CN117186637B - Bio-based PA56 composite material and preparation method and application thereof - Google Patents
Bio-based PA56 composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117186637B CN117186637B CN202311288222.3A CN202311288222A CN117186637B CN 117186637 B CN117186637 B CN 117186637B CN 202311288222 A CN202311288222 A CN 202311288222A CN 117186637 B CN117186637 B CN 117186637B
- Authority
- CN
- China
- Prior art keywords
- bio
- preparation
- composite material
- attapulgite
- heating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229960000892 attapulgite Drugs 0.000 claims abstract description 60
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 60
- 239000011787 zinc oxide Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 29
- -1 polyol compound Chemical class 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000006641 stabilisation Effects 0.000 claims abstract 3
- 238000011105 stabilization Methods 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 108
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 60
- 238000010438 heat treatment Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 235000011037 adipic acid Nutrition 0.000 claims description 30
- 239000001361 adipic acid Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 23
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 22
- HYTJADYUOGDVRL-UHFFFAOYSA-N n-phenyl-n-(2-phenylpropan-2-yl)aniline Chemical compound C=1C=CC=CC=1C(C)(C)N(C=1C=CC=CC=1)C1=CC=CC=C1 HYTJADYUOGDVRL-UHFFFAOYSA-N 0.000 claims description 21
- 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 20
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 20
- 239000000376 reactant Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 2
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 19
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 33
- 239000000243 solution Substances 0.000 description 24
- 239000004677 Nylon Substances 0.000 description 23
- 229920001778 nylon Polymers 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 238000001125 extrusion Methods 0.000 description 17
- 238000005469 granulation Methods 0.000 description 17
- 230000003179 granulation Effects 0.000 description 17
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000012760 heat stabilizer Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920006118 nylon 56 Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyamides (AREA)
Abstract
The invention provides a bio-based PA56 composite material, and a preparation method and application thereof. The preparation method comprises the following steps: providing an aminated attapulgite modified bio-based PA56; uniformly mixing the bio-based PA56 and a heat stabilization aid to form a blend; extruding and granulating the blend to obtain the bio-based PA56 composite material, wherein the thermal stabilizing additive comprises zinc oxide, a polyol compound and an amine antioxidant. The bio-based PA56 composite material prepared by the method has high strength performance, and meanwhile, the thermal stability of the composite material is obviously improved, and good tensile strength is still maintained after thermal oxidative aging treatment.
Description
Technical Field
The invention relates to the field of bio-based nylon materials, in particular to a bio-based PA56 composite material, a preparation method and application thereof.
Background
The carcass cord in automobile tires is typically made of nylon, polyester, steel wire, or the like. Nylon as engineering plastic has relatively high mechanical performance, high impact performance, high heat resistance, high chemical resistance, easy forming and other features, and is one common material for curtain fabric.
Chinese patent CN 115161796A discloses a method for blending by adding wear-resistant and impact-resistant additives and silicon nitride to polyamide 6 chips, so as to improve the mechanical properties of modified polyamide yarns prepared from polyamide 6, thereby preparing a polyamide cord fabric with excellent mechanical properties. Chinese patent CN 116005447A discloses a process for dipping nylon 56 slice after melting, adding nano zeolite powder, mixing, spinning and weaving, wherein the dipping solution used in the said dipping is the dipping solution containing graphite powder and copper sulfate prepared by the invention.
However, although the mechanical properties of the existing bio-based PA56 cord fabric material can be improved to a certain extent by modification, the problem of performance degradation of the material in the long-term use process still exists. Therefore, providing a high strength and heat aging resistant bio-based nylon PA56 is one of the problems currently in the art that need to be addressed.
Disclosure of Invention
In order to solve all or part of the technical problems, the invention provides the following technical scheme:
one of the purposes of the invention is to provide a preparation method of a bio-based PA56 composite material, which comprises the following steps: providing an aminated attapulgite modified bio-based PA56; and uniformly mixing the bio-based PA56 and a heat stabilizing additive to form a blend, and extruding and granulating the blend to obtain the bio-based PA56 composite material, wherein the heat stabilizing additive comprises zinc oxide, a polyol compound and an amine antioxidant.
In some embodiments, the amine antioxidant comprises 4,4' -bis (phenylisopropyl) diphenylamine. The technical scheme has the beneficial effects that the 4,4' -di (phenyl isopropyl) diphenylamine can effectively eliminate free radicals in a nylon system, so that the prepared bio-based PA56 composite material has excellent heat aging resistance.
