Polyamide elastomer raw material composition and application thereof, polyamide elastomer and preparation method thereof

Abstract

The invention relates to the field of macromolecules, in particular to a polyamide elastomer raw material composition and application thereof, polyamide elastomer and a preparation method thereof. The raw material composition contains polyamide and polyether, wherein at least one end-capping group in the polyamide is an amino-terminated group; at least one end-capping group in the polyether is an ester group. When the raw material composition is used for preparing the polyamide elastomer, the advantages of high reaction speed, high production efficiency and the like are achieved, the reaction controllability is high, the molecular weight of the product is large, and the type, molecular weight and structure of the soft segment can be adjusted according to application requirements, so that the performance of the elastomer is effectively regulated and controlled.

Description

Technical Field

[0001] This invention relates to the field of polymers, specifically to a polyamide elastomer raw material composition and its application, polyamide elastomers and their preparation methods. Background Technology

[0002] Thermoplastic polyamide elastomer (TPAE) is a type of segmented block copolymer composed of high-melting-point crystalline polyamide hard segments and non-crystalline polyester or polyether soft segments. It is a material that combines the properties of rubber and thermoplastic plastics, and has the characteristics of high strength, excellent low-temperature performance, fatigue resistance, abrasion resistance, organic solvent resistance, and antistatic properties. It is widely used in sports equipment, medical devices, automotive parts, electronic and electrical products, aerospace, and daily necessities.

[0003] The main methods for preparing TPAEs are the diacid method, the isocyanate method, and the anionic polymerization method. The diacid method first prepares a PA prepolymer with dual-carboxyl-terminated groups through ring-opening polymerization of lactams or condensation polymerization of diacids with diamines or α,ω-amino acids. Then, the PA prepolymer is esterified with polyether under specific temperature and vacuum conditions to obtain a copolymer. This method was the earliest developed and is currently the most widely used and applied method, with most commercially available TPAEs prepared using this method. For example, S. Mumcu et al. of Hüels in Germany produced the first generation of commercial TPAEs using sebacic acid, dodecyl lactam, and polybutanediol as raw materials via melt polymerization. Subsequently, Arkema in France launched a series of elastomers with various hardnesses based on polyamide 11 and polyamide 12: the XX33 series and the Rnew series. Ube Industries in Japan launched the XPA series of polyamide elastomers with PA12 as the hard segment and polyether as the soft segment. This product series includes four varieties: 9044X2, 9055X1, 9055X2, and 9063X1, with Shore hardnesses of 44D, 62D, 54D, and 56D, respectively. In addition, the company has also developed four varieties of TPAE with rubber-like trade names: PAE600, 601, 1200, and 1201. This series of products has a flexural modulus of 49-294 MPa, a tensile strength of 20-29 MPa, a melting point of 150-170℃, a wide operating temperature range, and features good wear resistance, cold resistance, and chemical resistance.

[0004] The isocyanate process was first developed by Dow Chemical Company in the United States and mainly consists of two types. One method involves adding aliphatic diacids and reactive monomers such as polyethers to a reactor in a polar solution. After a period of reaction, isocyanate is added to initiate a chain extension reaction. Finally, impurities such as solvents are removed by precipitation or vacuum to obtain the elastomer. The other method involves reacting raw materials containing active hydrogen end groups, such as polyethers or polyols, with isocyanate to produce a low molecular weight prepolymer. Then, an aliphatic diacid is added, and the elastomer is obtained through melt polymerization or reactive extrusion.

[0005] The anionic polymerization method for preparing TPAE mainly involves three reaction steps: first, the polyether reacts with a diisocyanate (such as TDI) under anhydrous conditions to prepare an activator; second, an anionic initiator is prepared by catalyzing the ring-opening of caprolactam with an alkali metal (usually sodium); then, caprolactam and the activator react to prepare an intermediate; finally, the anionic initiator and the intermediate continue to react to obtain the elastomer. Currently, anionic polymerization can only be used to prepare ABA-type and star-shaped TPAEs, resulting in products with low molecular weight and poor performance. Moreover, anionic polymerization requires very high purity raw materials, making process control difficult.

[0006] Currently, relevant literature on the preparation of TPAE mainly focuses on the dicarboxylic acid method, including CN 109206613A, CN110003464A, CN 104910377B, CN 200910200343A, CN 104327266A, CN 105566639B, CN109970971A, CN 108752581A, CN 106565953A, CN 109705338A, CN 111378124A, CN111004389A, CN 108841002A, CN 108794742A, etc. However, the esterification reaction not only requires high reaction temperature, long reaction time, and high vacuum degree of the reaction system, but also has a small equilibrium constant, low reaction efficiency, and the prepared elastomer has a low molecular weight and poor performance. Meanwhile, excessively high reaction temperatures and excessively long reaction times not only increase production energy consumption, but also lead to a large number of side reactions during the reaction process, affecting the appearance and performance of the product. Sinopec Baling Petrochemical Co., Ltd. has disclosed a method for preparing polyamide elastomers through the reaction of carboxylic acids and esters, including CN 115477753A and CN115490850A. However, during the polycondensation reaction, because the transesterification reaction rate is greater than the esterification rate, transesterification reactions occur between hydroxyl-terminated polyesters, resulting in a very low degree of reaction between the polyamide prepolymer and the polyester.

