Modified polyether amine, preparation method and application thereof, and nylon elastomer

Abstract

The invention provides modified polyether amine, a preparation method and application thereof, and a nylon elastomer. The modified polyether amine is obtained by reacting polyether amine with a modifier, and the modifier comprises any one or more of ethylene carbonate, propylene carbonate or dimethyl carbonate. The tail end of the modified polyether amine is provided with two carbamate groups, so that the interaction force between molecules is increased, and the tensile strength and toughness of the nylon elastomer can be improved. Compared with other nylon elastomers in the prior art, the nylon elastomer prepared by taking the modified polyether amine as the soft segment provided by the invention has more excellent mechanical properties such as tensile strength, can meet the requirements of people on the medical industry, the automobile industry, the aerospace industry, the electronic and electrical industry and the like, and has a good market prospect. Meanwhile, the preparation methods of the modified polyether amine and the nylon elastomer are simple and convenient, and large-scale continuous production is easy to realize.

Description

Technical Field

[0001] The invention belongs to the technical field of nylon elastomers, and specifically relates to a modified polyetheramine and a preparation method and application thereof, and a nylon elastomer. Background Art

[0002] Thermoplastic polyamide elastomer, commonly known as nylon elastomer (TPAE for short), is a block copolymer containing polyamide hard segments and polyether soft segments. It has excellent physical and chemical properties and has broad application prospects. It has been widely used in many fields such as electronics and electrical, food packaging, automotive parts, sporting goods, and medical care, such as keyboard bases, suitcases, football shoe soles, medical hoses, catheters, etc. It can be seen that nylon elastomers have entered all aspects of people's daily lives.

[0003] Studies have shown that by adjusting the molecular weight of the hard and soft segments, the type of monomers, the relative proportion and the block mode, a series of nylon elastomers with different properties can be obtained to suit various functional uses. Generally, at room temperature, the nylon elastomer chain folds and crystallizes to form physical crosslinking points. At high temperatures, the crystals are destroyed and the crosslinking points are released, so that thermoplastic processing can be performed. Among them, the molecular weight of the hard segment and the soft segment determines the final mechanical properties of the elastomer, such as strength and modulus, as well as physical properties such as melting point, hardness, density and chemical stability.

[0004] Therefore, finding a suitable polyol soft segment and method is particularly critical for preparing nylon elastomers with excellent performance. Summary of the invention

[0005] In view of this, the purpose of the present invention is to provide a modified polyetheramine and its preparation method and application, and a nylon elastomer. The present invention can obtain a nylon elastomer with excellent mechanical properties by introducing the modified polyetheramine as a soft segment.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a modified polyetheramine obtained by reacting a polyetheramine with a modifier.

[0008] Preferably, the modifier includes any one or more of ethylene carbonate, propylene carbonate or dimethyl carbonate.

[0009] Preferably, the number average molecular weight of the modified polyetheramine is 400-2500.

[0010] Preferably, the molar ratio of the polyetheramine to the modifier is 1:(1.5-3).

[0011] Preferably, the number average molecular weight of the polyetheramine is 400-2000.

[0012] In a second aspect, the present invention provides a method for preparing the modified polyetheramine, comprising the following steps:

[0013] After the polyetheramine and the modifier are mixed, they are heated to 60-80°C, 80-90°C, and 90-120°C in sequence for three-stage reaction, and then the reduced pressure is applied at 140-180°C to obtain the modified polyetheramine.

[0014] Preferably, the reaction time of each of the three reaction stages is independently 1 to 5 hours.

[0015] Preferably, the decompression time is 1 to 5 hours.

[0016] In a third aspect, the present invention provides a use of the modified polyetheramine in the preparation of nylon elastomer.

[0017] In a fourth aspect, the present invention provides a nylon elastomer prepared from a nylon prepolymer, a modified polyetheramine and optional additives.

[0018] Preferably, the nylon prepolymer includes any one or more of nylon 1210 prepolymer, nylon 1010 prepolymer, nylon 610 prepolymer, nylon 6 prepolymer or nylon 66 prepolymer.

[0019] Preferably, the additive includes a catalyst and / or an antioxidant, the catalyst includes any one or more of tetrabutyl titanate, tetrabutyl zirconate or antimony acetate, preferably tetrabutyl titanate; the antioxidant includes any one or more of antioxidant 1010, antioxidant 1070, antioxidant 1076, antioxidant 1098, antioxidant sunnox508, antioxidant 2246, antioxidant 245 or sodium hypophosphite monohydrate, preferably sodium hypophosphite monohydrate.

[0020] Preferably, the molar ratio of the nylon prepolymer to the modified polyetheramine is 1:1.

[0021] Preferably, the mass of the additive is 2-10‰ of the sum of the masses of the nylon prepolymer and the modified polyether amine.

[0022] Preferably, the nylon elastomer has a tensile strength of more than 10 MPa, an elongation at break of more than 231%, and a Shore hardness of more than 20 HD.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The invention provides a modified polyetheramine, which is obtained by modifying a polyetheramine with a modifier (such as the modifier including any one or more of ethylene carbonate, propylene carbonate or dimethyl carbonate). During the modification process, an amine in the polyetheramine induces the modifier, such as a ring-opening reaction of a cyclic carbonate in ethylene carbonate, thereby obtaining the modified polyetheramine, which can not only improve the tensile strength of a nylon elastomer that finally uses the modified polyetheramine as a soft segment, but also improve its toughness.