In some embodiments, the polyol compound has a structure of formula I,
the technical scheme has the beneficial effects that the polyol compound with the structure shown in the formula I has stronger acting force with nylon resin and good compatibility with the nylon resin, and the polyol with the structure shown in the formula I is preferentially thermally degraded and dehydrated with nylon under the high-temperature effect, and a large number of benzene ring structures contained in the polyol compound can form a compact carbon layer to effectively block oxygen and heat, so that the prepared bio-based PA56 composite material has excellent thermal ageing performance.
In some embodiments, the zinc oxide has a particle size of 20-100nm. When the particle size of the zinc oxide is within the range, the zinc oxide particles can be dispersed in the nylon matrix; if the content is below this range, zinc oxide particles are aggregated and are not easy to disperse; if the amount is above this range, the zinc oxide particles may lose the properties of the nylon matrix.
In some embodiments, the content of the heat stabilizing additive in the blend is 2-6wt% of the bio-based PA56. When the content of the heat stabilizing additive is within the range, the mechanical strength and heat aging performance of the nylon resin can be maintained; if it is less than this range, the nylon resin may have poor heat aging properties; if it is higher than this range, the mechanical strength of the nylon resin is low.
In some embodiments, the mass ratio of zinc oxide, polyol compound, and amine antioxidant in the blend is 1-3:1.
In a partially preferred embodiment, the blend comprises, in parts by weight, 100 parts bio-based PA56, 1-2 parts zinc oxide, 1-2 parts polyol compound, and 0.5-1 parts amine antioxidant.
In some embodiments, the preparation method specifically includes: providing a mixed reactant comprising aminated attapulgite, adipic acid, pentylene diamine, and a catalyst; heating the mixed reactant to 190-230 ℃ in a protective atmosphere and maintaining for 1-3 h; and then heating to 250-280 ℃, and carrying out vacuum reaction for 30-90 min to obtain the aminated attapulgite modified bio-based PA56.
In some preferred embodiments, the method of making comprises: heating the mixed reactant to 200-220 ℃ and maintaining for 1.5-2.5h, then heating to 260-270 ℃, and carrying out vacuumizing reaction for 45-60 min to obtain the aminated attapulgite modified bio-based PA56. The protective atmosphere is, for example, inert gas and/or nitrogen. In this suitable temperature range, the polymeric plastic can be lifted without causing degradation and ageing.
In some embodiments, the preparation method specifically includes: heating the solution in which the aminated attapulgite is dispersed to 50-80 ℃, then adding adipic acid into the solution, stirring for 2-4h, then adding pentanediamine, and adding the catalyst under a protective atmosphere to obtain the mixed reactant.
Further, the preparation method specifically comprises the following steps:
(1) Dispersing aminated attapulgite in water to form an aminated attapulgite water solution, placing the aminated attapulgite water solution in a reaction kettle, heating to 50-80 ℃, adding adipic acid into the reaction kettle, stirring for 2-4h, adding a pentylene diamine solution, introducing nitrogen to replace and discharge air in the reaction kettle, keeping stirring for 30min, and adding a catalyst;
(2) Heating the reaction kettle to 190-230 ℃, maintaining for 1-3h, then releasing the pressure to normal pressure, heating the reaction kettle to 250-280 ℃, and performing vacuum reaction for 30-90 min to obtain bio-based PA56;
(3) And uniformly mixing the bio-based PA56 and the heat stabilizing auxiliary agent to form a blend, and extruding and granulating the blend to obtain the bio-based PA56 composite material.
In some embodiments, the catalyst includes, but is not limited to, sodium hypophosphite.
In some embodiments, the catalyst is present in the mixed reactants in an amount of from 0.05 to 0.15% of the combined mass of adipic acid and pentamethylenediamine.
In some embodiments, the molar ratio of the pentylene diamine to the adipic acid in the mixed reactants is from 1.0 to 1.03:1.
In some embodiments, the aminated attapulgite is present in the mixed reactant in an amount of 0.1-2% of the combined mass of the pentamethylenediamine and adipic acid. The technical scheme has the beneficial effects that when the content of the aminated attapulgite is within the range, the aminated attapulgite can be dispersed in the in-situ polymerization process, the heterogeneous nucleation effect is achieved on the nylon resin, and the mechanical strength of the nylon resin is improved.
