Environment-friendly high-toughness high-low temperature resistant corrosion-resistant polyamide elastomer and preparation and application thereof

Abstract

The present application relates to a kind of environment-friendly high toughness high-temperature resistant corrosion-resistant polyamide elastomer and its preparation and application, belong to high polymer synthesis field.The present application provides a kind of polyamide elastomer, the structural formula of the polyamide elastomer is as shown in formula I.The present application has prepared a kind of environment-friendly high toughness high-temperature resistant corrosion-resistant elastomer with new structure, due to the introduction of biphenyl, naphthalene ring structure, it is endowed with excellent heat, corrosion resistance and outstanding rigid-flexible mechanical properties (tensile strength reaches nearly 80MPa, and its elongation at break can reach 900%).

Description

Technical Field

[0001] This invention relates to an environmentally friendly, high-strength, tough, high- and low-temperature resistant, corrosion-resistant polyamide elastomer, its preparation and application, and belongs to the field of polymer synthesis. Background Technology

[0002] Polyamide elastomers are widely used in aerospace oil-resistant sealing components, electronic packaging, surface coatings, sports equipment such as sports shoes and sports machinery, and infrastructure such as plastic running tracks due to their excellent elasticity, deformation, and mechanical properties. Traditional elastomers mainly include polyurethane (PU) and polyester copolymers (TPE, TPA, etc.), which all have good mechanical properties and elastic deformation. However, because their molecular chains contain ester bonds, they have poor resistance to highly corrosive environments. At the same time, their heat resistance is not high, and the long-term operating temperature is generally less than 130°C. It is also difficult to achieve both high strength and high elastic deformation at the same time. In addition, when used as coating materials, their adhesion and adhesion to the substrate material are limited and need to be further improved. Summary of the Invention

[0003] The purpose of this invention is to address the shortcomings of existing technologies by providing an environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer. Its key feature is that it uses biphenyl dicarboxylic acid monomer, naphthalene dicarboxylic acid monomer, aliphatic diamine, polyetheramine, catalyst, end-capping agent, water, etc., as raw materials. Under the action of a catalyst, a one-step polycondensation reaction is carried out to prepare a high-performance, environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant elastomer with a novel structure.

[0004] The technical solution of this invention:

[0005] The first technical problem to be solved by this invention is to provide an environmentally friendly, high-strength, tough, high-low temperature resistant, and corrosion-resistant polyamide elastomer, the structural formula of which is shown in Formula I:

[0006]

[0007] in,

[0008] At least one of them;

[0009] At least one of them;

[0010]

[0011] Any one of the following; 20≤n≤300.

[0012] Furthermore, the environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer is selected from one of the substances shown in the following structural formulas:

[0013] Furthermore, the environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer has a tensile strength of 39–87 MPa, an elongation at break of 800–1050%, and a Vicat softening point of 114–151°C; that is, the elastomer obtained by the present invention simultaneously possesses the characteristics of high and low temperature resistance, high strength, ultra-high toughness, and high bonding strength.

[0014] The second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned environmentally friendly, high-strength, tough, high-low temperature resistant and corrosion-resistant polyamide elastomer, wherein the preparation method is to obtain the polyamide elastomer by a one-step polycondensation reaction of each raw material under the action of a catalyst;

[0015] The raw materials include: biphenyl dicarboxylic acid monomer, naphthalene dicarboxylic acid monomer, aliphatic diamine, polyetheramine, catalyst, capping agent or water; the proportions of each raw material are as follows:

[0016]

[0017]

[0018] Furthermore, the biphenyl dicarboxylic acid monomer is

[0019] At least one of them;

[0020] The naphthalic acid monomer is

[0021] At least one of them;

[0022] The aliphatic diamine is selected from:

[0023]

[0024] any one of them;

[0025] The polyetheramine is selected from:

[0026]

[0027] Any one of them.

[0028] Furthermore, the end-capping agent is:

[0029]

[0030] Any one of them.

[0031] Furthermore, the catalyst is selected from: triphenyl phosphonite, phosphorous acid, sodium hypophosphite, sodium phosphite, trimethylchlorosilane, triethylsilane chloride, stannous chloride, stannous octoate, and heteropolyacid unilateral chromium (C). 52 H 119 CrMo6N4O24 ), heteropolyacid unilateral iron (C 52 H 119 FeMo6N4O 24 ), heteropolyacid unilateral manganese (C 52 H 119 M n Mo6N4O 24 ), heteropolyacid unilateral aluminum (C 52 H 119 AlMo6N4O 24 It may be any one of N,N'-dicyclohexylcarbodiimide (DCC), benzotriazole-N,N,N',N'-tetramethylurea hexafluorophosphate (HBTU), or 1-hydroxybenzotriazole (HOBT).