[0007] Therefore, it is of great significance to further strengthen the design, development and research of TPAE. Summary of the Invention

[0008] The purpose of this invention is to overcome the problems of low reaction efficiency and small molecular weight of products in the preparation of polyamide elastomers by traditional methods, and to provide a polyamide elastomer raw material composition and its application, as well as a polyamide elastomer and its preparation method. The reaction of polyurethane using the raw material composition of this invention offers strong controllability, produces products with large molecular weights, and allows for adjustment of the type, molecular weight, and structure of the soft segments according to application requirements, thereby effectively controlling the properties of the elastomer.

[0009] The inventors of this invention have discovered that raw materials for preparing polyamide elastomers can be used to prepare TPAE via electrophilic reactions. Based on this, the first aspect of this invention provides a polyamide elastomer raw material composition comprising: polyamide and polyether; wherein at least one end-capping group of the polyamide is a terminal amino group; and at least one end-capping group of the polyether is an ester group.

[0010] The second aspect of the present invention provides the use of the polyamide elastomer raw material composition described in the first aspect of the present invention in the electrophilic reaction preparation of polyamide elastomers.

[0011] A third aspect of the present invention provides a method for preparing a polyamide elastomer, the method comprising: performing an electrophilic reaction on the raw material composition described in the first aspect of the present invention in the presence of a solvent.

[0012] The fourth aspect of the present invention provides a polyamide elastomer prepared by the preparation method described in the third aspect of the present invention.

[0013] Compared with the prior art, the present invention has at least the following beneficial effects: The polyamide elastomer raw material composition of this invention can prepare polyamide elastomers through electrophilic reaction. The preparation of polyamide elastomers using this raw material composition has the advantages of fast reaction speed, high production efficiency, strong reaction controllability, large product molecular weight, and the type, molecular weight and structure of soft segments can be adjusted according to application requirements, thereby effectively controlling the performance of the elastomer. Attached Figure Description

[0014] Figure 1 This is the infrared spectrum of polyamide 1211 with amino-terminated ends in Example 1; Figure 2 It is the polyamide in Example 1- b -Infrared spectrum of polyethylene glycol elastomer; Figure 3 It is the polyamide in Example 1- b -Polyethylene glycol elastomers 1 H NMR spectrum. Detailed Implementation

[0015] 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.

[0016] The first aspect of the present invention provides a polyamide elastomer raw material composition comprising: a polyamide and a polyether; wherein at least one end-capping group of the polyamide is a terminal amino group; and at least one end-capping group of the polyether is an ester group.

[0017] Polyamide elastomers are polymers composed of alternating polyamide and polyether segments, possessing the advantages of both polyamides and polyethers. The polymer microphase separation structure is more pronounced, significantly improving the product's acid and alkali resistance and flexibility. The polyamide elastomer raw material composition of this invention achieves in-situ copolymerization of polyamide and polyether in the preparation of polyamide elastomers. This method is simple to operate, has a short process flow, requires low equipment investment, is easy to control, and is environmentally friendly. The resulting polyamide elastomer exhibits excellent mechanical properties.

[0018] According to a preferred embodiment of the present invention, the terminal amino group has the structure -NH-R-NH2 or -NH2, where R is an alkylene group having not less than 4 carbon atoms, preferably R is C4-C. 20 Alkylene.

[0019] According to a preferred embodiment of the present invention, the structure of the ester group is as shown in formula (I). Formula (I), In equation (I), R1 is C1-C 10 Alkyl groups.

[0020] C1-C in this invention 10 The alkyl group can be a straight-chain alkyl group or a branched alkyl group, preferably a straight-chain alkyl group. Preferably, in formula (I), R1 is a C1-C4 alkyl group, such as methyl, ethyl, propyl, or butyl.

[0021] According to a preferred embodiment of the present invention, the two end groups in the polyamide are each independently terminal amino groups. The polyamide elastomer prepared from the raw material composition of the foregoing embodiments has a higher molecular weight and superior mechanical properties.

[0022] According to a preferred embodiment of the present invention, the two end groups in the polyether are each independently an ester group. The polyamide elastomer prepared from the raw material composition of the foregoing embodiments has a higher molecular weight and superior mechanical properties.

[0023] According to the present invention, polyamide is a general term for polymers containing repeating structural unit amide groups (-NHCO-) ​​in the main chain of a macromolecule. It can be a conventional type in the art. Preferably, the viscosity-average molecular weight of the polyamide is 400-20000, for example, 400, 1000, 2000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000 or 20000. Preferably, the polyamide includes at least one of polyamide 6, polyamide 9, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 1010, polyamide 612, polyamide 1212, polyamide 46, polyamide 1313, polyamide 1011, polyamide 1012, polyamide 1211, polyamide 1013, polyamide 1110, polyamide 1111, polyamide 1112 and polyamide 1210.

[0024] The polyamide in this invention can be obtained commercially or by conventional preparation methods in the art. According to a preferred embodiment of this invention, the preparation method of the polyamide includes: polymerizing a mixture containing a reactive monomer, water, optionally a capping agent and optionally an antioxidant; wherein the reactive monomer is a diacid and a diamine, or a lactam, or a mixture of a lactam and a diacid and a diamine.

[0025] According to the present invention, the specific types of diacids, diamines, and lactams can be selected according to the specific type of polyamide ultimately desired. Specifically, the diacid includes at least one of diacids and their derivatives having 2-20 carbon atoms, preferably including C6-C... 12 The dicarboxylic acid includes at least one of the following: dicarboxylic acid and its derivatives. Specific dicarboxylic acids that can be listed include adipic acid, sebacic acid, undecanoic acid, dodecanoic acid, etc.; the diamine includes at least one of the following: diamines having 2-20 atoms and their derivatives, preferably including C6-C. 12 At least one of the diamines and their derivatives, such as hexamethylenediamine, decanediamine, dodecanediamine, etc.; lactams include lactams with 4-10 carbon atoms, such as caprolactam.

