Polyether-polyester-polyamide block copolymer containing sulfonate and preparation method thereof

Abstract

The invention discloses a sulfonate grafted polyether-polyester-polyamide block copolymer and a synthesis method thereof, and belongs to the field of materials. The invention provides a block copolymer elastomer material taking polycaprolactam as a hard segment and polyether and polyester as soft segments, and specific sulfonic acid groups are introduced to meet specific applications. According to the invention, caprolactam, 6-aminocaproic acid, aliphatic dibasic acid, aliphatic diamine, polyether glycol, sulfonate grafted polyester polyol BY-3305 and the like are used as raw materials, and macromolecular sulfonate grafted polyester polyol BY-3305 is used as a sulfonate grafting agent, so that the reaction efficiency is higher than that of a small molecular monomer containing a sulfonic acid group, and fewer reaction byproducts are generated; the polymerization reaction can be smoothly carried out. The sulfonate grafted polyether-polyester-polyamide block copolymer elastomer is obtained through one-step melt polymerization, and has the advantages of being simple and convenient in synthesis method, low in production cost, high in strength, adjustable in performance and the like.

Description

Technical Field

[0001] The invention belongs to the field of materials, and in particular relates to a sulfonate grafted polyether-polyester-polyamide block copolymer and a preparation method thereof. Background Art

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

[0003] Due to its unique structure, PEBA possesses many exceptional properties, including excellent mechanical properties, resistance to mechanical fatigue, and ease of processing. PEBA's composition includes hard-segment polyamides such as PA6 and PA12, while soft-segment polyethers include polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), and polyetheramine (PO). The properties of PEBA produced by reacting different types of polyamides with polyethers, such as mechanical properties, water absorption, and resistivity, vary significantly.

[0004] PEBA elastomers can be modified by different methods to meet the use requirements in different directions. For example, different groups can be added to the molecular chain to achieve purposes such as antistatic and antibacterial, or various additives can be directly doped into the polymer to make its performance more in line with actual use requirements. Among the currently disclosed synthesis methods of polyamide polymers containing sulfonic acid groups, Patent CN105778445A discloses a synthesis method of a polymer antistatic agent with sulfonic acid groups by step-polymerizing a benzene ring with sulfonic acid groups and carboxyl groups (such as sodium 5-sulfoisophthalic acid, potassium 5-sulfoisophthalic acid) with caprolactam, polyethylene glycol, adipic acid, methanesulfonic acid, etc.; Patent CN104610542A discloses a polyamide with sulfonic acid groups and a preparation method thereof, the process of which is to mix a monomer containing a sulfonic acid group (5-sulfosalicylic acid or 2-amino-5-sulfobenzoic acid) with a polyamide monomer, a catalyst, etc., and carry out a melt polymerization reaction. The prepared polyamide containing sulfonic acid groups can be used for Spinning into fibers or processing 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 a monomer constituting polyamide blocks, and polyethylene oxide as a polyether segment. The polyether polyamide copolymer obtained by this method has certain thermal stability; Patent CN116082634 discloses a method for preparing sulfonic acid-modified furan-based polyamide, which is a method of using 2,5-furandicarbonyl chloride, 4,4'-diaminodiphenyl ether, and 2,5-diaminobenzenesulfonic acid as polymerization monomers to generate an environmentally friendly new 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 often suffer from drawbacks such as complex reaction steps, lengthy reaction times, low monomer conversion efficiency, toxic reactants, and insufficient mechanical properties, hindering large-scale industrial production. Furthermore, segmented polyamide copolymer elastomers produced using caprolactam as a raw material offer low production costs and are therefore suitable for commercial applications. However, their low reactivity hinders their commercialization. Summary of the Invention