In some embodiments, the aminated attapulgite clay has a diameter of 20-50nm and a length of 300-900nm. The technical scheme has the beneficial effects that the length-diameter ratio in the range can be used as a nucleating agent and has an enhancement effect on nylon resin.
In a part of the preferred embodiment, the mixed reactants comprise, in mass percent, 50 to 100 parts of pentyenediamine, 70 to 150 parts of adipic acid, 50 to 150 parts of water, 0.1 to 5 parts of aminated attapulgite, and 0.1 to 2 parts of a catalyst.
In some embodiments, the method of preparing aminated attapulgite comprises: and (3) reacting the attapulgite with gamma-aminopropyl triethoxysilane to obtain the aminated attapulgite.
Further, the preparation method of the aminated attapulgite clay can comprise the following steps: placing attapulgite in toluene for ultrasonic dispersion for 30-60 min, then adding gamma-aminopropyl triethoxysilane in the stirring process, heating to 110-130 ℃ and refluxing in toluene for 24-30 h; and after the reaction is finished, cooling, filtering and washing are carried out to obtain the aminated attapulgite. Preferably, the mass ratio of the attapulgite to the gamma-aminopropyl triethoxysilane is, for example, 50:1-100:1.
The second purpose of the invention is to provide the bio-based PA56 composite material prepared by the preparation method in any one of the technical schemes.
The invention also aims to provide the application of the bio-based PA56 composite material in the technical scheme in preparing the cord fabric.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the invention, the amino active groups are introduced into the surface of the nano attapulgite, and the nano particles are connected to the surface of the nylon salt in the polymerization process, so that the attapulgite is well dispersed in the nylon resin, the heterogeneous nucleation effect is achieved on the nylon resin, the bonding acting force of the attapulgite and the nylon resin is promoted, and the high-strength performance of the nylon resin is realized.
(2) According to the invention, the composite heat stability additive is added in the melt blending process, and the heat stability of the PA56 composite material is effectively improved through the synergistic effect of the zinc oxide, the polyol compound and the amine antioxidant. Specifically, in-situ polymerization reaction is carried out on aminated attapulgite and nylon resin, on one hand, the attapulgite promotes nylon crystallization, on the other hand, magnesium and aluminum elements in the attapulgite can interact with nylon amide groups, and zinc elements in the composite zinc oxide have a coordination effect, so that the stability of the amide groups can be effectively improved, and the heat aging performance of the nylon resin is improved; in addition, hydroxyl groups in the polyol compound in the composite heat stabilizing additive can interact with amide groups to play an internal lubricating role, so that the spinning processability of the PA56 is improved; the amine antioxidant can effectively remove free radicals in the thermo-oxidative aging process, protect the amide group from being broken, and further improve the thermal stability of the PA56.
(3) The invention further discloses a polyol compound which comprises a structure shown in the formula I, wherein a large number of benzene rings and hydroxyl structures contained in the structure can be aged before PA56 in the thermal oxidation aging process to form a compact carbon layer, so that the attack of oxygen and free radicals is effectively blocked.
(4) After the bio-based PA56 composite material provided by the invention is subjected to thermal oxidative aging treatment for 1000 hours at 130 ℃, the tensile strength retention rate is maintained to be more than 83%, and the bio-based PA56 composite material has good heat resistance.
Detailed Description
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention. Specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
Unless otherwise indicated, the raw materials and reagents used in the present invention may be obtained from commercial sources. Wherein, the part is specifically from: pentanediamine (Kaiser), sodium hypophosphite (Ala Ding Shiji), zinc oxide (Ala-order reagent), a polyol compound represented by formula I (Tokyo Co., ltd., hereinafter abbreviated as 101S), 4' -bis (phenylisopropyl) diphenylamine (commercially available), and attapulgite (commercially available).
The preparation method of the aminated attapulgite in the following embodiment of the invention comprises the following steps: 50g of attapulgite is placed in 1000mL of toluene for ultrasonic dispersion treatment for 30min, then 2g of gamma-aminopropyl triethoxysilane is slowly added under the action of mechanical stirring, and the temperature is raised until the toluene is refluxed for reaction for 24h. And after the reaction is finished, cooling, filtering and washing with ethanol to obtain the aminated attapulgite.