[0025] According to tests, the tensile strength of the nylon elastomer is above 10 MPa, the elongation at break is above 231%, and the Shore hardness is above 20 HD. DETAILED DESCRIPTION

[0026] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] The invention provides a modified polyetheramine obtained by reacting a polyetheramine with a modifier.

[0028] In the present invention, the number average molecular weight of the polyetheramine is 400-2000, such as 400, 600, 800, 1000, 1200, 1400, 1600, 1800 or 2000.

[0029] The number average molecular weight of the polyetheramine cannot be too high, otherwise it will affect the performance of the subsequent prepared products, therefore, it is more preferably 400-1000.

[0030] In the present invention, the modifier includes any one or more of ethylene carbonate, propylene carbonate or dimethyl carbonate.

[0031] The present invention has no particular limitation on the sources of the above-mentioned modifier and polyetheramine, and they may be common commercial products.

[0032] The present invention modifies the polyetheramine with the above modifier, and the amine in the polyetheramine induces the modifier, such as the ring-opening reaction of the cyclic carbonate in ethylene carbonate, to obtain the modified polyetheramine, which is very beneficial for the subsequent preparation of nylon elastomers with excellent mechanical properties.

[0033] The molar ratio of the polyetheramine to the modifier has an influence on the molecular weight and molecular weight distribution of the modified polyetheramine. In some embodiments of the present invention, the molar ratio of the polyetheramine to the modifier is 1:(1.5-3), such as 1:1.5, 1:1.8, 1:2.0, 1:2.3, 1:2.5, 1:2.7 or 1:3, etc., preferably 1:(1.8-2.3). After testing, the number average molecular weight of the modified polyetheramine finally prepared is 400-2500, such as 400, 600, 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200 or 2500, etc., preferably 400-1000.

[0034] The present invention also provides a method for preparing the modified polyetheramine, comprising the following steps:

[0035] After the polyetheramine and the modifier are mixed, they are heated to 60-80°C, 80-90°C, and 90-120°C in sequence for three-stage reaction, and then the reduced pressure is applied at 140-180°C to obtain the modified polyetheramine.

[0036] According to the present invention, the polyetheramine and the modifier are first mixed. In some embodiments of the present invention, the polyetheramine and the modifier are preferably placed in a three-necked round-bottom flask equipped with a mechanical stirrer in a certain proportion and mixed.

[0037] After the mixing is completed, the mixture is heated to 60-80°C, 80-90°C, and 90-120°C for three-stage reaction, such as 60°C, 80°C, and 90°C for three-stage reaction, or 70°C, 85°C, and 100°C for three-stage reaction, or 80°C, 90°C, and 120°C for three-stage reaction. The time of each reaction in the three-stage reaction is independently 1-5h, such as 1h, 2h, 3h, 4h, or 5h. The present invention adopts a three-stage reaction to prepare the modified polyetheramine. Compared with a one-step or two-step reaction, the molecular weight distribution of the modified polyetheramine obtained by the three-stage reaction is more uniform.

[0038] After the three-stage reaction is completed, according to the present invention, the pressure is reduced at 140-180° C. for 1-5 hours, preferably at 150-170° C. for 2-4 hours, to obtain the target product, i.e., the modified polyetheramine. The purpose of the pressure reduction is to remove unreacted monomers and low molecular weight polymers.

[0039] The preparation method of the modified polyetheramine provided by the present invention is simple, convenient, easy to implement, does not require expensive equipment, and is conducive to large-scale or industrialized production.

[0040] The present invention also provides the use of the modified polyetheramine in the preparation of nylon elastomer. In the application, the modified polyetheramine is used as the soft segment of the nylon elastomer.

[0041] Specifically, the present invention provides a nylon elastomer prepared from a nylon prepolymer, a modified polyetheramine and optional additives.

[0042] In the present invention, the nylon prepolymer as the hard segment of the nylon elastomer includes but is not limited to any one or more of nylon 1210 prepolymer, nylon 1010 prepolymer, nylon 6 prepolymer, nylon 610 prepolymer or nylon 66 prepolymer.

[0043] The present invention has no particular limitation on the source of the nylon prepolymer, and the nylon prepolymer can be prepared by a method known to those skilled in the art or directly purchased from a commercial product.

[0044] In the present invention, the additive includes a catalyst and / or an antioxidant, the catalyst includes any one or more of tetrabutyl titanate, tetrabutyl zirconate or antimony acetate, preferably tetrabutyl titanate; the antioxidant includes any one or more of antioxidant 1010, antioxidant 1070, antioxidant 1076, antioxidant 1098, antioxidant sunnox508, antioxidant 2246, antioxidant 245 or sodium hypophosphite monohydrate, preferably sodium hypophosphite monohydrate.

[0045] In some embodiments of the present invention, the molar ratio of the nylon prepolymer to the modified polyetheramine is 1:1.

[0046] It should be noted that the present invention has no particular limitation on the preparation method of the nylon elastomer, and the elastomer can be prepared according to methods well known to those skilled in the art.