[0026] According to the present invention, when the reactant monomer contains a diacid and a diamine, in order to ensure that at least one end group in the end group of the final polyamide is a terminal amino group, the molar ratio of the diamine to the diacid is generally selected to be greater than 1, and preferably the molar ratio of the diamine to the diacid is (1.1-2.5):1.

[0027] According to the present invention, in the preparation of polyamide, the optional end-capping agent refers to the addition or omission of the end-capping agent as needed. Those skilled in the art will understand that when the reactant monomer contains a diacid and a diamine, the excess diamine itself can play the role of end-capping, so that the end-capping group of the final polyamide is amino. In this case, no additional end-capping agent needs to be added. When the reactant monomer is only a lactam, an end-capping agent can be added. Preferably, the end-capping agent is a diamine, and preferably, the number of carbon atoms in the diamine end-capping agent corresponds to the same number of carbon atoms in the lactam. Preferably, the molar ratio of the reactant monomer to the end-capping agent is (1-20):1, and more preferably (10-15):1.

[0028] According to the present invention, when preparing polyamide, the antioxidant optionally refers to an antioxidant that can be added or not added as needed. The purpose of adding an antioxidant during the polymerization process is mainly to improve the antioxidant capacity of the polymer. It is preferred to add an antioxidant during the polymerization reaction. Based on the total mass of the polymerization reaction system, the amount of antioxidant added is 0.01-8 wt%, preferably 0.1-1.5 wt%. The type of antioxidant can be a conventional type in the art, such as at least one of antioxidant 1010, antioxidant 1076, antioxidant 1024, antioxidant 1330, antioxidant 1098 and antioxidant 1216.

[0029] According to the present invention, in the preparation of polyamide, the role of water mainly includes promoting the forward shift of the polymerization reaction. The amount of water used is only required to maximize the promotion of the polymerization reaction, and the amount of water used is generally 0.5-10 wt% of the mass of the reactant monomer.

[0030] According to the present invention, it is understood in the art that polyamides are generally prepared by polycondensation of diacids and diamines or ring-opening reactions of lactams. That is, when preparing polyamides, specific polymerization reaction conditions can be selected according to actual needs. Specifically, the polymerization reaction temperature is 25-300°C, and the reaction time is 0.1-48 h. Preferably, the reaction can be carried out first at 100-200°C for 1-20 h, followed by a reaction at 220-300°C for 0.5-28 h. After that, vacuum distillation is carried out, specifically at a vacuum pressure of 5 Pa-5000 Pa, a temperature of 50-400°C, and a time of 0.2-24 h, to remove the solvent and unreacted raw materials.

[0031] As can be understood in this invention, during the polymerization process, all polymerization reactions prior to vacuum distillation are carried out in a closed container, and the reaction pressure is the pressure of the polymerization system itself.

[0032] According to the present invention, when preparing polyamide, the crude polyamide product obtained after the polymerization reaction may contain oligomers and other impurities. The crude polyamide product can be purified after the polymerization reaction. Generally, solvent extraction is used to remove the oligomers and impurities and then drying is used to obtain polyamide. Preferably, the solvent used for extraction is at least one of water, ethanol, methanol, ethyl acetate, acetone, N,N-dimethylformamide, tetrahydrofuran, acetonitrile, chloroform and dimethyl sulfoxide.

[0033] According to the present invention, in polyamide elastomers, polyethers are generally used as soft segments. The appropriate type and length of polyether can be selected according to the needs of the final polyamide elastomer. Preferably, the average molecular weight of the polyether is 200-20000, for example, 200, 300, 400, 600, 800, 1000, 1500, 1800, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000 or 20000, preferably 1000-5000. Preferably, the polyether includes alkane polyethers and / or fluorinated polyethers.

[0034] According to the present invention, alkane polyethers refer to polyethers whose macromolecular chains contain only C, H, and O, and preferably the alkane polyethers include at least one of polyethylene glycol, polypropylene glycol, polybutane glycol, polycaprolactone diol and their derivatives.

[0035] According to the present invention, fluorinated polyether refers to alkane polyether, which is a polyether in which some or all of the H atoms in the macromolecular chain of the polyether are replaced by F atoms. Preferably, the fluorinated polyether is selected from at least one of perfluoropolyethers and their derivatives.

[0036] According to the present invention, conventional polyethers are generally dihydroxyl-terminated. In order to obtain polyethers with ester-terminated groups, in one embodiment, at least one polyether with ester-terminated groups is obtained from a dihydroxyl-terminated polyether by oxidation and esterification.

[0037] According to a preferred embodiment of the present invention, a method for preparing at least one polyether with an ester-terminated group includes: a) In the presence of a solvent and an oxidant, the polyether with dihydroxyl groups undergoes an oxidation reaction, followed by a first extraction and separation to obtain a carboxyl-terminated polyether. b) The carboxyl-terminated polyether and alkyl alcohol (preferably C1-C1) in step a) 10 Alkyl alcohols undergo esterification reactions.

[0038] According to the present invention, the solvent in step a) is mainly a polyether that disperses the dihydroxyl groups so that the oxidation reaction can occur better. Those skilled in the art can select the solvent as needed. In one embodiment, the solvent in step a) is selected from at least one of acetonitrile, toluene, benzonitrile, diethylene glycol dimethyl ether, ethylene glycol, acetone, tetrahydrofuran, diethylene glycol dimethyl ether, perfluorocyclic ether, hydrofluoroether and 1,3-bis(trifluoromethyl)benzene; preferably, in step a), the mass ratio of the solvent to the dihydroxyl-terminated polyether is (2-10):1.