[0032] Furthermore, the preparation method of the above-mentioned environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer includes the following steps:

[0033] 24.2–121 parts of biphenyl dicarboxylic acid monomer, 108–194.4 parts of naphthalene dicarboxylic acid monomer, 30–208.8 parts of aliphatic diamine, 40–1000 parts of polyetheramine, 0.1–40 parts of catalyst, and 10–500 parts of deionized water were added to a reaction vessel. The mixture was heated to 50–100°C under a nitrogen atmosphere and stirred for 0.5–1 h, maintaining the pH of the solution at 7.5–8.5. Subsequently, the reaction vessel was sealed, and the temperature was increased. In the first stage, the temperature was raised to 210–230°C and reacted for 1–3 h; then, the temperature was raised to 231–250°C and reacted for 1–3 h, with venting performed during the process. Repeat 1-3 times; then heat the reactor to 251-280℃, maintain a vacuum of -0.08 to -0.095MPa, and continue the reaction for 2-6 hours. Use negative pressure to draw 0.1-20 parts of the end-capping agent into the reactor and continue the reaction for 0.5-2 hours. Stop the polymerization reaction, introduce nitrogen into the reactor until the pressure returns to normal, open the bottom discharge valve of the reactor, and continue to use 0.02-0.1MPa nitrogen to extrude the material in the reactor from the discharge valve to the feed port of the twin-screw extruder. Then, exhaust, extrude, pelletize, and dry to obtain environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer resin.

[0034] Furthermore, in the above preparation method, the process conditions of the twin-screw extruder are as follows:

[0035] The screw speed is controlled at 80-300 rpm, the feeding rate is 3-40, and the temperature of each section of the extruder is as follows: Section 1 (feeding port): 220-260℃, Section 2: 220-260℃, Section 3: 220-260℃, Section 4: 220-260℃, Section 5: 271-290℃, Section 6: 271-290℃, Section 7: 271-290℃, Section 8: 271-290℃, Section 9: 271-290℃, Section 10: 271-290℃, Section 11: 271-290℃, Section 12: 271-290℃, Section 13: 271-290℃, Section 14 (die): 280-290℃.

[0036] In this invention, unless otherwise specified, all parts of raw materials are by weight.

[0037] The third technical problem to be solved by the present invention is to point out that the above-mentioned environmentally friendly, high-strength, tough, high-low temperature resistant and corrosion-resistant polyamide elastomer can be used as a compatibilizer, active additive, soft plastic or coating material.

[0038] Furthermore, the environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer is used as an interface compatibilizer for inert resins such as fluororesins and metals such as aluminum sheets / titanium sheets / stainless steel.

[0039] Furthermore, the environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer is used as a high-impact active additive.

[0040] Furthermore, the environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer is used as a protective coating, etc.

[0041] The beneficial effects of this invention are:

[0042] 1. This invention produces an environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant elastomer with a novel structure. Due to the introduction of biphenyl and naphthalene ring structures, the resin is endowed with excellent thermal and corrosion resistance properties as well as outstanding mechanical properties that combine rigidity and flexibility (tensile strength reaches nearly 80 MPa, while its elongation at break can reach 900%).

[0043] 2. The present invention uses water as a solvent in the synthesis process, which is green and pollution-free; in addition, the one-pot polymerization method is used, which has a short process, simple process and good stability.

[0044] 3. The reaction of this invention is carried out in two stages. Compared with traditional technical methods, it can more effectively control the end groups of the product. The use of end groups containing tertiary amine structures can avoid the problems of easy oxidation and degradation of active amino and carboxyl groups during processing. At the same time, the introduction of positively charged tertiary amine end groups endows the resin with good bonding properties, which is beneficial to the subsequent bonding with inert materials.

[0045] 4. In this invention, after polymerization is completed, a reaction vessel combined with a twin-screw extrusion pelletizing process is adopted, which makes the whole process completely continuous, saves energy consumption of secondary melting, and is more low-carbon.

[0046] 5. Compared with traditional elastomers, the elastic material obtained by the present invention has better high and low temperature performance, corrosion resistance, mechanical properties and bonding properties, and can adapt to more demanding use environments. Attached image description:

[0047] Figure 1 The results are infrared test results of the elastomers obtained in Examples 1 to 6 of this invention.

[0048] Figure 2 The mechanical property test results (stress-strain curves and tensile strength) of the elastomers obtained in Examples 1 to 6 of this invention are shown.

