CN115197416B - Continuous solid phase polycondensation method for producing PA46 and PA MXD6 - Google Patents
Continuous solid phase polycondensation method for producing PA46 and PA MXD6 Download PDFInfo
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- CN115197416B CN115197416B CN202211000441.2A CN202211000441A CN115197416B CN 115197416 B CN115197416 B CN 115197416B CN 202211000441 A CN202211000441 A CN 202211000441A CN 115197416 B CN115197416 B CN 115197416B
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- 238000006068 polycondensation reaction Methods 0.000 title claims abstract description 39
- 239000007790 solid phase Substances 0.000 title claims abstract description 28
- 229920003189 Nylon 4,6 Polymers 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229920006121 Polyxylylene adipamide Polymers 0.000 title claims abstract description 9
- 239000004677 Nylon Substances 0.000 claims abstract description 65
- 229920001778 nylon Polymers 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000012266 salt solution Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 13
- 150000004985 diamines Chemical class 0.000 claims abstract description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229920006883 PAMXD6 Polymers 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000010924 continuous production Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004383 yellowing Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 24
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 238000003860 storage Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000001361 adipic acid Substances 0.000 description 8
- 235000011037 adipic acid Nutrition 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 6
- 150000003384 small molecules Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 229920003231 aliphatic polyamide Polymers 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004953 Aliphatic polyamide Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- SNCZNSNPXMPCGN-UHFFFAOYSA-N butanediamide Chemical class NC(=O)CCC(N)=O SNCZNSNPXMPCGN-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- -1 decanediamine Chemical compound 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XGSHEASGZHYHBU-UHFFFAOYSA-N tetradecane-1,1-diamine Chemical compound CCCCCCCCCCCCCC(N)N XGSHEASGZHYHBU-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- FRXCPDXZCDMUGX-UHFFFAOYSA-N tridecane-1,1-diamine Chemical compound CCCCCCCCCCCCC(N)N FRXCPDXZCDMUGX-UHFFFAOYSA-N 0.000 description 2
- XJIAZXYLMDIWLU-UHFFFAOYSA-N undecane-1,1-diamine Chemical compound CCCCCCCCCCC(N)N XJIAZXYLMDIWLU-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- 229920006154 PA11T Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229920006119 nylon 10T Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006115 poly(dodecamethylene terephthalamide) Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
- C08G69/30—Solid state polycondensation
Abstract
The invention relates to a continuous solid phase polycondensation method for producing PA46 and PA MXD6, comprising the steps of: diamine, dicarboxylic acid, auxiliary agent and water are subjected to salification reaction in a salification reaction device group to obtain nylon salt solution; introducing a nylon salt solution into a reactor for a first polycondensation reaction to obtain a nylon prepolymer A; after the nylon prepolymer A is dried, introducing the nylon prepolymer A into a solid-phase tackifying device for carrying out a second polycondensation reaction, and further improving the polymerization degree to obtain a nylon prepolymer B; and (3) carrying out a third polycondensation reaction on the nylon prepolymer B in an extruder under the protection of inert atmosphere to obtain the high-temperature-resistant nylon. Compared with the prior art, the method realizes continuous production, can avoid the yellowing and black spots of the product to a great extent, and has stable quality and excellent performance among each batch of the product; compared with other high temperature resistant nylon methods, the method has the advantages of continuous production process, shorter reaction period, higher production efficiency and lower energy consumption and cost.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a continuous solid phase polycondensation method for producing PA46 and PA MXD 6.
Background
With the development of scientific technology, in order to meet the personalized demands of various fields such as daily household appliances, industrial production, aerospace, information communication and the like, the common polyamide resin is gradually replaced by novel polyamide with more excellent performance due to the defects of strong water absorption, large change of the size along with different humidity, poor rigidity and the like. The high-temperature resistant nylon has good heat resistance, mechanical property, dimensional stability, electrical insulation, solvent resistance and chemical resistance besides a plurality of general properties of common polyamide. Therefore, the method has important application in the fields of automobiles, electronic appliances and the like, and is the field of research and development hotspots at home and abroad at present.
