CN116903849A - Preparation method of high-temperature nylon PA6T copolymer and high-temperature nylon PA6T copolymer - Google Patents
Preparation method of high-temperature nylon PA6T copolymer and high-temperature nylon PA6T copolymer Download PDFInfo
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- CN116903849A CN116903849A CN202311166937.1A CN202311166937A CN116903849A CN 116903849 A CN116903849 A CN 116903849A CN 202311166937 A CN202311166937 A CN 202311166937A CN 116903849 A CN116903849 A CN 116903849A
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- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 title claims abstract description 71
- 229920001778 nylon Polymers 0.000 title claims abstract description 70
- 239000004677 Nylon Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 46
- XGJHPGPVESLKKD-UHFFFAOYSA-N 2-ethylbutane-1,4-diamine Chemical compound CCC(CN)CCN XGJHPGPVESLKKD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000007790 solid phase Substances 0.000 claims abstract description 19
- 239000008187 granular material Substances 0.000 claims description 27
- 239000012266 salt solution Substances 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 abstract description 15
- 230000008018 melting Effects 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 14
- 238000010128 melt processing Methods 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000004687 Nylon copolymer Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 150000004985 diamines Chemical class 0.000 description 13
- 239000002253 acid Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920006119 nylon 10T Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- LKWSTQPRPRGLDP-UHFFFAOYSA-N 4-(azacycloundecane-1-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1CCCCCCCCCC1 LKWSTQPRPRGLDP-UHFFFAOYSA-N 0.000 description 1
- NPKDHUPJIUWYFG-UHFFFAOYSA-N 4-(azecane-1-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1CCCCCCCCC1 NPKDHUPJIUWYFG-UHFFFAOYSA-N 0.000 description 1
- 101100184727 Rattus norvegicus Pmpca gene Proteins 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 238000004904 shortening 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
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A preparation method of a high-temperature nylon PA6T copolymer and the high-temperature nylon PA6T copolymer belong to the technical field of chemical synthesis. According to the invention, on the basis of 1, 6-hexamethylenediamine and terephthalic acid, 2-ethylbutane-1, 4-diamine is introduced as a raw material, and the high-temperature PA6T nylon copolymer with high molecular weight and high melting point is obtained through salt formation, pre-polycondensation, solid-phase post-polycondensation and other reactions in sequence, so that the high-temperature resistance of the polymer can be maintained, and the subsequent melt processing is facilitated. The high-temperature nylon prepared by the method has excellent mechanical properties, low production cost and simple synthesis process, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of a high-temperature nylon PA6T copolymer and the high-temperature nylon PA6T copolymer.
Background
The high-temperature nylon is a nylon material which can be used in an environment with the temperature of more than 150 ℃ for a long time, the melting point is up to 290-320 ℃, and the high-temperature nylon modified by glass fibers has better thermal performance. Because of their excellent properties of high temperature resistance, wear resistance, impact resistance, fatigue resistance, oil resistance, etc., high temperature nylon is widely used in automobile parts, mechanical parts, electronic and electrical parts, etc.
Currently, the high-temperature nylon which has been industrially produced mainly comprises semi-aromatic nylons such as poly (hexamethylene terephthalamide) (PA 6T), poly (nonylene terephthalamide) (PA 9T) and poly (decylene terephthalamide) (PA 10T). PA9T and PA10T limit their use to some extent due to the high cost of diamine raw materials. PA6T has a melting point above its decomposition temperature and is difficult to melt process and mold, so a third monomer has to be introduced to improve the crystallization behavior, making it suitable for injection molding.
Existing PA6T typically incorporates adipic acid as a third monomer to form a PA6T/66 copolymer. However, the introduction of adipic acid reduces the proportion of the benzene ring structure, thereby affecting the high temperature resistance and the subsequent melt processing performance.
