CN118063957B - Flexible hydrolysis-resistant extrusion polyamide material, preparation method thereof and nylon tube - Google Patents
Flexible hydrolysis-resistant extrusion polyamide material, preparation method thereof and nylon tube Download PDFInfo
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- CN118063957B CN118063957B CN202410461627.0A CN202410461627A CN118063957B CN 118063957 B CN118063957 B CN 118063957B CN 202410461627 A CN202410461627 A CN 202410461627A CN 118063957 B CN118063957 B CN 118063957B
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000004952 Polyamide Substances 0.000 title claims abstract description 51
- 229920002647 polyamide Polymers 0.000 title claims abstract description 51
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 48
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 48
- 238000001125 extrusion Methods 0.000 title claims abstract description 28
- 239000004677 Nylon Substances 0.000 title claims abstract description 12
- 229920001778 nylon Polymers 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 80
- 239000012745 toughening agent Substances 0.000 claims abstract description 42
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 37
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000000314 lubricant Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 23
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical group CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 17
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical group CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- -1 styrene-ethylene-butylene-styrene Chemical class 0.000 claims description 11
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 9
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 4
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims description 4
- 229920006132 styrene block copolymer Polymers 0.000 claims description 4
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 claims description 3
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 3
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 3
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 3
- 229920001955 polyphenylene ether Polymers 0.000 claims description 2
- KFROBPVFLIZCHZ-UHFFFAOYSA-N bis(6-methylheptyl) benzene-1,4-dicarboxylate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC(C)C)C=C1 KFROBPVFLIZCHZ-UHFFFAOYSA-N 0.000 abstract description 8
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 abstract description 8
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 abstract description 8
- OHPZPBNDOVQJMH-UHFFFAOYSA-N n-ethyl-4-methylbenzenesulfonamide Chemical compound CCNS(=O)(=O)C1=CC=C(C)C=C1 OHPZPBNDOVQJMH-UHFFFAOYSA-N 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 5
- 102100035474 DNA polymerase kappa Human genes 0.000 description 14
- 101710108091 DNA polymerase kappa Proteins 0.000 description 14
- 239000004721 Polyphenylene oxide Substances 0.000 description 10
- 229920006380 polyphenylene oxide Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920006152 PA1010 Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- C08L77/02—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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a flexible hydrolysis-resistant extrusion polyamide material, a preparation method thereof and a nylon tube, which comprises the following raw materials in percentage by mass: 20-52% of polyamide resin, 20-50% of polyphenyl ether resin, 3-7% of compatilizer, 8-14% of toughening agent, 10-14% of composite plasticizer, 0.3-0.6% of antioxidant and 0.4-0.7% of lubricant; the composite plasticizer comprises a first plasticizer and a second plasticizer; the first plasticizer is selected from N-butyl benzene sulfonamide and/or N-ethyl p-toluene sulfonamide; the second plasticizer is selected from one or more of dioctyl terephthalate, diisooctyl terephthalate and dinonyl phthalate. The polyamide resin is modified by adopting the specific type of composite plasticizer and jointly acting with the polyphenyl ether resin, so that the polyamide material has good flexibility, high impact strength and strong hydrolysis resistance, and also has excellent 120 ℃ hydrolysis resistant tensile strength and salt-resistant impact strength.
Description
Technical Field
The invention belongs to the technical field of modified plastics, and particularly relates to a flexible hydrolysis-resistant extrusion polyamide material, a preparation method thereof and a nylon tube.
Background
The polyamide is the basic resin with the maximum yield, the maximum variety, the maximum application and the excellent comprehensive performance in five general engineering plastics, but the nylon macromolecular chain has larger water absorption due to the existence of amino groups, so that the polyamide is limited to be used in some special environments, in recent years, companies at home and abroad develop some hydrolysis resistance agents successively, the hydrolysis resistance of the polyamide material can be obviously improved, and the mechanical performance of the polyamide material is reduced to a certain extent; such as: tensile strength, impact properties, etc. of the material.
Disclosure of Invention
In view of the above, the invention aims to provide a flexible hydrolysis-resistant extrusion polyamide material, a preparation method thereof and a nylon pipe, wherein the polyamide material has the comprehensive properties of good flexibility, high impact strength, strong hydrolysis resistance and the like.
The invention provides a flexible hydrolysis-resistant extrusion polyamide material, which comprises the following raw materials in percentage by mass:
20-52% of polyamide resin, 20-50% of polyphenyl ether resin, 3-7% of compatilizer, 8-14% of toughening agent, 10-14% of composite plasticizer, 0.3-0.6% of antioxidant and 0.4-0.7% of lubricant;
The composite plasticizer includes a first plasticizer and a second plasticizer; the first plasticizer is selected from N-butyl benzene sulfonamide and/or N-ethyl p-toluene sulfonamide; the second plasticizer is selected from one or more of dioctyl terephthalate, diisooctyl terephthalate and dinonyl phthalate.