The high temperature resistant nylon is one kind of polyamide resin capable of being used at 150 deg.c for long period and includes mainly wholly aromatic polyamide, semi-aromatic polyamide and partially aliphatic polyamide. Wholly aromatic polyamides have poor processability compared with semi-aromatic polyamides and aliphatic polyamides due to an excessively high melting point. The semi-aromatic polyamide has the advantages of excellent heat resistance, mechanical property, low water absorption rate and the like, and also has good toughness and processability. In addition, the aliphatic polyamide with the same methylene number in diamine and dicarboxylic acid chain segments in the molecular chain structure has higher symmetry and regularity, and the formed hydrogen bond has high density, so the aliphatic polyamide also has higher heat resistance.
At present, most of industrially produced high temperature resistant nylon is semi-aromatic polyamide, aliphatic nylon and copolymer of benzene ring-containing polyamide, such as PA6T, PA9T, PA10T, PA11T, PA12T, PA46, PPA and the like. The production method mainly comprises batch two-step polycondensation, solid-phase batch polymerization, continuous solid-phase polycondensation and the like. The intermittent two-step polycondensation is to synthesize nylon salt first, then melt-polycondensate at the temperature 10-20 deg.c higher than the melting point of the polymer to synthesize prepolymer, and finally solid-phase post-polymerization. The solid phase intermittent polycondensation is to add nylon salt into a polymerization kettle, react under high pressure at the temperature below the melting point, then react under normal pressure, and then continue to heat up or vacuum to obtain powdery nylon product. The method improves the problems of yellowing and blackness of the intermittent two-step method product, improves the product performance, but has the advantages of low reaction rate, low efficiency, poor product stability, high degree of dependence on manpower and high cost. Compared with the batch process, the continuous polycondensation process has greatly shortened polymerization period, raised production efficiency, excellent product performance and stable quality.
Patent CN112979941a discloses a continuous solid phase polycondensation method for producing high temperature resistant nylon, which comprises the steps of reacting wet powdery nylon salt, catalyst and antioxidant at 20-210 ℃ under high pressure, and then gradually increasing the reaction temperature along the material conveying direction. The material conveying powdery material is prepolymerized in a first reactor and releases steam to react under positive pressure; further polymerization is carried out under the condition of micro positive pressure in the second reactor, or further polymerization is carried out under the condition of negative pressure in the third reactor, or polymerization is carried out under the condition of micro positive pressure (the second reactor) and then the negative pressure (the third reactor). The temperature was further increased and further polymerized under negative pressure. The method improves automation degree, reduces artificial dependence degree, and has stable and good product quality. However, the raw materials used in this patent are wet powdered nylon salt, and the solvent content is 5-20%. In practice, there are difficulties in the transfer of such materials, such as the transfer of the materials from the salt forming tank to the starting material storage tank and from the starting material storage tank to the first polymerization reactor. When the polymerization reaction is heated, the salt on the kettle wall may be carbonized, fallen and mixed into the material, so that the product quality is affected.
Patent CN1939954a discloses a continuous preparation method of polyamide, which comprises salifying with water as solvent, introducing salt solution into tubular reaction device for amidation reaction, adding the obtained mixture into continuous reaction device, reacting at a temperature above the melting point of target product, removing water while increasing polymerization degree, introducing the product into horizontal twin-screw reaction device, and final polymerizing at a temperature above the melting point of target product. The continuous preparation method adopts a melt polymerization mode and is mainly used for preparing aromatic and semi-aromatic polyamide. Although melt polymerization can rapidly increase the molecular weight of the polymer, product discharge is a difficult point, and problems such as adhesion to a kettle, direct contact of high-temperature discharged products with air, easy oxidation and the like are commonly existed.
