodiment describes a method for synthesizing a polyester-polyamide block copolymer, comprising the following steps:

[0151] Add each raw material according to the ingredient list in Table 3 (Comparative Example 4), and purge the air in the reaction flask with high-purity nitrogen for 10 minutes.

[0152] The material was heated to 250°C in an oil bath under continuous nitrogen purging and held for 4 hours. Then, the temperature was maintained at 250°C and a vacuum was applied until the system residual pressure was 20 mmHg for 3 hours to obtain the polyether-polyamide block copolymer.

[0153] The experiment revealed that the comparative ratio showed almost no reaction, and the product, once extracted, was a blocky solid with a hard, inelastic texture, which did not meet the characteristics of block polymer elastomers.

[0154] Tables 1-2 below are a summary of the raw material composition and copolymer properties of Examples 1-9.

[0155] Table 1. Summary of raw material composition and copolymer properties in Examples 1-4

[0156]

[0157] Table 2. Summary of raw material composition and copolymer properties in Examples 5-9

[0158]

[0159] Table 3. Summary of raw material composition and copolymer properties of Comparative Examples 1-4

[0160]

[0161] The test methods and standards for various performance properties in this invention are as follows: Tensile properties: tested according to GB / T1040-2006 standard, the test instrument model is INSTRON3366 from INSTRON Corporation, and the tensile rate is 50mm / min;

[0162] Surface resistivity: Tested according to GB / T3048.5 standard, the testing instrument model is ZC-90G of Shanghai Taiou Electronics Co., Ltd., and the test voltage is 100V;

[0163] Shore hardness: tested according to GB / T531 standard;

[0164] Fourier transform infrared (FTIR) characterization: A Nicolet IS50 infrared spectrometer was used.

[0165] Water absorption rate: tested according to GB / T1034-2008 standard.

[0166] From Table 1 and Table 2, we can see that:

[0167] Comparative examples 1-9 show that by changing the ratio of BY-3305 to PTMG or PEG in the copolymer, a series of products with different tensile strengths, elongation at break, water absorption rates, and surface resistivity can be obtained.

[0168] Comparing Examples 3 and 4, it can be seen that, within a certain range, the elasticity of the polymer increases with the increase of polyether PEG content, while the surface resistivity decreases with the increase of BY-3305.

[0169] Comparing Examples 2 and 3, it can be seen that, compared with PEG, the copolymer obtained by reacting PTMG and BY-3305 has higher tensile strength and elongation at break; while the product obtained by copolymerizing PEG and BY-3305 has higher water absorption and lower surface resistivity.

[0170] Comparing Example 5 with Comparative Example 1, it can be seen that adding BY-3305 will slightly reduce the mechanical properties of the copolymer, but it can change the structure of the copolymer and introduce specific sulfonic acid groups to meet specific applications.

[0171] Comparing Examples 1-9: Example 5 exhibits the best tensile strength and elongation at break, with a tensile strength of 46.79 MPa and an elongation at break of 590.86%, making it the example that achieves the highest tensile strength and elongation at break; Example 4 has a surface resistivity of 1.88*10⁻⁶. 11 Example 1 is an embodiment that achieves the best antistatic performance; Example 6 has a water absorption rate of up to 28.16%, which is an embodiment that achieves the best water absorption performance.

[0172] Currently, few of the publicly disclosed invention patents involve the synthesis of sulfonate-grafted polyether-polyester-polyamide structural copolymers. The disclosed synthesis methods all adopt a synthetic route that attaches small molecule monomers containing sulfonic acid groups to the molecular chain of polyether-polyamide copolymers. This approach has drawbacks such as complex reaction steps, low monomer conversion rate, and insufficient polymer mechanical properties, which are not conducive to large-scale commercial production.

[0173] This invention employs a synthesis method that copolymerizes sulfonate-grafted polyester BY-3305 with polyether polyol and polyamide, overcoming the drawbacks of previous methods. It has the advantages of simple synthesis steps and high conversion rate. BY-3305, as a sulfonate-grafted polyester, inherently possesses a certain degree of elasticity, and its mechanical properties will not be affected when added in appropriate amounts.

[0174] The novel sulfonate-grafted polyether-polyester-polyamide structural copolymer and its synthesis method proposed in this invention have the advantages of simple synthesis method and excellent mechanical properties of copolymer, and are expected to be widely used in the fields of antistatic polymer materials, water-absorbing fiber materials, and solid battery electrolytes in the future.

[0175] The technical features of the above embodiments can be combined arbitrarily. This document only illustrates several implementation methods of this patent and is not intended to limit the invention. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of this invention should be within the protection scope of this invention. Those skilled in the art can make various changes or modifications within the scope of the claims, which do not affect the substantive content of this invention.