[0006] In order to solve the above problems, the present invention discloses a sulfonate grafted polyether-polyester-polyamide block copolymer and a preparation method thereof, which meets specific uses by introducing specific sulfonate groups. The present invention adopts a synthesis method of copolymerizing sulfonate grafted polyester polyol BY-3305 with polyether polyol and polyamide, which solves the drawbacks of previous solutions, has higher reaction efficiency and fewer reaction by-products than small molecule monomers containing sulfonic acid groups, and has the advantages of simple synthesis steps and high conversion rate. BY-3305, as a sulfonate grafted polyester polyol, itself has a certain elasticity and will not affect the mechanical properties of the copolymer when added in an appropriate amount. The polyether-polyester-polyamide block copolymer described in the present invention is obtained by one-step melt polymerization, and has the advantages of simple synthesis method, low production cost, high strength, and adjustable performance.

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

[0008] The aliphatic dibasic acid is 1,6-hexanediol, 1,10-decanedioic acid or 1,12-carbon dodecanedioic acid; the aliphatic diamine is 1,6-hexanediamine, 1,10-decanediamine or 1,12-carbon dodecanediamine; the polyether diol is polytetramethyleneimine (PTMG) or polyethylene glycol (PEG), and has a molecular weight of 250 to 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 prepared by melt polymerization of caprolactam, 6-aminocaproic acid, adipic acid, decanediamine, PTMG1000 or PEG, and sulfonate-grafted polyester polyol BY-3305 in the presence of catalysts antimony acetate, phosphoric acid, antioxidant 1010, and triphenyl phosphite.

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

[0011] Preferably, the best performance ratio for achieving tensile strength and elongation at break is:

[0012] Caprolactam: 22.04 parts by mass; 6-aminocaproic acid: 2.45 parts by mass; adipic acid: 4.06 parts by mass; decanediamine: 3.45 parts by mass; PTMG1000: 7.50 parts by mass; BY-33056: 0.50 parts by mass; antioxidant 1010: 0.20 parts by mass; triphenyl phosphite: 0.10 parts by mass; antimony acetate: 0.04 parts by mass; phosphoric acid: 0.10 parts by mass.

[0013] Preferably, the best performance ratio that can achieve the highest water absorption rate is:

[0014] Caprolactam: 22.04 parts by mass; 6-aminocaproic acid: 2.45 parts by mass; adipic acid: 4.06 parts by mass; decanediamine: 3.45 parts by mass; PEG1000: 7.50 parts by mass; BY-33056: 0.50 parts by mass; antioxidant 1010: 0.20 parts by mass; triphenyl phosphite: 0.10 parts by mass; antimony acetate: 0.04 parts by mass; phosphoric acid: 0.10 parts by mass.

[0015] Preferably, the best performance ratio to achieve the lowest surface resistivity is:

[0016] Caprolactam: 22.18 parts by mass; 6-aminocaproic acid: 2.47 parts by mass; adipic acid: 3.90 parts by mass; decanediamine: 3.45 parts by mass; PEG1000: 4.00 parts by mass; BY-33056: 4.00 parts by mass; antioxidant 1010: 0.20 parts by mass; triphenyl phosphite: 0.10 parts by mass; antimony acetate: 0.04 parts by mass; phosphoric acid: 0.10 parts by mass.

[0017] Preferably, the method comprises the following steps:

[0018] (1) Add caprolactam, 6-aminocaproic acid, aliphatic dibasic acid, aliphatic diamine, polyether diol, sulfonate grafted polyester polyol BY-3305, antioxidant and catalyst required for the reaction into a three-necked flask and pass nitrogen for 5 to 20 minutes;

[0019] (2) The three-necked flask was heated to 210-265° C. under nitrogen protection and kept reacting under this condition for 3-5 hours. The small molecules produced by the reaction were distilled out from the condenser of the distillation head;

[0020] (3) The three-necked flask was kept at a constant temperature of 210-265° C. and vacuumed for 1.5-3.5 h to obtain the product.