[0039] According to the present invention, the oxidant in step a) can be a conventional oxidant in the art. In one embodiment, the oxidant is selected from at least one of potassium permanganate, hydrogen peroxide, potassium dichromate, perchloric acid, concentrated sulfuric acid, and potassium chlorate. Preferably, the molar ratio of the oxidant to the solvent to the polyether with dihydroxyl groups is 1-20:1.

[0040] According to the present invention, in step a), the oxidation reaction conditions are only required to oxidize the terminal hydroxyl group to a carboxyl group. Preferably, the oxidation reaction temperature is 25-300°C, more preferably 60-200°C; and preferably, the oxidation reaction time is 0.2-72 h, more preferably 1-32 h.

[0041] According to the present invention, in step a), the oxidation reaction is generally carried out in a closed container, and the pressure during the reaction is generally the pressure generated by the system itself.

[0042] According to the present invention, the crude polyether product obtained by the oxidation reaction is a carboxyl-terminated polyether containing solvent and possible other impurities. The carboxyl-terminated polyether can be separated by a first extraction and separation method, that is, the material after the oxidation reaction is subjected to a first extraction and separation using an extractant. Specifically, in step a), the first extraction and separation method is as follows: the extractant is added to the material after the oxidation reaction at room temperature (generally 15-30°C), stirred for a certain period of time, and then allowed to stand for separation. The lower layer is taken to obtain the polyether with double carboxyl-terminated polyether. Preferably, the extractant is at least one of dichloromethane, ethanol, methanol, water, ethyl acetate, ethylene glycol, perfluorocyclic ether, hydrofluoroether, n-hexane, and cyclopentane.

[0043] According to the present invention, C1-C can be listed in step b). 10 Alcohols include methanol, ethanol, propanol, butanol, etc.

[0044] According to the present invention, in step b), the amount of alkyl alcohol added is sufficient to allow all the carboxyl groups in the polyether with double-ended carboxyl groups to be esterified into ester groups. Preferably, the mass ratio of alkyl alcohol to polyether with double-ended carboxyl groups is (5-35):1.

[0045] According to the present invention, in step b), the esterification reaction conditions are such that the carboxyl-terminated polyether and the alkyl alcohol can react smoothly to produce ester groups. Preferably, the temperature of the esterification reaction is 40-120°C, and the time of the esterification reaction is 2-48h.

[0046] According to the present invention, as long as the purpose of the present invention can be achieved, the amount of polyamide and polyether in the raw material composition can be selected within a wide range. In a preferred embodiment, the molar ratio of polyamide to polyether is (0.3-2):1, for example, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 1:1, 1.1:1, 1.3:1 or 1.5:1, preferably (0.4-1.5):1.

[0047] The second aspect of the present invention provides the use of the polyamide elastomer raw material composition described in the first aspect of the present invention in the electrophilic reaction preparation of polyamide elastomers.

[0048] The polyamide elastomer raw material composition of the present invention can prepare polyamide elastomers through electrophilic reaction. Compared with the existing esterification reaction for preparing polyamide elastomers, the reaction efficiency of preparing polyamide elastomers through the raw material composition of the present invention is high and the product molecular weight is large.

[0049] According to a preferred embodiment of the present invention, the electrophilic reaction is N δ- Attack C δ+ Electrophilic reaction.

[0050] Compared to traditional preparation methods, the ester groups of the amino-terminated polyamide polyether ester in this invention are obtained through N... δ- Attack C δ+ It can perform electrophilic reactions, which are highly controllable, produce products with large molecular weights, and allow for the adjustment of the type, molecular weight, and structure of the soft segments according to application requirements, thereby effectively controlling the performance of the elastomer.

[0051] A third aspect of the present invention provides a method for preparing a polyamide elastomer, the method comprising: performing an electrophilic reaction on the raw material composition described in the first aspect of the present invention in the presence of a solvent.

[0052] The electrophilic reaction in this invention can be carried out in the presence of solution, which is a solution method. The reaction conditions are mild, the viscosity of the reaction system is low, the effective collision between reactive groups is increased, the solvent can be recycled and reused, the reaction is highly controllable, the product has a large molecular weight, and the type, molecular weight and structure of the soft segment can be adjusted according to the application requirements, thereby effectively controlling the performance of the elastomer.

[0053] According to a preferred embodiment of the present invention, the conditions for the electrophilic reaction include: a temperature of 25-300°C, preferably 100-200°C; and a reaction time determined according to conditions such as temperature, for example, a time of 0.5-72h, preferably 3-48h.

[0054] According to the present invention, when preparing polyamide elastomers, the type of solvent is only required to promote the electrophilic reaction. Preferably, the solvent includes at least one selected from sulfolane, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone, acetonitrile, hydrofluoroether, diethylene glycol dimethyl ether, and toluene.

[0055] According to the present invention, when preparing polyamide elastomers, the amount of solvent used is only sufficient to promote the electrophilic reaction, and preferably the mass of the polyamide elastomer raw material composition is 10-50 wt% of the solvent mass.

[0056] According to the present invention, the target product after the electrophilic reaction contains some solvents and other small molecule impurities, which can be removed by conventional vacuum distillation in the art.

[0057] The fourth aspect of the present invention provides a polyamide elastomer prepared by the preparation method described in the third aspect of the present invention.