The patent with application number 202211163801.0 discloses fluorine-containing diamine, fluorine-containing high temperature resistant nylon and a preparation method thereof, and the fluorine-containing high temperature resistant nylon is prepared by polymerizing specific fluorine-containing diamine monomer, diacid and catalyst, wherein the fluorine-containing diamine monomer is introduced into a high temperature resistant nylon main chain, but the fluorine-containing diamine monomer has a complex structure, and the catalyst is required in the reaction process, so that the reaction cost is increased, and the industrial production is not facilitated.
Disclosure of Invention
The invention aims to solve the problems of the PA6T copolymer in the prior art, and provides a preparation method of the high-temperature nylon PA6T copolymer and the high-temperature nylon PA6T copolymer prepared by the method, so that the high-temperature resistance of the PA6T material is maintained to the maximum extent, and the subsequent melt processing is facilitated.
The technical scheme adopted for realizing the purpose of the invention is as follows:
the preparation method of the high-temperature nylon PA6T copolymer comprises the following steps:
s1: preparing a terephthalic acid aqueous solution, and dropwise adding 1, 6-hexamethylenediamine and 2-ethylbutane-1, 4-diamine into the terephthalic acid aqueous solution to obtain a salt solution;
s2: the salt solution is subjected to pre-polycondensation reaction, and the reacted materials are subjected to cooling, pressure relief and granulating processes to obtain prepolymer granules;
s3: and (3) under the inert atmosphere gas flow, carrying out solid-phase post-polycondensation reaction on the prepolymer granules to obtain the high-temperature nylon PA6T copolymer.
In the preparation method of the high-temperature nylon PA6T copolymer, the problem that the high-temperature resistance and the melt processing performance of the copolymer are affected due to the fact that the benzene ring structure proportion is reduced caused by adipic acid serving as a third monomer is solved by introducing 2-ethylbutane-1, 4-diamine which has a structure similar to that of 1, 6-Hexamethylenediamine (HMDA) as a comonomer. In the preparation method of the high-temperature nylon PA6T copolymer, 2-ethylbutane-1, 4-diamine is used as a comonomer, so that the high-temperature resistance of the copolymer can be maintained by keeping a higher proportion of a benzene ring structure, the crystallization behavior of the copolymer can be improved, and the subsequent melt processing and even direct injection molding are facilitated.
Further, in the above-mentioned method for preparing a high temperature nylon PA6T copolymer, the order of dropwise adding 1, 6-hexamethylenediamine and 2-ethylbutane-1, 4-diamine to the terephthalic acid aqueous solution is not limited, and the molar ratio of 1, 6-hexamethylenediamine to 2-ethylbutane-1, 4-diamine is 3:7 to 8:2.
Further, in the preparation method of the high temperature nylon PA6T copolymer, in the step S1, when 1, 6-hexamethylenediamine and 2-ethylbutane-1, 4-diamine are dropwise added into the terephthalic acid aqueous solution, the temperature of the terephthalic acid aqueous solution is kept at 40-100 ℃.
Further, since the melting point of 1, 6-hexamethylenediamine is 42 to 46 ℃, in the above-mentioned method for producing a high temperature nylon PA6T copolymer, the temperature of the aqueous terephthalic acid solution at the time of dropwise adding 1, 6-hexamethylenediamine and 2-ethylbutane-1, 4-diamine to the aqueous terephthalic acid solution in step S1 is preferably 60 to 80 ℃.
Further, in the above method for preparing a high temperature nylon PA6T copolymer, the pH of the salt solution in step S1 is 7.10 to 7.80, preferably 7.30 to 7.60. The pH value of the nylon salt solution is measured, so that the pH value is too high, the content of free diamine is high, and the stability of the nylon salt is poor; if the pH is too low, it means that the unreacted terephthalic acid is too much, the molecular weight of the polymerization product is too low, and the product properties of the PA6T copolymer are affected.