[0049] Figure 3 The Vicat softening point test results are for the elastomers obtained in Examples 1 to 6 of this invention. Detailed Implementation

[0050] This invention employs an electrophilic substitution route, using biphenyl diacid and naphthalic acid monomers to co-condense with aliphatic diamines and polyetheramine monomers to prepare novel polyamide elastomers with different chain segment units. The molecular chain structure has a wide range of tunable range (various diacid monomers with different structures can be copolymerized with diamine monomers), which can significantly optimize its service temperature. Since there is no ester group structure in the entire molecular chain segment, and the presence of rigid structures such as biphenyl and naphthalene rings, its corrosion resistance is relatively improved. At the same time, the high-density amide structure also greatly enhances its mechanical properties. In addition, the tertiary amine structure endows the resin with excellent interfacial adhesion properties.

[0051] The present invention will be specifically described below through embodiments. It should be noted that these embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments based on the above content of the present invention.

[0052] Example 1 (Biphenyl-10-naphthalic acid-90-C14-80%-400%-20%)

[0053] 24.2 g of 4,4'-biphenyldicarboxylic acid monomer, 194.4 g of 1,4-naphthalenedicarboxylic acid monomer, 182.4 g of 1,14-tetradecanediamine, and polyetheramine-400 were added. 80g of N,N-dimethylethylenediamine (NDM), 0.1g of heteropoly acid, and 100g of deionized water were added to a reactor. The mixture was heated to 50°C under a nitrogen atmosphere and stirred for 0.5 hours, maintaining the solution pH at 7.5. The reactor was then sealed, and the temperature was increased to 210°C for the first stage and reacted for 1 hour. The temperature was then increased to 231°C and reacted for another hour, with one venting operation. The reactor was then heated to 251°C, maintaining a vacuum of -0.08 MPa, and reacted for 2 hours. Simultaneously, 0.1g of NDM was drawn into the reactor using negative pressure, and the reaction continued for another 0.5 hours. The polymerization reaction was then stopped, and nitrogen was introduced into the reactor until atmospheric pressure was restored. The bottom valve of the reactor outlet was then opened. The material in the reactor is extruded from the discharge valve to the feed inlet of the twin-screw extruder using 0.02MPa nitrogen gas. The screw speed is controlled at 80rpm and the feeding rate is 3. The temperatures of each section of the extruder are as follows: Section 1 (feed inlet): 220℃, Section 2: 230℃, Section 3: 230℃, Section 4: 240℃, Section 5: 271℃, Section 6: 280℃, Section 7: 280℃, Section 8: 290℃, Section 9: 290℃, Section 10: 290℃, Section 11: 290℃, Section 12: 290℃, Section 13: 290℃, Section 14 (die): 280℃. After degassing, extrusion, pelletizing, and drying, the environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer resin is obtained.

[0054] For detailed infrared characterization, please refer to Figure 1 As shown, the mechanical properties and Vicat softening point (the standard impact specimen was placed in a silicone oil bath, and under a load of 1.82 MPa and a temperature increase of 2℃ / min, the specimen was subjected to a 1 mm...) 2 Temperature when the needle is pressed in 1mm (e.g.) Figure 2-3 As shown: the tensile strength is 39.5 MPa, the elongation at break is 882.3%, the Vicat softening point is 131.8℃, and the corrosion resistance test results are shown in Table 1. It exhibits excellent resistance in traditional alkanes, alcohols, acetone, hydrochloric acid (1 mol / L), and NaOH (1 mol / L), showing a significant improvement in corrosion resistance compared to traditional thermoplastic elastomers such as PU and TPE. When applied as an interfacial compatibilizer between fluoropolymers and aluminum and titanium sheets, its peel strength reaches 8.02 N / cm and 8.24 N / cm, respectively.

[0055] Example 2 (Biphenyl-50-naphthalic acid-50-C12-70%-1000-30%)

[0056] 108g of 3,3'-biphenyl dicarboxylic acid monomer, 121g of 2,6-naphthalenedicarboxylic acid monomer, 140g of decanediamine, and polyetheramine-1000 were added. 300g of sodium phosphite, 1g of sodium phosphite, and 500g of deionized water were added to a reactor. The mixture was heated to 60°C under a nitrogen atmosphere and stirred for 0.5 hours, maintaining the pH of the solution at 7.5. The reactor was then sealed, and the temperature was increased to 210°C for the first stage and reacted for 1 hour. The temperature was then increased to 231°C and reacted for another hour, with one venting operation. The reactor was then heated to 251°C, maintaining a vacuum of -0.08 MPa, and reacted for 2 hours. Simultaneously, 3g of the end-capping agent N,N-dimethylethylenediamine was drawn into the reactor using negative pressure, and the reaction continued for another 0.5 hours. The polymerization reaction was then stopped, and nitrogen gas was introduced into the reactor until atmospheric pressure was restored. The bottom valve of the reactor outlet was then opened. Continuing to use 0.02MPa nitrogen gas, the material in the reactor is extruded from the discharge valve to the feed inlet of the twin-screw extruder. The screw speed is controlled at 80rpm, the feeding rate is 3, and the temperatures of each section of the extruder are as follows: Section 1 (feed inlet): 220℃, Section 2: 230℃, Section 3: 230℃, Section 4: 240℃, Section 5: 271℃, Section 6: 280℃, Section 7: 280℃, Section 8: 290℃, Section 9: 290℃, Section 10: 290℃, Section 11: 290℃, Section 12: 290℃, Section 13: 290℃, Section 14 (die): 280℃. After degassing, extrusion, pelletizing, and drying, the environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer resin is obtained.