Example 1
1.25g of aminated attapulgite is dispersed in 50g of water by ultrasonic, then the mixture is added into a reaction kettle to be heated to 80 ℃, 70g of adipic acid and 50g of water are added into the reaction kettle to be stirred for 2 hours, then 50g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.1g of sodium hypophosphite catalyst is added; heating the reaction kettle to 200 ℃, keeping for 1.5 hours, then gradually releasing the pressure to normal pressure, heating the reaction kettle to 275 ℃, and carrying out vacuum reaction for 60 minutes to obtain bio-based PA56;
1000g of bio-based PA56, 10g of zinc oxide, 10g of 101S and 5g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
Example 2
4g of aminated attapulgite is ultrasonically dispersed in 60g of water, then the mixture is added into a reaction kettle to be heated to 80 ℃, then 142g of adipic acid and 70g of water are added into the reaction kettle to be stirred for 3 hours, then 100g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 210 ℃, maintaining for 2 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 275 ℃, and vacuumizing for 90 minutes to obtain bio-based PA56;
1000g of bio-based PA56, 20g of zinc oxide, 15g of 101S and 8g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
Example 3
1.5g of aminated attapulgite is dispersed in 60g of water by ultrasonic, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56, 30g of zinc oxide, 15g of 101S and 10g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
Example 4
1.5g of aminated attapulgite is dispersed in 60g of water by ultrasonic, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56, 8g of zinc oxide, 8g of 101S and 4g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder, so that the bio-based PA56 composite material is obtained.
Example 5
1.5g of aminated attapulgite is dispersed in 60g of water by ultrasonic, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56, 24g of zinc oxide, 24g of 101S and 12g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder, so that the bio-based PA56 composite material is obtained.
Comparative example 1
Adding 70g of adipic acid and 50g of water into a reaction kettle, stirring for 2 hours, then adding 50g of pentylene diamine solution, introducing nitrogen to replace and discharge air in the kettle, keeping stirring for 30 minutes, and adding 0.1g of sodium hypophosphite catalyst; heating the reaction kettle to 200 ℃, keeping for 1.5 hours, then gradually releasing the pressure to normal pressure, heating the reaction kettle to 275 ℃, and carrying out vacuum reaction for 60 minutes to obtain bio-based PA56;
1000g of bio-based PA56 and 5g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
Comparative example 2
Adding 70g of adipic acid and 50g of water into a reaction kettle, stirring for 2 hours, then adding 50g of pentylene diamine solution, introducing nitrogen to replace and discharge air in the kettle, keeping stirring for 30 minutes, and then adding 0.1g of sodium hypophosphite catalyst; heating the reaction kettle to 200 ℃, keeping for 1.5 hours, then gradually releasing the pressure to normal pressure, heating the reaction kettle to 275 ℃, and carrying out vacuum reaction for 60 minutes to obtain bio-based PA56;
1000g of bio-based PA56 and 10g of zinc oxide are subjected to reactive extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
Comparative example 3
1.5g of aminated attapulgite is dispersed in 60g of water by ultrasonic, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace the air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain bio-based PA56;
1000g of bio-based PA56 and 15g of 101S are subjected to reactive extrusion and granulation in a double-screw extruder, so that the bio-based PA56 composite material is obtained.
Comparative example 4
1.5g of aminated attapulgite is dispersed in 60g of water by ultrasonic, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56 and 55g of 101S are subjected to reactive extrusion and granulation in a double-screw extruder, so that the bio-based PA56 composite material is obtained.
Comparative example 5
1.5g of aminated attapulgite is dispersed in 60g of water by ultrasonic, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56 and 55g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
Comparative example 6
1.5g of aminated attapulgite is dispersed in 60g of water by ultrasonic, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56 and 55g of zinc oxide are subjected to reactive extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
Comparative example 7
1.5g of aminated attapulgite is dispersed in 60g of water by ultrasonic, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56, 30g of zinc oxide and 25g of 101S are subjected to reactive extrusion and granulation in a double-screw extruder, so that the bio-based PA56 composite material is obtained.