[0021] In order to solve the technical problem of the present invention, the technical solution proposed is: a polyether-polyester-polyamide block copolymer prepared according to any of the above methods, 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 a one-step polymerization reaction using caprolactam, 6-aminocaproic acid, an aliphatic dibasic acid, an aliphatic diamine, a polyether diol, and a sulfonate-grafted polyester polyol BY-3305 as raw materials in the presence of a polymerization catalyst. This polyether-polyester-polyamide block copolymer exhibits excellent mechanical properties. Its mechanical properties, surface resistivity, and water absorption can be adjusted within a certain range. It also exhibits certain antistatic properties and can be used in various applications, including electronic components and sports equipment.

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

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

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

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

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

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

[0031] Caprolactam: polyether: sulfonate grafted polyester polyol BY-3305: diamine: dibasic acid = 1: 0.057~0.72: 0~0.72: 0.013~0.36: 0.02~0.79.

[0032] In order to increase the polymerization reaction rate, the 6-amino acid accounts for more than 5% of the total mass fraction of 6-aminocaproic acid and caprolactam;

[0033] In order to improve the conversion rate of reactants and obtain high molecular polymers, the following should be satisfied: the molar number of carboxyl groups in the aliphatic dibasic acid is equal to or close to the sum of the molar numbers of hydroxyl groups in the polyether diol, amino groups in the aliphatic diamine, and hydroxyl groups in the sulfonate grafted polyester polyol.

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

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

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

[0037] The caprolactam, 6-aminocaproic acid, aliphatic dibasic acid, aliphatic diamine, polyether diol, sulfonate grafted polyester polyol BY-3305, antioxidant and catalyst required for the reaction are added to the reactor, and high-purity nitrogen is introduced for 5 to 20 minutes.

[0038] Under nitrogen protection and mechanical stirring, the reaction material is heated to approximately 250° C. and maintained at this temperature for 3 to 5 hours. The water and other small molecular compounds released by the reaction are distilled out through a condenser at the distillation head.

[0039] Then reduce the nitrogen flow rate and connect the reaction to a vacuum system. The reaction conditions are controlled at a system residual pressure of 5-20 mmHg and an internal temperature of about 250°C. Continue the reaction under these conditions for 1.5 to 3.5 hours. When the reaction is complete, take out the product.

[0040] It should be noted that the sulfonate grafted polyether-polyester-polyamide block copolymer elastomer can be obtained at a reaction temperature in the range of 210-265°C. In this temperature range, a lower temperature requires a longer reaction time, while a higher temperature requires a shorter reaction time.

[0041] Beneficial effects:

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

[0043] 2. This invention utilizes a one-step process to prepare sulfonate-grafted polyether-polyester-polyamide block copolymer elastomers. The materials are fed once, and the product can be directly synthesized by simply controlling the temperature and vacuum level according to process requirements. This method offers advantages such as a simple synthesis method and excellent mechanical properties of the copolymer. It is expected to have broad applications in antistatic polymer materials, absorbent fiber materials, solid battery electrolytes, and other fields.

[0044] 3. The present invention introduces a macromolecular sulfonate grafted polyester polyol comonomer, which not only introduces a sulfonic acid group into the product structure but also introduces a polyester segment into the elastomer.

[0045] The present invention adjusts the ratio of macromolecular sulfonate grafted polyester polyol comonomer to polyethers such as PTMG and PEG to obtain a sulfonate grafted polyether-polyester polyamide block copolymer elastomer with adjustable water absorption, surface resistance and mechanical properties to adapt to different application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[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 DESCRIPTION

[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 a part of the embodiments of the present invention and do not limit other rights of the present invention.