[0047] Exemplarily, the present invention provides a method for preparing a nylon elastomer, comprising the following specific steps:

[0048] a. Weigh the raw materials of dodecanediamine and sebacic acid in a molar ratio of 1:(1-2) and add them to the polymerization reactor, then add an appropriate amount of deionized water and 1-5‰ antioxidant, seal the reactor and replace the air in the reactor with high-purity nitrogen, repeat 3-5 times; then turn on the heating, start stirring (150r / min) when the temperature reaches 150°C and keep the temperature constant for 30min to make the materials fully melt and mix; then increase the reaction temperature to 200°C and keep the temperature constant for 2h; then slowly release the pressure in the reactor through the valve until it reaches normal pressure, then take out the material from the lower discharge port, and obtain a white nylon prepolymer (nylon 1210 prepolymer) after cooling, crushing and drying. The molecular weight of the prepolymer is 600-8000, which is reserved for the next polymerization;

[0049] b. Add the nylon prepolymer and the modified polyetheramine polymer in an equal molar ratio into a polymerization reactor, and then add 1 to 5‰ (the ratio of the total mass of the solid raw materials, the same below) of the catalyst and 1 to 5‰ of the antioxidant, respectively, close the reaction system and repeatedly evacuate and introduce nitrogen 5 times to exclude the original air in the reaction system to ensure an anaerobic environment;

[0050] c. Turn on the heating, and start stirring when the temperature rises to 150°C, and stir at this temperature for 30 minutes to fully melt and mix the materials evenly. The stirring speed is 200r / min, and then the temperature is raised to 220°C and the reaction is kept at this temperature for 2 hours, and then the temperature is raised to 250°C and the reaction is kept at this temperature for 30 minutes; then the reaction system is vacuumed, and when the negative pressure indication reaches -0.100MPa, the vacuuming is stopped and the reaction is continued for 3 hours under this condition;

[0051] d. Push the water tank to the appropriate position of the discharge port, set the temperature of the polymerization kettle discharge port to 250℃, turn on the lower discharge port heating switch, discharge the material after 10 minutes, open the discharge port valve at the bottom of the polymerization kettle, close the exhaust valve, open the nitrogen inlet valve to flush in a little nitrogen, and adjust the pressure in the kettle after the bottom of the kettle is discharged so that the material enters the water tank for cooling at a uniform speed. After the material is cooled in the water tank and drawn into suitable lines, cut off the irregular excess waste, and pelletize the qualified and uniform nylon lines on the pelletizer, adjust the speed of the pelletizer, so that the discharge speed matches the speed of the pelletizer, and can be continuously cut into uniform and regular particles. The particles are finally dried to obtain nylon elastomer.

[0052] The above preparation method is only an exemplary description, and those skilled in the art can conventionally adjust the type of nylon prepolymer for different nylon elastomers. In addition, some parameters of the above preparation method, such as temperature, time, pressure, rotation speed, etc., can be conventionally optimized and adjusted.

[0053] The present invention takes nylon 1210 prepolymer as an example, uses it as a hard segment, and uses modified polyetheramine as a soft segment. The nylon elastomer obtained after polymerization has a tensile strength of more than 10MPa, an elongation at break of more than 231%, and a Shore hardness of more than 20HD.

[0054] In summary, the nylon elastomer prepared with modified polyetheramine as the soft segment provided by the present invention has better mechanical properties, such as tensile strength, compared with other nylon elastomers in the prior art, and can meet people's needs in the medical industry, automobile industry, aerospace industry, and electronic and electrical industry, and has good market prospects.

[0055] Meanwhile, the present invention adopts a two-step method to carry out polymerization in a polymerization kettle, finally opens the discharge port valve at the bottom of the polymerization kettle, closes the exhaust valve, opens the nitrogen inlet valve to flush in a small amount of nitrogen, adjusts the pressure in the kettle after the bottom of the kettle is discharged so that the material enters the water tank for cooling at a uniform speed, cuts off the irregular excess waste after the material is cooled in the water tank and drawn into suitable lines, pelletizes the qualified nylon lines with uniform thickness on a pelletizer, adjusts the speed of the pelletizer so that the discharge speed matches the speed of the pelletizer, and can be continuously cut into particles of uniform size, and the particles are finally dried to obtain a nylon elastomer. The preparation method is simple and easy to implement, and is easy to realize large-scale continuous production.

[0056] In order to further illustrate the present invention, the following examples are provided for detailed description. The experimental raw materials used in the following examples of the present invention are all common commercially available products.

[0057] Example 1

[0058] Weigh and mix dodecanediamine and sebacic acid in a molar ratio of (1:1.1) and add them to a polymerization reactor, then add 10% deionized water and 2‰ antioxidant sodium hypophosphite monohydrate, seal the reactor and replace the air in the reactor with high-purity nitrogen, repeat 3 to 5 times; then turn on the heating, start stirring (150r / min) when the temperature reaches 150°C and keep the temperature constant for 30min to make the materials fully melt and mix; then increase the reaction temperature to 200°C and keep the temperature constant for 2h; then slowly release the pressure in the reactor through a valve until it reaches normal pressure, then take out the material from the lower discharge port, and obtain nylon 1210 prepolymer with a molecular weight Mw=3510 after cooling, crushing and drying;

[0059] The polyetheramine (M W =400) and ethylene carbonate (molar ratio of 1:2.05) were placed in a 500mL three-necked round-bottom flask equipped with a mechanical stirrer, heated to 60°C, reacted for 2h, heated to 80°C, reacted for 1h, and then reacted at 90°C for 1h, and finally, a modified polyetheramine was obtained. Finally, the pressure was reduced at 170°C for 2h to obtain a high-purity modified polyetheramine polymer with a molecular weight of Mw=570;