According to the research, in the preparation method of the high-temperature nylon PA6T copolymer, nylon salt generated by the reaction of diamine and terephthalic acid has a great influence on subsequent polymerization, and when the nylon salt contains excessive terephthalic acid, the polycondensation reaction can be stopped in advance, so that the molecular weight of a polymerization product is not high; when the diamine is excessively large, the imidization reaction is liable to occur. In the polymerization process of high-temperature nylon, diamine in the system is easily volatilized to evaporate out of the system due to the high temperature, so that a certain excess of diamine is generally selected. In some embodiments of the invention, the total amine molar amount is selected to be about 2% greater than the total acid molar amount.
In the preparation method of the high-temperature nylon PA6T copolymer, the mass fraction of the salt solution in the step S1 is 20-60%, preferably 30-50%, wherein the mass fraction of the salt solution is calculated according to the formula: mass fraction of salt solution = (mass of acid + mass of diamine)/total mass of solution × 100%, mass of acid is mass of all acids added in solution, mass of diamine is mass of all diamines added in solution.
The salt solution obtained in the step S1 is subjected to pre-polycondensation reaction at a certain temperature and pressure through research, an oligomer polymer is gradually formed through controlling the reaction time of the pre-polycondensation, and then the prepolymer granules are obtained through the processes of cooling, pressure relief and granulating.
In some embodiments of the present invention, the reaction temperature of the pre-polymerization reaction is 170 to 250 ℃, preferably 180 to 240 ℃.
Further, in some embodiments of the present invention, the pre-polymerization reaction is performed at a pressure of 0.5 to 3.0 MPa, preferably 1.0 to 2.5 MPa.
Further, in some embodiments of the present invention, the reaction time of the pre-polycondensation reaction is 0.5 to 5.0 hours, preferably 1.0 to 4.0 hours.
Through researches, the temperature and the reaction time of the solid-phase finishing reaction have certain influence on the reaction rate of the polymer and the molecular weight of the polymer, and the improvement of the solid-phase finishing reaction temperature is beneficial to accelerating the reaction rate of the solid-phase finishing reaction and shortening the reaction time of the solid-phase finishing reaction, but the excessive reaction temperature can cause side reaction and even degradation, so that the increase of the polymerization degree of the polymer is limited. The reaction time of solid phase post-polycondensation is prolonged, which is favorable for improving the relative molecular weight of the polymer, but too long reaction time can lead to the material to be in a high-temperature state for a long time, thereby increasing the possibility of side reaction.
In some embodiments of the invention, the reaction temperature of the solid phase finishing reaction is 240 to 295 ℃, preferably 250 to 280 ℃.
Further, in some embodiments of the present invention, the reaction time for the solid phase post-polycondensation reaction is 1.0 to 5.0 hours, preferably 2.0 to 4.5 hours.
In some embodiments of the invention, the solid phase finishing reaction employs a fixed bed reactor, a fluidized bed reactor, a rotary drum reactor, or a stirred tank reactor, which can achieve uniform heating of the copolymer.
In the preparation method of the high-temperature nylon PA6T copolymer, the solid-phase post-polycondensation reaction replaces vacuumizing in a manner of continuously introducing inert atmosphere, so that water generated in the reaction can be removed, the solid-phase post-polycondensation reaction moves forward, a nylon product with high relative viscosity and high molecular weight is obtained, and the problem of oxidative discoloration of the product caused by system oxygen leakage in the vacuumizing process is avoided.
In some embodiments of the invention, the inert atmosphere flow rate for the solid phase finishing reaction is 0.02 to 0.25 m/s, preferably 0.05 to 0.20 m/s. In a specific embodiment, the inert atmosphere is one or more of nitrogen, helium, argon, neon and carbon dioxide. In a specific embodiment, the inert atmosphere is nitrogen.
Further, according to the high-temperature nylon PA6T copolymer obtained by the preparation method of the high-temperature nylon PA6T copolymer, the chain segment molar ratio of 1, 6-hexamethylenediamine to 2-ethylbutane-1, 4-diamine in the high-temperature nylon PA6T copolymer is 40:60-78:22.