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

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

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

[0052] 6-aminohexanoic acid, CP, was obtained from Shanghai Bid Pharmaceutical Technology Co., Ltd.;

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

[0054] 1,6-Hexanedioic acid, AR, was obtained from Aladdin Reagent Co., Ltd.;

[0055] 1,10-Decanediamine, CP, was obtained from Shanghai Myril Biochemical Technology Co., Ltd.;

[0056] Antimony acetate, CP, was obtained from Shanghai Myril Biochemical Technology Co., Ltd.;

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

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

[0059] Polytetrahydrofuran, CP, molecular weight 250, 1000, 2000, selected from Shanghai Mairui Biochemical Technology Co., Ltd.;

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

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

[0062] Example 1

[0063] A method for synthesizing a polyether-polyester-polyamide block copolymer of this embodiment comprises the following steps:

[0064] The raw materials were added according to the ingredient list of Example 1 in Table 1, and high-purity nitrogen was introduced to replace the air in the reaction flask for 10 minutes.

[0065] The material was heated to 250° C. in an oil bath under continuous nitrogen flow and maintained for 4 h, and then vacuumed to a system residual pressure of 15 mmHg while maintaining 250° C. for 2.5 h to obtain a polyether-polyester-polyamide block copolymer.

[0066]

[0067] The structural formula of the product of this embodiment is as follows:

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

[0069] Example 2

[0070] A method for synthesizing a polyether-polyester-polyamide block copolymer of this embodiment comprises the following steps:

[0071] The raw materials were added according to the ingredient list of Example 2 in Table 1, and high-purity nitrogen was introduced to replace the air in the reaction flask for 10 minutes.

[0072] The material was heated to 250° C. in an oil bath under continuous nitrogen flow and maintained for 4 h, and then vacuumed to a system residual pressure of 10 mmHg while maintaining 250° C. for 2 h to obtain a polyether-polyester-polyamide block copolymer.

[0073] Example 3

[0074] A method for synthesizing a polyether-polyester-polyamide block copolymer according to the present invention comprises the following steps:

[0075] The raw materials were added according to the ingredient list of Example 3 in Table 1, and high-purity nitrogen was introduced to replace the air in the reaction flask for 10 minutes.

[0076] The material was heated to 250° C. in an oil bath under continuous nitrogen flow and maintained for 5 h, and then vacuumed to a system residual pressure of 10 mmHg while maintaining 250° C. for 2 h to obtain a polyether-polyester-polyamide block copolymer.

[0077]

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

[0079] Example 4

[0080] A method for synthesizing a polyether-polyester-polyamide block copolymer of this embodiment comprises the following steps:

[0081] The raw materials were added according to the ingredient list of Example 4 in Table 1, and high-purity nitrogen was introduced to replace the air in the reaction flask for 10 minutes.

[0082] The material was heated to 250° C. in an oil bath under continuous nitrogen flow and maintained for 5 h, and then vacuumed to a system residual pressure of 10 mmHg while maintaining 250° C. for 2 h to obtain a polyether-polyester-polyamide block copolymer.

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

[0084]

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

[0086] The specific steps include:

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

[0088] (2) The three-necked flask was heated to 250° C. under nitrogen protection and kept at this condition for 5 h. The small molecules produced by the reaction were distilled out from the condenser of the distillation head;

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

[0090] The infrared spectrum of Example 4 is shown in Figure 1 , as can be seen from the figure, its characteristic peaks are as follows: 3300cm -1 The NH bond stretching vibration peak in the block polymer amide bond is 2929 cm -1 and 2859cm -1 The symmetric and asymmetric stretching vibration peaks of CH, 1733 cm -1 The stretching vibration peak of carbonyl is at 1635 cm -1 The NH bending vibration peak of secondary amide is 1097 cm -1 The symmetrical stretching vibration peak of the ester group -COO- has a wavelength of 687 cm -1 The CC stretching vibration is caused by the CC in-plane swing characteristic peak. -1 The disappearance of the nearby free -OH peak indicates that both PEG and BY-3305 have completely undergone block copolymerization reaction with the PA6 hard segment.

[0091] Example 5

[0092] A method for synthesizing a polyether-polyester-polyamide block copolymer of this embodiment comprises the following steps:

[0093] According to the ingredients listed in Table 2 for Example 5, 22.04 g of caprolactam, 2.45 g of 6-aminocaproic acid, 4.06 g of adipic acid, 3.45 g of decanediamine, 7.5 g of PTMG1000, and 0.5 g of BY-3305 were added to a 250 ml three-necked flask. Additionally, 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 introduced to displace the air in the reaction flask for 5 minutes.

