High-temperature resistant semi-aromatic polyamide, method for preparing the same, composition, and molded article.

Abstract

This invention provides a high-temperature resistant semi-aromatic polyamide resin, a method for preparing the same, and its composition and molded articles. [Solution] The polymer monomer of the polyamide resin comprises a diamine monomer and a diacid monomer, the diamine monomer comprises diamine monomer A1 and diamine monomer A2, the diacid monomer comprises diacid monomer B1 and diacid monomer B2, and the number of carbon atoms of diamine monomer A1 is C A1 and the number of carbon atoms of diamine monomer A2 C A2 C A1 -C A2 Satisfying ≥ 4, diacid monomer B1 is selected from aromatic dicarboxylic acids having 7 to 12 carbon atoms and their derivatives, and diacid monomer B2 is selected from aliphatic dicarboxylic acids having 4 to 18 carbon atoms. [Effects] The polyamide resin of the present invention has better fluidity. The one-step condensation polymerization process of the high-temperature resistant semi-aromatic polyamide of the present invention is easy to melt and discharge, and the molten material has good fluidity and stability.

Description

Detailed description of the invention

[0001] [Technical Field] This invention belongs to the field of polymer materials, and more particularly to high-temperature resistant semi-aromatic polyamides.

[0002] [Background technology] High-temperature resistant polyamides, possessing high heat resistance, dimensional stability, good mechanical strength, and melt processability, are widely used in fields such as electronic equipment, automotive engine components, and aerospace. Semi-aromatic polyamides with long carbon chains are particularly useful. Due to their rigid benzene ring structure, the raw materials have excellent dimensional stability and mechanical strength, and the long carbon chain structure results in low resistance in the internal rotational parts, giving the raw materials good toughness and low water absorption. However, semi-aromatic polyamides with long carbon chains have many molecular chain entanglements and poor molten fluidity, making the melt discharge stage of a one-step polymerization process and injection molding of the finished product extremely difficult.

[0003] Currently, the main methods used to improve polymer fluidity include (1) reducing the polymer's molecular weight, (2) adding fluidity modifiers, (3) increasing the processing temperature, and (4) increasing the shear rate or shear stress. However, all of the above methods have unavoidable problems. Reducing the polymer's molecular weight can significantly lower its melt viscosity and increase its melt fluidity, but it also significantly reduces the material's mechanical properties. When adding fluidity modifiers and melt-mixing them with polyamide, issues such as the compatibility of the additive with the matrix, additive precipitation, and odor must also be considered. Increasing the processing temperature can improve the fluidity of the polyamide molten material, but the narrow processing range for high-temperature resistant polyamides and excessively high processing temperatures can lead to problems such as degradation over time at high temperatures and gel formation due to crosslinking, potentially making the melting process even more difficult. Polyamide molten material is a pseudoplastic fluid, and its apparent viscosity decreases with increasing shear rate or shear stress. However, if the shear rate or shear stress is too high, mechanical decomposition of the material may occur.

[0004] Chinese patent CN101200591B discloses a highly fluid, high-temperature resistant nylon composite material. The fluidity is improved by introducing 0.1 to 10% by weight of a fluidity improver (e.g., silicone compounds, montanic acid derivatives, and polymeric wax lubricants) into a semi-aromatic polyamide matrix with poor fluidity. After treating the fluidity improver with a coupling agent, it is mixed with the polyamide matrix and granulated to improve compatibility. The fluidity improver has excellent external and internal lubrication effects and can effectively reduce friction between the polyamide matrix and processing equipment, as well as friction between polyamide molecular chains. Chinese patent CN1368994A discloses a highly fluid polyamide composition. The fluidity of a high molecular weight polyamide is improved by adding 0.5 to 20% by weight of a polyamide oligomer with a higher melting point than the high molecular weight polyamide matrix to the high molecular weight polyamide matrix. By using a polyamide oligomer (average molecular weight 5,000 g / mol or less) as a plasticizer with high molecular weight polyamide, a certain plasticizing effect can be obtained, and the compatibility between the polyamide oligomer and the high molecular weight polyamide matrix is ​​also good. However, this method has the disadvantage of being complicated because it requires the preparation and melt-mixing of two types of polyamide first. Chinese patent CN101798456B discloses a nylon composite material having a star-shaped branching structure. Fluidity is improved by adding 0.05 to 5% by weight of a star-shaped branching agent (such as tricarboxylic acid benzenesulfonic acid, triaminotriphenylmethane, and trihydroxypropylene oxide) containing at least three reactive functional groups to the polyamide matrix. The star-shaped branching agent is used as a plasticizer, enabling rotational motion of molecules and improving the fluidity of the polyamide during injection molding. However, specific data on the relevant fluidity improvement are not provided. This method has the disadvantage that partial crosslinking of the polyamide matrix occurs due to the introduction of the branching agent. Moderate crosslinking contributes to improving the mechanical properties of materials, but it significantly reduces the fluidity of the molten material. Finding a balance between the two is difficult.