[0058] The polyamide elastomer prepared by the method of the present invention has the advantage of a large molecular weight, and preferably the average molecular weight of the polyamide elastomer is 5,000-80,000.

[0059] The present invention will be described in detail below through examples. In the following examples and comparative examples: molecular weight was determined by the Ubbelohde viscosity method, mechanical properties were tested using a CMT4104 electronic universal testing machine, and the test was conducted according to the method of GB / T 1040.1-2006, with a tensile rate of 20 mm / min.

[0060] Example 1 First, 15.2 g of undecanoic acid, 18.3 g of dodecanoic acid diamine, 0.37 g of deionized water, and 0.13 g of antioxidant 1010 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 160 °C for 3 h, then at 250 °C and 1.7 MPa for 2 h, and finally at a vacuum of 50 Pa for another 2 h. After the reaction, the material was cooled to 150 °C and discharged to obtain crude polyamide. The crude product was extracted with acetone to remove oligomers and impurities, and then dried to obtain amino-terminated polyamide 1211 (viscosity-average molecular weight 3376) for later use.

[0061] 11.3 g of dihydroxyl-terminated polyethylene glycol with an average molecular weight of 4000 was dissolved in 50 mL of acetonitrile to form a solution. Then, 1.5 g of potassium permanganate was added, and the mixture was reacted at 60 °C for 15 h. After the reaction was complete, the system was allowed to cool to room temperature, and ethanol was added with stirring to extract unreacted substances and impurities. After extraction, the mixture was allowed to stand and separated, and the lower layer was collected for later use. 1.2 g of ethanol was then added to the lower layer, and the mixture was reacted at 50 °C for 10 h. After the reaction was complete, the dihydroxyl-terminated polyethylene glycol was obtained.

[0062] 10.88 g of amino-terminated polyamide 1211 was dissolved in 50 g of N,N-dimethylformamide at 120 °C to obtain a polyamide solution. Then, the above-mentioned ester-terminated polyethylene glycol material was added to the polyamide solution and reacted at 120 °C for 8 h. After the reaction was complete, the solvent N,N-dimethylformamide and other small molecule impurities were removed by vacuum distillation to obtain the product polyamide- b - Polyethylene glycol elastomer, with the following structural formula.

[0063]

[0064] Polyamide- b The molecular weight and mechanical properties of polyethylene glycol elastomers are shown in Table 1.

[0065] The infrared spectrum of polyamide 1211 with amino-terminated ends is as follows: Figure 1 As shown, polyamide- b -Infrared spectrum of polyethylene glycol elastomers Figure 2 As shown. It can be seen that it is located at 3301 cm. -1 The infrared absorption peak at 1634 cm⁻¹ is attributed to the stretching vibration of the NH group in the amide bond. -1 The infrared absorption peak at 1542 cm⁻¹ corresponds to the stretching vibration of the amide carbonyl group (C=O) of secondary amides, representing the amide I band. -1 The characteristic peaks at this location are coupled vibrational peaks caused by the NH bending vibration and CN stretching vibration of secondary amides, which are amide II bands. These characteristic peaks prove the presence of amide bonds. Furthermore, in polyamide- b - In the infrared spectrum of polyethylene glycol elastomer, located at 1107 cm⁻¹ -1 The antisymmetric stretching vibration peak of COC appeared at this point.

[0066] Polyamide- b -Polyethylene glycol elastomers 1 H NMR such as Figure 3 As shown. From Figure 3As can be seen, the chemical shift at 3.71 ppm corresponds to the absorption of a hydrogen atom on the methylene group bonded to NH in the amide group; the chemical shift at 2.61 ppm corresponds to the absorption of a hydrogen atom on the methylene group bonded to C=O in the ester group; the chemical shift at 1.85 ppm corresponds to the hydrogen atom on a methylene group separated from the C=O in the amide group; the chemical shift at 1.92 ppm corresponds to the hydrogen atom on a methylene group separated from the NH in the amide group; and the absorption at 1.46 ppm is attributed to the hydrogen atom absorption of the remaining methylene groups in the aliphatic chain. Furthermore, the H at chemical shift 2.87 ppm is attributed to the H on the methylene group bonded to C=O in the amide group in the PA1211 segment; and the chemical shift at 4.05 ppm corresponds to the absorption of a hydrogen atom on a methylene group separated from the CO in the ester group in the PEG chain. Combined with the infrared spectrum and 1H NMR, the successful preparation of the elastomer is further confirmed. Example 2 First, 22.9 g of caprolactam, 1.5 g of deionized water, 0.23 g of antioxidant 1216, and 1.7 g of hexamethylenediamine (the end-capping agent) were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 130 °C for 0.5 h, then at 240 °C under 5 MPa for 5 h, and finally under a vacuum of 1000 Pa for 3 h. After the reaction, the material was cooled to 150 °C and discharged to obtain crude polyamide. The crude product was extracted with tetrahydrofuran to remove oligomers and impurities, and then dried to obtain amino-terminated polyamide 6 (viscosity-average molecular weight 4559) for later use.

[0067] 8.7 g of dihydroxyl-terminated polytetrahydrofuran with an average molecular weight of 2000 was dissolved in 80 mL of acetone to form a solution. Then, 2.7 g of hydrogen peroxide was added, and the mixture was reacted at 120 °C for 6 h. After the reaction was complete, the system was allowed to cool to room temperature, and ethyl acetate was added and stirred to extract unreacted substances and impurities. After extraction, the mixture was allowed to stand and separated, and the lower layer was collected for later use. 3.1 g of methanol was further added to the lower layer, and the mixture was reacted at 110 °C for 2 h. After the reaction was complete, the dihydroxyl-terminated polytetrahydrofuran was obtained.