[0094] The material was heated to 250° C. in an oil bath under continuous nitrogen flow and maintained for 3.5 h, and then vacuumed to a system residual pressure of 15 mmHg while maintaining 250° C. for 2.5 h to obtain a polyether-polyester-polyamide block copolymer.

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

[0096]

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

[0098] The specific steps include:

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

[0100] (2) The three-necked flask was heated to 250° C. under nitrogen protection and kept at this condition for 3.5 h. The small molecules produced by the reaction were distilled out from the condenser of the distillation head;

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

[0102] The FTIR spectrum of Example 5 is shown in Figure 2 , as can be seen from the figure, its characteristic peaks are as follows: 3300cm -1 The NH bond stretching vibration peak in the block polymer amide bond is 2930 cm -1 and 2856cm -1 The symmetric and asymmetric stretching vibration peaks of CH, 1733 cm -1 The stretching vibration peak of carbonyl is at 1635 cm-1 The NH bending vibration peak of secondary amide is at 1107 cm -1 The symmetrical stretching vibration peak of the ester group -COO- has a wavelength of 685 cm -1 The CC stretching vibration is caused by the CC in-plane swing characteristic peak. -1 The disappearance of the nearby free -OH peak indicates that PTMG and BY-3305 have completely reacted with the PA6 hard segment.

[0103] Example 6

[0104] A method for synthesizing a polyether-polyester-polyamide block copolymer of this embodiment comprises the following steps:

[0105] The raw materials were added according to the ingredient list of Example 6 in Table 2, and high-purity nitrogen was introduced to replace the air in the reaction flask for 15 minutes.

[0106] The material was heated to 250° C. in an oil bath under continuous nitrogen flow and maintained for 3.5 h, and then vacuumed to a system residual pressure of 20 mmHg while maintaining 250° C. for 3 h to obtain a polyether-polyester-polyamide block copolymer.

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

[0108]

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

[0110] The specific steps include:

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

[0112] (2) The three-necked flask was heated to 250° C. under nitrogen protection and kept at this condition for 3.5 h. The small molecules produced by the reaction were distilled out from the condenser of the distillation head;

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

[0114] Since Example 6 has the same structural formula as Example 4 and its infrared spectrum is also the same, it also shows that the PEG segment and BY-3305 segment in Example 6 have copolymerized with the PA6 segment.

[0115] Example 7

[0116] A method for synthesizing a polyether-polyester-polyamide block copolymer of this embodiment comprises the following steps:

[0117] The raw materials were added according to the ingredient list of Example 7 in Table 2, and high-purity nitrogen was introduced to replace the air in the reaction flask for 20 minutes.

[0118] The material was heated to 250° C. in an oil bath under the condition of continuous nitrogen flow and maintained for 3 h, and then vacuumed to a system residual pressure of 20 mmHg while maintaining 250° C. for 3 h to obtain a polyether-polyester-polyamide block copolymer.

[0119] Example 8

[0120] A method for synthesizing a polyether-polyester-polyamide block copolymer of this embodiment comprises the following steps:

[0121] The raw materials were added according to the ingredient list of Example 8 in Table 2, and high-purity nitrogen was introduced to replace the air in the reaction flask for 10 minutes.

[0122] The material was heated to 250° C. in an oil bath under continuous nitrogen flow and maintained for 4 h, and then vacuumed to a system residual pressure of 5 mmHg for 1.5 h while maintaining 250° C. to obtain a polyether-polyester-polyamide block copolymer.

[0123] Example 9

[0124] A method for synthesizing a polyether-polyester-polyamide block copolymer of this embodiment comprises the following steps:

[0125] The raw materials were added according to the ingredient list of Example 9 in Table 2, and high-purity nitrogen was introduced to replace the air in the reaction flask for 10 minutes.