Disclosure of Invention
The object of the present invention is to overcome at least one of the above-mentioned drawbacks of the prior art by providing a continuous solid phase polycondensation process for the production of PA46 and PAMXD 6. The method not only can remarkably improve the production efficiency and reduce the labor dependence and labor cost, but also has relatively low reaction temperature required by solid-phase polymerization, saves energy consumption, and can effectively control the occurrence of side reactions such as ring and the like.
The aim of the invention can be achieved by the following technical scheme:
a continuous solid phase polycondensation process for producing PA46 and PAMXD6 comprising the steps of:
diamine, dicarboxylic acid and water are subjected to salification reaction in a salification reaction device group to obtain nylon salt solution;
introducing the completely reacted nylon salt solution into a salt solution temporary storage tank, and uniformly mixing for later use;
introducing the nylon salt solution in the salt solution temporary storage tank into a tubular reactor with an exhaust hole for a first polycondensation reaction to obtain nylon prepolymer A;
introducing the nylon prepolymer A into a drying system, removing solvent micromolecules, introducing into a solid-phase tackifying device for a second polycondensation reaction, and further improving the polymerization degree at a temperature below the melting point of a final product to obtain a nylon prepolymer B;
and under the protection of inert atmosphere, carrying out a third polycondensation reaction on the nylon prepolymer B in an extruder, granulating and subpackaging by the extruder to obtain the high-temperature-resistant nylon.
Further, the diamine includes at least one of butanediamine, hexanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, m-xylylenediamine or p-xylylenediamine.
Further, the dicarboxylic acid comprises at least one of terephthalic acid, isophthalic acid, 2, 6-naphthalene dicarboxylic acid, 1, 4-cyclohexane diacid, 1, 3-cyclohexane diacid or adipic acid.
Further, the salification reaction comprises an auxiliary agent, wherein the auxiliary agent comprises at least one of sodium hypophosphite, an antioxidant 1010, an antioxidant s9228, an antioxidant SH120 and an antioxidant B215, and sodium hypophosphite is preferred.
Further, the molar ratio of diamine to dicarboxylic acid is (1-1.1): 1, preferably (1.01-1.05): 1; the concentration of the nylon salt solution is 20-50wt%.
Further, the salt-forming reaction is carried out at a temperature of 60 to 95 ℃, preferably 75 to 90 ℃, and the salt solution is weakly alkaline when the reaction is complete.
Further, the reaction temperature of the first polycondensation reaction is 160-280 ℃, preferably 220-280 ℃, the exhaust polymerization time is 0.5-2h, and the amount of small molecules excluding the solvent is 65-75wt% of the total mass of the added solvent. Since the polycondensation reaction is a reversible reaction, removal of the solvent can promote the reaction to proceed in the forward direction.
Further, the drying temperature is 120-140 ℃ and is equal to N 2 、CO 2 At least one of Ar or He under atmosphere protection, wherein N is preferred 2 . The drying equipment can be spray dryer with inlet temperature of 180-220deg.C, outlet temperature of 80-100deg.C, and atomizer speed of 200-400Hz.
Further, the temperature of the second polycondensation reaction is 220-260 ℃, if the melting temperature of the final product is T mx The actual reaction temperature ranges from 220 ℃ to T mx The reaction time is 4-24 hours, preferably 6-8 hours, and the inert gas is used for purging, so as to bring out small molecules of the solvent, thereby improving the polymerization degree of the reactants.
Further, the temperature of the third polycondensation reaction is in the range of 260 to 320 ℃. If the final product has a melting temperature T mx The actual reaction temperature is slightly higher than T mx 。
The high temperature resistant nylon product comprises one of the following repeating units (A) to (D),
in the formula (D), n is 6, 9, 10, 11, 12, 13 or 14.
Compared with the prior art, the invention has the following advantages:
(1) The method realizes continuous production, can avoid yellowing and black spots of the product to a great extent, and has stable quality and excellent performance among each batch of the product.