Comparative example 8
1.5g of aminated attapulgite is dispersed in 60g of water by ultrasonic, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56, 30g of zinc oxide and 25g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
Comparative example 9
1.5g of aminated attapulgite is dispersed in 60g of water by ultrasonic, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56, 25g of 101S and 30g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
Comparative example 10
1.5g of non-aminated attapulgite is ultrasonically dispersed in 60g of water, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace air in the kettle to be discharged, and after the mixture is kept stirred for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56, 30g of zinc oxide, 15g of 101S and 10g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
Comparative example 11
1.5g of attapulgite is ultrasonically dispersed in 60g of water, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace and discharge air in the kettle, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56, 6g of zinc oxide, 6g of 101S and 6g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
Comparative example 12
1.5g of attapulgite is ultrasonically dispersed in 60g of water, then the mixture is added into a reaction kettle to be heated to 80 ℃, 112g of adipic acid and 60g of water are added into the reaction kettle to be stirred for 3 hours, then 80g of pentanediamine solution is added, nitrogen is introduced to replace and discharge air in the kettle, and after stirring is maintained for 30 minutes, 0.2g of sodium hypophosphite catalyst is added; heating the reaction kettle to 220 ℃, maintaining for 3 hours, gradually releasing the pressure to normal pressure, heating the reaction kettle to 270 ℃, and vacuumizing for reaction for 70 minutes to obtain the bio-based PA56;
1000g of bio-based PA56, 30g of zinc oxide, 30g of 101S and 10g of 4,4' -di (phenylisopropyl) diphenylamine are subjected to reaction extrusion and granulation in a double-screw extruder to obtain the bio-based PA56 composite material.
The bio-based PA56 composite materials prepared in examples 1 to 5 and comparative examples 1 to 12 were tested for relative viscosity, physical and mechanical properties, crystallization properties and aging resistance, and the test results are shown in table 1, and the test methods are as follows:
(1) Sulfuric acid relative viscosity test:
the relative viscosity of the biobased PA56 composite was measured at a concentration of 0.1g/ml in concentrated sulfuric acid at 25 ℃.
(2) Physical and mechanical property test
The prepared biobased PA56 composite was injection molded into dumbbell shaped bars, which were tested for tensile strength according to ISO standards.
(3) Crystallization Performance test
The bio-based PA56 composite material is tested by a Differential Scanning Calorimeter (DSC), and after being heated from 50 ℃ to 270 ℃ for 5min at a heating rate of 5 ℃/min under nitrogen atmosphere, the temperature is reduced to 50 ℃ at a cooling rate of 5 ℃/min, and the temperature corresponding to the maximum peak on the cooling curve is the crystallization temperature (Tc).
(4) Thermal aging resistance test
The prepared bio-based PA56 composite material is injection molded into dumbbell-shaped bars, and the tensile strength retention rate of the material is tested after thermal oxidative aging treatment is carried out for 1000 hours at 130 ℃.
TABLE 1 Properties of biobased PA56 composite materials of examples 1-5, comparative examples 1-12
As can be seen from the combination of reference examples 1 to 3 and comparative examples 1 to 3, the bio-based PA56 composite materials of examples 1 to 3 have a tensile strength superior to that of comparative examples 1 to 3, and a tensile strength retention rate after a thermal oxidative aging treatment at 130 ℃ for 1000 hours is high because the introduction of the composite thermal stabilizing additives of examples 1 to 3 improves heat resistance of the composite materials, while the aminated attapulgite clay is introduced during in-situ polymerization, which can promote crystallization properties of the bio-based PA56 composite materials.
Comparative examples 1 and 2 it is known that comparative examples 1 and 2 do not add aminated attapulgite and that the use of zinc oxide alone or 4,4' -di (phenylisopropyl) diphenylamine as a heat stabilizer results in a composite material prepared in comparative examples 1 and 2 having lower initial strength and lower retention of strength after aging than in example 1.
Comparative example 3 and comparative example 3 it is seen that comparative example 3 adds aminated attapulgite but uses a single polyol as a heat stabilizer, resulting in a composite with improved initial strength but lower strength retention after aging than example 3.
Comparative examples 3 and comparative examples 4-6 were found to use either zinc oxide, 101S, or 4,4' -bis (phenylisopropyl) diphenylamine alone as a heat stabilizer, resulting in composites obtained in comparative examples 4-6 having lower initial strength and lower retention of strength after aging than example 3.
Comparative examples 3 and comparative examples 7 to 9, it was found that the use of two of zinc oxide, 101S and 4,4' -di (phenylisopropyl) diphenylamine as heat stabilizers resulted in the composites of comparative examples 4 to 6 having lower initial strength and lower retention of strength after aging than example 3.