[0126] The material was heated to 250° C. in an oil bath under continuous nitrogen flow and maintained for 3.5 h, and then vacuumed to a system residual pressure of 10 mmHg while maintaining 250° C. for 2 h to obtain a polyether-polyester-polyamide block copolymer.

[0127] Comparative Example 1

[0128] The synthesis method of a polyether-polyamide block copolymer in this comparative example comprises the following steps:

[0129] 22.01 g (0.1945 mol) of caprolactam, 2.45 g (0.0187 mol) of 6-aminocaproic acid, 4.09 g (0.0280 mol) of adipic acid, 3.45 g (0.0200 mol) of decanediamine, and 8 g (0.0080 mol) of PTMG1000 were added to a 250 ml three-necked flask. Also added were 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. High-purity nitrogen was introduced to displace the air in the reaction flask for 10 minutes.

[0130] The material was heated to 250° C. in an oil bath under continuous nitrogen flow and maintained for 5 h, and then vacuumed to a system residual pressure of 10 mmHg at 250° C. for 2 h to obtain a polyether-polyamide block copolymer.

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

[0132]

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

[0134] Comparative Example 2

[0135] The synthesis method of a polyether-polyamide block copolymer in this comparative example comprises the following steps:

[0136] Add the raw materials according to the ingredient list of Comparative Example 2 in Table 3, and introduce high-purity nitrogen to replace the air in the reaction flask for 10 minutes.

[0137] The material was heated to 250° C. in an oil bath under the condition of continuous nitrogen flow and maintained for 3.5 hours, and then vacuumed to a system residual pressure of 20 mmHg while maintaining 250° C. for 3.5 hours to obtain a polyether-polyamide block copolymer.

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

[0139]

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

[0141] Comparative Example 3

[0142] The synthesis method of a polyester-polyamide block copolymer in this comparative example comprises the following steps:

[0143] The raw materials were added according to the ingredient list of Comparative Example 3 in Table 3, and high-purity nitrogen was introduced to replace the air in the reaction flask for 10 minutes.

[0144] The material was heated to 250° C. in an oil bath under the condition of continuous nitrogen flow and maintained for 4 h, and then vacuumed to a system residual pressure of 10 mmHg while maintaining 250° C. for 2 h to obtain a polyether-polyamide block copolymer.

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

[0146]

[0147] Where x = 10 to 150.

[0148] During the experiment, it was found that the comparative example hardly reacted, and the product was a block-like solid after being taken out, with a hard and inelastic texture, which did not meet the characteristics of a block polymer elastomer.

[0149] Comparative Example 4

[0150] A method for synthesizing a polyester-polyamide block copolymer of this embodiment comprises the following steps:

[0151] The raw materials were added according to the ingredient list of Comparative Example 4 in Table 3, and high-purity nitrogen was introduced to replace the air in the reaction flask for 10 minutes.

[0152] The material was heated to 250° C. in an oil bath under the condition of continuous nitrogen flow and maintained for 4 h, and then vacuumed to a system residual pressure of 20 mmHg while maintaining the temperature at 250° C. for 3 h to obtain a polyether-polyamide block copolymer.

[0153] During the experiment, it was found that the comparative example hardly reacted, and the product was a block-like solid after being taken out, with a hard and inelastic texture, which did not meet the characteristics of a block polymer elastomer.

[0154] The following Tables 1-2 are a list of raw material compositions and copolymer properties of Examples 1 to 9.

[0155] Table 1 Raw material composition and copolymer properties of Examples 1 to 4

[0156]

[0157] Table 2 Raw material composition and copolymer properties of Examples 5-9

[0158]

[0159] Table 3 Raw material composition and copolymer properties of comparative examples 1-4

[0160]

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

[0162] Surface resistivity: tested according to GB / T3048.5 standard, the test 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 spectroscopy FTIR characterization: NICOLET IS50 infrared spectrometer was used;

[0165] Water absorption: 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 and elongations at break as well as different water absorption rates and surface resistivities can be obtained.