[0060] Mix nylon 1210 prepolymer and modified polyetheramine polymer in an equal molar ratio and add them to the reactor. Then add 2‰ (total mass of solid raw materials) of tetrabutyl titanate and 2‰ of antioxidant sodium hypophosphite monohydrate. Close the reaction system and repeatedly evacuate and introduce nitrogen 5 times to remove the original air in the reaction system to ensure an oxygen-free environment. Turn on the heating, and when the temperature rises to 150°C, turn on the stirring, and keep stirring at this temperature for 30 minutes to fully melt and mix the materials evenly. The stirring speed is 100r / min; then heat to 220°C and keep the temperature for 4 hours; then heat to 250°C and keep the temperature for 30 minutes; then evacuate the reaction system again, stop evacuating when the negative pressure reaches -0.100MPa, and continue to react for 3 hours under this condition; then stop heating and stirring, push the water tank to the appropriate position of the discharge port, and set the discharge port temperature of the polymerization kettle to 250°C. Turn on the heating switch of the lower discharge port, discharge the material after 10 minutes, open the discharge port valve at the bottom of the polymerization kettle, close the exhaust valve, open the nitrogen inlet valve to flush in a little nitrogen, and adjust the pressure in the kettle after the bottom of the kettle is discharged so that the material enters the water tank for cooling at a uniform speed. After the material is cooled in the water tank and drawn into suitable lines, cut off the irregular excess waste, and pelletize the qualified and uniform nylon lines on the pelletizer, adjust the speed of the pelletizer to match the discharge speed with the speed of the pelletizer, and can continuously cut into uniform and regular particles. Finally, the particles are dried to obtain nylon elastomer.

[0061] Example 2

[0062] Weigh and mix dodecanediamine and sebacic acid in a molar ratio of (1:1.1) and add them to a polymerization reactor, then add 10% deionized water and 2‰ antioxidant sodium hypophosphite monohydrate, seal the reactor and replace the air in the reactor with high-purity nitrogen, repeat 3 to 5 times; then turn on the heating, start stirring (150r / min) when the temperature reaches 150°C and keep the temperature constant for 30min to make the materials fully melt and mix; then increase the reaction temperature to 200°C and keep the temperature constant for 2h; then slowly release the pressure in the reactor through a valve until it reaches normal pressure, then take out the material from the lower discharge port, and obtain nylon 1210 prepolymer with a molecular weight Mw=3510 after cooling, crushing and drying;

[0063] The polyetheramine (M W =400) and ethylene carbonate (molar ratio of 1:2.3) were placed in a 500mL three-necked round-bottom flask equipped with a mechanical stirrer, heated to 60°C, reacted for 2h, heated to 80°C, reacted for 1h, and then reacted at 90°C for 1h. Finally, the pressure was reduced at 170°C for 2h to obtain a high-purity modified polyetheramine polymer; molecular weight Mw = 500;

[0064] Mix nylon 1210 prepolymer and modified polyetheramine polymer in an equal molar ratio and add them to the reactor. Then add 2‰ (total mass of solid raw materials) of tetrabutyl titanate and 2‰ of antioxidant sodium hypophosphite monohydrate. Close the reaction system and repeatedly evacuate and introduce nitrogen 5 times to remove the original air in the reaction system to ensure an oxygen-free environment. Turn on the heating, and when the temperature rises to 150°C, turn on the stirring, and keep stirring at this temperature for 30 minutes to fully melt and mix the materials evenly. The stirring speed is 100r / min; then heat to 220°C and keep the temperature for 4 hours; then heat to 250°C and keep the temperature for 30 minutes; then evacuate the reaction system again, stop evacuating when the negative pressure reaches -0.100MPa, and continue to react for 3 hours under this condition; then stop heating and stirring, push the water tank to the appropriate position of the discharge port, and set the discharge port temperature of the polymerization kettle to 250°C. Turn on the heating switch of the lower discharge port, discharge the material after 10 minutes, open the discharge port valve at the bottom of the polymerization kettle, close the exhaust valve, open the nitrogen inlet valve to flush in a little nitrogen, and adjust the pressure in the kettle after the bottom of the kettle is discharged so that the material enters the water tank for cooling at a uniform speed. After the material is cooled in the water tank and drawn into suitable lines, cut off the irregular excess waste, and pelletize the qualified and uniform nylon lines on the pelletizer, adjust the speed of the pelletizer to match the discharge speed with the speed of the pelletizer, and can continuously cut into uniform and regular particles. Finally, the particles are dried to obtain nylon elastomer.

[0065] Example 3

[0066] Weigh and mix dodecanediamine and sebacic acid in a molar ratio of (1:1.1) and add them to a polymerization reactor, then add 10% deionized water and 2‰ antioxidant sodium hypophosphite monohydrate, seal the reactor and replace the air in the reactor with high-purity nitrogen, repeat 3 to 5 times; then turn on the heating, start stirring (150r / min) when the temperature reaches 150°C and keep the temperature constant for 30min to make the materials fully melt and mix; then increase the reaction temperature to 200°C and keep the temperature constant for 2h; then slowly release the pressure in the reactor through a valve until it reaches normal pressure, then take out the material from the lower discharge port, and obtain nylon 1210 prepolymer with a molecular weight Mw=3510 after cooling, crushing and drying;

[0067] The polyetheramine (M W =600) and ethylene carbonate (molar ratio of 1:2.05) were placed in a 500mL three-necked round-bottom flask equipped with a mechanical stirrer, heated to 65°C, reacted for 2h, heated to 85°C, reacted for 1h, and then reacted at 95°C for 1h. Finally, the pressure was reduced at 175°C for 2h to obtain a high-purity modified polyetheramine polymer with a molecular weight of Mw=780;