[0068] 15.3 g of amino-terminated polyamide 6 was dissolved in 100 g of dimethyl sulfoxide at 150 °C to obtain a polyamide solution. Then, the above-mentioned ester-terminated polytetrahydrofuran material was added to the polyamide solution and reacted at 150 °C for 5 h. After the reaction was complete, the solvent dimethyl sulfoxide and other small molecule impurities were removed by vacuum distillation to obtain the product polyamide- b - Polytetrahydrofuran elastomer.

[0069] Polyamide- b The molecular weight and mechanical properties of polytetrahydrofuran elastomers are shown in Table 1.

[0070] Example 3 First, 12.9 g of dodecanoic acid, 14.3 g of hexamethylenediamine, 0.5 g of deionized water, and 0.11 g of antioxidant 1076 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 170 °C for 3 h, then at 260 °C and 3.7 MPa for 1 h, and finally at a vacuum of 600 Pa for another 2 h. After the reaction was completed, the material was cooled to 150 °C and discharged to obtain crude polyamide. The crude product was extracted with ethanol to remove oligomers and impurities, and then dried to obtain amino-terminated polyamide 612 (viscosity-average molecular weight 2761) for later use.

[0071] 10.2 g of a dihydroxyl-terminated perfluoropolyether with an average molecular weight of 2000 was dissolved in 45 mL of hydrofluoroether to form a solution. Then, 3.1 g of potassium dichromate was added, and the mixture was reacted at 160 °C and 0.8 MPa for 24 h. After the reaction was complete, the system was allowed to cool to room temperature, and a perfluorocyclic ether was added with stirring to extract unreacted substances and impurities. After extraction, the mixture was allowed to stand and separated, and the lower layer was collected for later use. 4.7 g of methanol was then added to the lower layer, and the mixture was reacted at 25 °C for 12 h. After the reaction was complete, the di-ester-terminated perfluoropolyether material was obtained.

[0072] 12.2 g of amino-terminated polyamide 612 was dissolved in 65 g of sulfolane at 200 °C to obtain a polyamide solution. Then, the above-mentioned perfluoropolyether material with ester-terminated groups was added to the polyamide solution and reacted at 65 °C for 3 h. After the reaction was completed, the solvent sulfolane and other small molecule impurities were removed by vacuum distillation to obtain the product polyamide- b - Perfluoropolyether elastomer.

[0073] Polyamide- b The molecular weight and mechanical properties of perfluoropolyether elastomers are shown in Table 1.

[0074] Example 4 First, 12.5 g of adipic acid, 13.6 g of hexamethylenediamine, 0.43 g of deionized water, and 0.2 g of antioxidant 1330 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 120 °C and 2.1 MPa for 6 h, then at 280 °C and 2.8 MPa for 0.5 h, and finally under a vacuum of 8000 Pa for 4 h. After the reaction, the material was cooled to 135 °C and discharged to obtain crude polyamide. The crude product was extracted with chloroform to remove oligomers and impurities, and then dried to obtain amino-terminated polyamide 66 (viscosity-average molecular weight 6218) for later use.

[0075] 13.7 g of dihydroxyl-terminated polypropylene glycol with an average molecular weight of 4000 was dissolved in 100 mL of diethylene glycol dimethyl ether to form a solution. Then, 1.9 g of concentrated sulfuric acid was added, and the reaction was carried out at 110 °C for 72 h. After the reaction was completed, the system was allowed to cool to room temperature, and dichloromethane was added with stirring to extract unreacted substances and impurities. After extraction, the mixture was allowed to stand and separated, and the lower layer was collected for later use. 6.3 g of butanol was further added to the lower layer, and the reaction was carried out at 75 °C for 48 h. After the reaction was completed, the di-ester-terminated polypropylene glycol material was obtained.

[0076] 10.7 g of amino-terminated polyamide 66 was dissolved in 80 g of N-methylpyrrolidone at 130 °C to obtain a polyamide solution. Then, the above-mentioned ester-terminated polypropylene glycol material was added to the polyamide solution and reacted at 130 °C for 8 h. After the reaction was complete, the solvent N-methylpyrrolidone and other small molecule impurities were removed by vacuum distillation to obtain the product polyamide- b - Polypropylene glycol elastomer.

[0077] Polyamide- b The molecular weight and mechanical properties of polypropylene glycol elastomers are shown in Table 1.

[0078] Example 5 First, 10.1 g of sebacic acid, 13.6 g of decanediamine, 0.6 g of deionized water, and 0.3 g of antioxidant 1098 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 100 °C for 12 h, then at 260 °C and 3.3 MPa for 16 h, and finally at a vacuum of 5000 Pa for another 5 h. After the reaction was completed, the material was cooled to 170 °C and discharged to obtain crude polyamide. The crude product was extracted with acetone to remove oligomers and impurities, and then dried to obtain amino-terminated polyamide 1010 (viscosity-average molecular weight 5964) for later use.

[0079] 8.8 g of dihydroxy-terminated polytetrahydrofuran with an average molecular weight of 1500 was dissolved in 55 mL of toluene to form a solution. Then, 3.9 g of potassium permanganate was added, and the mixture was reacted at 130 °C for 2 h. After the reaction was complete, the system was allowed to cool to room temperature, and ethylene glycol was added with stirring to extract unreacted substances and impurities. After extraction, the mixture was allowed to stand and separated, and the lower layer was collected for later use. 4.7 g of propanol was further added to the lower layer, and the mixture was reacted at 95 °C for 3 h. After the reaction was complete, the dihydroxy-terminated polytetrahydrofuran was obtained.