Compared with the prior art, the invention has the beneficial effects that:
(1) By selecting 2-ethylbutane-1, 4-diamine with a structure similar to that of 1, 6-Hexamethylenediamine (HMDA) as a comonomer, the high temperature resistance of PA6T can be maintained to the maximum extent, and the subsequent melt processing is facilitated.
(2) In the synthesis process of the PA6T copolymer, a catalyst is not required to be added, and the reaction cost is reduced.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a high temperature nylon PA6T copolymer according to examples 1-4 of the present invention.
FIG. 2 is an infrared absorption spectrum of high temperature 6T/ET prepared in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
All numerical designations such as pH, temperature, length, flow, including ranges, are approximations. It is to be understood that the term "about" is not always preceded by the explicit recitation of all numerical designations. It is also to be understood that the agents described herein are merely examples and that equivalents thereof are known in the art, although not always explicitly recited.
The invention provides a preparation method of a high-temperature nylon PA6T copolymer, and a flow chart of the preparation method is shown in figure 1. As shown in fig. 1, the method comprises the steps of:
s1: dissolving a certain amount of terephthalic acid in water, respectively dripping melted 1, 6-hexamethylenediamine and 2-ethylbutane-1, 4-diamine into the terephthalic acid solution at a certain temperature, and controlling the pH value of the solution to form a salt solution with a certain mass fraction;
optionally, the molar ratio of the 1, 6-hexamethylenediamine to the 2-ethylbutane-1, 4-diamine is 3:7-8:2;
optionally, the temperature is 40-100 ℃, preferably 60-80 ℃;
optionally, the pH value of the solution is 7.10-7.80, preferably 7.30-7.60;
optionally, the mass fraction of the salt solution in the step S1 is 20-60%, preferably 30-50%;
s2: the salt solution is subjected to pre-polycondensation reaction for a period of time at a certain temperature and pressure, and the reacted material is subjected to cooling, pressure relief and granulating to obtain prepolymer granules, wherein water and byproducts are also produced in the pre-polycondensation reaction process;
optionally, the reaction temperature of the pre-polycondensation reaction is 170-250 ℃, preferably 180-240 ℃;
optionally, the pressure of the pre-polycondensation reaction is 0.5-3.0 MPpa, preferably 1.0-2.5 MPa;
optionally, the reaction time of the pre-polycondensation reaction is 0.5-5.0 h, preferably 1.0-4.0 h;
s3: carrying out solid-phase post-polycondensation reaction on the prepolymer granules for a period of time under a certain temperature and inert atmosphere gas flow to obtain the high-temperature nylon PA6T copolymer;
optionally, the reaction temperature of the solid phase post-polycondensation reaction is 240-295 ℃, preferably 250-280 ℃;
optionally, the reaction time of the solid phase post-polycondensation reaction is 1.0-5.0 h, preferably 2.0-4.5 h.
According to the high-temperature nylon PA6T copolymer obtained by the preparation method of the high-temperature nylon PA6T copolymer, the chain segment molar ratio of 1, 6-hexamethylenediamine to 2-ethylbutane-1, 4-diamine in the high-temperature nylon PA6T copolymer is 40:60-78:22.
Example 1: preparation of high temperature Nylon PA6T/ET
S1: 1.66 kg terephthalic acid is dissolved in 3.36 kg water, 0.92 kg of 1, 6-hexamethylenediamine and 0.26 kg of 2-ethylbutane-1, 4-diamine (the molar quantity of the total amine is about 2 percent compared with the molar quantity of the total acid) are respectively dripped into the system under the condition of keeping the temperature of 60 ℃, and the final pH value of the solution is controlled to be 7.30-7.50, so that a salt solution with the mass fraction of 45.8 percent is formed;
s2: controlling the reaction temperature of the salt solution to 190-200 ℃, controlling the pressure to 1.2-1.3 MPa, controlling the residence time to 1.0-1.5 h, then cooling, decompressing and discharging, crushing the obtained granules to an average size of 3.0-5.0 mm by using a granulator, and drying for later use to obtain granules 2.47 and kg;
s3: and (3) placing the dried granules in a rotary drum reactor with the volume of 15.0-L, controlling the reaction temperature to be 250-260 ℃, introducing high-purity nitrogen from one side of the rotary drum reactor in a rotating state of 100 rpm, controlling the gas flow rate to be 0.05-0.10 m/s, controlling the residence time to be 2.0-2.5 h, and rapidly transferring the products into water to be rapidly cooled after the reaction is finished.