[0005] Currently, patented methods for improving the fluidity of polyamides primarily focus on mixing. These methods involve introducing low-molecular-weight or high-molecular-weight lubricants, polyamides identical to the low-molecular-weight matrix, polyolefins with linear or branched structures, liquid crystal polymers, star-shaped branching agents, etc., into the polyamide matrix via twin-screw melt extrusion to improve the fluidity of the polyamide molten material. While this melt mixing method can improve the melt processability of semi-aromatic polyamides with long carbon chains to some extent, it cannot solve the problem of melt discharge in one-step polymerization methods from a polymerization perspective.

[0006] [Summary of the Invention] To solve the problems of prior art and products, the present invention provides a high-temperature resistant semi-aromatic polyamide resin and a method for preparing the same.

[0007] The polymer monomer of the polyamide resin comprises a diamine monomer and a diacid monomer, the diamine monomer comprises diamine monomer A1 and diamine monomer A2, and the diacid monomer comprises diacid monomer B1 and diacid monomer B2. The number of carbon atoms in the diamine monomer A1 is C A1 and the number of carbon atoms of diamine monomer A2 C A2 C A1 -C A2 Satisfying ≥4, the diacid monomer B1 is selected from aromatic dicarboxylic acids having 7 to 12 carbon atoms and their derivatives, and the diacid monomer B2 is selected from aliphatic dicarboxylic acids having 4 to 18 carbon atoms.

[0008] Furthermore, the derivatives of aromatic dicarboxylic acids having 7 to 12 carbon atoms include esters of aromatic dicarboxylic acids having 7 to 12 carbon atoms, preferably including dimethyl terephthalate and dimethyl isophthalate.

[0009] In this invention, diamine monomers are abbreviated as diamine. A1 represents the number of carbon atoms in diamine A1, and similarly C A2 This represents the number of carbon atoms in diamine A2. A1 , C A2They are all integers. C A1 -C A2 The difference of is also an integer.

[0010] In some embodiments, the number of carbon atoms (C) of diamine monomer A1 and diamine monomer A2 satisfies 4 ≦ C A1 -C A2 ≦ 10. In some preferred embodiments of the present invention, diamine monomer A1 includes one or more of 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine and 1,14-tetradecanediamine.

[0011] In some preferred embodiments of the present invention, diamine monomer A2 includes one or more of 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine and 1,10-decanediamine.

[0012] In some preferred embodiments of the present invention, diamine monomer A1 is selected from diamines having 8 to 14 carbon atoms, preferably selected from diamines having 4 to 11 carbon atoms.

[0013] In some preferred embodiments of the present invention, diamine monomer A2 is selected from diamines having 4 to 10 carbon atoms, preferably selected from diamines having 4 to 7 carbon atoms.

[0014] In some preferred embodiments of the present invention, diacid monomer B1 includes one or more of terephthalic acid, dimethyl terephthalate, isophthalic acid, and dimethyl isophthalate.

[0015] In some preferred embodiments of the present invention, diacid monomer B2 comprises one or more of 1,4-succinic acid, 1,5-glutaric acid, 1,6-adipic acid, 1,7-heptanediic acid, 1,8-octanedioic acid, 1,9-nonanediic acid, 1,10-decanediic acid, 1,11-undecanediic acid, 1,12-dodecanediic acid, 1,13-tridecanediic acid, 1,14-tetradecanediic acid, 1,15-pentadecanedioic acid, 1,16-hexadecanedioic acid, 1,17-heptadecanedioic acid, and 1,18-octadecanediic acid.

[0016] In some preferred embodiments of the present invention, the molar ratio of the total number of moles of diamine monomer A2 and diacid monomer B2 to the total number of moles of polymer monomer is (0.040~0.099):1.

[0017] In some preferred embodiments of the present invention, the molar ratio of the diamine monomer to the diacid monomer is (1.01 to 1.03):1.

[0018] The diamine and / or diacid may be a diamine and / or diacid derived from a chemical or biological substance, preferably a diamine and / or diacid derived from a biological substance.

