CN115490848A - Polyamide resin and polymerization method and application thereof - Google Patents
Polyamide resin and polymerization method and application thereof Download PDFInfo
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- CN115490848A CN115490848A CN202211129855.5A CN202211129855A CN115490848A CN 115490848 A CN115490848 A CN 115490848A CN 202211129855 A CN202211129855 A CN 202211129855A CN 115490848 A CN115490848 A CN 115490848A
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- polyamide resin
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 8
- 238000006116 polymerization reaction Methods 0.000 title claims description 7
- 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 38
- 239000000446 fuel Substances 0.000 claims abstract description 13
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000004427 diamine group Chemical group 0.000 claims abstract description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 18
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-UHFFFAOYSA-N 0.000 claims description 8
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 239000005711 Benzoic acid Substances 0.000 claims description 7
- 235000010233 benzoic acid Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 17
- 230000014759 maintenance of location Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a polyamide resin, which comprises the following repeating units: diacid unit: terephthalic acid accounting for 20-40mol% of diacid unit, and linear chain aliphatic diacid with 9 or more carbon atoms accounting for 60-80mol% of diacid unit; diamine unit (b): 1,10-decamethylenediamine and 1,12-dodecamethylenediamine in a molar ratio of 9:1-5:5. The polyamide resin has the advantages of high strength, high elongation at break and good high-temperature solvent resistance, and is suitable for fuel pipe materials.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to polyamide resin and a polymerization method and application thereof.
Background
With the rapid increase of automobile requirements, the problems of energy shortage and environmental pollution are brought to the society. Reducing fuel consumption and environmental pollution has become a key problem which is urgently needed to be solved in the current automobile industry development and social sustainable development, and realizing light weight of automobiles is one of the most effective ways for saving energy and is also an important target pursued by international advanced automobile manufacturers. The transformation of plastic-substituted steel is completed by more and more parts in the fuel system, wherein the single-layer fuel pipe in the fuel delivery system adopts the aliphatic long carbon chain polyamide material such as PA11 and the like in a large amount.
However, due to the increasing shortage of petroleum resources, the mixed fuel oil prepared by adding ethanol into gasoline gradually becomes the trend of energy conservation and emission reduction. The advent and application of mixed fuels places higher demands on the fuel delivery line system. As a material of the fuel pipe, the material not only needs higher strength and toughness, but also has higher mixed fuel resistance. Aliphatic long-carbon-chain polyamide materials such as PA11 have good toughness and good tolerance to gasoline, but have poor tolerance to ethanol in the mixed fuel oil. The long-carbon-chain aliphatic polyamide material is contacted with ethanol for a long time, so that the strength and the toughness are obviously reduced, the oil pipe is cracked and failed, on one hand, serious potential safety hazards of automobiles are caused, on the other hand, hydrocarbon seeps out after the oil pipe is cracked, and the hydrocarbon is one of main sources of hydrocarbon emission of automobiles and causes harm to the environment.
Disclosure of Invention
The invention aims to provide a polyamide resin which has the advantages of high-temperature solvent resistance, high strength and high elongation at break.
Another object of the present invention is to provide a polymerization method and use of the above polyamide resin.
The invention is realized by the following technical scheme:
a polyamide resin comprising the following repeating units:
diacid unit: terephthalic acid accounting for 20-40mol% of diacid unit, and linear chain aliphatic diacid with 9 or more carbon atoms accounting for 60-80mol% of diacid unit;
diamine unit (b): 1,10-decamethylenediamine and 1,12-dodecamethylenediamine in a molar ratio of 9:1-5:5.
Preferably, the proportion of terephthalic acid in the diacid units is from 26 to 34mol%; more preferably, the terephthalic acid content of the diacid units is 29 to 31 mole percent.
The linear aliphatic diacid with 9 or more carbon atoms is selected from at least one of 1,9-azelaic acid, 1,10-sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid and 1,14-tetradecanedioic acid.