[0068] Mix nylon 1210 prepolymer and modified polyetheramine polymer in an equal molar ratio and add them to the reactor. Then add 2‰ (total mass of solid raw materials) of tetrabutyl titanate and 2‰ of antioxidant sodium hypophosphite monohydrate. Close the reaction system and repeatedly evacuate and introduce nitrogen 5 times to remove the original air in the reaction system to ensure an oxygen-free environment. Turn on the heating, and when the temperature rises to 150°C, turn on the stirring, and keep stirring at this temperature for 30 minutes to fully melt and mix the materials evenly. The stirring speed is 100r / min; then heat to 220°C and keep the temperature for 4 hours; then heat to 250°C and keep the temperature for 30 minutes; then evacuate the reaction system again, stop evacuating when the negative pressure reaches -0.100MPa, and continue to react for 3 hours under this condition; then stop heating and stirring, push the water tank to the appropriate position of the discharge port, and set the discharge port temperature of the polymerization kettle to 250°C. Turn on the heating switch of the lower discharge port, discharge the material after 10 minutes, open the discharge port valve at the bottom of the polymerization kettle, close the exhaust valve, open the nitrogen inlet valve to flush in a little nitrogen, and adjust the pressure in the kettle after the bottom of the kettle is discharged so that the material enters the water tank for cooling at a uniform speed. After the material is cooled in the water tank and drawn into suitable lines, cut off the irregular excess waste, and pelletize the qualified and uniform nylon lines on the pelletizer, adjust the speed of the pelletizer to match the discharge speed with the speed of the pelletizer, and can continuously cut into uniform and regular particles. Finally, the particles are dried to obtain nylon elastomer.

[0069] Example 4

[0070] Weigh and mix dodecanediamine and sebacic acid in a molar ratio of (1:1.1) and add them to a polymerization reactor, then add 10% deionized water and 2‰ antioxidant sodium hypophosphite monohydrate, seal the reactor and replace the air in the reactor with high-purity nitrogen, repeat 3 to 5 times; then turn on the heating, start stirring (150r / min) when the temperature reaches 150°C and keep the temperature constant for 30min to make the materials fully melt and mix; then increase the reaction temperature to 200°C and keep the temperature constant for 2h; then slowly release the pressure in the reactor through a valve until it reaches normal pressure, then take out the material from the lower discharge port, and obtain nylon 1210 prepolymer with a molecular weight Mw=3510 after cooling, crushing and drying;

[0071] The polyetheramine (M W =600) and ethylene carbonate (molar ratio of 1:2.3) were placed in a 500mL three-necked round-bottom flask equipped with a mechanical stirrer, heated to 65°C, reacted for 2h, heated to 85°C, reacted for 1h, and then reacted at 95°C for 1h. Finally, the pressure was reduced at 175°C for 2h to obtain a high-purity modified polyetheramine polymer with a molecular weight of Mw=720;

[0072] Mix nylon 1210 prepolymer and modified polyetheramine polymer in an equal molar ratio and add them to the reactor. Then add 2‰ (total mass of solid raw materials) of tetrabutyl titanate and 2‰ of antioxidant sodium hypophosphite monohydrate. Close the reaction system and repeatedly evacuate and introduce nitrogen 5 times to remove the original air in the reaction system to ensure an oxygen-free environment. Turn on the heating, and when the temperature rises to 150°C, turn on the stirring, and keep stirring at this temperature for 30 minutes to fully melt and mix the materials evenly. The stirring speed is 100r / min; then heat to 220°C and keep the temperature for 4 hours; then heat to 250°C and keep the temperature for 30 minutes; then evacuate the reaction system again, stop evacuating when the negative pressure reaches -0.100MPa, and continue to react for 3 hours under this condition; then stop heating and stirring, push the water tank to the appropriate position of the discharge port, and set the discharge port temperature of the polymerization kettle to 250°C. Turn on the heating switch of the lower discharge port, discharge the material after 10 minutes, open the discharge port valve at the bottom of the polymerization kettle, close the exhaust valve, open the nitrogen inlet valve to flush in a little nitrogen, and adjust the pressure in the kettle after the bottom of the kettle is discharged so that the material enters the water tank for cooling at a uniform speed. After the material is cooled in the water tank and drawn into suitable lines, cut off the irregular excess waste, and pelletize the qualified and uniform nylon lines on the pelletizer, adjust the speed of the pelletizer to match the discharge speed with the speed of the pelletizer, and can continuously cut into uniform and regular particles. Finally, the particles are dried to obtain nylon elastomer.

[0073] Example 5

[0074] Weigh and mix dodecanediamine and sebacic acid in a molar ratio of (1:1.1) and add them to a polymerization reactor, then add 10% deionized water and 2‰ antioxidant sodium hypophosphite monohydrate, seal the reactor and replace the air in the reactor with high-purity nitrogen, repeat 3 to 5 times; then turn on the heating, start stirring (150r / min) when the temperature reaches 150°C and keep the temperature constant for 30min to make the materials fully melt and mix; then increase the reaction temperature to 200°C and keep the temperature constant for 2h; then slowly release the pressure in the reactor through a valve until it reaches normal pressure, then take out the material from the lower discharge port, and obtain nylon 1210 prepolymer with a molecular weight Mw=3510 after cooling, crushing and drying;

[0075] The polyetheramine (M W =1000) and ethylene carbonate (molar ratio of 1:1.9) were placed in a 500mL three-necked round-bottom flask equipped with a mechanical stirrer, heated to 65°C, reacted for 2h, heated to 85°C, reacted for 1h, and then reacted at 95°C for 1h. Finally, the pressure was reduced at 175°C for 2h to obtain a high-purity modified polyetheramine polymer with a molecular weight of Mw=1200;