[0019] The polyamide resin contains diamine units and diacid units formed by the polymerization reaction of a diamine monomer and a diacid monomer, and the total weight of the diamine units and diacid units in the polyamide resin is 97% or more, preferably 99% or more, of the polyamide resin. The polyamide resin may also contain 0.01 to 3% of additives.

[0020] The additives include, but are not limited to, one of the following: end-capturing agents, catalysts, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, nucleating agents, fluorescent whitening agents, and antistatic agents, or a combination of two or more of these.

[0021] Furthermore, the antioxidant is one or more selected from phenol antioxidants, inorganic phosphate antioxidants, phosphite antioxidants, and carbon free radical scavenger antioxidants. The catalyst is one or more selected from potassium hypophosphite, sodium hypophosphite, calcium hypophosphite, magnesium hypophosphite, and zinc hypophosphite. The end-capping agent is one or more selected from acetic acid, benzoic acid, and cyclohexanecarboxylic acid.

[0022] In the case of long-chain semi-aromatic polyamides, due to the entanglement of long chains, there are variations in the fluidity of the polyamide melt. In the present invention, a third comonomer (amine monomer A2) and a fourth comonomer (acid monomer B2) are introduced and copolymerized. The difference in the number of carbon atoms between the two diamine monomers used is 4 or more (i.e., C A1 -C A2 ≧4), and it has been found through many experiments that the copolyamide obtained in this case has better fluidity than the copolyamide obtained when the difference in the number of carbon atoms is less than 4 (i.e., C A1 -C A2 <4). Furthermore, the greater the difference, the higher the irregularity of the polymer chain, the fewer the chain entanglements, and the better the fluidity of the copolyamide.

[0023] In some preferred embodiments of the present invention, the content of polyamine in the polyamide resin is 0.8 wt% or less, preferably 0.5 wt% or less, preferably 0.2 wt% or less, or preferably 0, and the polyamine is one or more selected from thioether polyamine compounds, polyethyleneimine, and polyaminopolyetheramine. Preferably, the number average molecular weight of the polyamine is 2,500 - 5,000 g / mol.

[0024] In some embodiments, during the preparation of the polyamide resin, a small amount of polyamine and copolyamide can be optionally introduced for in-situ polymerization. In some embodiments, by introducing an appropriate amount of polyamine, a trace amount of chemical bonds exist between the macromolecular chains of the copolyamide, further improving the tensile strength, flexural strength, and impact strength of the material.

[0025] Furthermore, the relative viscosity of the polyamide resin is 1.8 to 2.6, preferably 2.0 to 2.5.

[0026] Furthermore, the melting point of the polyamide resin is 265 to 315°C, preferably 271 to 310°C.

[0027] Furthermore, the tensile strength of the polyamide resin is 65 to 105 MPa, preferably 75 to 95 MPa.

[0028] Furthermore, the flexural strength of the polyamide resin is 80 to 140 MPa, preferably 90 to 125 MPa.

[0029] Furthermore, the flow length of the polyamide resin is 600 mm or more, preferably 850 mm or more.

[0030] The present invention further provides a method for preparing a high-temperature resistant semi-aromatic polyamide resin. This method is (1) A step of heating an aqueous solution of polyamide salt to 120-140°C, removing the water and concentrating it, and then heating it to 230-260°C to react; and (2) Includes a degassing process to reduce pressure.

[0031] Those skilled in the art know that polyamide salts are also known as nylon salts. Nylon salts are salts formed by reactions between polymer monomers (including diamine monomer A1, diamine monomer A2, diacid monomer B1, and diacid monomer B2), and polyamides are obtained by polycondensation reactions of nylon salts.

[0032] Furthermore, this method includes the steps of (1) heating an aqueous solution of polyamide salt to 120-140°C, removing the water and concentrating it, and then heating it to 240-255°C to react; and (2) Includes a degassing process to reduce pressure.

[0033] Furthermore, this method includes, before step (1), step (a) of adding diamine monomer A1, diamine monomer A2, diacid monomer B1 and diacid monomer B2 to water, heating the resulting system to 70-95°C, and optionally holding it at 70-95°C for 0.5-3 hours to form an aqueous solution of the polyamide salt. Furthermore, this method includes, before step (1), step (a) of adding diamine monomer A1, diamine monomer A2, diacid monomer B1 and diacid monomer B2 to water, heating these compounds to 70-90°C, and optionally keeping them warm at 70-90°C for 0.5-3 hours to form an aqueous solution of the polyamide salt. Then, in step (a), the heating step is carried out in an atmosphere of nitrogen or an inert gas. The inert gas may include one or more of argon or helium.