[0080] 16.3 g of amino-terminated polyamide 1010 was dissolved in 120 g of N,N-dimethylformamide at 100 °C to obtain a polyamide solution. Then, polytetrahydrofuran with ester-terminated groups was added to the polyamide solution and reacted at 100 °C for 48 h. After the reaction was complete, the solvent-dependent hydroxyl-terminated polyethylene glycol and other small molecule impurities were removed by vacuum distillation to obtain the product polyamide- b - Polytetrahydrofuran elastomer.

[0081] Polyamide- b The molecular weight and mechanical properties of polytetrahydrofuran elastomers are shown in Table 1.

[0082] Comparative Example 1 First, 17.2 g of undecanoic acid, 15.3 g of dodecanoic acid diamine, 0.37 g of deionized water, and 0.13 g of antioxidant 1010 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 160 °C for 3 h, then at 250 °C and 1.7 MPa for 2 h, and finally at a vacuum of 50 Pa for another 2 h. After the reaction was completed, the material was cooled to 150 °C and discharged to obtain crude polyamide. The crude product was extracted with acetone to remove oligomers and impurities, and the double-carboxyl-terminated polyamide 1211 (viscosity-average molecular weight 3376) was dried for later use.

[0083] 11.3 g of hydroxyl-terminated polyethylene glycol (same as in Example 1) with an average molecular weight of 4000 was dissolved in 50 mL of acetonitrile to form a hydroxyl-terminated polyethylene glycol solution for later use.

[0084] 10.88 g of carboxyl-terminated polyamide 1211 was dissolved in N,N-dimethylformamide at 120 °C, followed by the addition of the aforementioned hydroxyl-terminated polyethylene glycol solution, and the reaction was carried out at 120 °C for 8 h. After the reaction was completed, the solvent and other small molecule impurities were removed by vacuum distillation to obtain polyamide- b - Polyethylene glycol elastomer.

[0085] Polyamide- b The molecular weight and mechanical properties of polytetrahydrofuran elastomers are shown in Table 1.

[0086] Comparative Example 2 First, 22.9 g of caprolactam, 1.5 g of deionized water, 0.23 g of antioxidant 1216, and 1.7 g of capping agent adipic acid were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 130 °C for 0.5 h, then at 240 °C under 5 MPa for 5 h, and finally under a vacuum of 1000 Pa for 3 h. After the reaction, the material was cooled to 150 °C and discharged to obtain crude polyamide. The crude product was extracted with tetrahydrofuran to remove oligomers and impurities, and then dried to obtain carboxyl-terminated polyamide 6 (viscosity-average molecular weight 4270) for later use.

[0087] Dissolve 8.5 g of dihydroxy-terminated polytetrahydrofuran (same as in Example 2) with an average molecular weight of 2000 in 80 mL of acetone to form a dihydroxy-terminated polytetrahydrofuran solution for later use.

[0088] 15.3 g of bi-carboxyl-terminated polyamide 6 was dissolved in 100 g of dimethyl sulfoxide at 150 °C to obtain a polyamide solution. Then, the above-mentioned bi-hydroxyl-terminated polytetrahydrofuran solution was added, and the reaction was carried out at 150 °C for 5 h. After the reaction was completed, the solvent dimethyl sulfoxide and other small molecule impurities were removed by vacuum distillation to obtain the product polyamide- b - Polytetrahydrofuran elastomer.

[0089] Polyamide- b The molecular weight and mechanical properties of polytetrahydrofuran elastomers are shown in Table 1.

[0090] Comparative Example 3 First, 20.8 g of dodecanoic acid, 10.1 g of hexamethylenediamine, 0.5 g of deionized water, and 0.11 g of antioxidant 1076 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 170 °C for 3 h, then at 260 °C and 3.7 MPa for 1 h, and finally at a vacuum of 600 Pa for another 2 h. After the reaction was completed, the material was cooled to 150 °C and discharged to obtain crude polyamide. The crude product was extracted with ethanol to remove oligomers and impurities, and then dried to obtain carboxyl-terminated polyamide 612 (viscosity-average molecular weight of 2310) for later use.

[0091] 10.2 g of a hydroxyl-terminated perfluoropolyether (same as in Example 3) with an average molecular weight of 2000 was dissolved in 45 mL of hydrofluoroether to form a hydroxyl-terminated perfluoropolyether solution for later use.

[0092] 12.2 g of carboxyl-terminated polyamide 612 was dissolved in 65 g of sulfolane at 200 °C to obtain a polyamide solution. Then, the above-mentioned hydroxyl-terminated perfluoropolyether solution was added, and the reaction was carried out at 200 °C for 3 h. After the reaction was completed, the solvent and other small molecule impurities were removed by vacuum distillation to obtain the product polyamide- b - Perfluoropolyether elastomer.

[0093] Polyamide- b The molecular weight and mechanical properties of perfluoropolyether elastomers are shown in Table 1.

[0094] Comparative Example 4 First, 18.1 g of adipic acid, 13.3 g of hexamethylenediamine, 0.43 g of deionized water, and 0.2 g of antioxidant 1330 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 120 °C and 2.1 MPa for 6 h, then at 280 °C and 2.8 MPa for 0.5 h, and finally under a vacuum of 8000 Pa for 4 h. After the reaction, the material was cooled to 135 °C and discharged to obtain crude polyamide. The crude product was extracted with chloroform to remove oligomers and impurities, and then dried to obtain carboxyl-terminated polyamide 66 (viscosity-average molecular weight 6101) for later use.