[0057] For detailed infrared characterization, please refer to Figure 1 As shown, the mechanical properties and Vicat softening point (the standard impact specimen was placed in a silicone oil bath, and under the conditions of 1.82 MPa and 2℃ / min heating, the specimen was subjected to a 1 mm...) 2 Temperature when the needle is pressed in 1mm (e.g.) Figure 2-3 As shown in Table 1, the tensile strength is 55.7 MPa, the elongation at break is 958.6%, the Vicat softening point is 114.5℃, and the corrosion resistance test results are as follows: it exhibits excellent resistance to traditional alkanes, alcohols, acetone, hydrochloric acid (1 mol / L), and NaOH (1 mol / L), showing a significant improvement in corrosion resistance compared to traditional thermoplastic elastomers such as PU and TPE; when applied as an interfacial compatibilizer between fluoropolymers and aluminum and titanium sheets, its peel strength reaches 8.91 N / cm and 8.78 N / cm, respectively.

[0058] Example 3 (Biphenyl-40-naphthalic acid-60-C10-60%-2000-40%)

[0059] 96.8 g of 3,3'-biphenyl dicarboxylic acid monomer, 129.6 g of 1,4-naphthalenedicarboxylic acid monomer, 103.2 g of decanediamine, and polyetheramine-2000 were added. 800g of N,N'-dicyclohexylcarbodiimide, 3g of N,N'-dicyclohexylcarbodiimide, and 500g of deionized water were added to a reactor. The mixture was heated to 70°C under a nitrogen atmosphere and stirred for 1 hour, with the pH of the solution controlled at 8. The reactor was then sealed, and the temperature was increased to 210°C in the first stage and reacted for 1 hour. The temperature was then increased to 231°C and reacted for 2 hours, with venting twice during this period. The reactor was then heated to 260°C, maintaining a vacuum of -0.08 MPa, and reacted for another 2 hours. Simultaneously, 5g of the end-capping agent N,N-dimethyl-p-phenylenediamine was drawn into the reactor using negative pressure, and the reaction continued for 1 hour. The polymerization reaction was then stopped, and nitrogen gas was introduced into the reactor until atmospheric pressure was restored. The bottom valve of the reactor outlet was then opened. Continue to use 0.06MPa nitrogen gas to extrude the material in the reactor from the discharge valve to the feed port of the twin-screw extruder. Control the screw speed at 180rpm, the feeding rate at 5, and the temperatures of each section of the extruder as follows: Section 1 (feed port): 220℃, Section 2: 230℃, Section 3: 230℃, Section 4: 230℃, Section 5: 271℃, Section 6: 280℃, Section 7: 280℃, Section 8: 280℃, Section 9: 290℃, Section 10: 290℃, Section 11: 290℃, Section 12: 290℃, Section 13: 290℃, Section 14 (die): 290℃. After venting, extrusion, pelletizing, and drying, the environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer resin is obtained.

[0060] For detailed infrared characterization, please refer to Figure 1 As shown, the mechanical properties and Vicat softening point (the standard impact specimen was placed in a silicone oil bath, and under the conditions of 1.82 MPa and 2℃ / min heating, the specimen was subjected to a 1 mm...) 2 Temperature when the needle is pressed in 1mm (e.g.) Figure 2-3 As shown: the tensile strength is 62.3 MPa, the elongation at break is 1032.8%, the Vicat softening point is 116.2℃, and the corrosion resistance test results are shown in Table 1. It exhibits excellent resistance in traditional alkanes, alcohols, acetone, hydrochloric acid (1 mol / L), and NaOH (1 mol / L), showing a significant improvement in corrosion resistance compared to traditional thermoplastic elastomers such as PU and TPE. When applied as an interfacial compatibilizer between fluoropolymers and aluminum and titanium sheets, its peel strength reaches 9.12 N / cm and 9.08 N / cm, respectively.