The product is proved to be a PA6T copolymer by infrared and nuclear magnetic detection, the relative viscosity of the obtained product is 3.25 (concentrated sulfuric acid is taken as a solvent), the nuclear magnetic result shows that the mole ratio of 1, 6-hexamethylenediamine chain segment and 2-ethylbutane-1, 4-diamine chain segment in the polymer is 78/22, the melting point is 310 ℃ by DSC, and the yellow index is-1.5.
Example 2: preparation of high temperature Nylon PA6T/ET
S1: 1.66 kg terephthalic acid is dissolved in 3.36 kg water, 0.78 kg of 1, 6-hexamethylenediamine and 0.40 kg of 2-ethylbutane-1, 4-diamine (the molar quantity of the total amine is about 2 percent compared with the molar quantity of the total acid) are respectively dripped into the system under the condition of keeping the temperature of 60 ℃, and the final pH value of the solution is controlled to be 7.30-7.50, so that a salt solution with the mass fraction of 45.8 percent is formed;
s2: controlling the reaction temperature of the salt solution to 220-230 ℃, controlling the pressure to 1.8-2.2 MPa, controlling the residence time to 2.0-3.0 h, then cooling, decompressing and discharging, crushing the obtained granules to an average size of 3.0-5.0 mm by using a granulator, and drying for standby to obtain granules 2.46 and kg;
s3: and (3) placing the dried granules in a fixed bed reactor with the inner diameter of 25-mm, controlling the reaction temperature to 267-275 ℃, introducing high-purity nitrogen from the bottom of a reaction tube, controlling the gas flow rate to 0.10-0.15 m/s, controlling the residence time to 3.0-4.0 h, and rapidly transferring the products into water to be rapidly cooled after the reaction is finished.
The product is proved to be a PA6T copolymer by infrared and nuclear magnetic detection, the relative viscosity of the obtained product is 3.32 (concentrated sulfuric acid is used as a solvent), the nuclear magnetic result shows that the mole ratio of 1, 6-hexamethylenediamine chain segment and 2-ethylbutane-1, 4-diamine chain segment in the polymer is 66/34, the melting point is 306 ℃ by DSC, and the yellow index is-1.7.
Example 3: preparation of high temperature Nylon PA6T/ET
S1: 1.66 kg terephthalic acid is dissolved in 4.64 kg water, 0.65 kg of 1, 6-hexamethylenediamine and 0.53 kg of 2-ethylbutane-1, 4-diamine (the molar quantity of the total amine is about 2 percent compared with the molar quantity of the total acid) are respectively dripped into the system under the condition of keeping 80 ℃, and the final pH value of the solution is controlled to be 7.40-7.60, so that a salt solution with the mass fraction of 38.0 percent is formed;
s2: controlling the reaction temperature of the salt solution at 230-240 ℃, controlling the pressure at 2.0-2.4 MPa, controlling the residence time at 2.5-3.5 h, then cooling, decompressing and discharging, crushing the obtained granules to an average size of 3.0-5.0 mm by using a granulator, and drying for later use to obtain granules 2.45-kg;
s3: placing the dried granules in a fluidized bed reactor with an inner diameter of 25-mm, controlling the reaction temperature to 270-280 ℃, introducing high-purity nitrogen from the bottom of a reaction tube, controlling the gas flow rate to 0.15-0.20 m/s, controlling the residence time to 2.5-4.5 h, and rapidly transferring the products into water to be rapidly cooled after the reaction is finished.