(2) Compared with other high temperature resistant nylon methods, the method has the advantages of continuous production process, shorter reaction period, higher production efficiency and lower energy consumption and cost.
(3) The high-temperature resistant nylon product obtained by the method has high melting point, high glass transition temperature, excellent heat resistance, electrical insulation, wear resistance, oil resistance and chemical resistance, excellent mechanical property and dimensional stability, and can be widely applied to the fields of electronic appliances, automobiles, fibers and the like.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
The materials and reagents used in the following examples were purchased from commercial sources.
A method for continuously producing high temperature resistant nylon, comprising the steps of:
adding dicarboxylic acid and a solvent into a salifying kettle, starting stirring, adding diamine after the dicarboxylic acid is dissolved, adjusting the pH value of the solution by adding diamine, and fully reacting to obtain a butanediamide salt solution;
introducing the obtained butanediamide salt solution into a salt solution temporary storage tank for mixing for standby;
continuously introducing the nylon salt solution in the salt solution temporary storage tank into a tubular reactor, draining water through an exhaust port after reacting for 3 hours, and continuing to react after closing an exhaust valve to obtain a mixture of nylon prepolymer and water;
introducing the mixture of the nylon prepolymer and water into a spray dryer, and removing solvent micromolecules to obtain nylon prepolymer solid;
and (3) conveying the obtained nylon prepolymer solid into a continuous solid-phase tackifying device by utilizing a gas conveying device, fully reacting under the atmosphere of nitrogen blowing, conveying an obtained product through an extruder, conveying inert gas, cooling after the reaction is finished, granulating and subpackaging to obtain the high-temperature-resistant nylon.
The diamine includes at least one of butanediamine, hexanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, m-xylylenediamine or p-xylylenediamine. The dicarboxylic acid includes at least one of terephthalic acid, isophthalic acid, 2, 6-naphthalene dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, 1, 3-cyclohexane dicarboxylic acid, or adipic acid. The auxiliary agent comprises at least one of sodium hypophosphite, antioxidant 1010, antioxidant s9228, antioxidant SH120 and antioxidant B215, preferably sodium hypophosphite. The molar ratio of diamine to dicarboxylic acid is (1-1.1): 1; the concentration of the nylon salt solution is 20-50wt%.
The salt forming reaction temperature is 60-95 deg.c, and the salt solution is slightly alkaline when the reaction is completed. The reaction temperature of the first polycondensation reaction is 160-240 ℃, the exhaust polymerization time is 0.5-2h, the solvent micromolecules are removed, and the discharge amount is 65-75wt% of the total mass of the added solvent. The drying temperature in the drying system is 120-140 deg.C, and N is 2 、CO 2 At least one of Ar or He under atmosphere protection, wherein N is preferred 2 . The drying equipment can be spray dryer with inlet temperature of 180-220deg.C, outlet temperature of 80-100deg.C, and atomizer speed of 200-400Hz. The temperature of the second polycondensation reaction is 220-260 ℃, if the melting temperature of the final product is T mx The actual reaction temperature ranges from 220 ℃ to T mx The reaction time is 4-24 hours, preferably 6-8 hours, and the inert gas is used for purging, so as to bring out small molecules of the solvent, thereby improving the polymerization degree of the reactants. The temperature of the third polycondensation reaction is in the range of 260-320 ℃. If the final product has a melting temperature T mx The actual reaction temperature is slightly higher than T mx 。
Example 1
A method for continuously producing high temperature resistant nylon, comprising the steps of:
(1) Adding 14.6kg of adipic acid and 80.0kg of deionized water (serving as a solvent) into a salifying kettle, starting stirring, adding 9.0kg of butanediamine after the adipic acid is dissolved, replacing nitrogen for 3 times, heating to 80 ℃, adjusting the pH value of the solution to 7.2 by adding butanediamine, and reacting for 1 hour to obtain an adipoyl butanediamine salt solution;
(2) Introducing the butanediamide salt solution in the salifying reaction device group obtained in the step (1) into a salt solution temporary storage tank for mixing for later use;
(3) Continuously introducing the nylon salt solution in the salt solution temporary storage tank into a tubular reactor, setting the reaction temperature to 230 ℃, draining 65wt% through an exhaust port after 3 hours of reaction, closing an exhaust valve, and reacting for 1 hour to obtain a mixture of nylon prepolymer and water;
(4) Introducing the mixture obtained in the step (3) into a spray dryer to remove solvent small molecules. Setting the inlet temperature to be 200 ℃, the outlet temperature to be 80 ℃ and the speed of the atomizer to be 200Hz;
(5) Conveying the nylon prepolymer solid obtained in the step (4) into a continuous solid-phase viscosifier by using a gas conveying device, and reacting for 6 hours at 240 ℃ under the atmosphere of nitrogen blowing;
(6) And (3) conveying inert gas carbon dioxide to the product obtained in the step (5) through an extruder, wherein the reaction temperature is 310 ℃, cooling after the reaction is finished, granulating and subpackaging to obtain a high-temperature-resistant nylon PA46 product.