Comparative example 3 and comparative example 10, polymerization using non-aminated attapulgite clay and compounding of zinc oxide, 101S and 4,4' -di (phenylisopropyl) diphenylamine as heat stabilizers resulted in PA56 having lower viscosity and crystallization temperature than example 3, and lower initial strength and retention of strength after aging than example 3.
Comparative example 3 and comparative examples 11 and 12 are known to use zinc oxide, 101S and 4,4' -bis (phenylisopropyl) diphenylamine as heat stabilizers at an addition ratio of less than 2% or more than 6% to PA56 resin, resulting in lower initial strength and lower retention of strength after aging for the composite materials obtained in comparative examples 11 and 12 than in example 3.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (15)
1. A method for preparing a bio-based PA56 composite material, comprising:
providing an aminated attapulgite modified bio-based PA56;
uniformly mixing the bio-based PA56 and a heat stabilization aid to form a blend, wherein the content of the heat stabilization aid in the blend is 2-6wt% of the bio-based PA56;
extruding and granulating the blend to obtain a bio-based PA56 composite material, wherein the heat stabilizing additive comprises zinc oxide, a polyol compound and an amine antioxidant in a mass ratio of 1-3:1-3:1;
wherein the amine antioxidant comprises 4,4' -bis (phenylisopropyl) diphenylamine;
the polyol compound has a structure shown in a formula I,
。
2. the method of manufacturing according to claim 1, characterized in that: the particle size of the zinc oxide is 20-100nm.
3. The method of manufacturing according to claim 1, characterized in that: the blend comprises, by weight, 100 parts of bio-based PA56, 1-2 parts of zinc oxide, 1-2 parts of a polyol compound and 0.5-1 part of an amine antioxidant.
4. The preparation method according to claim 1, characterized in that it comprises in particular: providing a mixed reactant comprising aminated attapulgite, adipic acid, pentylene diamine, and a catalyst; heating the mixed reactant to 190-230 ℃ in a protective atmosphere and maintaining for 1-3 h; and then heating to 250-280 ℃, and carrying out vacuum reaction for 30-90 min to obtain the aminated attapulgite modified bio-based PA56.
5. The preparation method according to claim 4, which comprises the following steps: and heating the solution in which the aminated attapulgite is dispersed to 50-80 ℃, adding adipic acid into the solution, stirring for 2-4h, adding pentanediamine, and adding the catalyst under a protective atmosphere to obtain the mixed reactant.
6. The method according to claim 4, comprising: heating the mixed reactant to 200-220 ℃ and maintaining for 1.5-2.5h, then heating to 260-270 ℃, and carrying out vacuumizing reaction for 45-60 min to obtain the aminated attapulgite modified bio-based PA56.
7. The preparation method according to any one of claims 4 to 6, characterized in that: the catalyst comprises sodium hypophosphite and/or sodium antimonate.
8. The preparation method according to any one of claims 4 to 6, characterized in that: the content of the catalyst in the mixed reactant is 0.05-0.15% of the total mass of the adipic acid and the pentanediamine.
9. The preparation method according to any one of claims 4 to 6, characterized in that: in the mixed reactant, the molar ratio of the pentanediamine to the adipic acid is 1.0-1.03:1.
10. The preparation method according to any one of claims 4 to 6, characterized in that: in the mixed reactant, the content of the aminated attapulgite is 0.1-2% of the total mass of the pentanediamine and the adipic acid.
11. The preparation method according to any one of claims 4 to 6, characterized in that: the diameter of the aminated attapulgite is 20-50nm, and the length is 300-900nm.
12. The preparation method according to any one of claims 4 to 6, characterized in that: the mixed reactant comprises, by mass, 50-100 parts of pentanediamine, 70-150 parts of adipic acid, 50-150 parts of water, 0.1-5 parts of aminated attapulgite and 0.1-2 parts of catalyst.
13. The method of manufacturing according to claim 1, comprising: mixing attapulgite and gamma-aminopropyl triethoxysilane according to the mass ratio of 50:1-100:1, and refluxing in toluene for 24-30 hours for reaction to obtain the aminated attapulgite.