[0061] Example 4 (Biphenyl-30-naphthoic acid-70-cyclohexanediamine-70%-1000-30%)

[0062] 72.6 g of 3,3'-biphenyl dicarboxylic acid monomer, 151.2 g of 2,6-naphthalenedicarboxylic acid monomer, 79.8 g of cyclohexanediamine, and polyetheramine-1000 were added. 300g of N,N'-dicyclohexylcarbodiimide, 5g of N,N'-dicyclohexylcarbodiimide, and 450g of deionized water were added to a reactor. The mixture was heated to 80°C under a nitrogen atmosphere and stirred for 1 hour, maintaining the solution pH at 8. The reactor was then sealed, and the temperature was increased to 210°C for the first stage and reacted for 1 hour. The temperature was then increased to 240°C and reacted for 2 hours, with two venting cycles. The reactor was then heated to 270°C, maintaining a vacuum of -0.09 MPa, and reacted for 4 hours. Simultaneously, 10g of the end-capping agent N,N-dimethylpropylenediamine was drawn into the reactor using negative pressure, and the reaction continued for 1 hour. The polymerization reaction was then stopped, and nitrogen gas was introduced into the reactor until atmospheric pressure was restored. The bottom valve of the reactor outlet was then opened. Continue to use 0.06MPa nitrogen gas to extrude the material in the reactor from the discharge valve to the feed port of the twin-screw extruder. Control the screw speed at 190rpm, the feeding rate at 8, and the temperatures of each section of the extruder as follows: Section 1 (feed port): 220℃, Section 2: 220℃, Section 3: 230℃, Section 4: 230℃, Section 5: 280℃, Section 6: 280℃, Section 7: 280℃, Section 8: 280℃, Section 9: 280℃, Section 10: 290℃, Section 11: 290℃, Section 12: 290℃, Section 13: 290℃, Section 14 (die): 290℃. After venting, extrusion, pelletizing, and drying, the environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer resin is obtained.

[0063] For detailed infrared characterization, please refer to Figure 1 As shown, the mechanical properties and Vicat softening point (the standard impact specimen was placed in a silicone oil bath, and under the conditions of 1.82 MPa and 2℃ / min heating, the specimen was subjected to a 1 mm...) 2 Temperature when the needle is pressed in 1mm (e.g.) Figure 2-3 As shown: the tensile strength is 71.7 MPa, the elongation at break is 979.5%, the Vicat softening point is 133.9℃, and the corrosion resistance test results are shown in Table 1. It exhibits excellent resistance in traditional alkanes, alcohols, acetone, hydrochloric acid (1 mol / L), and NaOH (1 mol / L), showing a significant improvement in corrosion resistance compared to traditional thermoplastic elastomers such as PU and TPE. When applied as an interfacial compatibilizer between fluoropolymers and aluminum and titanium sheets, its peel strength reaches 9.03 N / cm and 9.21 N / cm, respectively.

[0064] Example 5 (Biphenyl-40-naphthoic acid-60-octanediamine-70%-1000-30%)

[0065] 96.8 g of 3,3'-biphenyl dicarboxylic acid monomer, 129.6 g of 2,6-naphthalenedicarboxylic acid monomer, 100.8 g of octyl diamine, and polyetheramine-1000 300g of triethylsilane, 15g of triethylsilane chloride, and 400g of deionized water were added to a reactor. The mixture was heated to 90°C under a nitrogen atmosphere and stirred for 1 hour, with the pH of the solution controlled at 8.5. The reactor was then sealed, and the temperature was increased to 210°C in the first stage and reacted for 1 hour. The temperature was then increased to 250°C and reacted for 2 hours, with venting performed three times during this period. The reactor was then heated to 280°C, maintaining a vacuum of -0.09MPa, and reacted for 5 hours. Simultaneously, 11g of the end-capping agent N,N,N'-trimethylpropylenediamine was drawn into the reactor using negative pressure, and the reaction continued for 1 hour. The polymerization reaction was then stopped, and nitrogen gas was introduced into the reactor until atmospheric pressure was restored. The bottom valve of the reactor outlet was then opened. Continuing with 0.06MPa nitrogen gas, the material in the reactor is extruded from the discharge valve to the feed inlet of a twin-screw extruder. The screw speed is controlled at 220rpm, the feeding rate is 12, and the temperatures of each section of the extruder are as follows: Section 1 (feed inlet): 220℃, Section 2: 230℃, Section 3: 240℃, Section 4: 250℃, Section 5: 275℃, Section 6: 275℃, Section 7: 280℃, Section 8: 280℃, Section 9: 280℃, Section 10: 285℃, Section 11: 285℃, Section 12: 290℃, Section 13: 290℃, Section 14 (die): 290℃. After venting, extrusion, pelletizing, and drying, the environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer resin is obtained.