The resulting PA46 was subjected to a property measurement at a melting point of 290.42 ℃and a relative viscosity of 2.05, and the detailed test data are shown in Table 1.
Example 2
A method for continuously producing high temperature resistant nylon, comprising the steps of:
(1) Adding 14.6kg of adipic acid and 80.0kg of deionized water (serving as a solvent) into a salifying kettle, starting stirring, adding 9.0kg of butanediamine after the adipic acid is dissolved, replacing nitrogen for 3 times, heating to 80 ℃, adjusting the pH value of the solution to 7.5 by adding butanediamine, and reacting for 1 hour to obtain an adipoyl butanediamine salt solution;
(2) Introducing the butanediamide salt solution in the salifying reaction device group obtained in the step (1) into a salt solution temporary storage tank for mixing for later use;
(3) Continuously introducing the nylon salt solution in the salt solution temporary storage tank into a tubular reactor, setting the reaction temperature to 240 ℃, draining 75wt% through an exhaust port after 3 hours of reaction, closing an exhaust valve, and reacting for 1 hour to obtain a mixture of nylon prepolymer and water;
(4) Introducing the mixture obtained in the step (3) into a spray dryer to remove solvent small molecules. Setting the inlet temperature to be 200 ℃, the outlet temperature to be 80 ℃ and the speed of the atomizer to be 200Hz;
(5) Conveying the nylon prepolymer solid obtained in the step (4) into a continuous solid-phase viscosifier by using a gas conveying device, and reacting for 8 hours at 220 ℃ under the atmosphere of nitrogen blowing;
(6) And (3) conveying inert gas carbon dioxide to the product obtained in the step (5) through an extruder, wherein the reaction temperature is 310 ℃, cooling after the reaction is finished, granulating and subpackaging to obtain a high-temperature-resistant nylon PA46 product.
The resulting PA46 was subjected to a property measurement at a melting point of 292.19 ℃and a relative viscosity of 2.17, and the detailed test data are shown in Table 1.