[0076] Mix nylon 1210 prepolymer and modified polyetheramine polymer in an equal molar ratio and add them to the reactor. Then add 2‰ (total mass of solid raw materials) of tetrabutyl titanate and 2‰ of antioxidant sodium hypophosphite monohydrate. Close the reaction system and repeatedly evacuate and introduce nitrogen 5 times to remove the original air in the reaction system to ensure an oxygen-free environment. Turn on the heating, and when the temperature rises to 150°C, turn on the stirring, and keep stirring at this temperature for 30 minutes to fully melt and mix the materials evenly. The stirring speed is 100r / min; then heat to 220°C and keep the temperature for 4 hours; then heat to 250°C and keep the temperature for 30 minutes; then evacuate the reaction system again, stop evacuating when the negative pressure reaches -0.100MPa, and continue to react for 3 hours under this condition; then stop heating and stirring, push the water tank to the appropriate position of the discharge port, and set the discharge port temperature of the polymerization kettle to 250°C. Turn on the heating switch of the lower discharge port, discharge the material after 10 minutes, open the discharge port valve at the bottom of the polymerization kettle, close the exhaust valve, open the nitrogen inlet valve to flush in a little nitrogen, and adjust the pressure in the kettle after the bottom of the kettle is discharged so that the material enters the water tank for cooling at a uniform speed. After the material is cooled in the water tank and drawn into suitable lines, cut off the irregular excess waste, and pelletize the qualified and uniform nylon lines on the pelletizer, adjust the speed of the pelletizer to match the discharge speed with the speed of the pelletizer, and can continuously cut into uniform and regular particles. Finally, the particles are dried to obtain nylon elastomer.

[0077] Example 6

[0078] Weigh and mix dodecanediamine and sebacic acid in a molar ratio of (1:1.1) and add them to a polymerization reactor, then add 10% deionized water and 2‰ antioxidant sodium hypophosphite monohydrate, seal the reactor and replace the air in the reactor with high-purity nitrogen, repeat 3 to 5 times; then turn on the heating, start stirring (150r / min) when the temperature reaches 150°C and keep the temperature constant for 30min to make the materials fully melt and mix; then increase the reaction temperature to 200°C and keep the temperature constant for 2h; then slowly release the pressure in the reactor through a valve until it reaches normal pressure, then take out the material from the lower discharge port, and obtain nylon 1210 prepolymer with a molecular weight Mw=3510 after cooling, crushing and drying;

[0079] The polyetheramine (M W =2000) and ethylene carbonate (molar ratio of 1:1.95) were placed in a 500mL three-necked round-bottom flask equipped with a mechanical stirrer, heated to 65°C, reacted for 2h, heated to 85°C, reacted for 1h, and then reacted at 95°C for 1h. Finally, the pressure was reduced at 175°C for 2h to obtain a high-purity modified polyetheramine polymer with a molecular weight of Mw=2200;

[0080] Mix nylon 1210 prepolymer and modified polyetheramine polymer in an equal molar ratio and add them to the reactor. Then add 2‰ (total mass of solid raw materials) of tetrabutyl titanate and 2‰ of antioxidant sodium hypophosphite monohydrate. Close the reaction system and repeatedly evacuate and introduce nitrogen 5 times to remove the original air in the reaction system to ensure an oxygen-free environment. Turn on the heating, and when the temperature rises to 150°C, turn on the stirring, and keep stirring at this temperature for 30 minutes to fully melt and mix the materials evenly. The stirring speed is 100r / min; then heat to 220°C and keep the temperature for 4 hours; then heat to 250°C and keep the temperature for 30 minutes; then evacuate the reaction system again, stop evacuating when the negative pressure reaches -0.100MPa, and continue to react for 3 hours under this condition; then stop heating and stirring, push the water tank to the appropriate position of the discharge port, and set the discharge port temperature of the polymerization kettle to 250°C. Turn on the heating switch of the lower discharge port, discharge the material after 10 minutes, open the discharge port valve at the bottom of the polymerization kettle, close the exhaust valve, open the nitrogen inlet valve to flush in a little nitrogen, and adjust the pressure in the kettle after the bottom of the kettle is discharged so that the material enters the water tank for cooling at a uniform speed. After the material is cooled in the water tank and drawn into suitable lines, cut off the irregular excess waste, and pelletize the qualified and uniform nylon lines on the pelletizer, adjust the speed of the pelletizer to match the discharge speed with the speed of the pelletizer, and can continuously cut into uniform and regular particles. Finally, the particles are dried to obtain nylon elastomer.

[0081] Comparative Example 1

[0082] Weigh and mix the raw materials of dodecanediamine and sebacic acid in a molar ratio of (1:1.5) and add them to a polymerization reactor, then add 10% deionized water and 2‰ antioxidant sodium hypophosphite monohydrate, seal the reactor and replace the air in the reactor with high-purity nitrogen, repeat 3 to 5 times; then turn on the heating, start stirring (150r / min) when the temperature reaches 150°C and keep the temperature constant for 30min to make the materials fully melt and mix; then increase the reaction temperature to 200°C and keep the temperature constant for 2h; then slowly release the pressure in the reactor through a valve until it reaches normal pressure, then take out the material from the lower discharge port, obtain nylon 1210 prepolymer after cooling, crushing and drying, and measure the molecular weight; the molecular weight Mw=1000;