[0066] For detailed infrared characterization, please refer to Figure 1 As shown, the mechanical properties and Vicat softening point (the standard impact specimen was placed in a silicone oil bath, and under the conditions of 1.82 MPa and 2℃ / min heating, the specimen was subjected to a 1 mm...) 2 Temperature when the needle is pressed in 1mm (e.g.) Figure 2-3 As shown in Table 1, the tensile strength is 80.2 MPa, the elongation at break is 951.9%, the Vicat softening point is 146.6℃, and the corrosion resistance test results are as follows: it exhibits excellent resistance to traditional alkanes, alcohols, acetone, hydrochloric acid (1 mol / L), and NaOH (1 mol / L), showing a significant improvement in corrosion resistance compared to traditional thermoplastic elastomers such as PU and TPE; when applied as an interfacial compatibilizer between fluoropolymers and aluminum and titanium sheets, its peel strength reaches 9.46 N / cm and 9.94 N / cm, respectively.

[0067] Example 6 (Biphenyl-40-naphthoic acid-60-diaminodicyclohexyldimethylmethane-80%-400%-30%)

[0068] 96.8 g of 4,4'-biphenyl dicarboxylic acid monomer, 129.6 g of 2,6-naphthalenedicarboxylic acid monomer, 185.6 g of diaminodicyclohexyldimethylmethane, and polyetheramine-400 were added. 120g of benzotriazole-N,N,N',N'-tetramethylurea hexafluorophosphate (HBTU), 35g of benzotriazole, and 320g of deionized water were added to a reactor. The mixture was heated to 85°C under a nitrogen atmosphere and stirred for 1 hour, maintaining the pH of the solution at 8.3. The reactor was then sealed, and the temperature was increased to 210°C for the first stage and reacted for 1 hour. The temperature was then increased to 245°C and reacted for 3 hours, with venting performed three times during this period. The reactor was then heated to 275°C, maintaining a vacuum of -0.09 MPa, and reacted for 4.5 hours. Simultaneously, 20g of the end-capping agent N,N,N'-trimethylpropylenediamine was drawn into the reactor using negative pressure, and the reaction continued for 1 hour. The polymerization reaction was then stopped, and nitrogen gas was introduced into the reactor until the pH returned to normal. Under normal pressure, open the bottom valve of the reactor discharge and continue to use 0.07MPa nitrogen to extrude the material in the reactor from the discharge valve to the feed port of the twin-screw extruder. Control the screw speed at 240rpm and the feeding rate at 40. The temperatures of each section of the extruder are as follows: Section 1 (feed port): 220℃, Section 2: 230℃, Section 3: 235℃, Section 4: 245℃, Section 5: 275℃, Section 6: 275℃, Section 7: 280℃, Section 8: 280℃, Section 9: 285℃, Section 10: 285℃, Section 11: 285℃, Section 12: 290℃, Section 13: 290℃, Section 14 (die): 285℃. After venting, extrusion, pelletizing, and drying, the environmentally friendly, high-strength, tough, high- and low-temperature resistant, and corrosion-resistant polyamide elastomer resin is obtained.

[0069] For detailed infrared characterization, please refer to Figure 1 As shown, the mechanical properties and Vicat softening point (the standard impact specimen was placed in a silicone oil bath, and under the conditions of 1.82 MPa and 2℃ / min heating, the specimen was subjected to a 1 mm...) 2 Temperature when the needle is pressed in 1mm (e.g.) Figure 2-3 As shown in Table 1, the tensile strength is 86.3 MPa, the elongation at break is 848.3%, the Vicat softening point is 150.7℃, and the corrosion resistance test results are as follows: it exhibits excellent resistance to traditional alkanes, alcohols, acetone, hydrochloric acid (1 mol / L), and NaOH (1 mol / L), showing a significant improvement in corrosion resistance compared to traditional thermoplastic elastomers such as PU and TPE; when applied as an interfacial compatibilizer between fluoropolymers and aluminum and titanium sheets, its peel strength reaches 10.18 N / cm and 9.80 N / cm, respectively.