The product is proved to be a PA6T copolymer by infrared and nuclear magnetic detection, the relative viscosity of the obtained product is 3.32 (concentrated sulfuric acid is used as a solvent), the nuclear magnetic result shows that the mole ratio of 1, 6-hexamethylenediamine chain segment and 2-ethylbutane-1, 4-diamine chain segment in the polymer is 55/45, the melting point is 304 ℃ by DSC, and the yellow index is-1.9.
Example 4: preparation of high temperature Nylon PA6T/ET
S1: 1.66 kg terephthalic acid is dissolved in 2.84 kg water, 0.47 kg of 1, 6-hexamethylenediamine and 0.71 kg of 2-ethylbutane-1, 4-diamine (the molar quantity of the total amine is about 2% compared with the molar quantity of the total acid) are dropwise added into the system under the condition of keeping 70 ℃, and the final pH value of the solution is controlled to be 7.40-7.60, so that a salt solution with the mass fraction of 50.0% is formed.
S2: controlling the reaction temperature of the salt solution to 220-230 ℃, controlling the pressure to 1.6-2.0 MPa, controlling the residence time to 2.0-3.0 h, then cooling, decompressing and discharging, crushing the obtained granules to an average size of 3.0-5.0 mm by using a granulator, and drying for later use to obtain granules 2.45-kg;
s3: and (3) placing the dried granules in a rotary drum reactor with the volume of 15.0-L, controlling the reaction temperature to 260-270 ℃, introducing high-purity nitrogen from one side of the rotary drum reactor in a rotating state of 100 rpm, controlling the gas flow rate to 0.15-0.20 m/s, controlling the residence time to 2.5-4.0 h, and rapidly transferring the products into water to be rapidly cooled after the reaction is finished.
The product is proved to be a PA6T copolymer by infrared and nuclear magnetic detection, the relative viscosity of the obtained product is 3.31 (concentrated sulfuric acid is taken as a solvent), the nuclear magnetic result shows that the mole ratio of 1, 6-hexamethylenediamine chain segment and 2-ethylbutane-1, 4-diamine chain segment in the polymer is 40/60, the melting point is 302 ℃ by DSC, and the yellow index is-1.5.
Comparative example 1: preparation of high temperature Nylon PA6T/ET
S1: as in example 1;
s2: as in example 1;
s3: placing the dried granules in a rotary drum reactor with the volume of 15.0L, controlling the reaction temperature to be 250-260 ℃, vacuumizing by a vacuum pump under the rotation state of 100 rpm, controlling the vacuum in the reactor to be 50-200 Pa, controlling the residence time to be 2.0-2.5 h, after the reaction is finished, rapidly cooling, charging nitrogen into the reactor to break the vacuum, and rapidly transferring the product into water.
The product is proved to be a PA6T copolymer by infrared and nuclear magnetic detection, the relative viscosity of the obtained product is 3.27 (concentrated sulfuric acid is taken as a solvent), the nuclear magnetic result shows that the mole ratio of 1, 6-hexamethylenediamine chain segment and 2-ethylbutane-1, 4-diamine chain segment in the polymer is 78/22, the melting point is 308 ℃ by DSC, and the yellow index is 2.0.
Comparative example 2: preparation of high temperature Nylon PA6T/ET
S1: same as in example 2;
s2: same as in example 2;
s3: placing the dried granules in a fixed bed reactor with an inner diameter of 25-mm, controlling the reaction temperature to 267-275 ℃, vacuumizing by a vacuum pump, controlling the vacuum in the reactor to 50-200 Pa, controlling the residence time to 3.0-4.0 h, finishing the reaction, rapidly cooling, filling nitrogen into the reactor to break the vacuum, and rapidly transferring the product into water.