Preferably, the linear aliphatic diacid with 9 or more carbon atoms is selected from 1,10-sebacic acid, 1,12-dodecanedioic acid.
Preferably, the molar ratio of 1,10-decamethylenediamine to 1,12-dodecamethylenediamine in the diamine units is 7:3-6:4.
The relative viscosity of the polyamide resin is in the range of 2.0 to 3.0.
The melting point range of the polyamide resin is 170-200 ℃.
The polymerization method of the polyamide resin of the present invention comprises the steps of: adding reaction raw materials of diamine and diacid into a pressure kettle according to the proportion; adding benzoic acid, a catalyst sodium hypophosphite and deionized water; the addition amount of the benzoic acid is 2-3% of the total weight of the diamine and the diacid, the weight of the sodium hypophosphite is 0.05-0.15% of the weight of the other materials except the deionized water, and the weight of the deionized water is 25-35% of the total weight of the materials; vacuumizing, filling high-purity nitrogen as protective gas, heating to 195-205 ℃ within 1.5-2.5 hours under stirring, keeping the temperature of the reaction mixture and stirring for 0.5-1.5 hours, then raising the temperature of reactants to 260-280 ℃ under stirring, continuing to perform 1.5-2.5 hours under 3.1-3.3 MPa, removing the formed water to keep the pressure constant, then gradually reducing the pressure to normal pressure, and discharging after the reaction is finished to obtain the polyamide resin.
The polyamide resin has the tensile strength of more than 50MPa, the elongation at break of more than 190 percent and good high-temperature solvent resistance (after ethanol is aged for 500 hours, the tensile strength retention rate is more than or equal to 80 percent and the elongation at break retention rate is more than or equal to 50 percent), and is suitable for preparing vehicle-mounted fuel system parts, particularly chemical resistance of an oil pipeline at higher engine temperature, and higher tensile strength and elongation at break of the oil pipeline due to the fact that the oil pipeline needs to resist tensile and high-frequency vibration.
The invention has the following beneficial effects
According to the invention, a specific amount of terephthalic acid repeating units are added into long carbon chain nylon repeating units (the number of carbon atoms is more than or equal to 9), and a diamine structural unit is a compound of 1,10-decamethylenediamine and 1,12-dodecamethylenediamine in a molar ratio of 9:1-5:5, so that the ethanol resistance can be improved on the premise of keeping high strength and high elongation at break, and the method is suitable for preparing vehicle-mounted fuel system components.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention.
The examples and comparative examples used the following sources of raw materials:
the polymerized monomers are commercially available: 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, terephthalic acid, 1,6-adipic acid, 1,9-azelaic acid, 1,10-sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid.
Benzoic acid: analytical grade, available from Sigma-Aldrich;
sodium hypophosphite: analytically pure, purchased from Sigma-Aldrich;
examples and comparative examples polymerization method of polyamide resin: adding reaction raw materials of diamine and diacid into a pressure kettle according to the proportion in the table; adding benzoic acid, a catalyst sodium hypophosphite and deionized water; the addition amount of the benzoic acid is 2-3% of the total amount of the diamine and the diacid, the weight of the sodium hypophosphite is 0.10% of the weight of the materials except the deionized water, and the weight of the deionized water is 30% of the total weight of the materials; vacuumizing, filling high-purity nitrogen as protective gas, heating to 200 ℃ within 2 hours under stirring, keeping the temperature of the reaction mixture under stirring for 1 hour, then heating the temperature of reactants to 270 ℃ under stirring, continuing the reaction for 2 hours under 3.2 MPa, keeping the pressure constant by removing the formed water, then gradually reducing the pressure to normal pressure, and discharging after the reaction is finished to obtain the polyamide resin.