[0176] The present invention is not limited to the specific technical solutions described in the above embodiments. All technical solutions formed by equivalent substitutions are within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a sulfonate-containing polyether-polyester-polyamide block copolymer, characterized in that, The polyether-polyester-polyamide block copolymer is formed by melt polymerization of caprolactam, 6-aminohexanoic acid, aliphatic dicarboxylic acid, aliphatic diamine, polyether diol, and sulfonate-grafted polyester polyol BY-3305 as raw materials in the presence of a catalyst and antioxidant. The aliphatic dicarboxylic acid is 1,6-adipic acid, 1,10-decanoic acid, or 1,12-dodecanoic acid; the aliphatic diamine is 1,6-hexanediamine, 1,10-decanediamine, or 1,12-dodecanodiamine; the polyether diol is hydroxyl-terminated polytetrahydrofuran (PTMG) or polyethylene glycol (PEG) with a molecular weight of 250-2000; the catalyst is one or more of phosphoric acid, antimony trioxide, or antimony acetate; the antioxidant is one or more of antioxidant 1010, antioxidant 1076, or triphenyl phosphite; the mass ratio of each raw material during synthesis is: caprolactam : polyether diol : sulfonate-grafted polyester polyol BY-3305 : aliphatic diamine : aliphatic dicarboxylic acid = 1∶0.057~0.72∶0~0.72∶0.013~0.36∶0.02~0.79; wherein the sulfonate-grafted polyester polyol BY-3305 is not 0; 6-aminohexanoic acid accounts for more than 5% of the total mass fraction of caprolactam and 6-aminohexanoic acid; the molar number of the aliphatic dicarboxylic acid is equal to the sum of the molar numbers of the polyether diol, aliphatic diamine, and sulfonate-grafted polyester polyol BY-3305.

2. The method for preparing the sulfonate-containing polyether-polyester-polyamide block copolymer according to claim 1, characterized in that, The polyether-polyester-polyamide block copolymer is formed by melt polymerization of caprolactam, 6-aminohexanoic acid, 1,6-adipic acid, 1,10-decanediamine, PTMG or PEG, and sulfonate-grafted polyester polyol BY-3305 as raw materials in the presence of antimony acetate catalyst, phosphoric acid, antioxidant 1010, and triphenyl phosphite.

3. The method for preparing the sulfonate-containing polyether-polyester-polyamide block copolymer according to claim 1, characterized in that, The catalyst is used at a mass fraction of 0.01-1% of the block copolymer; the antioxidant is used at a mass fraction of 0.05-1% of the block copolymer.

4. The method for preparing the sulfonate-containing polyether-polyester-polyamide block copolymer according to claim 2, characterized in that: The optimal performance ratio of PTMG (PTMG1000) for achieving tensile strength and elongation at break is: Caprolactam: 22.04 parts by weight; 6-Aminohexanoic acid: 2.45 parts by weight; 1,6-Adipic acid: 4.06 parts by weight; 1,10-Decanediamine: 3.45 parts by weight; PTMG1000: 7.50 parts by weight; BY-3305: 0.50 parts by weight; Antioxidant 1010: 0.20 parts by weight; Triphenyl phosphite: 0.10 parts by weight; Antimony acetate: 0.04 parts by weight; Phosphoric acid: 0.10 parts by weight.

5. The method for preparing the sulfonate-containing polyether-polyester-polyamide block copolymer according to claim 2, characterized in that: The optimal formulation for achieving the highest water absorption rate using PEG1000 is: Caprolactam: 22.04 parts by weight; 6-Aminohexanoic acid: 2.45 parts by weight; 1,6-Adipic acid: 4.06 parts by weight; 1,10-Decanediamine: 3.45 parts by weight; PEG1000: 7.50 parts by weight; BY-3305: 0.50 parts by weight; Antioxidant 1010: 0.20 parts by weight; Triphenyl phosphite: 0.10 parts by weight; Antimony acetate: 0.04 parts by weight; Phosphoric acid: 0.10 parts by weight.

6. The method for preparing the sulfonate-containing polyether-polyester-polyamide block copolymer according to claim 2, characterized in that: The optimal performance ratio for PEG1000 to achieve the lowest surface resistivity is: Caprolactam: 22.18 parts by weight; 6-Aminohexanoic acid: 2.47 parts by weight; 1,6-Adipic acid: 3.90 parts by weight; 1,10-Decanediamine: 3.45 parts by weight; PEG1000: 4.00 parts by weight; BY-3305: 4.00 parts by weight; Antioxidant 1010: 0.20 parts by weight; Triphenyl phosphite: 0.10 parts by weight; Antimony acetate: 0.04 parts by weight; Phosphoric acid: 0.10 parts by weight.

7. The method for preparing the sulfonate-containing polyether-polyester-polyamide block copolymer according to any one of claims 1 to 6, characterized in that: Includes the following steps: (1) Add the required caprolactam, 6-aminohexanoic acid, aliphatic dicarboxylic acid, aliphatic diamine, polyether diol, sulfonate-grafted polyester polyol BY-3305, antioxidant, and catalyst to a three-necked flask and purge with nitrogen for 5-20 minutes. (2) Heat the three-necked flask to 210-265℃ under nitrogen protection and maintain this condition for 3-5 hours. The small molecules produced by the reaction are distilled out through the condenser of the distillation head. (3) Keep the three-necked flask at a constant temperature of 210-265℃ and continuously evacuate for 1.5-3.5 hours to obtain the product.

8. The sulfonate-containing polyether-polyester-polyamide block copolymer obtained by any one of claims 1-6, characterized in that: The sulfonate-containing polyether-polyester-polyamide block copolymer has the following structural formula: ； In the formula, c=2-4, x=10-150, y=2-10, m=3~50, and PET represents the residues of sulfonate-grafted polyester polyol BY-3305.

Images