Example 3
A method for continuously producing high temperature resistant nylon, comprising the steps of:
(1) Adding 10.3 kg (70 mol) of adipic acid and 20.5 kg of deionized water (serving as a solvent) into a salifying kettle, starting stirring, adding 9.9 kg (73 mol) of m-xylylenediamine after adipic acid is dissolved, replacing nitrogen for 3 times, heating to 80 ℃, adjusting the pH value of the solution to 7.2 by adding m-xylylenediamine, and reacting for 30 minutes to obtain m-xylylenediamine adipoyl salt solution;
(2) Introducing the m-xylylenediamine adipoyl salt solution obtained in the step (1) into a salt solution temporary storage tank for mixing for standby;
(3) Continuously introducing the nylon salt solution in the salt solution temporary storage tank into a tubular reactor, setting the reaction temperature to 260 ℃, draining 70wt% through an exhaust port after 3 hours of reaction, closing an exhaust valve, and reacting for 1 hour to obtain a mixture of nylon prepolymer and water;
(4) Introducing the mixture obtained in the step (3) into a spray dryer to remove solvent small molecules. Setting the inlet temperature to be 200 ℃, the outlet temperature to be 80 ℃ and the speed of the atomizer to be 200Hz;
(5) Conveying the nylon prepolymer solid obtained in the step (4) into a continuous solid-phase viscosifier by using a gas conveying device, and reacting for 6 hours at 230 ℃ under the atmosphere of nitrogen blowing;
(6) And (3) conveying inert gas carbon dioxide to the product obtained in the step (5) through an extruder, cooling after the reaction is completed at the reaction temperature of 270 ℃, granulating again and subpackaging to obtain a high-temperature-resistant nylon PA MXD6 product.
The properties of the resulting PA MXD6 were measured, the melting point was 236.47 ℃and the relative viscosity was 2.07, and the detailed test data are shown in Table 1.
Table 1A list of properties of the products obtained in examples 1-3
The invention emphasizes that the continuous method is used for producing the aliphatic high-temperature resistant nylon, the method can also be used for producing the semi-aromatic high-temperature resistant nylon, and certain preparation methods provided by the prior art are suitable for preparing a small amount of semi-aromatic nylon in a laboratory. In addition, the reaction conditions of the two are different, the nylon salt solution is concentrated at 55-160 ℃ and then heated to 265-285 ℃ for prepolymerization in certain prior art, the concentration step is omitted, the prepolymerization is directly carried out in a tubular reactor to obtain a prepolymer, and the tackifying granulation is carried out.
In conclusion, the invention can obviously improve the production efficiency and reduce the labor dependence and labor cost. For example, the solid-phase polymerization reaction temperature is lower, the energy consumption is saved, and the occurrence of side reactions such as cyclization can be effectively reduced, so that the prepared nylon has stable quality, good mechanical properties and excellent heat resistance, such as higher notch impact strength.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (7)
1. A continuous solid phase polycondensation process for producing PA46 and PA MXD6 comprising the steps of:
the diamine, dicarboxylic acid and solvent are subjected to salification reaction in a salification reaction device group to obtain nylon salt solution;
introducing a nylon salt solution into a reactor for a first polycondensation reaction to obtain a nylon prepolymer A;
after the nylon prepolymer A is dried, introducing the nylon prepolymer A into a solid-phase tackifying device for carrying out a second polycondensation reaction, and further improving the polymerization degree to obtain a nylon prepolymer B;
under the protection of inert atmosphere, carrying out a third polycondensation reaction on the nylon prepolymer B in an extruder to obtain PA46 or PAMXD6;
the reactor is a tubular reactor with an exhaust hole;
the temperature of the third polycondensation reaction is 260-320 ℃.
2. A continuous solid phase polycondensation process for producing PA46 and PAMXD6 according to claim 1, wherein an auxiliary agent is added during the salification reaction, said auxiliary agent comprising at least one of sodium hypophosphite, antioxidant 1010, antioxidant s9228, antioxidant SH120, or antioxidant B215.
3. A continuous solid phase polycondensation process for producing PA46 and PAMXD6 according to claim 1, wherein the molar ratio of diamine to dicarboxylic acid is 1 to 1.1; the concentration of the nylon salt solution is 20-50wt%.
4. A continuous solid phase polycondensation process for producing PA46 and PAMXD6 according to claim 1, wherein the temperature of the salt forming reaction is between 60 ℃ and 95 ℃.
5. A continuous solid phase polycondensation process for producing PA46 and PAMXD6 according to claim 1, wherein the reaction temperature of the first polycondensation is 160-280 ℃, the vent polymerization time is 0.5-2h, and the amount of the removed solvent is 65-75wt% of the total mass of the added solvent.