The test methods are as follows:
(1) Relative viscosity test: with reference to GB12006.1-89, the relative viscosity eta of polyamides having a concentration of 0.25 g/dl is measured in 98% concentrated sulfuric acid at 25 + -0.01 deg.C r 。
(2) Melting point test: reference is made to ASTM D3418-2003, standard Test Method for Transition Temperatures of Polymers By Differential Scanning calibration; the specific test method comprises the following steps: testing the melting point of the sample by adopting a Perkin Elmer Dimond DSC analyzer; nitrogen atmosphere, the flow rate is 50mL/min; during testing, the temperature is firstly raised to 300 ℃ at the speed of 20 ℃/min, the temperature is kept for 2min at the temperature of 300 ℃, the thermal history of the resin is removed, then the resin is cooled to 50 ℃ at the speed of 20 ℃/min, the temperature is kept for 2min at the temperature of 50 ℃, the temperature is raised to 300 ℃ at the speed of 20 ℃/min, and the endothermic peak temperature at the moment is set as the T melting point;
(3) Tensile strength and elongation at break test: referring to GB/T1040.1-2018, the tensile property of plastics is measured; injection molding the resin into 1A type sample strips, and testing at a tensile speed of 10mm/min under the conditions of (23 +/-2) ° C/(50 +/-5)% RH;
(4) And (3) testing the high-temperature ethanol resistance: the resin is injected into a 1A sample strip, placed in a mixed solvent of ethanol and water (the mass ratio of the ethanol to the water is 90/10), heated to 135 ℃, aged for 500 hours, taken out of the sample strip, tested for tensile strength and elongation at break, and calculated for retention rate.
Table 1: examples content of each unit (mol%) of the polyamide resin and test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| Terephthalic acid (TPA) | 2 | 2 | 2 | 2 | 2 | 2.6 | 2.9 | 3.1 |
| 1,9-azelaic acid | ||||||||
| 1,10 sebacic acid | 8 | 8 | 8 | 8 | 8 | 7.4 | 7.1 | 6.9 |
| 1,11 undecanedioic acid | ||||||||
| 1,12-Dodecanedioic acid | ||||||||
| 1,13 tridecanedioic acid | ||||||||
| 1,14 tetradecanedioic acid | ||||||||
| 1,10 decamethylenediamine | 9 | 8 | 7 | 6 | 5 | 7 | 7 | 7 |
| 1,12-dodecadiamine | 1 | 2 | 3 | 4 | 5 | 3 | 3 | 3 |
| Relative viscosity | 2.528 | 2.535 | 2.552 | 2.575 | 2.566 | 2.551 | 2.577 | 2.538 |
| Melting point of DEG C | 175 | 173 | 171 | 169 | 167 | 182 | 188 | 192 |
| Initial tensile strength, MPa | 52 | 53 | 53 | 51 | 51 | 54 | 55 | 57 |
| Initial elongation at break% | 215 | 223 | 230 | 236 | 243 | 218 | 212 | 207 |
| Retention of tensile strength after aging% | 80 | 81 | 83 | 85 | 80 | 84 | 86 | 85 |
| Initial breaking elongation retention after aging% | 50 | 51 | 52 | 54 | 50 | 54 | 55 | 56 |
From examples 1 to 5, 1,10-decamethylenediamine is preferred: 1,12-dodecadiamine has a molar ratio of 7:3-6:4, and has better ethanol resistance.
As can be seen from examples 3/6 to 10, the proportion of terephthalic acid in the diacid units is from 26 to 34mol%; more preferably, the terephthalic acid content in the diacid units is 29 to 31 mole percent.