[0083] Polyetheramine (MW = 400) and ethylene carbonate (molar ratio of 1:2.05) were placed in a 500 mL three-necked round-bottom flask equipped with a mechanical stirrer, heated to 60°C, reacted for 2 hours, heated to 80°C, reacted for another hour, and then reacted at 90°C for 1 hour. Finally, the pressure was reduced at 170°C for 2 hours to obtain a high-purity modified polyetheramine polymer; molecular weight Mw = 570;

[0084] Mix nylon 1210 prepolymer and modified polyetheramine polymer in an equal molar ratio and add them to the reactor. Then add 2‰ (total mass of solid raw materials) of tetrabutyl titanate and 2‰ of antioxidant sodium hypophosphite monohydrate. Close the reaction system and repeatedly evacuate and introduce nitrogen 5 times to remove the original air in the reaction system to ensure an oxygen-free environment. Turn on the heating, and when the temperature rises to 150°C, turn on the stirring, and keep stirring at this temperature for 30 minutes to fully melt and mix the materials evenly. The stirring speed is 100r / min; then heat to 220°C and keep the temperature for 4 hours; then heat to 250°C and keep the temperature for 30 minutes; then evacuate the reaction system again, stop evacuating when the negative pressure reaches -0.100MPa, and continue to react for 3 hours under this condition; then stop heating and stirring, push the water tank to the appropriate position of the discharge port, and set the discharge port temperature of the polymerization kettle to 250°C. Turn on the heating switch of the lower discharge port, discharge the material after 10 minutes, open the discharge port valve at the bottom of the polymerization kettle, close the exhaust valve, open the nitrogen inlet valve to flush in a little nitrogen, and adjust the pressure in the kettle after the bottom of the kettle is discharged so that the material enters the water tank for cooling at a uniform speed. After the material is cooled in the water tank and drawn into suitable lines, cut off the irregular excess waste, and pelletize the qualified and uniform nylon lines on the pelletizer, adjust the speed of the pelletizer to match the discharge speed with the speed of the pelletizer, and can continuously cut into uniform and regular particles. Finally, the particles are dried to obtain nylon elastomer.

[0085] Comparative Example 2

[0086] Weigh and mix the raw materials of dodecanediamine and sebacic acid according to the molar ratio of (1:1.1) and add them to a polymerization reactor, then add 10% deionized water and 2‰ antioxidant sodium hypophosphite monohydrate, seal the reactor and replace the air in the reactor with high-purity nitrogen, repeat 3 to 5 times; then turn on the heating, start stirring (150r / min) when the temperature reaches 150°C and keep the temperature constant for 30min to make the materials fully melt and mix; then increase the reaction temperature to 200°C and keep the temperature constant for 2h; then slowly release the pressure in the reactor through the valve until it reaches normal pressure, then take out the material from the lower discharge port, obtain nylon 1210 prepolymer after cooling, crushing and drying, and measure the molecular weight; the molecular weight Mw=3510;

[0087] The nylon 1210 prepolymer was mixed with polytetrahydrofuran (Mw=570, the selected polytetrahydrofuran had the same molecular weight as the modified polyetheramine polymer in Example 1) in an equal molar ratio and added to a reactor. Then, 2‰ (based on the total mass of the solid raw materials) of tetrabutyl titanate and 2‰ of an antioxidant sodium hypophosphite monohydrate were added thereto. The reaction system was closed and repeatedly evacuated and nitrogen was introduced 5 times to remove the original air in the reaction system to ensure an anaerobic environment. Turn on the heating, and when the temperature rises to 150°C, start stirring, and keep stirring at this temperature for 30 minutes to make the materials fully melted and mixed evenly, and the stirring speed is 100r / min; then raise the temperature to 220°C and keep the reaction at this temperature for 4 hours; then raise the temperature to 250°C and keep the reaction at this temperature for 30 minutes; then evacuate the reaction system, and stop evacuating when the negative pressure indication reaches -0.100MPa, and continue the reaction under this condition for 3 hours; then stop heating and stirring, push the water tank to the appropriate position of the discharge port, and set the discharge port temperature of the polymerization kettle to 250°C. Turn on the heating switch of the lower discharge port, discharge the material after 10 minutes, open the discharge port valve at the bottom of the polymerization kettle, close the exhaust valve, open the nitrogen inlet valve to flush in a little nitrogen, and adjust the pressure in the kettle after the bottom of the kettle is discharged so that the material enters the water tank for cooling at a uniform speed. After the material is cooled in the water tank and drawn into suitable lines, cut off the irregular excess waste, and pelletize the qualified and uniform nylon lines on the pelletizer, adjust the speed of the pelletizer to match the discharge speed with the speed of the pelletizer, and can continuously cut into uniform and regular particles. Finally, the particles are dried to obtain nylon elastomer.

[0088] Comparative Example 3

[0089] Weigh and mix the raw materials of dodecanediamine and sebacic acid according to the molar ratio of (1:1.1) and add them to a polymerization reactor, then add 10% deionized water and 2‰ antioxidant sodium hypophosphite monohydrate, seal the reactor and replace the air in the reactor with high-purity nitrogen, repeat 3 to 5 times; then turn on the heating, start stirring (150r / min) when the temperature reaches 150°C and keep the temperature constant for 30min to make the materials fully melt and mix; then increase the reaction temperature to 200°C and keep the temperature constant for 2h; then slowly release the pressure in the reactor through the valve until it reaches normal pressure, then take out the material from the lower discharge port, obtain nylon 1210 prepolymer after cooling, crushing and drying, and measure the molecular weight; the molecular weight Mw=3510;