[0168] Comparison of Example 3 and Example 4 shows that, within a certain range, the elasticity of the polymer increases with the increase of the polyether PEG content, and the surface resistivity decreases with the increase of BY-3305.

[0169] Comparing Example 2 with Example 3, it can be seen that compared with PEG, the copolymer obtained by the reaction of PTMG and BY-3305 has higher breaking strength and elongation at break; and the product obtained by the copolymerization of PEG and BY-3305 has higher water absorption and lower surface resistivity.

[0170] Comparison of Example 5 with Comparative Example 1 shows that the addition of BY-3305 slightly reduces the mechanical properties of the copolymer, but can change the structure of the copolymer and introduce specific sulfonic acid groups to meet specific applications.

[0171] Comprehensive comparison of Examples 1-9: Example 5 has the best tensile strength and elongation at break, with a tensile strength of 46.79 MPa and an elongation at break of 590.86%, which is the embodiment that can achieve the highest tensile strength and elongation at break; the surface resistivity of Example 4 is 1.88*10 11 , which is an embodiment that can achieve the best antistatic performance; the water absorption rate of Example 6 can reach 28.16%, which is an embodiment that can achieve the best water absorption performance.

[0172] Among the currently disclosed invention patents, few involve the synthesis of sulfonate-grafted polyether-polyester-polyamide structural copolymers. The disclosed synthesis methods all adopt a synthetic route in which small molecular monomers containing sulfonic acid groups are grafted into the molecular chain of polyether-polyamide copolymers. These methods have disadvantages such as complex reaction steps, low monomer conversion rate, and insufficient mechanical properties of the polymer, which are not conducive to large-scale commercial production.

[0173] The present invention adopts a synthesis method of copolymerizing sulfonate-grafted polyester BY-3305 with polyether polyol and polyamide, which solves the drawbacks of previous solutions and has the advantages of simple synthesis steps and high conversion rate. BY-3305, as a sulfonate-grafted polyester, itself has a certain elasticity and will not affect the mechanical properties of the copolymer when added in an appropriate amount.

[0174] The novel sulfonate-grafted polyether-polyester-polyamide structure copolymer and its synthesis method proposed in the present invention have the characteristics of simple synthesis method and excellent mechanical properties of the copolymer. In the future, it is expected to be widely used in the fields of antistatic polymer materials, water-absorbent fiber materials, solid battery electrolytes, etc.

[0175] The technical features of the above-described embodiments may be combined in any combination. The description herein merely illustrates several implementation methods of this patent and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall fall within the scope of protection of the present invention. Those skilled in the art may make various changes or modifications within the scope of the claims, which shall not affect the essence of the present invention.

[0176] The present invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent replacement are within the protection scope required by the present invention.

Claims

1. A method for preparing a polyether-polyester-polyamide block copolymer containing sulfonate, characterized in that: The polyether-polyester-polyamide block copolymer is prepared by melt polymerization of caprolactam, 6-aminocaproic acid, aliphatic dibasic acid, aliphatic diamine, polyether diol, and sulfonate grafted polyester polyol BY-3305 as raw materials in the presence of a catalyst and an antioxidant; The aliphatic dibasic acid is 1,6-hexanediol, 1,10-decanedioic acid or 1,12-carbon dodecanedioic acid; the aliphatic diamine is 1,6-hexanediamine, 1,10-decanediamine or 1,12-carbon dodecanediamine; the polyether diol is hydroxy-terminated polytetramethylene glycol (PTMG) or polyethylene glycol (PEG) with a molecular weight of 250 to 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.

2. The method for preparing a sulfonate-containing polyether-polyester-polyamide block copolymer according to claim 1, wherein: The polyether-polyester-polyamide block copolymer is prepared by melt polymerization of caprolactam, 6-aminocaproic acid, adipic acid, decanediamine, PTMG or PEG, and sulfonate grafted polyester polyol BY-3305 as raw materials in the presence of catalysts such as antimony acetate, phosphoric acid, antioxidant 1010, and triphenyl phosphite.