[0070] Table 1. Corrosion resistance test results of the elastomers obtained in Examples 1-6

[0071]

[0072]

[0073] +-: Swelling, ++: Dissolved at room temperature, -: Insoluble

[0074] Comparative Example 1 (Biphenyl-10-naphthalic acid-90-C14-80%-400-20%) without tertiary amine capping agent

[0075] 24.2 g of 4,4'-biphenyl dicarboxylic acid monomer, 194.4 g of 1,4-naphthalenedicarboxylic acid monomer, 182.4 g of tetradecanediamine, and polyetheramine-400 were added. 80g of heteropolyacid, 0.1g of manganese monoxide, and 100g of deionized water were added to a reactor. The mixture was heated to 50°C under a nitrogen atmosphere and stirred for 0.5 hours, maintaining the pH of the solution at 7.5. The reactor was then sealed, and the temperature was increased to 210°C for the first stage and reacted for 1 hour. The temperature was then increased to 231°C and reacted for another hour, with one venting operation. The reactor was then heated to 251°C, maintaining a vacuum of -0.08MPa, and reacted for 2 hours. The polymerization reaction was then stopped, and nitrogen gas was introduced into the reactor until atmospheric pressure was restored. The bottom valve of the reactor outlet was opened, and nitrogen gas was continued to be introduced at 0.02MPa to discharge the product. The material inside the vessel is extruded from the discharge valve into the feed inlet of the twin-screw extruder. The screw speed is controlled at 80 rpm, the feeding rate is 3, and the temperatures of each section of the extruder are as follows: Section 1 (feed inlet): 220℃, Section 2: 230℃, Section 3: 230℃, Section 4: 240℃, Section 5: 271℃, Section 6: 280℃, Section 7: 280℃, Section 8: 290℃, Section 9: 290℃, Section 10: 290℃, Section 11: 290℃, Section 12: 290℃, Section 13: 290℃, Section 14 (die): 280℃. After degassing, extrusion, pelletizing, and drying, polyamide elastomer resin is obtained.

[0076] The mechanical properties and Vicat softening point are as follows:

[0077] Its tensile strength is 36.9 MPa, elongation at break is 789.3%, and Vicat softening point (when a standard impact specimen is placed in a silicone oil bath and heated at 1.82 MPa and 2℃ / min, the specimen is 1 mm thick). 2 The temperature at which the needle tip is pressed into the hole to 1 mm is 130.0℃. The corrosion resistance test results are shown in Table 1. It exhibits similar resistance to the resin obtained in Example 1 in traditional alkanes, alcohols, acetone, hydrochloric acid (1 mol / L), and NaOH (1 mol / L), but its resistance to alkaline solutions is poor. When applied as an interfacial compatibilizer between fluoropolymers and aluminum and titanium sheets, its peel strength is only 2.46 N / cm and 2.83 N / cm, respectively.

[0078] Comparative Example 2 (Biphenyl-10-naphthalenedicarboxylic acid-90-C14-80%-PEG-800-20%)

[0079] 24.2 g of 4,4'-biphenyldicarboxylic acid monomer, 194.4 g of 1,4-naphthalenedicarboxylic acid monomer, 182.4 g of tetradecanediamine, 0.1 g of heteropolyacid mono-manganese, and 100 g of deionized water were added to a reaction vessel. The mixture was heated to 50°C under a nitrogen atmosphere and stirred for 0.5 h, maintaining the pH of the solution at 7.5. Subsequently, the reaction vessel was sealed, and the temperature was increased to 210°C in the first stage and reacted for 1 h; then increased to 231°C and reacted for another 1 h, with one venting during the process. The reaction vessel was then evacuated to a vacuum of -0.08 MPa. PEG-800 was then added... A mixture of 160g of PEG-800 and 1g of titanate ester was added to a sealed feeding tank. After heating to 80℃ and melting uniformly, the valve between the feeding tank and the reactor was opened. PEG-800 and the titanate ester catalyst were then drawn into the reactor under negative pressure. The feeding tank was purged with 0.1MPa nitrogen gas. After purging, all connecting valves between the feeding tanks were closed. The reactor temperature was then raised to 251℃, and a vacuum of -0.08MPa was maintained. The reaction was continued for 2 hours. The polymerization reaction was then stopped, and nitrogen gas was introduced into the reactor until atmospheric pressure was restored. The bottom discharge valve of the reactor was opened, and the material in the reactor was continuously discharged from the bottom valve using 0.02MPa nitrogen gas. The material is extruded through the discharge valves to the feed inlet of the twin-screw extruder. The screw speed is controlled at 80 rpm, the feed rate is 3, and the temperatures of each section of the extruder are as follows: Section 1 (feed inlet): 220℃, Section 2: 230℃, Section 3: 230℃, Section 4: 240℃, Section 5: 271℃, Section 6: 280℃, Section 7: 280℃, Section 8: 290℃, Section 9: 290℃, Section 10: 290℃, Section 11: 290℃, Section 12: 290℃, Section 13: 290℃, Section 14 (die): 280℃. After degassing, extrusion, pelletizing, and drying, polyamide elastomer resin is obtained.