Preferably, the mass ratio of the first plasticizer to the second plasticizer is 2:1-1:4.
Preferably, the viscosity of the polyphenyl ether resin is 0.35-0.45 dL/g;
The compatilizer is selected from maleic anhydride grafted polyphenylene sulfide, and the grafting rate is 0.2-1.2wt%.
Preferably, the toughening agent is selected from one or more of ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, maleic anhydride grafted ethylene octene copolymer, and maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer.
Preferably, the polyamide resin is selected from one or more of PA6, PA56, PA510, PA610, PA612, PA1010, PA1012, PA1212, PA11, and PA 12.
Preferably, the antioxidant comprises one or more of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1 h,3h,5 h) -trione, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
Preferably, the lubricant is selected from one or more of oxidized polyethylene wax, montan acid wax and pentaerythritol stearate.
The invention provides a preparation method of the flexible hydrolysis-resistant extrusion polyamide material, which comprises the following steps:
mixing polyamide resin, polyphenyl ether resin, compatilizer, toughening agent, antioxidant and lubricant to obtain a mixture;
mixing the mixture with a composite plasticizer, carrying out melt mixing, extruding, cooling, drying and granulating to obtain a flexible hydrolysis-resistant extruded polyamide material;
The composite plasticizer includes a first plasticizer and a second plasticizer; the first plasticizer is selected from N-butyl benzene sulfonamide and/or N-ethyl p-toluene sulfonamide; the second plasticizer is selected from one or more of dioctyl terephthalate, diisooctyl terephthalate and dinonyl phthalate.
Preferably, the temperatures of the heating zones 1# to 10# and the head at the time of extrusion are 220 ℃, 260 ℃, 255 ℃, 250 ℃ and 250 ℃ in order.
The invention provides a nylon pipe which is prepared from the flexible hydrolysis-resistant extrusion polyamide material.
The invention provides a flexible hydrolysis-resistant extrusion polyamide material, which comprises the following raw materials in percentage by mass: 20-52% of polyamide resin, 20-50% of polyphenyl ether resin, 3-7% of compatilizer, 8-14% of toughening agent, 10-14% of composite plasticizer, 0.3-0.6% of antioxidant and 0.4-0.7% of lubricant; the composite plasticizer includes a first plasticizer and a second plasticizer; the first plasticizer is selected from N-butyl benzene sulfonamide and/or N-ethyl p-toluene sulfonamide; the second plasticizer is selected from one or more of dioctyl terephthalate, diisooctyl terephthalate and dinonyl phthalate. The polyamide resin is modified by adopting the specific type of composite plasticizer and the polyphenyl ether resin, so that the polyamide material has the comprehensive properties of good flexibility, high impact strength, strong hydrolysis resistance and the like. In addition, the modified polypropylene has excellent 120 ℃ hydrolysis resistance tensile strength and salt (ZnCl 2) post impact strength.
Detailed Description
The invention provides a flexible hydrolysis-resistant extrusion polyamide material, which comprises the following raw materials in percentage by mass:
20-52% of polyamide resin, 20-50% of polyphenyl ether resin, 3-7% of compatilizer, 8-14% of toughening agent, 10-14% of composite plasticizer, 0.3-0.6% of antioxidant and 0.4-0.7% of lubricant;
The composite plasticizer includes a first plasticizer and a second plasticizer; the first plasticizer is selected from N-butyl benzene sulfonamide and/or N-ethyl p-toluene sulfonamide;
The second plasticizer is selected from one or more of dioctyl terephthalate, diisooctyl terephthalate and dinonyl phthalate.
The flexible hydrolysis-resistant extrusion polyamide material provided by the invention adopts a specific kind of composite plasticizer, and the specific kind of composite plasticizer acts together with polyphenylene oxide resin to modify the polyamide resin, so that the polyamide material has the comprehensive properties of good flexibility, high impact strength, strong hydrolysis resistance and the like.
The preparation raw materials of the flexible hydrolysis-resistant extrusion polyamide material provided by the invention comprise 20-52% of polyamide resin; the specific amount of polyamide resin is 20%、21%、22%、23%、24%、25%、26%、27%、28%、29%、30%、31%、32%、33%、34%、35%、36%、37%、38%、39%、40%、41%、42%、43%、44%、45%、46%、47%、48%、49%、50%、51%、 or 52%. The polyamide resin is an aliphatic polyamide resin, preferably selected from one or more of PA6, PA56, PA510, PA610, PA612, PA1010, PA1012, PA1212, PA11 and PA 12. And the relative viscosity of the polyamide resin is 2.4-3.7 by using GB/T12006.1-2009 and 96% (mass fraction) concentrated sulfuric acid method test.