The product is proved to be a PA6T copolymer by infrared and nuclear magnetic detection, the relative viscosity of the obtained product is 3.01 (concentrated sulfuric acid is taken as a solvent), the nuclear magnetic result shows that the mole ratio of 1, 6-hexamethylenediamine chain segment and 2-ethylbutane-1, 4-diamine chain segment in the polymer is 66/34, the melting point is 302 ℃ by DSC, and the yellow index is 1.7.
Comparative example 3: preparation of high temperature Nylon PA6T/66
S1: dissolving 0.91 kg terephthalic acid and 0.66 kg adipic acid in 3.36 kg water, dropwise adding 1.18kg of 1, 6-hexamethylenediamine (the molar quantity of total amine is about 2% compared with the molar quantity of total acid) into a system under the condition of keeping 80 ℃, and controlling the final pH of the solution to be 7.30-7.50 to form a salt solution with the mass fraction of 45.0%;
s2: controlling the reaction temperature of the salt solution at 230-240 ℃, controlling the pressure at 2.0-2.4 MPa, controlling the residence time at 2.5-3.5 h, then cooling, decompressing and discharging, crushing the obtained granules to an average size of 3.0-5.0 mm by using a granulator, and drying for later use to obtain granules 2.38 and kg;
s3: placing the dried granules in a fluidized bed reactor with an inner diameter of 25-mm, controlling the reaction temperature to 270-280 ℃, introducing high-purity nitrogen from the bottom of a reaction tube, controlling the gas flow rate to 0.15-0.20 m/s, controlling the residence time to 2.5-4.5 h, and rapidly transferring the products into water to be rapidly cooled after the reaction is finished.
The product is proved to be a PA6T/66 copolymer by infrared and nuclear magnetic detection, the relative viscosity of the obtained product is 3.28 (concentrated sulfuric acid is used as a solvent), the nuclear magnetic result shows that the mole ratio of terephthalic acid chain segments to adipic acid chain segments in the polymer is 55/45, the melting point is 295 ℃ by DSC, and the yellow index is-1.7.
Comparative example 4: preparation of high temperature Nylon PA6T/66
S1: dissolving 0.63 kg terephthalic acid and 0.94 kg adipic acid in 3.36 kg water, dropwise adding 1.18kg of 1, 6-hexamethylenediamine (the molar quantity of total amine is about 2% compared with the molar quantity of total acid) into a system under the condition of keeping 70 ℃, and controlling the final pH of the solution to be 7.30-7.50 to form a salt solution with the mass fraction of 45.0%;
s2: controlling the reaction temperature to 220-230 ℃, controlling the pressure to 1.6-2.0 MPa, controlling the residence time to 2.0-3.0 h, then cooling, decompressing and discharging, crushing the obtained granules to an average size of 3.0-5.0 mm by using a granulator, and drying for later use to obtain granules 2.38 and kg;
s3: and (3) placing the dried granules in a rotary drum reactor with the volume of 15.0-L, controlling the reaction temperature to be 250-260 ℃, introducing high-purity nitrogen from one side of the rotary drum reactor in a rotating state of 100 rpm, controlling the gas flow rate to be 0.15-0.20 m/s, controlling the residence time to be 2.5-4.0 h, and rapidly transferring the products into water to be rapidly cooled after the reaction is finished.
The product is proved to be a PA6T/66 copolymer by infrared and nuclear magnetic detection, the relative viscosity of the obtained product is 3.33 (concentrated sulfuric acid is used as a solvent), the nuclear magnetic result shows that the mole ratio of terephthalic acid chain segment to adipic acid chain segment in the polymer is 40/60, the melting point is 292 ℃ by DSC, and the yellow index is-1.8.
The results of the products of examples 1 to 4 and comparative examples 1 to 4 are summarized in Table 1.
Table 1 summary of results for high temperature nylons of examples 1-4 and comparative examples 1-4
Comparative examples 1 to 4, it can be seen that: in the PA6T/ET copolymer, when the segments of the 2-ethylbutane-1, 4-diamine containing ethyl are increased, the glass transition temperature and the melting point of the PA6T/ET copolymer are reduced, but the descending trend is not obvious, and the higher melting point is still maintained.
Comparative example 1 and comparative example 1 (example 2 and comparative example 2), it can be seen that: in the step S3, the system is easy to leak oxygen by vacuumizing, so that the product is oxidized and discolored, and the yellow index does not reach the standard.
Comparative example 3 and comparative example 3 (example 4 and comparative example 4), it can be seen that: when the ratio of the mole ratio of 1, 6-hexamethylenediamine segment to 2-ethylbutane-1, 4-diamine segment to the mole ratio of terephthalic acid segment to adipic acid segment is the same, the melting point and glass transition temperature of the PA6T/ET copolymer are both higher than those of the PA6T/66 copolymer. This means that the proportion of the benzene ring structure can be maintained by selecting 2-ethylbutane-1, 4-diamine as a comonomer, which is favorable for improving heat resistance.
In summary, by selecting 2-ethylbutane-1, 4-diamine (EBA) with a structure similar to that of 1, 6-Hexamethylenediamine (HMDA) as a comonomer, the high temperature resistance of PA6T can be maintained and the processing problem thereof can be solved. Therefore, the method can provide high-temperature nylon products with better performance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (12)
1. The preparation method of the high-temperature nylon PA6T copolymer is characterized by comprising the following steps:
s1: preparing a terephthalic acid aqueous solution, and dropwise adding 1, 6-hexamethylenediamine and 2-ethylbutane-1, 4-diamine into the terephthalic acid aqueous solution to obtain a salt solution;
s2: the salt solution is subjected to pre-polycondensation reaction, and the material after the reaction is subjected to cooling, pressure relief and granulating processes to obtain prepolymer granules;
s3: and (3) under the inert atmosphere gas flow, carrying out solid-phase post-polycondensation reaction on the prepolymer granules to obtain the high-temperature nylon PA6T copolymer.
2. The method for preparing the high-temperature nylon PA6T copolymer according to claim 1, wherein the molar ratio of 1, 6-hexamethylenediamine to 2-ethylbutane-1, 4-diamine is 3:7-8:2.
3. The method for preparing the high-temperature nylon PA6T copolymer according to claim 1, wherein the pH of the salt solution is 7.10-7.80.
4. The preparation method of the high-temperature nylon PA6T copolymer according to claim 1, wherein the mass fraction of the salt solution is 20-60%.
5. The method for preparing a high temperature nylon PA6T copolymer according to claim 1, wherein the temperature in step S1 is 40-100 ℃.
6. The method for preparing a high temperature nylon PA6T copolymer according to claim 1, wherein the temperature of the pre-polycondensation reaction is 170-250 ℃.
7. The method for preparing a high temperature nylon PA6T copolymer according to claim 1, wherein the pressure of the pre-polycondensation reaction is 0.5 to 3.0 MPa.
8. The method for preparing a high temperature nylon PA6T copolymer according to claim 1, wherein the reaction time of the pre-polycondensation reaction is 0.5 to 5.0 hours.
9. The method for preparing a high temperature nylon PA6T copolymer according to claim 1, wherein the solid phase finishing reaction temperature is 240-295 ℃.
10. The method for preparing a high temperature nylon PA6T copolymer according to claim 1, wherein the reaction time of the solid phase post-polycondensation reaction is 1.0 to 5.0 hours.
11. The method for preparing a high temperature nylon PA6T copolymer according to claim 1, wherein the flow rate of the inert atmosphere is 0.02-0.25 m/s.
12. The high-temperature nylon PA6T copolymer obtained by the method for preparing the high-temperature nylon PA6T copolymer according to any one of claims 1 to 11, wherein the chain segment molar ratio of 1, 6-hexamethylenediamine to 2-ethylbutane-1, 4-diamine in the high-temperature nylon PA6T copolymer is 40:60 to 78:22.
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