[0080] The tensile strength of the obtained product is 35.3 MPa, and the elongation at break is 762%. It degrades or even dissolves in strong acids and alkalis, and its mechanical properties drop sharply. In addition, when used as an interfacial compatibilizer for fluoropolymers such as polytetrafluoroethylene propylene and aluminum and titanium sheets, its peel strength is only 2.2 N / cm.

Claims

1. A method for preparing a polyamide elastomer, characterized in that, The preparation method involves preparing the polyamide elastomer by a one-step polycondensation reaction of the raw materials under the action of a catalyst. The raw materials include: biphenyl dicarboxylic acid monomer, naphthalene dicarboxylic acid monomer, aliphatic diamine, polyetheramine, catalyst, capping agent or water; the proportions of each raw material are as follows: Biphenyl dicarboxylic acid 24.2–121 parts by weight Naphthalenedicarboxylic acid 108-194.4 parts by weight Aliphatic diamines 30-208.8 parts by weight 40-1000 parts by weight of polyetheramine Catalyst 0.1 to 40 parts by weight 10-500 parts by weight of deionized water End-capping agent: 0.1–20 parts by weight; The capping agent is: ； The method for preparing the polyamide elastomer includes the following steps: 24.2–121 parts by weight of biphenyl dicarboxylic acid monomer, 108–194.4 parts by weight of naphthalene dicarboxylic acid monomer, 30–208.8 parts by weight of aliphatic diamine, 40–1000 parts by weight of polyetheramine, 0.1–40 parts by weight of catalyst, and 10–500 parts by weight of deionized water were added to a reaction vessel. The mixture was heated to 50–100°C under a nitrogen atmosphere and stirred for 0.5–1 h, maintaining the pH of the solution at 7.5–8.

5. Subsequently, the reaction vessel was sealed, and the temperature was increased. In the first stage, the temperature was raised to 210–230°C and reacted for 1–3 h; then, the temperature was increased to 231–250°C. The reaction is carried out for 1-3 hours, with venting 1-3 times in between. Then the reactor is heated to 251-280℃, and the vacuum degree is maintained at -0.08 to -0.095MPa. The reaction is continued for 2-6 hours, and 0.1-20 parts by weight of the end-capping agent is drawn into the reactor using negative pressure. The reaction is continued for 0.5-2 hours. The polymerization reaction is stopped, and nitrogen is introduced into the reactor until the pressure returns to normal. The bottom valve of the reactor is opened, and 0.02-0.1MPa nitrogen is used to extrude the material in the reactor from the discharge valve to the feed port of the twin-screw extruder. The material is then vented, extruded, pelletized, and dried to obtain the polyamide elastomer. The biphenyl dicarboxylic acid monomer is The naphthalic acid monomer is The aliphatic diamine is selected from: The polyetheramine is selected from:

2. The method for preparing a polyamide elastomer according to claim 1, characterized in that, The tensile strength of the polyamide elastomer is 39–87 MPa; or the elongation at break of the polyamide elastomer is 800–1050%; or the Vicat softening point of the polyamide elastomer is 114–151 °C.

3. A method for preparing a polyamide elastomer according to any one of claims 1 or 2, characterized in that, The catalyst is selected from any one of the following: triphenyl phosphite, phosphorous acid, sodium hypophosphite, sodium phosphite, trimethylchlorosilane, triethylsilane chloride, tin chloride, stannous octoate, heteropolyacid unilateral chromium, heteropolyacid unilateral iron, heteropolyacid unilateral manganese, heteropolyacid unilateral aluminum, N,N'-dicyclohexylcarbodiimide, benzotriazole-N,N,N',N'-tetramethylurea hexafluorophosphate, or 1-hydroxybenzotriazole.

4. The method for preparing a polyamide elastomer according to claim 1, characterized in that, In the preparation method, the process conditions of the twin-screw extruder are as follows: The screw speed is controlled at 80-300 rpm, the feeding rate is 3-40, and the temperatures of each section of the extruder are as follows: Section 1: 220-260℃, Section 2: 220-260℃, Section 3: 220-260℃, Section 4: 220-260℃, Section 5: 271-290℃, Section 6: 271-290℃, Section 7: 271-290℃, Section 8: 271-290℃, Section 9: 271-290℃, Section 10: 271-290℃, Section 11: 271-290℃, Section 12: 271-290℃, Section 13: 271-290℃, Section 14: 280-290℃.

5. Use of a polyamide elastomer as a compatibilizer, active additive, soft plastic or coating material, wherein the polyamide elastomer is a polyamide elastomer prepared by any one of claims 1 to 4.

6. The use of the polyamide elastomer according to claim 5 as a compatibilizer, active additive, soft plastic, or coating material, characterized in that, The polyamide elastomer is used as an interfacial compatibilizer between inert resin and metal. or: The polyamide elastomer is used as a protective coating.

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