CN115490848B - Polyamide resin and polymerization method and application thereof - Google Patents
Polyamide resin and polymerization method and application thereof Download PDFInfo
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- CN115490848B CN115490848B CN202211129855.5A CN202211129855A CN115490848B CN 115490848 B CN115490848 B CN 115490848B CN 202211129855 A CN202211129855 A CN 202211129855A CN 115490848 B CN115490848 B CN 115490848B
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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 description 6
- 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 30
- 239000000446 fuel Substances 0.000 claims abstract description 13
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 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
- 238000010438 heat treatment Methods 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
- 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
- 239000000376 reactant Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000002360 preparation method 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
- 238000012360 testing method Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 2
- 238000011161 development Methods 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
- 238000002156 mixing Methods 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
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement 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
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002356 single layer 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
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 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 mol% and linear aliphatic diacid with 9 or more carbon atoms accounting for 60-80mol% of diacid unit mol% are prepared; diamine unit: 1, 10-decanediamine and 1, 12-dodecanediamine in a molar ratio of 9:1 to 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, a polymerization method and application thereof.
Background
With the rapid increase of automobile demands, the problems of energy deficiency and environmental pollution are brought to society. The reduction of fuel consumption and environmental pollution has become a key problem to be solved urgently in the development of the automobile industry and the sustainable development of society nowadays, and the realization of the weight reduction of automobiles is one of the most effective ways to save energy and is also an important target pursued by international advanced automobile manufacturers. The conversion of plastic steel is completed by more and more parts in the fuel system, wherein a single-layer fuel pipe in the fuel delivery system is made of aliphatic long carbon chain polyamide materials such as PA 11.
However, due to the increasing shortage of petroleum resources, mixed fuel oil with ethanol added to gasoline has gradually become a trend of energy conservation and emission reduction. The advent and use of mixed fuels has placed higher demands on fuel delivery piping systems. As a material of the fuel pipe, not only high strength and toughness are required, but also high fuel mixing resistance is achieved. The aliphatic long carbon chain polyamide materials such as PA11 and the like have good toughness and good tolerance performance to gasoline, but have poor tolerance performance to ethanol in mixed fuel oil. The long-time contact of the aliphatic long-carbon chain polyamide material with ethanol can cause remarkable reduction of strength and toughness, so that oil pipe breakage and failure are caused, on one hand, serious automobile safety hidden danger is caused, on the other hand, hydrocarbon can ooze after oil pipe breakage, and the hydrocarbon is one of main sources of automobile hydrocarbon emission 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, good strength and good 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 repeating units of:
diacid unit: terephthalic acid accounting for 20-40mol% of diacid unit mol% and linear aliphatic diacid with 9 or more carbon atoms accounting for 60-80mol% of diacid unit mol% are prepared;
diamine unit: 1, 10-decanediamine and 1, 12-dodecanediamine in a molar ratio of 9:1 to 5:5.
Preferably, the terephthalic acid content of the diacid units is 26-34 mole percent; more preferably, the terephthalic acid content of the diacid units is 29 to 31 mole percent.
The straight-chain aliphatic diacid with the carbon number of 9 or more is at least one selected from 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 straight-chain aliphatic diacid with the carbon number of 9 and above is selected from one of 1, 10-sebacic acid, 1, 12-dodecanedioic acid.
Preferably, the molar ratio of 1, 10-decanediamine to 1, 12-dodecanediamine in the diamine units is from 7:3 to 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 diamine and diacid serving as reaction raw materials into a pressure kettle according to a mixing ratio; adding benzoic acid, sodium hypophosphite serving as a catalyst and deionized water; the addition amount of the benzoic acid is 2-3% of the total weight of diamine and diacid, the weight of sodium hypophosphite is 0.05-0.15% of the weight of other materials except deionized water, and the weight of deionized water is 25-35% of the total weight of materials; vacuumizing, filling high-purity nitrogen as a shielding gas, heating to 195-205 ℃ in 1.5-2.5 hours under stirring, keeping the temperature of the reaction mixture under stirring for 0.5-1.5 hours, then heating the temperature of the reactant to 260-280 ℃ under stirring, continuing to carry out 1.5-2.5 hours under 3.1-3.3 MPa, keeping the pressure constant by removing formed water, gradually reducing the pressure to normal pressure, and discharging after the reaction is completed to obtain the polyamide resin.