TABLE 1:
| example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | Example 15 | |
| Terephthalic acid (TPA) | 3.4 | 4 | 2.9 | 2.9 | 2.9 | 2.9 | 2.9 |
| 1,9-azelaic acid | 7.1 | ||||||
| 1,10 sebacic acid | 6.6 | 6 | |||||
| 1,11 undecanedioic acid | 7.1 | ||||||
| 1,12 Dodecanedioic acid | 7.1 | ||||||
| 1,13 tridecanedioic acid | 7.1 | ||||||
| 1,14 tetradecanedioic acid | 7.1 | ||||||
| 1,10 decamethylenediamine | 7 | 7 | 7 | 7 | 7 | 7 | 7 |
| 1,12-dodecadiamine | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Relative viscosity | 2.517 | 2.566 | 2.551 | 2.595 | 2.559 | 2.54 | 2.552 |
| Melting point of | 199 | 218 | 186 | 184 | 182 | 180 | 192 |
| Initiation ofTensile strength, MPa | 59 | 61 | 54 | 53 | 53 | 52 | 56 |
| Initial elongation at break% | 201 | 191 | 213 | 215 | 215 | 217 | 207 |
| Retention of tensile strength after aging% | 84 | 83 | 83 | 87 | 84 | 84 | 84 |
| Retention of initial elongation at break after aging% | 54 | 52 | 53 | 56 | 55 | 54 | 54 |
From examples 7/11 to 15, it is understood that the linear aliphatic diacids having 9 or more carbon atoms are preferably 1,10-sebacic acid and 1,12-dodecanedioic acid, and that they are more excellent in ethanol resistance.
Table 2: comparative examples 1 to 5 content of each unit (mol%) of polyamide resin and test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Terephthalic acid (TPA) | 2.9 | 2.9 | 2.9 | 1 | 5 |
| 1,10 sebacic acid | 7.1 | 7.1 | 7.1 | 9 | 5 |
| 1,10-decamethylenediamine | 10 | 4 | 7 | 7 | |
| 1,12-dodecadiamine | 6 | 10 | 3 | 3 | |
| Relative viscosity | 2.53 | 2.548 | 2.5 | 2.574 | 2.514 |
| Melting point of DEG C | 195 | 182 | 192 | 173 | 226 |
| Initial tensile strength, MPa | 51 | 52 | 50 | 47 | 63 |
| Initial elongation at break% | 182 | 210 | 185 | 232 | 156 |
| Retention of tensile strength after aging% | 76 | 77 | 75 | 76 | 76 |
| Retention of initial elongation at break after aging% | 45 | 47 | 46 | 47 | 48 |
From comparative examples 1 to 6, it is understood that the ethanol resistance is poor when each unit is out of the range of the present invention. In particular, comparative example 6 has a low initial elongation at break although it has a good ethanol resistance, and is not suitable for producing a fuel pipe.
Table 3: comparative examples 6 to 10 Polyamide resins with respective Unit content (% by mol) and test results
| Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | |
| Terephthalic acid (TPA) | 10 | 4 | 4 | 4 | 4 |
| 1,6-adipic acid | 6 | ||||
| 1,10 sebacic acid | 6 | 6 | 6 | ||
| 1,6-hexanediamine | 7 | ||||
| 1,9-nonanediamine | 7 | 7 | |||
| 1,10-decamethylenediamine | 7 | 7 | 3 | ||
| 1,12-dodecadiamine | 3 | 3 | 3 | 3 | |
| Relative viscosity | 2.566 | 2.504 | 2.508 | 2.516 | 2.595 |
| Melting point of | 302 | 232 | 228 | 220 | 223 |
| Initial tensile strength, MPa | 75 | 60 | 59 | 60 | 61 |
| Initial elongation at break% | 8 | 147 | 135 | 175 | 172 |
| Retention of tensile strength after aging% | 82 | 77 | 75 | 78 | 78 |
| Retention of initial elongation at break after aging% | 48 | 45 | 44 | 46 | 48 |
As can be seen from comparative examples 7-10, it is difficult to substitute the technical solution of the present invention with other kinds of monomers.