[0090] Nylon 1210 prepolymer and polytetrahydrofuran (Mw = 780, the selected polytetrahydrofuran has the same molecular weight as the modified polyetheramine polymer in Example 3) in an equal molar ratio were mixed and added to the reactor, and then 2‰ (accounting for the total mass of the solid raw materials) of tetrabutyl titanate was added thereto, and 2‰ of the antioxidant sodium hypophosphite monohydrate was added, the reaction system was closed and repeatedly evacuated and nitrogen was introduced 5 times to remove the original air in the reaction system to ensure an anaerobic environment. Turn on the heating, and when the temperature rises to 150°C, start stirring, and keep stirring at this temperature for 30 minutes to make the materials fully melted and mixed evenly, and the stirring speed is 100r / min; then raise the temperature to 220°C and keep the reaction at this temperature for 4 hours; then raise the temperature to 250°C and keep the reaction at this temperature for 30 minutes; then evacuate the reaction system, and stop evacuating when the negative pressure indication reaches -0.100MPa, and continue the reaction under this condition for 3 hours; then stop heating and stirring, push the water tank to the appropriate position of the discharge port, and set the discharge port temperature of the polymerization kettle to 250°C. Turn on the heating switch of the lower discharge port, discharge the material after 10 minutes, open the discharge port valve at the bottom of the polymerization kettle, close the exhaust valve, open the nitrogen inlet valve to flush in a little nitrogen, and adjust the pressure in the kettle after the bottom of the kettle is discharged so that the material enters the water tank for cooling at a uniform speed. After the material is cooled in the water tank and drawn into suitable lines, cut off the irregular excess waste, and pelletize the qualified and uniform nylon lines on the pelletizer, adjust the speed of the pelletizer to match the discharge speed with the speed of the pelletizer, and can continuously cut into uniform and regular particles. Finally, the particles are dried to obtain nylon elastomer.

[0091] Performance Testing

[0092] The present invention tests the tensile strength, elongation at break and Shore hardness of the products obtained in the above embodiments and comparative examples, and the testing method is carried out in accordance with GB / T1040.2-2022.

[0093] The test results are shown in Table 1 below:

[0094] Table 1

[0095]

[0096]

[0097] It can be seen from Examples 1 to 6 in Table 1 that the nylon elastomer prepared by the process of the present invention has excellent mechanical properties. The nylon elastomer prepared by the process can be widely used in the automotive industry (such as brake hoses, oil pipes, etc.), the electronics industry (electronic and electrical parts), the medical industry, wire and cable sheaths, and other industries.

[0098] From the comparison between comparative example 1 and example 1, it can be seen that when the soft segment is the same, the larger the molecular weight of the hard segment is, the greater the tensile strength of the obtained nylon elastomer is; from the comparison between comparative example 2 and example 1, and the comparison between comparative example 3 and example 3, it can be seen that when the molecular weight of the hard segment is the same, the nylon elastomer synthesized by the modified polyetheramine has better tensile strength than the polytetrahydrofuran with the same molecular weight.

[0099] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A modified polyetheramine, characterized in that: Obtained by the reaction of polyetheramine and modifier; The modifier includes any one or more of ethylene carbonate, propylene carbonate or dimethyl carbonate; The number average molecular weight of the modified polyetheramine is 400-2500.

2. The modified polyetheramine according to claim 1, characterized in that The molar ratio of the polyetheramine to the modifier is 1:(1.5-3).

3. The modified polyetheramine according to claim 1 or 2, characterized in that The number average molecular weight of the polyetheramine is 400-2000.

4. A method for preparing a modified polyetheramine as claimed in any one of claims 1 to 3, characterized in that: The following steps are involved: After the polyetheramine and the modifier are mixed, they are heated to 60-80°C, 80-90°C, and 90-120°C in sequence for three-stage reaction, and then the reduced pressure is applied at 140-180°C to obtain the modified polyetheramine.

5. The preparation method according to claim 4, characterized in that: The reaction time of each of the three stages is independently 1 to 5 hours; The decompression time is 1 to 5 hours.

6. Use of the modified polyetheramine according to any one of claims 1 to 3 or the modified polyetheramine prepared by the preparation method according to claim 4 or 5 in the preparation of nylon elastomer.

7. A nylon elastomer, characterized in that: It is prepared from nylon prepolymer, modified polyether amine and optional additives; The modified polyetheramine is the modified polyetheramine described in any one of claims 1 to 3 or the modified polyetheramine prepared by the preparation method described in claim 4 or 5.

8. The nylon elastomer according to claim 7, characterized in that: The nylon prepolymer includes any one or more of nylon 1210 prepolymer, nylon 1010 prepolymer, nylon 610 prepolymer, nylon 6 prepolymer or nylon 66 prepolymer; The additive includes a catalyst and / or an antioxidant, the catalyst includes any one or more of tetrabutyl titanate, tetrabutyl zirconate or antimony acetate; the antioxidant includes any one or more of antioxidant 1010, antioxidant 1070, antioxidant 1076, antioxidant 1098, antioxidant sunnox508, antioxidant 2246, antioxidant 245 or sodium hypophosphite monohydrate.

9. The nylon elastomer according to claim 7 or 8, characterized in that: The molar ratio of the nylon prepolymer to the modified polyetheramine is 1:1; The mass of the additive is 2-10‰ of the sum of the masses of the nylon prepolymer and the modified polyether amine.

10. The nylon elastomer according to any one of claims 7 to 9, characterized in that The nylon elastomer has a tensile strength of more than 10 MPa, an elongation at break of more than 231%, and a Shore hardness of more than 20 HD.

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