[0034] Furthermore, in process (a), the heat retention time is 0.5 to 2 hours.

[0035] In step (1), water is removed and the solution is concentrated until the concentration of the polyamide salt reaches 40-80% by weight, preferably 55-65% by weight.

[0036] In step (1), the reaction time is 0.5 to 2 hours, preferably 1 to 1.5 hours.

[0037] In step (1), the pressure is maintained at 2.0 to 3.5 MPa, preferably 2.5 to 3 MPa, during the reaction.

[0038] In step (2), the degassing reduces the pressure in the reaction system to 0 to 0.1 MPa (gauge pressure), preferably 0 to 0.02 MPa (gauge pressure).

[0039] Unless otherwise specified, or unless otherwise clearly contradictory, the term "pressure" in this invention refers to gauge pressure.

[0040] In step (2), the temperature of the reaction system after the reduction in pressure is completed is 295-335°C.

[0041] More preferably, this method includes a vacuuming step (3) in which a vacuum is created to a vacuum level of -0.02 MPa or less, preferably -0.05 MPa to -0.1 MPa, and optionally this vacuum level is maintained for 0 to 300 seconds, preferably 0 to 90 seconds, more preferably 5 to 90 seconds, and even more preferably 5 to 50 seconds.

[0042] Furthermore, this method further includes the steps (4) of discharging, stretching into strips, and pelletizing.

[0043] Furthermore, this method includes adding an additive at any of steps (a), (1), (2), any (3), and any (4), wherein the additive is 0.01 to 3% of the total mass of the monomer, and the additive includes, but is not limited to, one of the following: end-capturing agents, catalysts, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, nucleating agents, fluorescent whitening agents, and antistatic agents, or a combination of two or more of these.

[0044] Furthermore, the end capping agent is C 2~16 Aliphatic carboxylic acid, C 7~10 This includes aromatic carboxylic acids, or combinations thereof. The aliphatic carboxylic acid end-captive is structurally a monocarboxylic acid having a linear, branched, or cyclic structure, preferably a saturated monocarboxylic acid having a linear, branched, or cyclic structure.

[0045] Furthermore, the catalyst comprises phosphates and hypophosphites, preferably alkali metal and / or alkaline earth metal phosphates, and alkali metal and / or alkaline earth metal hypophosphites, preferably one or more of potassium hypophosphite, sodium hypophosphite, calcium hypophosphite, and magnesium hypophosphite.

[0046] Furthermore, the antioxidant is one selected from phenolic antioxidants, inorganic phosphate antioxidants, phosphate antioxidants, and carbon free radical scavenging antioxidants, or a combination of two or more of these.

[0047] Furthermore, in step (4), the process of stretching the material into strips and then pelletizing it can be carried out under water cooling, with the cooling water temperature being, for example, 10 to 30°C.

[0048] One embodiment of the present invention is a method for preparing a high-temperature resistant semi-aromatic copolyamide, (a) Adding diamine monomer A1, diamine monomer A2, diacid monomer B1, and diacid monomer B2 to water, heating the resulting system to 70-90°C, and holding it at 70-90°C for 0.5-3 hours to form an aqueous solution of the polyamide salt; (1) Heat an aqueous solution of polyamide salt to 120-140°C, remove water and concentrate until the concentration of the aqueous solution of polyamide salt is 40-80% by weight, then heat to 240-255°C and react under a pressure of 2.5-3 MPa for 0.5-2 hours; (2) A step of reducing the pressure of the reaction system to 0 to 0.1 MPa (gauge pressure) by degassing, and then setting the temperature of the reaction system to 295 to 335°C after the reduction is complete; (3) A process of creating a vacuum of -0.05 MPa to -0.1 MPa and maintaining this vacuum for 0 to 300 seconds; and (4) Includes the process of discharge, stretching into strips, and pelletizing.

[0049] The parameters in process (a) and processes (1) to (4) are the same as described above.

[0050] The present invention provides a composition preferably comprising a high-temperature resistant semi-aromatic polyamide resin as described in any one of the above.

[0051] The present invention preferably provides a product prepared using a high-temperature resistant semi-aromatic polyamide resin or a composition thereof as described in any one of the above as a raw material.

[0052] Compared to the prior art, embodiments of the present invention have at least the following advantages.

[0053] 1. In the case of long-chain semi-aromatic polyamides, the fluidity of the polyamide molten product varies due to entanglement between the long chains. In this invention, copolymerization is carried out by introducing a third comonomer and a fourth comonomer. Numerous experiments have shown that copolyamides obtained when the difference in the number of carbon atoms of the two diamine monomers used is 4 or more exhibit good fluidity. Furthermore, the larger this difference, the higher the disorder of the polymer chain, the less entanglement there is, and the better the fluidity of the copolyamide.

[0054] 2. The one-step condensation polymerization process for high-temperature resistant semi-aromatic polyamides of the present invention has the advantages of easy melting and discharge, and good fluidity and stability of the polyamide molten material.

[0055] [Modes for carrying out the invention] To further clarify the object, technical proposal and advantages of the present invention, the technical proposal of embodiments will be described clearly and completely below with reference to embodiments of the present invention, but the embodiments described are only some, and not all, embodiments of the present invention. All other embodiments that can be obtained by those skilled in the art without creative effort based on embodiments of the present invention are all within the scope of the protection of the present invention.

[0056] The melting point was measured in accordance with the standard ISO 11357-3, with a heating rate of 20°C / min.

[0057] Relative viscosity η r It is measured using the following method: The concentrated sulfuric acid method using a Ubberohde viscometer involves accurately weighing 0.5 ± 0.0002 g of a dried polyamide sample, dissolving the sample in 50 mL of concentrated sulfuric acid (96%), and measuring and recording the flow time of the concentrated sulfuric acid (t0) and the flow time of the polyamide solution (t) in a constant temperature water bath at 25 ± 0.02 °C.

[0058] Formula for calculating relative viscosity: Relative viscosity η r = t / t0 Here, t represents the time it takes for the polyamide solution to flow, and t0 represents the time it takes for concentrated sulfuric acid to flow as the solvent.

[0059] The test method for mechanical properties is as follows: The bending test was performed in accordance with ISO-178 standard, under measurement conditions of 2 mm / min; The tensile test was performed in accordance with the ISO-572-2 standard, under measurement conditions of 50 mm / min; Impact testing will be conducted in accordance with ISO 180 standards.

[0060] The Archimedes helical flow length (simply called flow length) test is performed at a temperature 25°C above the melting point of the polyamide and at an injection pressure of 80 bar.

[0061] In the following embodiments, the antioxidant H10 is used as the antioxidant, acetic acid is used as the end-capturing agent, and sodium hypophosphite is used as the catalyst. Unless otherwise specified or clearly contradictory, "%" in the present invention and embodiments represents mass % relative to the total mass of the monomer.

[0062] [Example 1] 9.28 mol of 1,9-nonanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,5-pentanediamine, 0.90 mol of adipic acid, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capturing agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 130°C, the solution was concentrated by removing water until the concentration was 65 wt%. The solution was then heated to 240°C and reacted under a pressure of 2.5 MPa for 1 hour. The pressure in the reaction system was reduced to 0 MPa (gauge pressure) by degassing. The temperature of the reaction system after degassing was 317°C. Subsequently, the system was evacuated for 20 seconds until the vacuum level was -0.07 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0063] [Example 2] 9.28 mol of 1,9-nonanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,5-pentanediamine, 0.90 mol of adipic acid, 0.8% polyethyleneimine with a molecular weight of 3,000, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capturing agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 130°C, the solution was concentrated by removing water until the concentration was 65 wt%. The solution was then heated to 240°C and reacted under a pressure of 2.5 MPa for 1 hour. The pressure in the reaction system was reduced to 0 MPa (gauge pressure) by degassing. The temperature of the reaction system after degassing was 317°C. Subsequently, the system was evacuated for 20 seconds until the vacuum level was -0.07 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0064] [Example 3] 9.28 mol of 1,9-nonanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,5-pentanediamine, 0.90 mol of adipic acid, 0.4% of polyethyleneimine with a molecular weight of 3,000, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capturing agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 130°C, the solution was concentrated by removing water until the concentration was 65 wt%. The solution was then heated to 240°C and reacted under a pressure of 2.5 MPa for 1 hour. The pressure of the reaction system was reduced to 0 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction in pressure was 317°C. Subsequently, the system was evacuated for 20 seconds until the vacuum level was -0.07 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0065] [Example 4] 9.20 mol of 1,10-decanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,5-pentanediamine, 0.90 mol of adipic acid, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capturing agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 130°C, the solution was concentrated by removing water until the concentration was 60 wt%. The solution was then heated to 245°C and reacted under a pressure of 2.6 MPa for 1.2 hours. The pressure of the reaction system was reduced to 0.01 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction was completed was 323°C. Subsequently, the system was vacuumed for 10 seconds until the pressure was reduced to -0.08 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0066] [Example 5] 9.21 mol of 1,11-undecanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,5-pentanediamine, 0.90 mol of adipic acid, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capturing agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 135°C, the solution was concentrated by removing water until the concentration was 70 wt%. The solution was then heated to 245°C and reacted under a pressure of 3.0 MPa for 1.5 hours. The pressure of the reaction system was reduced to 0 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction was completed was 309°C. Subsequently, the system was vacuumed for 30 seconds until the pressure was reduced to -0.06 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0067] [Example 6] 9.20 mol of 1,12-dodecanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,5-pentanediamine, 0.90 mol of adipic acid, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capturing agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 140°C, the solution was concentrated by removing water until the concentration was 70 wt%. The solution was then heated to 250°C and reacted under a pressure of 3.0 MPa for 2 hours. The pressure of the reaction system was reduced to 0.01 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction was completed was 308°C. Subsequently, the system was vacuumed for 30 seconds until the pressure was reduced to -0.09 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0068] [Example 7] 9.20 mol of 1,12-dodecanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,5-pentanediamine, 0.90 mol of adipic acid, 0.8% polyethyleneimine with a molecular weight of 3,000, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capturing agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 140°C, the solution was concentrated by removing water until the concentration was 70 wt%. The solution was then heated to 250°C and reacted under a pressure of 3.0 MPa for 2 hours. The pressure of the reaction system was reduced to 0.01 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction in pressure was 308°C. Then, the system was vacuumed for 30 seconds until the pressure was reduced to -0.09 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0069] [Example 8] 9.23 mol of 1,13-tridecanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,5-pentanediamine, 0.90 mol of adipic acid, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capturing agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 140°C, the solution was concentrated by removing water until the concentration was 70 wt%. The solution was then heated to 255°C and reacted under a pressure of 3.0 MPa for 2 hours. The pressure of the reaction system was reduced to 0.01 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction was completed was 301°C. Then, the system was vacuumed for 10 seconds until the pressure was reduced to -0.10 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0070] [Example 9] 9.23 mol of 1,13-tridecanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,6-hexanediamine, 0.90 mol of adipic acid, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capping agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 140°C, the solution was concentrated by removing water until the concentration was 70 wt%. The solution was then heated to 255°C and reacted under a pressure of 3.0 MPa for 2 hours. The pressure of the reaction system was reduced to 0.01 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction was completed was 303°C. Subsequently, the system was vacuumed for 10 seconds until the pressure was reduced to -0.10 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0071] [Example 10] 9.76 mol of 1,10-decanediamine, 9.48 mol of terephthalic acid, 0.52 mol of 1,5-pentanediamine, 0.52 mol of octanedioic acid, 0.02% of catalyst, 0.3% of antioxidant, 0.20% of end-captive, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 130°C, the solution was concentrated by removing water until the concentration was 60 wt%. The solution was then heated to 245°C and reacted under a pressure of 2.6 MPa for 1.2 hours. The pressure of the reaction system was reduced to 0.01 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction was completed was 334°C. Subsequently, the system was vacuumed for 10 seconds until the pressure was reduced to -0.08 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0072] [Example 11] 9.20 mol of 1,9-nonanediamine, 9.02 mol of terephthalic acid, 0.98 mol of 1,5-pentanediamine, 0.98 mol of 1,10-decanediic acid, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capturing agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 130°C, the solution was concentrated by removing water until the concentration was 65 wt%. The solution was then heated to 240°C and reacted under a pressure of 2.5 MPa for 1 hour. The pressure in the reaction system was reduced to 0 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction in pressure was 313°C. Subsequently, the system was vacuumed for 20 seconds until the pressure was reduced to -0.07 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0073] [Example 12] 9.47 mol of 1,11-undecanediamine, 9.24 mol of terephthalic acid, 0.76 mol of 1,6-hexanediamine, 0.76 mol of 1,12-dodecanediic acid, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capping agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 135°C, the solution was concentrated by removing water until the concentration was 70 wt%. The solution was then heated to 245°C and reacted under a pressure of 3.0 MPa for 1.5 hours. The pressure of the reaction system was reduced to 0 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction was completed was 301°C. Subsequently, the system was vacuumed for 30 seconds until the pressure was reduced to -0.06 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0074] [Example 13] 9.23 mol of 1,13-tridecanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,8-octanediamine, 0.90 mol of adipic acid, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capping agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 140°C, the solution was concentrated by removing water until the concentration was 70 wt%. The solution was then heated to 255°C and reacted under a pressure of 3.0 MPa for 2 hours. The pressure of the reaction system was reduced to 0.01 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction was completed was 298°C. Then, the system was vacuumed for 10 seconds until the pressure was reduced to -0.10 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0075] [Comparative Example 1] 9.23 mol of 1,13-tridecanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,12-dodecanediamine, 0.90 mol of 1,12-dodecanediic acid, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capping agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 140°C, the solution was concentrated by removing water until the concentration was 70 wt%. The solution was then heated to 255°C and reacted under a pressure of 3.0 MPa for 2 hours. The pressure of the reaction system was reduced to 0.01 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction in pressure was 296°C. Subsequently, the system was vacuumed for 10 seconds until the pressure was reduced to -0.10 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0076] [Comparative Example 2] 9.20 mol of 1,10-decanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,9-nonanediamine, 0.90 mol of 1,12-dodecanediic acid, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capping agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 130°C, the solution was concentrated by removing water until the concentration was 60 wt%. The solution was then heated to 245°C and reacted under a pressure of 2.6 MPa for 1.2 hours. The pressure of the reaction system was reduced to 0.01 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction was completed was 317°C. Subsequently, the system was vacuumed for 10 seconds until the pressure was reduced to -0.08 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0077] [Comparative Example 3] 9.20 mol of 1,10-decanediamine, 9.10 mol of terephthalic acid, 0.90 mol of 1,5-pentanediamine, 0.90 mol of adipic acid, 1.5% of polyethyleneimine with a molecular weight of 3,000, 0.03% of catalyst, 0.3% of antioxidant, 0.24% of end-capturing agent, and water were uniformly mixed at a stirring speed of 70 rpm. The resulting system was heated to 90°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to prepare a 50 wt% polyamide salt solution. After heating the reaction system to 130°C, the solution was concentrated by removing water until the concentration was 60 wt%. The solution was then heated to 245°C and reacted under a pressure of 2.6 MPa for 1.2 hours. The pressure of the reaction system was reduced to 0.01 MPa (gauge pressure) by degassing. The temperature of the reaction system after the reduction was completed was 323°C. Subsequently, the system was vacuumed for 10 seconds until the pressure was reduced to -0.08 MPa to obtain a copolymer molten product. This copolymer molten material was stretched into strips and then pelletized to obtain a high-temperature resistant semi-aromatic polyamide.

[0078] [Table 1]

[0079] Finally, the embodiments described above are used solely to illustrate the technical concepts of the present invention and do not limit the invention. Although the present invention has been described in detail with reference to embodiments, it is still possible for those skilled in the art to modify the technical concepts described in the embodiments or to make equivalent substitutions to some or all of the technical features, and all modifications or substitutions do not cause the essence of the corresponding technical concepts to depart from the scope of the technical concepts of the embodiments of the present invention.

Claims

1. The polymer monomers of the polyamide resin include diamine monomers and diacid monomers. The diamine monomer comprises diamine monomer A1 and diamine monomer A2, and the diacid monomer comprises diacid monomer B1 and diacid monomer B2. The number of carbon atoms in the diamine monomer A1 is C Ａ１ and the number of carbon atoms of diamine monomer A2 C Ａ２ C Ａ１ -C Ａ２ Satisfying ≥ 4, A high-temperature resistant semi-aromatic polyamide resin characterized in that the diacid monomer B1 is selected from aromatic dicarboxylic acids having 7 to 12 carbon atoms and their derivatives, and the diacid monomer B2 is selected from aliphatic dicarboxylic acids having 4 to 18 carbon atoms.

2. The diamine monomer A1 comprises one or more of 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, and 1,14-tetradecanediamine, and / or The diamine monomer A2 is selected from diamines having 4 to 10 carbon atoms, preferably comprising one or more of 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine, and the diamine monomer A2 is preferably selected from diamines having 4 to 7 carbon atoms, and / or The aforementioned diacid monomer B1 comprises one or more of terephthalic acid, dimethyl terephthalate, isophthalic acid, and dimethyl isophthalate, and / or The aforementioned diacid monomer B2 comprises one or more of 1,4-succinic acid, 1,5-glutaric acid, 1,6-adipic acid, 1,7-heptanediic acid, 1,8-octanedioic acid, 1,9-nonanediic acid, 1,10-decanediic acid, 1,11-undecanediic acid, 1,12-dodecanediic acid, 1,13-tridecanediic acid, 1,14-tetradecanediic acid, 1,15-pentadecanedioic acid, 1,16-hexadecanedioic acid, 1,17-heptadecanedioic acid and 1,18-octadecanediic acid, and / or The polyamide resin contains diamine units and diacid units formed by a polymerization reaction between the diamine monomer and the diacid monomer, wherein the total weight of the diamine units and diacid units is 97% or more of the polyamide resin, more preferably 99% or more, and / or The polyamine content in the polyamide resin is 0.8% or less, preferably 0.5% or less, preferably 0.2% or less, preferably 0, and the polyamine is selected from one or more thioether polyamine compounds, polyethyleneimine and polyaminopolyetheramine, and / or The high-temperature resistant semi-aromatic polyamide resin according to claim 1, wherein the polyamide resin contains an additive, the content of which is 0.01 to 3%, and the additive is characterized in that it contains one of the following: an end sealant, a catalyst, a flame retardant, an antioxidant, an ultraviolet absorber, an infrared absorber, a crystal nucleating agent, a fluorescent whitening agent, and an antistatic agent, or a combination of two or more of these.

3. The molar ratio of the total number of moles of the diamine monomer A2 and the diacid monomer B2 to the total number of moles of the polymer monomer is (0.040 to 0.099):1, and / or, The high-temperature resistant semi-aromatic polyamide resin according to claim 1, characterized in that the molar ratio of the diamine monomer to the diacid monomer is (1.01 to 1.03):

1.

4. The relative viscosity of the polyamide resin is 1.8 to 2.6, preferably 2.0 to 2.5, and / or The melting point of the polyamide resin is 265 to 315°C, preferably 271 to 310°C, and / or The tensile strength of the polyamide resin is 65 to 105 MPa, preferably 75 to 95 MPa, and / or The flexural strength of the polyamide resin is 80 to 140 MPa, preferably 90 to 125 MPa, and / or The high-temperature resistant semi-aromatic polyamide resin according to any one of claims 1 to 3, characterized in that the flow length of the polyamide resin is 600 mm or more, preferably 850 mm or more.

5. (1) A step of heating an aqueous solution of polyamide salt to 120-140°C, removing the water and concentrating it, and then heating it to 230-260°C to cause a reaction, and (2) A method for preparing a high-temperature resistant semi-aromatic polyamide resin, including a degassing step to reduce pressure.

6. In step (1), the water is removed and the polyamide salt is concentrated until the concentration of the polyamide salt reaches 40 to 80% by weight, preferably 55 to 65% by weight, and / or In step (1), the reaction time is 0.5 to 2 hours, preferably 1 to 1.5 hours, and / or, In step (1), the reaction pressure is maintained at 2.0 to 3.5 MPa, preferably 2.5 to 3 MPa, and / or, In step (2), the degassing reduces the pressure in the reaction system to 0 to 0.1 MPa (gauge pressure), preferably 0 to 0.02 MPa (gauge pressure), and / or The method according to claim 5, characterized in that, in step (2), the temperature of the reaction system after the completion of reduced pressure is 295 to 335°C.

7. The process includes, before step (1), step (a) of adding diamine monomer A1, diamine monomer A2, diacid monomer B1, and diacid monomer B2 to water, heating the resulting system to 70-95°C, and optionally holding it at 70-95°C for 0.5-3 hours to form an aqueous solution of the polyamide salt, and / or, The method according to claim 5, characterized by including a vacuuming step (3) of creating a vacuum to a vacuum level of -0.02 MPa or less, preferably -0.05 MPa to -0.1 MPa, and optionally maintaining the vacuum level for 0 to 300 seconds, preferably 0 to 90 seconds, more preferably 5 to 90 seconds.

8. The process includes adding an additive at any of the following stages: (a), (1), (2), and any (3). The method according to claim 5, 6, or 7, characterized in that the additive is 0.01 to 3% of the total mass of the monomer, and the additive includes, but is not limited to, one of the following: an end-capturing agent, a catalyst, a flame retardant, an antioxidant, an ultraviolet absorber, an infrared absorber, a nucleating agent, a fluorescent whitening agent, and an antistatic agent, or a combination of two or more thereof.

9. A composition characterized by comprising a high-temperature resistant semi-aromatic polyamide resin according to any one of claims 1 to 4.

10. A product prepared using a high-temperature resistant semi-aromatic polyamide resin according to any one of claims 1 to 4 or the composition according to claim 9 as a raw material.

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