Claims (9)
1. A polyamide resin, characterized by comprising the following repeating units:
diacid unit: terephthalic acid accounting for 20-40mol% of diacid unit, and linear chain aliphatic diacid with 9 or more carbon atoms accounting for 60-80mol% of diacid unit;
diamine unit (b): 1,10-decamethylenediamine and 1,12-dodecamethylenediamine in a molar ratio of 9:1-5:5.
2. The polyamide resin according to claim 1, wherein the proportion of terephthalic acid in the diacid unit is 26 to 34mol%; more preferably, the terephthalic acid content in the diacid units is 29 to 31 mole percent.
3. The polyamide resin as claimed in claim 1, wherein the linear aliphatic diacid having 9 or more carbon atoms is one selected from 1,9-azelaic acid, 1,10-sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid.
4. The polyamide resin as claimed in claim 3, wherein the linear aliphatic diacid having 9 or more carbon atoms is one selected from 1,10-sebacic acid and 1,12-dodecanedioic acid.
5. The polyamide resin as claimed in claim 1, wherein the molar ratio of 1,10-decamethylenediamine and 1,12-dodecamethylenediamine is 7:3-6:4.
6. The polyamide resin as claimed in claim 1, wherein the polyamide resin has a relative viscosity in the range of 2.0 to 3.0.
7. The polyamide resin as claimed in claim 1, wherein the polyamide resin has a melting point in the range of 170-200 ℃.
8. A process for the polymerization of a polyamide resin according to any one of claims 1 to 7, characterized in that it comprises the following steps: adding reaction raw materials of diamine and diacid into a pressure kettle according to a ratio; adding benzoic acid, a catalyst sodium hypophosphite and deionized water; the addition amount of the benzoic acid is 2-3% of the total weight of the diamine and the diacid, the weight of the sodium hypophosphite is 0.05-0.15% of the weight of the other materials except the deionized water, and the weight of the deionized water is 25-35% of the total weight of the materials; vacuumizing, filling high-purity nitrogen as a protective gas, heating to 195-205 ℃ within 1.5-2.5 hours under stirring, keeping the temperature of the reaction mixture and stirring for 0.5-1.5 hours, then raising the temperature of reactants to 260-280 ℃ under stirring, then continuing to perform 1.5-2.5 hours under 3.1-3.3 MPa, removing the formed water to keep the pressure constant, then gradually reducing the pressure to normal pressure, discharging after the reaction is finished, and obtaining the polyamide resin.
9. Use of a polyamide resin according to any one of claims 1 to 7 for the production of a vehicle fuel system component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211129855.5A CN115490848B (en) | 2022-09-16 | 2022-09-16 | Polyamide resin and polymerization method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211129855.5A CN115490848B (en) | 2022-09-16 | 2022-09-16 | Polyamide resin and polymerization method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN115490848A true CN115490848A (en) | 2022-12-20 |
| CN115490848B CN115490848B (en) | 2023-12-19 |
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| CN116355208A (en) * | 2023-04-17 | 2023-06-30 | 珠海万通特种工程塑料有限公司 | Semi-aromatic polyamide resin and composite material, and preparation method and application thereof |
| CN116376011A (en) * | 2023-04-28 | 2023-07-04 | 珠海万通特种工程塑料有限公司 | Polyamide resin and polymerization method and application thereof |
| CN116769156A (en) * | 2023-04-28 | 2023-09-19 | 珠海万通特种工程塑料有限公司 | Polyamide resin, polymerization method and application thereof |
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| CN116355208A (en) * | 2023-04-17 | 2023-06-30 | 珠海万通特种工程塑料有限公司 | Semi-aromatic polyamide resin and composite material, and preparation method and application thereof |
| CN116376011A (en) * | 2023-04-28 | 2023-07-04 | 珠海万通特种工程塑料有限公司 | Polyamide resin and polymerization method and application thereof |
| CN116769156A (en) * | 2023-04-28 | 2023-09-19 | 珠海万通特种工程塑料有限公司 | Polyamide resin, polymerization method and application thereof |
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