3. The method for preparing a sulfonate-containing polyether-polyester-polyamide block copolymer according to claim 1, wherein: The mass ratio of each raw material during its synthesis is: caprolactam: polyether diol: sulfonate grafted polyester polyol BY-3305: aliphatic diamine: aliphatic dibasic acid = 1: 0.057-0.72: 0-0.72: 0.013-0.36: 0.02-0.79; 6-aminocaproic acid accounts for more than 5% of the total mass fraction of caprolactam and 6-aminocaproic acid; the amount of the catalyst is 0.01-1% by mass of the polymer; the amount of the antioxidant is 0.05-1% by mass of the polymer; the molar number of the aliphatic dibasic acid is equal to the sum of the molar numbers of the polyether diol, the aliphatic diamine, and the sulfonate-grafted polyester polyol BY-3305.

4. The method for preparing a sulfonate-containing polyether-polyester-polyamide block copolymer according to claim 1, wherein: The best performance ratio to achieve tensile strength and elongation at break is: Caprolactam: 22.04 parts by mass; 6-aminocaproic acid: 2.45 parts by mass; adipic acid: 4.06 parts by mass; Decanediamine: 3.45 parts by mass; PTMG1000: 7.50 parts by mass; BY-3305: 0.50 parts by mass; Antioxidant 1010: 0.20 parts by mass; Triphenyl phosphite: 0.10 parts by mass; Antimony acetate: 0.04 parts by mass; Phosphoric acid: 0.10 parts by mass.

5. The method for preparing a sulfonate-containing polyether-polyester-polyamide block copolymer according to claim 1, wherein: The optimal performance ratio to achieve the highest water absorption rate is: caprolactam: 22.04 mass parts; 6-aminocaproic acid: 2.45 mass parts; adipic acid: 4.06 mass parts; Decanediamine: 3.45 parts by mass; PEG1000: 7.50 parts by mass; BY-3305: 0.50 parts by mass; Antioxidant 1010: 0.20 parts by mass; Triphenyl phosphite: 0.10 parts by mass; Antimony acetate: 0.04 parts by mass; Phosphoric acid: 0.10 parts by mass.

6. The method for preparing a sulfonate-containing polyether-polyester-polyamide block copolymer according to claim 1, wherein: The best performance ratio to achieve the lowest surface resistivity is: Caprolactam: 22.18 parts by mass; 6-aminocaproic acid: 2.47 parts by mass; adipic acid: 3.90 parts by mass; decanediamine: 3.45 parts by mass; PEG1000: 4.00 parts by mass; BY-3305: 4.00 parts by mass; antioxidant 1010: 0.20 parts by mass; triphenyl phosphite: 0.10 parts by mass; antimony acetate: 0.04 parts by mass; Phosphoric acid: 0.10 parts by mass.

7. The method for preparing a sulfonate-containing polyether-polyester-polyamide block copolymer according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) Add caprolactam, 6-aminocaproic acid, aliphatic dibasic acid, aliphatic diamine, polyether diol, sulfonate grafted polyester polyol BY-3305, antioxidant and catalyst required for the reaction into a three-necked flask and pass nitrogen for 5 to 20 minutes; (2) The three-necked flask was heated to 210-265°C under nitrogen protection and kept at this condition for 3-5 hours. The small molecules produced by the reaction were distilled out from the condenser of the distillation head; (3) The three-necked flask was kept at a constant temperature of 210-265° C. and vacuumed for 1.5-3.5 h to obtain the product.

8. The polyether-polyester-polyamide block copolymer prepared according to any one of claims 1 to 6, characterized in that: The sulfonate grafted polyether-polyester-polyamide block copolymer has the following structural formula: 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 polyol BY-3305.

Images