14. The bio-based PA56 composite material prepared by the preparation method according to any one of claims 1 to 13.
15. Use of the biobased PA56 composite of claim 14 in the manufacture of a cord fabric.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311288222.3A CN117186637B (en) | 2023-10-07 | 2023-10-07 | Bio-based PA56 composite material and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311288222.3A CN117186637B (en) | 2023-10-07 | 2023-10-07 | Bio-based PA56 composite material and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN117186637A CN117186637A (en) | 2023-12-08 |
CN117186637B true CN117186637B (en) | 2024-04-02 |
Family
ID=88986963
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311288222.3A Active CN117186637B (en) | 2023-10-07 | 2023-10-07 | Bio-based PA56 composite material and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117186637B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0182470A3 (en) * | 1984-09-27 | 1987-04-01 | Uniroyal, Inc. | Liquid rubber composition |
CN106566235A (en) * | 2015-10-13 | 2017-04-19 | 上海杰事杰新材料(集团)股份有限公司 | High-temperature-resistant nylon/attapulgite composite material and preparation method thereof |
CN115772287A (en) * | 2022-11-16 | 2023-03-10 | 宁国市赛科思橡胶有限公司 | Low-pressure-change high-temperature-resistant hot oil nitrile rubber compound and preparation method thereof |
CN115960402A (en) * | 2022-12-27 | 2023-04-14 | 宁国市赛科思橡胶有限公司 | Hydrogenated butyronitrile mixed rubber resistant to long-time high temperature and preparation method thereof |
CN116003899A (en) * | 2023-02-16 | 2023-04-25 | 广东安拓普聚合物科技有限公司 | Composite material based on bio-based polyethylene and preparation method thereof |
-
2023
- 2023-10-07 CN CN202311288222.3A patent/CN117186637B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0182470A3 (en) * | 1984-09-27 | 1987-04-01 | Uniroyal, Inc. | Liquid rubber composition |
CN106566235A (en) * | 2015-10-13 | 2017-04-19 | 上海杰事杰新材料(集团)股份有限公司 | High-temperature-resistant nylon/attapulgite composite material and preparation method thereof |
CN115772287A (en) * | 2022-11-16 | 2023-03-10 | 宁国市赛科思橡胶有限公司 | Low-pressure-change high-temperature-resistant hot oil nitrile rubber compound and preparation method thereof |
CN115960402A (en) * | 2022-12-27 | 2023-04-14 | 宁国市赛科思橡胶有限公司 | Hydrogenated butyronitrile mixed rubber resistant to long-time high temperature and preparation method thereof |
CN116003899A (en) * | 2023-02-16 | 2023-04-25 | 广东安拓普聚合物科技有限公司 | Composite material based on bio-based polyethylene and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN117186637A (en) | 2023-12-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3955664B2 (en) | Heat resistant partially aromatic polyamide | |
RU2648910C2 (en) | Olefin-maleic anhydride copolymer compositions and uses thereof | |
EP2944674B1 (en) | Polyamide composition and molded article | |
US10611882B2 (en) | Stabilized polyamide | |
EP3024892B1 (en) | Polyamide composition | |
CN110698848B (en) | High-toughness spray-free polyamide 66/6 material and preparation method thereof | |
CN117186637B (en) | Bio-based PA56 composite material and preparation method and application thereof | |
KR100532735B1 (en) | A Surface Treated Magnesium Hydroxide, Method of Preparation Thereof And A Polymeric Composite Material With Improved Flame Resistance | |
US20170044351A1 (en) | Thermoplastic molding compounds | |
CN110669334B (en) | High-toughness spraying-free polyamide 66 material and preparation method thereof | |
KR100969498B1 (en) | Siloxane based amide modified nylons | |
CA2333404A1 (en) | Nucleation of polyamides in the presence of hypophosphite | |
CN110628211B (en) | Spraying-free polyamide 66/6 material and preparation method thereof | |
JP7194447B2 (en) | Thermoplastic resin composition and molded article obtained by molding the same | |
AU1345888A (en) | Blends of polyamides with graft compounds | |
JP3485717B2 (en) | Polyphthalamide resin compound | |
US4076696A (en) | Extrusion of polypyrrolidone | |
CN110684191B (en) | Spraying-free polyamide 66 material and preparation method thereof | |
CN110540748B (en) | Spraying-free polyamide 11 material and preparation method thereof | |
JP2700940B2 (en) | Polyamide resin composition | |
JPH08259809A (en) | Polyamide resin composition | |
JPH1060268A (en) | Polyamide resin composition | |
JP3368727B2 (en) | Polyamide monofilament | |
CN114410107A (en) | Multi-component copolymer body flame-retardant long-carbon-chain polyamide composition and preparation method thereof | |
CN115926319A (en) | Impact-resistant Krah pipe and processing technology thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |