Frangicarboxylic acid-based polyamide, method for producing the same, and Frangicarboxylic acid-based polyamide composition

Abstract

The present invention discloses a furandicarboxylic acid-based polyamide. The furandicarboxylic acid-based polyamide is derived from repeating units containing (A) 2,5-furandicarboxylic acid, (B) 1,4-cyclohexanedicarboxylic acid, and (C) 1,5-pentylenediamine, and (A) accounts for 10 to 45 mol% of the diacid units in terms of the total mol% of the diacid units. The use of bio-based 2,5-furandicarboxylic acid, which has the advantages of a melting point of 291 to 335°C and low water absorption (lower water absorption rate than polyamides with the same amide bond density), improves environmental protection. On the other hand, cyclohexane has a higher rigidity than aromatic rings and can form more hard carbon layers when burned. Furthermore, the furandicarboxylic acid-based polyamide has a high amide bond density and can achieve excellent synergistic effects when used in combination with a flame retardant, and the synergistic effects of the two provide excellent flame retardant effects.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly to furan dicarboxylic acid-based polyamides and furan dicarboxylic acid-based polyamide compositions.

Background Art

[0002] Conventional polyamide monomers are mainly derived from petroleum, and currently face problems such as excessive consumption of petroleum resources, a sharp increase in carbon dioxide emissions, and the intensification of the greenhouse effect. Reducing the use of petroleum-based monomers can suppress carbon dioxide emissions, prevent the greenhouse effect, solve problems of environmental pollution and resource constraints, and build a sustainable society. Bio-based high-temperature resistant polyamides mainly refer to polyamides obtained by polymerizing bio-based aliphatic diamines or bio-based aromatic ring diacids. Bio-based monomers are usually extracted from animals and plants, which can achieve green and sustainable development. At the same time, it can diversify high-temperature resistant polyamide products and meet the needs of more segmented industries.

[0003] As a result of market research and analysis, decanediamine, pentamethylenediamine, and furan dicarboxylic acid, which are bio-based monomers, are considered to be the bio-based high-temperature resistant polyamide monomer materials with the highest possibility of achieving substantial progress. Decanediamine is derived from castor oil plants and has already been mass-produced in China, but its selling price is high and its market competitiveness is weak. Pentamethylenediamine is obtained by fermenting glutamic acid, and large-scale production has been achieved in China. It has a low price and good market competitiveness. Furan dicarboxylic acid is the only bio-based aromatic ring diacid monomer that is currently known and has the highest possibility of being industrialized in the near future. Currently, research on furan dicarboxylic acid at home and abroad is in the stage of experimental research and development.

[0004] Chinese patent application CN106536187A discloses a furan-based polyamide using the bio-based monomer 2,5-franzicarboxylic acid, where the diamine is an aliphatic diamine, aromatic diamine, etc., and it has the advantage of good gas barrier properties. However, this gas barrier property is mainly achieved by polymerizing short-carbon chain diamines (1,3-propanediamine) to increase the density of amide bonds. However, this furan polyamide has poor flame retardancy. [Overview of the project] [Problems that the invention aims to solve]

[0005] The objective of the present invention is to provide a flangic acid-based polyamide that has the advantages of excellent flame retardancy, a high melting point, being bio-based and therefore environmentally friendly, and having a low water absorption rate.

[0006] Another object of the present invention is to provide a composition containing the above-mentioned flanger carboxylic acid-based polyamide. [Means for solving the problem]

[0007] This invention is achieved by the following technical solution.

[0008] The frangic acid-based polyamide is derived from repeating units comprising (A) 2,5-frangic acid, (B) 1,4-cyclohexanedicarboxylic acid, and (C) 1,5-pentylenediamine, where (A) accounts for 10 to 45 mol% of the total molar percentage of the diacid units.

[0009] Preferably, in terms of the total mole percent of diacid units, (A) accounts for 10 to 30 mol% of the diacid units.

[0010] More preferably, in terms of the total mole percent of diacid units, (A) accounts for 10 to 15 mol% of the diacid units.

[0011] More preferably, the melting point and water absorption rate are higher when (A) is present in proportion to the diacid units.

[0012] The relative viscosity of the aforementioned flange carboxylic acid-based polyamide is 1.8 to 2.4.

[0013] The melting point of the aforementioned flanger carboxylic acid-based polyamide is 291 to 335°C.

[0014] The water absorption rate of the aforementioned flanger carboxylic acid-based polyamide is 3.3% or less.

[0015] In a pressure vessel equipped with a magnetic coupling stirrer, condenser tube, gas phase port, supply port, and pressure-resistant explosion-proof port, reaction materials (diamine, diacitor) are added in predetermined proportions. Next, benzoic acid, sodium hypophosphite (catalyst), and deionized water are added so that the amount of benzoic acid is 2-3% of the total weight of the diamine and diacitor, the weight of sodium hypophosphite is 0.05-0.15% of the weight of the other input materials other than deionized water, and the weight of deionized water is 25-35% of the total weight of the input materials. Vacuum suction is then applied, a protective gas as high-purity nitrogen is introduced, and the mixture is stirred for 2 hours. The reaction mixture is heated to 210-230°C and stirred at 210-230°C for 0.5-2 hours. Then, while stirring, the temperature of the reactants is raised to 220-240°C, and the reaction is sustained at a constant temperature of 220-240°C and a constant pressure of 2.1-2.3 MPa for 1-3 hours. The formed water is removed and the pressure is kept constant. After the reaction is complete, the materials are discharged, the prepolymer is vacuum-dried at 70-90°C to obtain a prepolymerization product, and the prepolymerization product is thickened in solid phase at 240-260°C and under a vacuum of 40-60 Pa for 8-12 hours to obtain a frangic acid-based polyamide.

[0016] A franc carboxylic acid-based polyamide composition, comprising: 40 to 70 parts by weight of the above-mentioned flanger carboxylic acid-based polyamide, 10 to 30 parts by weight of non-halogen flame retardant, Includes 0 to 50 parts by weight of reinforcing material.

[0017] The non-halogen flame retardants include phosphine-based flame retardants, phosphine-based flame retardants, hypophosphorite-based flame retardants, phosphonite-based flame retardants, phosphotite-based flame retardants, phosphine-based flame retardants, phosphine oxide-based flame retardants, phosphine-based flame retardants, hypophosphorite-based flame retardants, phosphonate-based flame retardants, phosphonate-based flame retardants, and phosphate-based flame retardants. 、 Polyphosphate-based flame retardants or phosphinate-based flame retardants It is at least one of the following.

[0018] The hypophosphate flame retardant is at least one selected from aluminum hypophosphite or calcium hypophosphite, the phosphinate flame retardant is at least one selected from aluminum dimethylphosphinate, aluminum diethylphosphinate, or aluminum methylethylphosphinate, and the phosphate flame retardant is bisphenol A bis(diphenyl phosphate) , Zolcinol (diphenyl phosphate), triphenyl phosphate, or Polyphosphate melamine Nka The polyphosphate-based flame retardant is at least one selected from the above, and the polyphosphate-based flame retardant is ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, or Melamine polyphosphate It is at least one of the following.

[0019] The reinforcing material is at least one selected from fibrous fillers and non-fibrous fillers, the fibrous filler is at least one selected from glass fibers, carbon fibers, basalt fibers, bamboo fibers, hemp fibers, cellulose fibers, or aramid fibers, and the non-fibrous filler is at least one selected from alumina, carbon black, clay, zirconium phosphate, kaolin, calcium carbonate, copper powder, diatomaceous earth, graphite, mica, silica, titanium dioxide, zeolite, talc, wollastonite, glass beads, or glass powder.

[0020] The polyamide molding composition of the present invention can be used in the manufacture of various electronic connector devices that require SMT (Surface Mount Technology) such as USB, TYPE-C, DDR, etc., and is widely used in fields such as electronics, electrical, and automotive.

Effects of the Invention

[0021] The present invention has the following beneficial effects compared with the prior art. 1. In the phthalic acid-based polyamide of the present invention, all the diacid units contain rigid rings. Compared with the aromatic ring, cyclohexane has higher rigidity and can form more hard carbon layers when burned. Furthermore, the polyamide resin of the present invention has a high amide bond density and exhibits excellent synergistic effects when used in combination with a flame retardant, so the flame retardant effect is good. 2. In the present invention, by adjusting the ratio of phthalic acid and cyclohexanedicarboxylic acid, a phthalic acid-based polyamide with a melting point in the range of 291 - 335 °C and having good heat resistance and processability can be produced. 3. Although the phthalic acid-based polyamide of the present invention has a high amide bond density (compared with PA10T, PA1010, PA6T, PA56, etc.), both the phthalic acid and cyclohexanedicarboxylic acid monomers have rigid rings, and cyclohexane has higher rigidity than the aromatic ring, so the water absorption rate is 3.3% or less. The polyamide of the present invention has strong rigidity of the molecular chain, and the rigid regions formed by these rigid molecular chains inhibit the diffusion of water molecules in the polyamide resin, so the water absorption rate is small and the dimensional stability is excellent.

Modes for Carrying Out the Invention

[0022] Hereinafter, the present invention will be described in detail with reference to specific examples. The following examples facilitate those skilled in the art to further understand the present invention, but do not limit the present invention in any form. For those skilled in the art, some modifications and improvements may be made without departing from the concept of the present invention. All of these belong to the protection scope of the present invention.

[0023] The sources of the raw materials used in the present invention are as follows. 2,5-Furandicarboxylic acid: purity 98%, purchased from Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences 1,4-Cyclohexanedicarboxylic acid: purity 98%, purchased from Sigma-Aldrich 1,6-Adipic acid: purity 98%, purchased from Sigma-Aldrich Terephthalic acid: purity 98%, purchased from Sigma-Aldrich 1,5-Pentylenediamine: purity 98%, purchased from Shanghai Kaisai Chemical Co., Ltd. 1,6-Hexamethylenediamine: purity 98%, purchased from Sigma-Aldrich 1,10-Decanediamine: purity 98%, purchased from Wuxi Yinda Nylon Co., Ltd. Benzoic acid: analytical pure, purchased from Sigma-Aldrich Sodium hypophosphite: analytical pure, purchased from Sigma-Aldrich Non-halogen flame retardant A: aluminum diethylphosphinate, OP1230, phosphorus content 23 - 24% by mass, purchased from Clariant Non-halogen flame retardant B: Melamine polyphosphate , MELAPUR200 - 70, nitrogen 42 - 44% by mass, phosphorus content 12 - 14% by mass, purchased from BASF Reinforcing material: glass fiber, ECS11 - 4.5 - 560A, average diameter 11 microns, purchased from China National Bluestar (Group) Co., Ltd.

[0024] The polyamide resins of the examples and comparative examples are obtained by the following similar method. The reaction materials (diamine, diacid) are added in the proportions shown in the table to a pressure vessel equipped with a magnetic coupling stirrer, condenser tube, gas phase port, supply port, and pressure-resistant explosion-proof port. Then, benzoic acid, sodium hypophosphite (catalyst), and deionized water are added so that the amount of benzoic acid is 2% of the total weight of the diamine and diacid, the weight of sodium hypophosphite is 0.08% of the weight of the other input materials other than deionized water, and the weight of deionized water is 25% of the total weight of the input materials. Vacuum is then applied, a protective gas is introduced as high-purity nitrogen, and the mixture is stirred for 2 hours. The mixture is heated to 30°C, the reaction mixture is stirred at 220°C for 0.5 to 2 hours, then the temperature of the reactants is raised to 240°C while stirring, and the reaction is sustained at a constant temperature of 240°C and a constant pressure of 2.3 MPa for 1 to 3 hours. The formed water is removed and the pressure is kept constant. After the reaction is complete, the materials are discharged, the prepolymer is vacuum-dried at 70 to 90°C to obtain a prepolymerization product, and the prepolymerization product is thickened in solid phase at 260°C and under a vacuum of 50 Pa for 8 to 12 hours to obtain a frangic acid-based polyamide (a polyamide that does not contain frangic acid). Test method:

[0025] (1) Test method for the relative viscosity of polyamide resin: Refer to GB12006.1-89 for the method of measuring the viscosity of polyamide. Specific test method: The relative viscosity ηr of polyamide at a concentration of 0.25 g / dl is measured in 98% concentrated sulfuric acid at 25 ± 0.01 °C.

[0026] (2) Method for testing the melting point of polyamides: Refer to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry. Specific test method: The melting point of the sample is tested using a Perkin Elmer Dimond DSC analyzer. The atmosphere is nitrogen and the flow rate is 50 mL / min. In the test, the temperature is first raised to 350°C at 20°C / min, and the sample is held at 350°C for 2 minutes to remove the thermal history of the resin. Then, it is cooled to 50°C at 20°C / min, held at 50°C for 2 minutes, and then the temperature is raised again to 350°C at 20°C / min. The endothermic peak temperature at this point is defined as the melting point Tm.

[0027] (3) Water absorption rate of polyamide: The sample is injection molded into a 20mm x 20mm x 2mm sample, and its weight is set to a0. Then, it is placed in water at 95°C for 240 hours, and its weight is set to a1. However, the water absorption rate = (a1 - a0) / a0 * 100%.

[0028] (4) Flame retardancy: Referring to the UL94 V-0 test standard, the dimensions of the standard rod-shaped test specimen are 125±5 mm in length, 13.0±0.5 mm in width, and 0.8 mm in thickness. Five test specimens are treated at 23±2°C and 50±5% for a minimum of 48 hours. The flame of the Bunsen burner is aligned with the center of the lower end of the test specimen, and the distance between the center of the top surface of the Bunsen burner tube and the lower end surface of the test specimen is maintained at 10±1 mm, and this distance is maintained at 10±0.5S. The Bunsen burner can be moved as needed to accommodate changes in the length and position of the test specimen. Immediately after applying the flame to the test specimen for 10±0.5S, the Bunsen burner was moved at a speed of approximately 300 mm / s to a distance of at least 150 mm from the test specimen. Simultaneously, the flaming burning time T1 (in s) of the test specimen is measured using a timing device. After the flame burning of the test specimen has stopped, even if the Bunsen burner has not been moved 150 mm away from the specimen, immediately maintain a distance of 10 ± 1 mm from the nozzle of the Bunsen burner to the lower end surface of the specimen, apply the flame again for 10 ± 0.5 S, remove the Bunsen burner when necessary to remove any drips, and immediately move the Bunsen burner at least 150 mm away from the specimen after applying the flame, simultaneously start the timing device to measure the flame burning time T2 and flameless burning time T3 of the specimen, and record T2 and T3. If all five splines have T1 + T2 + T3 < 10 S and no drips ignite the cotton below, the V-0 condition is considered to be met.

[0029] [Table 1]

[0030] As can be seen from Examples 1-6, the higher the content of 1,4-cyclohexanedicarboxylic acid, the higher the melting point and the lower the water absorption rate.

[0031] [Table 2]

[0032] The flange carboxylic acid-based polyamide resin in Comparative Example 1 has no practical use because its melting point exceeds its decomposition temperature.

[0033] As can be seen from Comparative Example 2, the higher the content of 2,5-franzicarboxylic acid, the higher the water absorption rate, the lower the melting point, and the lower the value of use.

[0034] As can be seen from Comparative Example 3, when 2,5-franzicarboxylic acid is replaced with terephthalic acid, the water absorption rate does not fall below 3.3%.

[0035] As can be seen from Comparative Example 5, when cyclohexanedioic acid is replaced with adipic acid, the water absorption rate increases even if the amide bond density decreases.

[0036] As can be seen from Comparative Example 6, when cyclohexanedioic acid is replaced with terephthalic acid, which has a similar structure, the water absorption rate remains high and the melting point remains low.

[0037] As can be seen from Comparative Example 7, when 1,5-pentylenediamine is changed to 1,6-hexamethylenediamine, the melting point decreases.

[0038] [Table 3]

[0039] Examples 9 ~ 16 As can be seen more clearly, the flanger carboxylic acid-based polyamide composition of the present invention has good flame retardancy.

[0040] [Table 4]

[0041] As can be seen from Comparative Examples 8-9, if the melting point is too high or too low, modification and processing / molding become impossible.

[0042] As can be seen from Comparative Examples 10-14, other diacid / diamine schemes exhibit inferior flame retardancy.

Claims

1. A franzicarboxylic acid-based polyamide characterized by being derived from repeating units comprising (A) 2,5-franzicarboxylic acid, (B) 1,4-cyclohexanedicarboxylic acid, and (C) 1,5-pentylenediamine, wherein (A) accounts for 10 to 45 mol% of the total molar percentage of the diacid units.

2. The frangic acid-based polyamide according to claim 1, characterized in that (A) accounts for 10 to 30 mol% of the total molar percentage of diacid units.

3. The frangic acid-based polyamide according to claim 2, characterized in that (A) accounts for 10 to 15 mol% of the total molar percentage of diacid units.

4. The flange carboxylic acid-based polyamide according to claim 1, characterized in that the relative viscosity of the flange carboxylic acid-based polyamide is 1.8 to 2.

4.

5. The flange carboxylic acid-based polyamide according to claim 1, characterized in that the melting point of the flange carboxylic acid-based polyamide is 291 to 335°C.

6. The flange carboxylic acid-based polyamide according to claim 1, characterized in that the water absorption rate of the flange carboxylic acid-based polyamide is 3.3% or less.

7. The process involves adding the reaction materials to a pressure vessel in predetermined proportions, then adding benzoic acid, sodium hypophosphate, and deionized water such that the amount of benzoic acid is 2-3% of the total weight of the diamine and diacid, the weight of sodium hypophosphate is 0.05-0.15% of the weight of the other input materials other than deionized water, and the weight of deionized water is 25-35% of the total weight of the input materials, then introducing a protective gas as high-purity nitrogen under vacuum suction, raising the temperature to 210-230°C within 2 hours while stirring, stirring the reaction mixture at 210-230°C for 0.5-2 hours, and then stirring... A method for producing a frangic acid-based polyamide according to any one of claims 1 to 6, comprising the steps of: raising the temperature of the reactants to 220 to 240°C, sustaining the reaction at a constant temperature of 220 to 240°C and a constant pressure of 2.1 to 2.3 MPa for 1 to 3 hours, removing the formed water and maintaining a constant pressure, discharging the materials after the reaction is complete, vacuum drying the prepolymer at 70 to 90°C to obtain a prepolymerization product, and thickening the prepolymerization product in solid phase for 8 to 12 hours under vacuum conditions of 240 to 260°C and 40 to 60 Pa to obtain a frangic acid-based polyamide.

8. A flanger carboxylic acid-based polyamide composition, characterized in that, per 100 parts by weight of the flanger carboxylic acid-based polyamide composition, it comprises, as a component, 40 to 70 parts by weight of the flanger carboxylic acid-based polyamide described in any one of claims 1 to 6, 10 to 30 parts by weight of a non-halogen flame retardant, and 0 to 50 parts by weight of a reinforcing material.

9. The non-halogen flame retardant is at least one selected from phosphine-based flame retardants, phosphinate-based flame retardants, hypophosphonite-based flame retardants, phosphonite-based flame retardants, phosphonite-based flame retardants, phosphite-based flame retardants, phosphine oxide-based flame retardants, phosphinate-based flame retardants, hypophosphonite-based flame retardants, phosphonate-based flame retardants, phosphonate-based flame retardants, phosphate-based flame retardants, polyphosphate-based flame retardants, or phosphinate-based flame retardants, and the hypophosphate-based flame retardant is at least one selected from aluminum hypophosphite or calcium hypophosphite, and the phosphinate-based flame retardant is The frangic acid-based polyamide composition according to claim 8, characterized in that the phosphate-based flame retardant is at least one selected from aluminum dimethylphosphinate, aluminum diethylphosphinate, or aluminum methylethylphosphinate, the phosphate-based flame retardant is at least one selected from bisphenol A bis(diphenyl phosphate), resorcinol(diphenyl phosphate), triphenyl phosphate, or melamine phosphate, and the polyphosphate-based flame retardant is at least one selected from ammonium polyphosphate, melamine polyphosphate, melamine pyrophosphate, or melamine polyphosphate.

10. The frangic acid-based polyamide composition according to claim 8, characterized in that the reinforcing material is at least one selected from fibrous fillers and non-fibrous fillers, the fibrous filler is at least one selected from glass fibers, carbon fibers, basalt fibers, bamboo fibers, hemp fibers, cellulose fibers, or aramid fibers, and the non-fibrous filler is at least one selected from alumina, carbon black, clay, zirconium phosphate, kaolin, calcium carbonate, copper powder, diatomaceous earth, graphite, mica, silica, titanium dioxide, zeolite, talc, wollastonite, glass beads, or glass powder.

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