CN117511197B - Hydrolysis-resistant extrusion-moldable polyamide material and preparation method and application thereof - Google Patents
Hydrolysis-resistant extrusion-moldable polyamide material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 81
- 239000004952 Polyamide Substances 0.000 title claims abstract description 77
- 229920002647 polyamide Polymers 0.000 title claims abstract description 77
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 56
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 56
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 40
- 229920001470 polyketone Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 21
- 239000012745 toughening agent Substances 0.000 claims abstract description 18
- 239000004970 Chain extender Substances 0.000 claims abstract description 16
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000004146 energy storage Methods 0.000 claims abstract description 7
- 239000000446 fuel Substances 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 9
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012768 molten material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 34
- 230000001590 oxidative effect Effects 0.000 abstract description 13
- 230000007774 longterm Effects 0.000 abstract description 11
- 238000012545 processing Methods 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000000956 alloy Substances 0.000 description 9
- 230000003301 hydrolyzing effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920006118 nylon 56 Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The invention provides a hydrolysis-resistant extrusion-formable polyamide material, a preparation method and application thereof, wherein the polyamide material comprises the following components in percentage by mass: 30-50% of polyamide resin, 33-48% of polyketone resin, 13-20% of toughening agent, 0.2-0.5% of chain extender, 0.6-1.0% of antioxidant and 0.4-0.8% of lubricant; the prepared polyamide material has the characteristics of excellent hydrolysis resistance and long-term thermal oxidative aging resistance, high impact strength and easiness in processing and forming, solves the technical problems of lower impact strength, poorer hydrolysis resistance and poorer thermal oxidative aging resistance of the existing polyamide material, can be used for preparing extrusion-formed polyamide pipes with heat resistance and hydrolysis resistance requirements, and is used for preparing cooling pipelines of fuel automobiles, new energy automobiles and energy storage industries, and belongs to the technical field of modified polyamide materials.
Description
Technical Field
The invention relates to the technical field of modified polyamide materials, in particular to a hydrolysis-resistant polyamide material capable of being extruded and molded, and a preparation method and application thereof.
Background
The polyamide has excellent mechanical property, wear resistance, high temperature resistance and chemical resistance, and excellent processing and molding characteristics, is a plastic resin with the largest yield and the widest application in the current general engineering plastics, but the amide group of the polyamide is easily influenced by environmental factors such as high temperature, ultraviolet rays, moisture and the like, so that the polymer chain of the polyamide is easy to generate reactions such as crosslinking, chain breakage, isomerization and the like, and the material performance is degraded.
Polyketone has the characteristics of excellent chemical resistance, hydrolysis resistance, abrasion resistance, high barrier property and the like, but has higher crystallinity, poorer extrusion molding processability, narrower processing temperature range, incapability of molding at lower temperature, easy yellowing and degradation at higher temperature, and even possible scorching and carbonization.
In order to combine the advantages of the two materials and expand the application range of the materials, the polyamide, the polyketone and the compatilizer are generally mixed according to a certain proportion to prepare an alloy material, and a plurality of patents at home at present have similar reports. Chinese patent No. 107189425A discloses a high wear-resistant polyamide/polyketone alloy, which comprises polyamide, polyketone, compatilizer, other assistants and petroleum needle coke, wherein the prepared alloy material has excellent wear resistance, good dimensional stability and low water absorption. The Chinese patent No. 115197559A discloses a polyphenyl ether/nylon 56/polyketone alloy material and a preparation method thereof, wherein the polyphenyl ether/nylon 56/polyketone alloy material comprises polyphenyl ether, nylon 56, polyketone, a compatilizer, a toughening agent, an antioxidant and a lubricant, so that the wear resistance, chemical resistance and processing fluidity of the polyphenyl ether material are effectively improved, and the prepared alloy material has good comprehensive performance. Both of the above schemes improve the wear resistance of the alloy material, but the impact strength of the alloy material is lower, and the hydrolysis resistance and the thermo-oxidative aging resistance of the alloy material are not improved, which limits the application range of the material. The above problems are to be solved.
Disclosure of Invention
The invention aims to provide a hydrolysis-resistant and extrusion-formable polyamide material, and a preparation method and application thereof, and aims to solve the technical problems of low impact strength, poor hydrolysis resistance and poor thermo-oxidative aging resistance of the existing polyamide material.
The invention provides a hydrolysis-resistant and extrusion-formable polyamide material, which comprises the following components in percentage by mass: 30-50% of polyamide resin, 33-48% of polyketone resin, 13-20% of toughening agent, 0.2-0.5% of chain extender, 0.6-1.0% of antioxidant and 0.4-0.8% of lubricant; wherein the antioxidant comprises hindered phenol antioxidants and phosphite antioxidants.
Preferably, the polyamide resin is an aliphatic polyamide, including any one or a combination of at least two of PA6, PA610, PA612, PA1012, and PA 12.
Preferably, the polyamide resin has a relative viscosity of 2.4 to 3.5 and a melt index of 4 to 10g/10min.
Preferably, the polyketone resin is a copolymer of carbon monoxide, ethylene and propylene, and the melt index thereof is 3-6 g/10min.
Preferably, the toughening agent comprises any one or a combination of at least two of ethylene-octene copolymer, maleic anhydride grafted ethylene-octene copolymer and glycidyl methacrylate grafted ethylene-octene copolymer.
Preferably, the chain extender is an ethylene-maleic anhydride copolymer.
Preferably, the hindered phenol antioxidant comprises any one or a combination of at least two of an antioxidant 1098, an antioxidant 1010 and an antioxidant XL-1, and the phosphite antioxidant comprises any one or a combination of two of an antioxidant 626 and an antioxidant 9228.
Preferably, the lubricant is any one or a combination of at least two of ethylene bis stearamide, pentaerythritol stearate and calcium stearate.
In a second aspect, the present invention provides a method for preparing a hydrolysis-resistant extrudable polyamide material according to any one of the preceding claims, comprising the steps of:
(1) Respectively weighing polyamide resin, polyketone resin, toughening agent, chain extender, antioxidant and lubricant according to mass percentage, and adding the materials into a high-speed mixer to be mixed for 3-5 min at high speed to obtain a uniform mixture;
(2) Putting the mixture into a parallel double-screw extruder for melt mixing to obtain a molten material, wherein the temperatures of a heating zone 1# to 10# of the extruder and a machine head are sequentially set at 250 ℃, 270 ℃, 265 ℃, 260 ℃ and 270 ℃ during the melt mixing, and the rotating speed of a host machine is set at 400-600 r/min;
(3) And (3) carrying out water cooling, air drying and granulating on the molten material to obtain the hydrolysis-resistant and extrusion-moldable polyamide material.
The third aspect of the invention provides the use of the hydrolysis-resistant, extrudable polyamide material of any of the above, for producing extruded polyamide tubing having heat and hydrolysis resistance requirements, and for producing cooling lines for fuel automobiles, new energy automobiles, and energy storage industries.
The invention provides a hydrolysis-resistant extrusion-formable polyamide material and a preparation method and application thereof, and compared with the prior art, the hydrolysis-resistant extrusion-formable polyamide material has the following beneficial effects:
(1) According to the invention, the polyamide resin and the polyketone resin with high viscosity are added as the base materials, and the polyamide resin and the polyketone resin are compounded for use, so that the polyamide material is easier to extrude and mold; in addition, the polyketone resin has excellent hydrolysis resistance, and can be used together with a chain extender E60 to obviously improve the hydrolysis resistance of the polyamide material;
(2) The antioxidant XL-1 and the antioxidant 1098 are added to be compounded to be used as hindered phenol antioxidants, and the hindered phenol antioxidants are matched with phosphite antioxidant S-9228 to be used, so that the long-term thermal oxidative aging resistance of the polyamide material can be obviously improved; the impact strength, the hydrolysis resistance and the long-term thermal oxidative aging resistance of the polyamide material are obviously improved by adding the toughening agent to be matched with the compound base material and the antioxidant;
the invention adopts polyamide resin with specific melt index, polyketone resin, toughening agent, chain extender and compound antioxidant as raw materials, and under the synergistic effect of the raw materials, the polyamide material has excellent hydrolysis resistance and long-term thermal oxidative aging resistance, also has the characteristics of high impact strength and easy processing and forming, and has the tensile strength of 43.5-46.9 MPa and the notch impact strength of 65.6-82.1 KJ/m 2 The tensile strength of the ethylene glycol after 1000 hours of hydrolytic aging at 135 ℃ is 36.9-42.6 MPa, and the impact strength of the ethylene glycol after 1000 hours of high-temperature aging at 150 ℃ is 30.3-37.0 KJ/m 2 The method can be used for preparing the extruded polyamide pipe with heat resistance and hydrolysis resistance requirements, and can be used for preparing cooling pipelines of fuel automobiles, new energy automobiles and energy storage industries.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
The invention provides a hydrolysis-resistant and extrusion-formable polyamide material, which is prepared from conventional commercial products, wherein the specific specification and manufacturer are shown in table 1.
Table 1 specification and manufacturer of raw materials
In order to confirm the reliability of the effect of the present invention, the present invention will be described below with reference to examples 1 to 6, and the comparative examples 1 to 8 are compared, the mass percentages of the components of examples 1 to 6 are shown in Table 2, and the mass percentages of the components of comparative examples 1 to 8 are shown in Table 3.
TABLE 2 mass percent of each component of examples 1-6
(unit: wt%)
TABLE 3 mass percent of each component of comparative examples 1 to 8
(unit: wt%)
The invention also provides a preparation method for respectively preparing hydrolysis-resistant and extrusion-moldable polyamide materials according to the components in the examples 1-6 and the comparative examples 1-8 in the table 2 and the table 3, which comprises the following steps:
(1) Respectively weighing polyamide resin, polyketone resin, toughening agent, chain extender, antioxidant and lubricant according to the mass percentages in tables 2 and 3, and then adding the materials into a high-speed mixer to be mixed for 3-5 min at high speed to obtain a uniform mixture;
(2) Putting the mixture into a parallel double-screw extruder for melt mixing to obtain a molten material, wherein the temperatures of a heating zone 1# to 10# of the extruder and a machine head are sequentially set at 250 ℃, 270 ℃, 265 ℃, 260 ℃ and 270 ℃ during the melt mixing, and the rotating speed of a host machine is set at 400-600 r/min;
(3) The molten material was water-cooled, air-dried and pelletized to obtain hydrolysis-resistant extrusion-moldable polyamide materials prepared according to the mass percentages of the components of examples 1 to 6 and comparative examples 1 to 8 in tables 2 and 3, respectively.
The hydrolysis-resistant extrudable polyamide materials prepared in examples 1 to 6 and comparative examples 1 to 8 were subjected to performance tests for mechanical properties including tensile strength, notched impact strength, hydrolysis-resistant tensile strength at 135℃and thermal oxidative aging impact strength at 150℃and processing and setting easiness, as follows:
(1) Mechanical properties: the hydrolysis-resistant extrudable polyamide materials prepared in examples 1 to 6 and comparative examples 1 to 8 were dried, and then the dried polyamide materials were injection molded into standard bars according to the ISO standard, and the standard bars were subjected to mechanical property test for tensile strength and notched impact strength, and tensile strength after ethylene glycol hydrolysis aging at 135 ℃ for 1000 hours and impact strength after high temperature aging at 150 ℃ for 1000 hours.
(2) Difficulty degree of processing and shaping: the hydrolysis-resistant extrudable polyamide materials prepared in examples 1 to 6 and comparative examples 1 to 8 were dried, and then the dried polyamide materials were extruded into polyamide pipes having a size of phi 6mm 1mm by a polyamide pipe extruder, and the extrusion and setting difficulties were observed.
The results of the performance test of the hydrolysis-resistant extrudable polyamide materials prepared in examples 1 to 6 and comparative examples 1 to 8 are shown in tables 4 and 5, respectively.
Table 4 results of Performance test of hydrolysis-resistant extrudable Polyamide materials of examples 1-6
Table 5 results of Performance test of hydrolysis-resistant extrudable Polyamide materials of comparative examples 1 to 8
As can be seen from tables 4 and 5:
comparative examples 1 to 6, hydrolysis-resistant, extrusion-moldable polyamide materials of examples 1 to 6 had tensile strengths of 43.5 to 46.9MPa and notched impact strengths of 65.6 to 82.1KJ/m 2 The appearance is good after the ethylene glycol is hydrolyzed and aged for 1000 hours at 135 ℃, the tensile strength after the hydrolysis and aging is 36.9-42.6 MPa, the appearance is good after the high-temperature aging is carried out for 1000 hours at 150 ℃, and the appearance is good after the high-temperature agingImpact strength of 30.3-37.0 KJ/m 2 The polyamide materials prepared in examples 1 to 6 of the present invention have excellent hydrolysis resistance and long-term thermal oxidative aging resistance, and also have the characteristics of high impact strength and easy processing and molding.
Comparing examples 1 to 6 with comparative example 1, when the polyketone resin is not added, the polyamide material prepared in comparative example 1 is subjected to hydrolytic aging, the surface of the material is cracked, the material is in a chalking state, failure decomposition of the material is already generated, and the tensile strength after hydrolytic aging cannot be measured, so that the polyketone resin can be used as a base material to remarkably improve the hydrolysis resistance of the polyamide material.
In comparative examples 1 to 6 and comparative example 2, when the polyamide resin was not added, the polyamide material obtained in comparative example 2 was difficult to process and shape, and it was found that the polyamide resin was used as a base material in combination with the polyketone resin, and the polyamide material was easier to extrusion-mold.
Comparative examples 1 to 6 and comparative examples 3 and 8, the notched impact strength, the tensile strength after hydrolytic aging and the impact strength after high temperature aging of the polyamide material prepared in comparative example 3 are significantly lower than those of examples 1 to 6 when the amount of the toughening agent is low; when the dosage of the toughening agent is higher, the notch impact strength, the tensile strength after hydrolytic aging and the impact strength after high-temperature aging of the polyamide material prepared in the comparative example 8 are obviously improved, but the tensile strength is obviously lower than that of examples 1-6, and the processing and shaping are difficult; from this, it is known that the addition of the toughening agent can significantly improve the impact strength, hydrolysis resistance and long-term thermal oxidative aging resistance of the polyamide material, but the addition amount thereof is suitable, and the addition amount thereof is most suitable, wherein the addition amount thereof accounts for 13 to 20 mass percent of the total amount.
Comparing examples 1 to 6 with comparative examples 4 to 6, when the copper salt antioxidant is selected without adding the hindered phenol antioxidant, the polyamide material prepared in comparative example 4 has cracking and powdering phenomena on the surface after high-temperature aging, the material is failed to decompose, and the impact strength after high-temperature aging cannot be measured, thereby indicating that the copper salt antioxidant does not have the effect of improving the ageing resistance in the polyamide material; when the antioxidant XL-1 or the antioxidant 1098 is singly used as a hindered phenol antioxidant, the impact strength of the polyamide material prepared in the comparative examples 5-6 after high-temperature aging is obviously lower than that of the examples 1-6, so that the long-term thermal oxidative aging resistance of the polyamide material can be obviously improved by adding the hindered phenol antioxidant, and the antioxidant XL-1 and the antioxidant 1098 are compounded to be used as the hindered phenol antioxidant, and when the hindered phenol antioxidant is matched with the phosphite antioxidant S-9228 to be used, the long-term thermal oxidative aging resistance of the polyamide material is more excellent.
Comparing examples 1 to 6 with comparative example 7, when the chain extender is not added, the tensile strength of the polyamide material obtained in comparative example 7 after hydrolytic aging is significantly lower than that of examples 1 to 6, and it is understood that the addition of the chain extender can significantly improve the hydrolysis resistance of the polyamide material.
The invention also provides an application of the hydrolysis-resistant extrusion-molded polyamide material prepared according to the components in percentage by mass of the embodiments 1-6 in the table 2, which is used for preparing extrusion-molded polyamide pipes with heat resistance and hydrolysis resistance requirements, and is used for preparing cooling pipelines of fuel automobiles, new energy automobiles and energy storage industries.
Compared with the prior art, (1) the invention adds the high-viscosity polyamide resin and the polyketone resin as base materials, and the polyamide resin and the polyketone resin are compounded for use, so that the polyamide material is easier to extrude and form; in addition, the polyketone resin has excellent hydrolysis resistance, and can be used together with a chain extender E60 to obviously improve the hydrolysis resistance of the polyamide material; (2) The antioxidant XL-1 and the antioxidant 1098 are added to be compounded to be used as hindered phenol antioxidants, and the hindered phenol antioxidants are matched with phosphite antioxidant S-9228 to be used, so that the long-term thermal oxidative aging resistance of the polyamide material can be obviously improved; the impact strength, the hydrolysis resistance and the long-term thermal oxidative aging resistance of the polyamide material are obviously improved by adding the toughening agent to be matched with the compound base material and the antioxidant; the invention adopts polyamide resin, polyketone resin, toughening agent, chain extender and compound antioxidant with specific melt index as raw materials, and the materials are cooperated with each otherUnder the same action, the polyamide material has excellent hydrolysis resistance and long-term thermal oxidative aging resistance, also has the characteristics of high impact strength and easy processing and forming, and has the tensile strength of 43.5-46.9 MPa and the notch impact strength of 65.6-82.1 KJ/m 2 The tensile strength of the ethylene glycol after 1000 hours of hydrolytic aging at 135 ℃ is 36.9-42.6 MPa, and the impact strength of the ethylene glycol after 1000 hours of high-temperature aging at 150 ℃ is 30.3-37.0 KJ/m 2 The method can be used for preparing the extruded polyamide pipe with heat resistance and hydrolysis resistance requirements, and can be used for preparing cooling pipelines of fuel automobiles, new energy automobiles and energy storage industries.
It should be noted that:
(1) In the above examples 1 to 6 and comparative examples 1 to 8, the polyamide resin PA6 BE3335-T, PA 612I 2-40 was used as the polyamide resin, and in actual production, the polyamide resin may BE aliphatic polyamide, and may BE any one or a combination of at least two of PA6, PA610, PA612, PA1012, and PA12, and the relative viscosity thereof is 2.4 to 3.5, and the melt index thereof is 4 to 10g/10min, and may BE selected according to actual conditions.
(2) In examples 1 to 6 and comparative examples 1 to 8, POK 630A, POK R was used as the polyketone resin, and in actual production, the polyketone resin was a copolymer of carbon monoxide, ethylene and propylene, and the melt index thereof was 3 to 6g/10min, and may be selected according to actual conditions.
(3) In examples 1 to 6 and comparative examples 1 to 8, FB521A was a maleic anhydride grafted ethylene-octene copolymer, SOG-03 was a glycidyl methacrylate grafted ethylene-octene copolymer, which was used as a toughening agent, and the toughening agent was any one or a combination of at least two of an ethylene-octene copolymer, a maleic anhydride grafted ethylene-octene copolymer, and a glycidyl methacrylate grafted ethylene-octene copolymer, which had an effect of increasing flexibility, and the actual production was selected according to the actual conditions.
(4) In examples 1 to 6 and comparative examples 1 to 8, E60 was an ethylene-maleic anhydride copolymer, and the chain extender was used as the chain extender in actual production.
(5) In the above examples 1 to 6 and comparative examples 1 to 8, the antioxidants 1098, XL-1 and S-9228 were used as antioxidants, and in actual production, the antioxidants include hindered phenol antioxidants and phosphite antioxidants, the hindered phenol antioxidants may be any one or a combination of at least two of the antioxidants 1098, 1010 and XL-1, and the phosphite antioxidants may be any one or a combination of two of the antioxidants 626 and 9228, and have an antioxidant effect. In the above comparative examples 1 to 8, copper salt H318 was used as a copper salt antioxidant, in contrast to examples 1 to 6.
(6) In examples 1 to 6 and comparative examples 1 to 8, PETS was pentaerythritol stearate, and as a lubricant, the lubricant may be any one or a combination of at least two of ethylene bis stearamide, pentaerythritol stearate and calcium stearate, and the lubricant may have a lubricating effect, and may be selected according to practical conditions in practical production.
The above embodiments are only for illustrating the technical solution of the present application, and are not limiting; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present application, and are intended to be included in the scope of the present application.
Claims (5)
1. The hydrolysis-resistant extrudable polyamide material is characterized by comprising the following components in percentage by mass: 30-50% of polyamide resin, 33-48% of polyketone resin, 13-20% of toughening agent, 0.2-0.5% of chain extender, 0.6-1.0% of antioxidant and 0.4-0.8% of lubricant;
wherein the relative viscosity of the polyamide resin is 2.4-3.5, and the melt index is 4-10 g/10min;
the polyketone resin is a copolymer of carbon monoxide, ethylene and propylene, and the melt index of the polyketone resin is 3-6 g/10min;
the toughening agent comprises any one or a combination of at least two of ethylene-octene copolymer, maleic anhydride grafted ethylene-octene copolymer and glycidyl methacrylate grafted ethylene-octene copolymer;
the antioxidant comprises hindered phenol antioxidants and phosphite antioxidants; the hindered phenol antioxidant is compounded with an antioxidant XL-1 and an antioxidant 1098, the phosphite antioxidant is an antioxidant 9228, and the hindered phenol antioxidant and the phosphite antioxidant are compounded;
the chain extender is an ethylene-maleic anhydride copolymer;
the hydrolysis-resistant and extrusion-moldable polyamide material is used for preparing extrusion-molded polyamide pipes with heat resistance and hydrolysis resistance requirements, and is used for preparing cooling pipelines of fuel automobiles, new energy automobiles and energy storage industries.
2. The hydrolysis resistant extrudable polyamide material of claim 1, wherein the polyamide resin is an aliphatic polyamide comprising any one or a combination of at least two of PA6, PA610, PA612, PA1012, PA 12.
3. The hydrolysis resistant extrudable polyamide material of claim 1, wherein the lubricant is any one or a combination of at least two of ethylene bis stearamide, pentaerythritol stearate, calcium stearate.
4. A process for the preparation of a hydrolysis-resistant extrudable polyamide material as defined in any one of claims 1 to 3, comprising the steps of:
(1) Respectively weighing polyamide resin, polyketone resin, toughening agent, chain extender, antioxidant and lubricant according to mass percentage, and adding the materials into a high-speed mixer to be mixed for 3-5 min at high speed to obtain a uniform mixture;
(2) Putting the mixture into a parallel double-screw extruder for melt mixing to obtain a molten material, wherein the temperatures of a heating zone 1# to 10# of the extruder and a machine head are sequentially set at 250 ℃, 270 ℃, 265 ℃, 260 ℃ and 270 ℃ during the melt mixing, and the rotating speed of a host machine is set at 400-600 r/min;
(3) And (3) carrying out water cooling, air drying and granulating on the molten material to obtain the hydrolysis-resistant and extrusion-moldable polyamide material.
5. Use of a hydrolysis-resistant, extrudable polyamide material according to any of claims 1 to 3 for producing extruded polyamide tubing with heat and hydrolysis resistance requirements, and for producing cooling lines for fuel automobiles, new energy automobiles and energy storage industry.
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