The polyamide resin has the advantages of tensile strength of more than 50MPa, elongation at break of more than 190 percent and good high-temperature resistant solvent (after the 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 components, particularly for oil delivery pipes, which need to have chemical resistance at higher engine temperature, and also need to resist stretching and high-frequency vibration, so that higher tensile strength and elongation at break are needed.
The invention has the following beneficial effects
According to the invention, a specific amount of terephthalic acid repeating units are added into the long carbon chain nylon repeating units (the carbon number is more than or equal to 9), and the diamine structural units are compounded by 1, 10-decanediamine and 1, 12-dodecanediamine in a molar ratio of 9:1-5:5, so that the improvement of ethanol resistance can be realized 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 present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The sources of the raw materials used in the examples and comparative examples are as follows:
the polymerized monomer is commercially available: 1, 6-hexamethylenediamine, 1, 9-nonylenediamine, 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: analytically pure, purchased from Sigma-Aldrich company;
sodium hypophosphite: analytically pure, purchased from Sigma-Aldrich company;
polymerization methods of example and comparative polyamide resins: adding diamine and diacid serving as reaction raw materials into an autoclave according to the proportion in a table; adding benzoic acid, sodium hypophosphite serving as a catalyst and deionized water; the addition amount of the benzoic acid is 2-3% of the total amount of diamine and diacid, the weight of sodium hypophosphite is 0.10% of the weight of other materials except deionized water, and the weight of the deionized water is 30% of the total weight of materials; vacuum pumping, filling high-purity nitrogen as protective gas, heating to 200 ℃ in 2 hours under stirring, keeping the temperature of the reaction mixture under stirring for 1 hour, then heating the temperature of the reactant to 270 ℃ under stirring, continuing to carry out for 2 hours under 3.2 MPa, keeping the pressure constant by removing the formed water, gradually reducing the pressure to normal pressure, discharging after the reaction is completed, and obtaining the polyamide resin.
The testing method comprises the following steps:
(1) Relative viscosity test: with reference to GB12006.1-89, the relative viscosity η of a polyamide having a concentration of 0.25 g/dl is measured in 98% concentrated sulfuric acid at 25.+ -. 0.01 ℃C r 。
(2) Melting point test: reference is made to ASTM D3418-2003,Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry; the specific test method comprises the following steps: testing the melting point of the sample by using a Perkin Elmer Dimond DSC analyzer; a nitrogen atmosphere with a flow rate of 50mL/min; during testing, the temperature is firstly increased to 300 ℃ at 20 ℃/min, the temperature is kept at 300 ℃ for 2min, the thermal history of the resin is removed, then the resin is cooled to 50 ℃ at 20 ℃/min, the temperature is kept at 50 ℃ for 2min, then the temperature is increased to 300 ℃ at 20 ℃/min, and the endothermic peak temperature at the moment is set as T melting point;
(3) Tensile strength and elongation at break test: measurement of tensile properties of plastics with reference to GB/T1040.1-2018; the resin is molded into 1A type sample bars, and the test is carried out at a stretching speed of 10mm/min under the test condition of (23+/-2) DEGC/(50+/-5)% RH;
(4) High temperature ethanol resistance test: the resin was injection molded into 1A bars, placed in a mixed solvent of ethanol and water (mass ratio of ethanol to water 90/10), heated to 135 ℃, aged for 500 hours, and after taking out the bars, tensile strength and elongation at break were measured, and retention was calculated.
Table 1: examples Polyamide resin content of units (mol%) and test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| Terephthalic acid | 2 | 2 | 2 | 2 | 2 | 2.6 | 2.9 | 3.1 |
| 1, 9-azelaic acid | ||||||||
| 1, 10-decanedioic 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-decanediamine | 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, DEG C | 175 | 173 | 171 | 169 | 167 | 182 | 188 | 192 |
| Initial tensile strength, MPa | 52 | 53 | 53 | 51 | 51 | 54 | 55 | 57 |
| Elongation at initial break% | 215 | 223 | 230 | 236 | 243 | 218 | 212 | 207 |
| Retention of tensile strength after aging% | 80 | 81 | 83 | 85 | 80 | 84 | 86 | 85 |
| Initial elongation at break retention after aging% | 50 | 51 | 52 | 54 | 50 | 54 | 55 | 56 |
As can be seen from examples 1-5, 1, 10-decamethylene diamine is preferred: the molar ratio of the 1, 12-dodecadiamine is 7:3-6:4, and the ethanol resistance is better.
As is clear from examples 3/6 to 10, the terephthalic acid content in the diacid unit is 26 to 34mol%; more preferably, the terephthalic acid content of the diacid units is 29 to 31 mole percent.
Continuing with table 1:
| example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | Example 15 | |
| Terephthalic acid | 3.4 | 4 | 2.9 | 2.9 | 2.9 | 2.9 | 2.9 |
| 1, 9-azelaic acid | 7.1 | ||||||
| 1, 10-decanedioic 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-decanediamine | 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, DEG C | 199 | 218 | 186 | 184 | 182 | 180 | 192 |
| Initial tensile strength, MPa | 59 | 61 | 54 | 53 | 53 | 52 | 56 |
| Elongation at initial break% | 201 | 191 | 213 | 215 | 215 | 217 | 207 |
| Retention of tensile strength after aging% | 84 | 83 | 83 | 87 | 84 | 84 | 84 |
| Initial elongation at break retention after aging% | 54 | 52 | 53 | 56 | 55 | 54 | 54 |
As is clear from examples 7/11 to 15, the linear aliphatic diacids having 9 or more carbon atoms are preferably 1, 10-sebacic acid or 1, 12-dodecanedioic acid, and are more resistant to ethanol.
Table 2: comparative examples 1 to 5 Polyamide resins content of units (mol%) and test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Terephthalic acid | 2.9 | 2.9 | 2.9 | 1 | 5 |
| 1, 10-decanedioic acid | 7.1 | 7.1 | 7.1 | 9 | 5 |
| 1, 10-decanediamine | 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, DEG C | 195 | 182 | 192 | 173 | 226 |
| Initial tensile strength, MPa | 51 | 52 | 50 | 47 | 63 |
| Elongation at initial break% | 182 | 210 | 185 | 232 | 156 |
| Retention of tensile strength after aging% | 76 | 77 | 75 | 76 | 76 |
| Initial elongation at break retention after aging% | 45 | 47 | 46 | 47 | 48 |
As is clear from comparative examples 1 to 6, each unit was inferior in ethanol resistance when it was out of the range of the present invention. In particular, comparative example 6, although having good ethanol resistance, has a very low initial elongation at break, and is not suitable for the production of fuel pipes.
Table 3: comparative examples 6 to 10 Polyamide resins content of units (mol%) and test results
| Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | |
| Terephthalic acid | 10 | 4 | 4 | 4 | 4 |
| 1, 6-adipic acid | 6 | ||||
| 1, 10-decanedioic acid | 6 | 6 | 6 | ||
| 1, 6-hexanediamine | 7 | ||||
| 1, 9-nonanediamine | 7 | 7 | |||
| 1, 10-decanediamine | 7 | 7 | 3 | ||
| 1, 12-dodecadiamine | 3 | 3 | 3 | 3 | |
| Relative viscosity | 2.566 | 2.504 | 2.508 | 2.516 | 2.595 |
| Melting point, DEG C | 302 | 232 | 228 | 220 | 223 |
| Initial tensile strength, MPa | 75 | 60 | 59 | 60 | 61 |
| Elongation at initial break% | 8 | 147 | 135 | 175 | 172 |
| Retention of tensile strength after aging% | 82 | 77 | 75 | 78 | 78 |
| Initial elongation at break retention after aging% | 48 | 45 | 44 | 46 | 48 |
As is evident from comparative examples 7 to 10, other types of monomers are difficult to replace the technical scheme of the present invention.
Claims (9)
1. A polyamide resin comprising repeating units of:
diacid unit: terephthalic acid accounting for 20-40mol% of diacid unit mol% and linear aliphatic diacid with 9 or more carbon atoms accounting for 60-80mol% of diacid unit mol% are prepared;
diamine unit: 1, 10-decanediamine and 1, 12-dodecanediamine in a molar ratio of 7:3 to 6:4.
2. The polyamide resin according to claim 1, wherein the terephthalic acid content of the diacid unit is 26 to 34mol%.
3. The polyamide resin according to claim 2, wherein the terephthalic acid content of the diacid unit is 29 to 31mol%.
4. The polyamide resin according to claim 1, wherein the linear aliphatic diacid having 9 or more carbon atoms is one selected from the group consisting 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.
5. The polyamide resin according to claim 4, wherein the linear aliphatic diacid having 9 or more carbon atoms is one selected from the group consisting of 1, 10-sebacic acid and 1, 12-dodecanedioic acid.
6. The polyamide resin of claim 1 wherein the polyamide resin has a relative viscosity in the range of 2.0 to 3.0.
7. The polyamide resin according to claim 1, wherein the polyamide resin has a melting point in the range of 170-200 ℃.
8. The method for polymerizing a polyamide resin according to any one of claims 1 to 7, comprising the steps of: adding diamine and diacid serving as reaction raw materials into a pressure kettle according to a proportion; adding benzoic acid, sodium hypophosphite serving as a catalyst and deionized water; the addition amount of the benzoic acid is 2-3% of the total weight of diamine and diacid, the weight of sodium hypophosphite is 0.05-0.15% of the weight of other materials except deionized water, and the weight of deionized water is 25-35% of the total weight of materials; vacuumizing, filling high-purity nitrogen as a shielding gas, heating to 195-205 ℃ in 1.5-2.5 hours under stirring, keeping the temperature of the reaction mixture under stirring for 0.5-1.5 hours, then heating the temperature of the reactant to 260-280 ℃ under stirring, continuing to carry out 1.5-2.5 hours under 3.1-3.3 MPa, keeping the pressure constant by removing formed water, gradually reducing the pressure to normal pressure, and discharging after the reaction is completed to obtain the polyamide resin.
9. Use of a polyamide resin according to any one of claims 1 to 7 for the preparation of vehicle fuel system components.
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 CN115490848A (en) | 2022-12-20 |
| CN115490848B true CN115490848B (en) | 2023-12-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017204A (en) * | 2014-05-20 | 2014-09-03 | 珠海万通化工有限公司 | Polyamide resin and polyamide composition formed by same |
| CN106046365A (en) * | 2016-07-15 | 2016-10-26 | 珠海万通特种工程塑料有限公司 | Semi-aromatic copolyamide resin and polyamide molding composition made of semi-aromatic copolyamide resin |
| CN110790920A (en) * | 2019-10-28 | 2020-02-14 | 金发科技股份有限公司 | Semi-aromatic polyamide and polyamide molding composition composed of same |
| CN111057233A (en) * | 2019-12-29 | 2020-04-24 | 无锡殷达尼龙有限公司 | Copolymerized semi-aromatic polyamide and preparation method thereof |
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| KR101437144B1 (en) * | 2011-12-13 | 2014-09-02 | 제일모직주식회사 | Polyamide resin, a method for preparing the same, and an article comprising the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017204A (en) * | 2014-05-20 | 2014-09-03 | 珠海万通化工有限公司 | Polyamide resin and polyamide composition formed by same |
| CN106046365A (en) * | 2016-07-15 | 2016-10-26 | 珠海万通特种工程塑料有限公司 | Semi-aromatic copolyamide resin and polyamide molding composition made of semi-aromatic copolyamide resin |
| CN110790920A (en) * | 2019-10-28 | 2020-02-14 | 金发科技股份有限公司 | Semi-aromatic polyamide and polyamide molding composition composed of same |
| CN111057233A (en) * | 2019-12-29 | 2020-04-24 | 无锡殷达尼龙有限公司 | Copolymerized semi-aromatic polyamide and preparation method thereof |
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