6. A continuous solid phase polycondensation process for the production of PA46 and PA MXD6 according to claim 1, wherein the solid phase polycondensation process is dryThe drying temperature is 120-140 ℃, and is N 2 、CO 2 At least one of Ar or He is performed under the protection of atmosphere.
7. A continuous solid phase polycondensation process for producing PA46 and PA MXD6 according to claim 1 characterized in that the temperature of the second polycondensation reaction is 220-260 ℃ for a reaction time of 4-24 hours.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07228693A (en) * | 1994-02-17 | 1995-08-29 | Kuraray Co Ltd | Production of polyamide |
| US6133406A (en) * | 1997-11-18 | 2000-10-17 | Mitsui Chemicals, Inc. | Process for preparing aromatic polyamides |
| CN102660019A (en) * | 2012-05-09 | 2012-09-12 | 金发科技股份有限公司 | High temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and preparation method and application thereof |
| CN104387581A (en) * | 2014-10-24 | 2015-03-04 | 江门市德众泰工程塑胶科技有限公司 | Method for preparing semi-aromatic copolymerized polyamide resin and resin |
| CN110818892A (en) * | 2019-12-13 | 2020-02-21 | 万华化学集团股份有限公司 | Preparation method and device of nylon |
| CN112795008A (en) * | 2021-03-31 | 2021-05-14 | 上海庚彩新材料科技有限公司 | Synthesis process of nylon MXD6 |
| CN112979941A (en) * | 2021-03-02 | 2021-06-18 | 郑州大学 | Continuous solid phase polycondensation method for producing high temperature resistant nylon |
| CN113061247A (en) * | 2021-03-31 | 2021-07-02 | 上海庚彩新材料科技有限公司 | High-temperature-resistant and easy-to-process polyamide copolymer and preparation method thereof |
| CN113801319A (en) * | 2021-09-22 | 2021-12-17 | 浙江新力新材料股份有限公司 | Rigid high-temperature-resistant nylon resin, and preparation method and application thereof |
| CN114316255A (en) * | 2022-01-21 | 2022-04-12 | 湖南世博瑞高分子新材料有限公司 | High-temperature-resistant nylon continuous melt polymerization method |
-
2022
- 2022-08-19 CN CN202211000441.2A patent/CN115197416B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07228693A (en) * | 1994-02-17 | 1995-08-29 | Kuraray Co Ltd | Production of polyamide |
| US6133406A (en) * | 1997-11-18 | 2000-10-17 | Mitsui Chemicals, Inc. | Process for preparing aromatic polyamides |
| CN102660019A (en) * | 2012-05-09 | 2012-09-12 | 金发科技股份有限公司 | High temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and preparation method and application thereof |
| CN104387581A (en) * | 2014-10-24 | 2015-03-04 | 江门市德众泰工程塑胶科技有限公司 | Method for preparing semi-aromatic copolymerized polyamide resin and resin |
| CN110818892A (en) * | 2019-12-13 | 2020-02-21 | 万华化学集团股份有限公司 | Preparation method and device of nylon |
| CN112979941A (en) * | 2021-03-02 | 2021-06-18 | 郑州大学 | Continuous solid phase polycondensation method for producing high temperature resistant nylon |
| CN112795008A (en) * | 2021-03-31 | 2021-05-14 | 上海庚彩新材料科技有限公司 | Synthesis process of nylon MXD6 |
| CN113061247A (en) * | 2021-03-31 | 2021-07-02 | 上海庚彩新材料科技有限公司 | High-temperature-resistant and easy-to-process polyamide copolymer and preparation method thereof |
| CN113801319A (en) * | 2021-09-22 | 2021-12-17 | 浙江新力新材料股份有限公司 | Rigid high-temperature-resistant nylon resin, and preparation method and application thereof |
| CN114316255A (en) * | 2022-01-21 | 2022-04-12 | 湖南世博瑞高分子新材料有限公司 | High-temperature-resistant nylon continuous melt polymerization method |
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