[0095] 13.7 g of dihydroxyl-terminated polypropylene glycol (same as in Example 4) with an average molecular weight of 4000 was dissolved in 100 mL of diethylene glycol dimethyl ether to form a dihydroxyl-terminated polypropylene glycol solution for later use.

[0096] 10.3 g of carboxyl-terminated polyamide 66 was dissolved in 80 g of N-methylpyrrolidone at 130 °C to obtain a polyamide solution. Then, the above-mentioned hydroxyl-terminated polypropylene glycol solution was added to the polyamide solution and reacted at 130 °C for 8 h. After the reaction was completed, the solvent N-methylpyrrolidone and other small molecule impurities were removed to obtain the product polyamide-b-polypropylene glycol elastomer.

[0097] The molecular weight and mechanical properties of polyamide-b-polypropylene glycol elastomer are shown in Table 1.

[0098] Comparative Example 5 First, 13.5 g of sebacic acid, 11.2 g of decanediamine, 0.6 g of deionized water, and 0.3 g of antioxidant 1098 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 100 °C for 12 h, then at 260 °C and 3.3 MPa for 16 h, and finally at a vacuum of 5000 Pa for 5 h. After the reaction, the material was cooled to 170 °C and discharged to obtain crude polyamide. The crude product was extracted with acetone to remove oligomers and impurities, and then dried to obtain carboxyl-terminated polyamide 1010 (average molecular weight 6089) for later use.

[0099] 8.8 g of dihydroxy-terminated polytetrahydrofuran (same as in Example 5) with an average molecular weight of 1500 was dissolved in 55 mL of toluene to form a dihydroxy-terminated polytetrahydrofuran material for later use.

[0100] 15.7 g of carboxyl-terminated polyamide 1010 was dissolved in 120 g of N,N-dimethylformamide at 100 °C to obtain a polyamide solution. Then, the ester-terminated polytetrahydrofuran material was added to the polyamide solution and reacted at 100 °C for 48 h. After the reaction was completed, the solvent N,N-dimethylformamide and other small molecule impurities were removed to obtain the product polyamide-b-polytetrahydrofuran elastomer.

[0101] The molecular weight and mechanical properties of polyamide-b-polytetrahydrofuran elastomer are shown in Table 1.

[0102] Table 1

[0103] 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 polyamide elastomer raw material composition, characterized in that, This raw material composition contains: polyamide and polyether; Wherein, at least one end-capping group of the polyamide is a terminal amino group; and at least one end-capping group of the polyether is an ester group.

2. The raw material composition according to claim 1, characterized in that, The terminal amino group has the structure -NH-R-NH2 or -NH2, where R is an alkylene group having at least 4 carbon atoms; and / or The structure of the ester group is shown in formula (I). Equation (I), In equation (I), R1 is C1-C 10 Alkyl groups.

3. The raw material composition according to claim 2, characterized in that, R is C4-C 20 alkylene groups; and / or Formula (I), R1 is a C1-C4 alkyl group.

4. The raw material composition according to claim 1, characterized in that, The two end-capped groups in the polyamide are each independently a terminal amino group; and / or The two end-capping groups in the polyether are each an ester group.

5. The raw material composition according to claim 1, characterized in that, The polyamide has a viscosity-average molecular weight of 400-20000; and / or The polyamide includes at least one of polyamide 6, polyamide 9, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 1010, polyamide 612, polyamide 1212, polyamide 46, polyamide 1313, polyamide 1011, polyamide 1012, polyamide 1211, polyamide 1013, polyamide 1110, polyamide 1111, polyamide 1112, and polyamide 1210.

6. The raw material composition according to claim 1, characterized in that, The polyether has an average molecular weight of 200-20000; and / or The polyethers include alkane polyethers and / or fluorinated polyethers.

7. The raw material composition according to claim 6, characterized in that, The alkane polyethers include at least one of polyethylene glycol, polypropylene glycol, polybutane glycol, and polycaprolactone diol and their derivatives; and / or The fluorinated polyether is selected from at least one of perfluoropolyethers and their derivatives.

8. The raw material composition according to any one of claims 1-7, characterized in that, At least one ester-terminated polyether is obtained from a polyether with dihydroxyl-terminated groups via oxidation or esterification; and / or The molar ratio of polyamide to polyether is (0.3-2):1, preferably (0.4-1.5):

1.

9. The use of the polyamide elastomer raw material composition according to any one of claims 1-8 in the electrophilic reaction preparation of polyamide elastomers.

10. The application according to claim 9, characterized in that, The electrophilic reaction is N δ- Attack C δ+ Electrophilic reaction.

11. A method for preparing a polyamide elastomer, characterized in that, The preparation method includes: In the presence of a solvent, the raw material composition according to any one of claims 1-8 undergoes an electrophilic reaction.

12. The preparation method according to claim 11, characterized in that, The conditions for the electrophilic reaction include: a temperature of 25-300°C; and / or a time of 0.2-72 h; and / or The solvent includes at least one selected from sulfolane, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone, acetonitrile, hydrofluoroether, diethylene glycol dimethyl ether, and toluene.

13. A polyamide elastomer prepared by the method of claim 11 or 12.

14. The polyamide elastomer according to claim 13, characterized in that, The polyamide elastomer has an average molecular weight of 5,000-80,000.

Images