The preparation raw materials of the flexible hydrolysis-resistant extrusion polyamide material provided by the invention comprise 20-50% of polyphenyl ether resin; the specific amount of the polyphenyl ether resin is 20%、21%、22%、23%、24%、25%、26%、27%、28%、29%、30%、31%、32%、33%、34%、35%、36%、37%、38%、39%、40%、41%、42%、43%、44%、45%、46%、47%、48%、49% or 50 percent. And adopting an Ubbelohde viscometer method, wherein the intrinsic viscosity of the polyphenyl ether resin is 0.35-0.45 dL/g. In a specific embodiment, the polyphenylene oxide is PPO ZM035 or PPO ZM045.
The preparation raw materials of the flexible hydrolysis-resistant extrusion polyamide material provided by the invention comprise 3-7% of a compatilizer; the specific amount of the compatilizer is 3%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5% or 7.0%. The compatilizer is selected from maleic anhydride grafted polyphenylene sulfide, and the grafting rate is 0.2-1.2wt%.
The preparation raw materials of the flexible hydrolysis-resistant extrusion polyamide material provided by the invention comprise 8-14% of a toughening agent; the specific amount of the toughening agent is 8%, 8.5%, 9.0%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5% or 14%. The notch impact strength of the polyamide material is more excellent by controlling the content of the toughening agent. The toughening agent is selected from one or more of ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, maleic anhydride grafted ethylene octene copolymer and maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer; the toughening agent in the invention is preferably a compound, and is preferably at least two of an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, a maleic anhydride grafted ethylene octene copolymer and a maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer; more preferably, the toughening agent is a composite of toughening agent a560 and toughening agent W1G. In a specific embodiment, the toughening agent is a toughening agent W1G or a composite of a toughening agent A560 and a toughening agent W1G in a mass ratio of 7:7; or a 10:4 mass ratio of toughener A560 to toughener W1G; or a 4:4 mass ratio of toughener A560 to toughener W1G; or a 5:6 mass ratio of toughener A560 to toughener W1G.
The preparation raw materials of the flexible hydrolysis-resistant extrusion polyamide material provided by the invention comprise 10-14% of a composite plasticizer; the plasticizer is used in an amount of in particular 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, or 14%. The composite plasticizer includes a first plasticizer and a second plasticizer; the first plasticizer is selected from N-butyl benzene sulfonamide and/or N-ethyl p-toluene sulfonamide; the second plasticizer is selected from one or more of dioctyl terephthalate, diisooctyl terephthalate and dinonyl phthalate. The plasticizer of the type can be used in a compounding way, has better compatibility with polyphenyl ether resin, reduces the melt viscosity of polyamide materials, is resistant to precipitation, is more suitable for extrusion, and has good flexibility; and the impact strength and hydrolysis resistance of the polyamide material can be improved. The compound plasticizer is a compound of N-BBSA and DINP. In a specific embodiment, the composite plasticizer is a mixture of N-BBSA and DINP in a mass ratio of 6:7; or a mixture of N-BBSA and DINP in a mass ratio of 1:1; or a mixture of N-BBSA and DINP in a mass ratio of 7:4; or a mixture of N-BBSA and DINP in a mass ratio of 3:11; or a mixture of N-BBSA and DINP in a mass ratio of 5:7; or a mixture of N-BBSA and DINP in a mass ratio of 1:2.
The mass ratio between the first plasticizer and the second plasticizer in the present invention allows the polyamide material to have a suitable tensile modulus (flexibility), impact (toughness) and better compatibility (no bleeding). The mass ratio of the first plasticizer to the second plasticizer is preferably 2:1-1:4.
The preparation raw materials of the flexible hydrolysis-resistant extrusion polyamide material provided by the invention comprise 0.3-0.6% of antioxidant; the antioxidant is specifically used in an amount of 0.3%, 0.35%, 0.4%, 0.45%, 0.50%, 0.55%, or 0.60%. The antioxidant is selected from hindered phenol antioxidant and/or phosphite antioxidant, preferably one or more of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite. In a specific embodiment, the antioxidant is a compound oxidant, specifically a compound of an antioxidant 1098 and an antioxidant 9228. More specifically, the antioxidant is a mixture of an antioxidant 1098 and an antioxidant 9228 in a mass ratio of 1:1; or a mixture of antioxidant 1098 and antioxidant 9228 in a mass ratio of 2:1; or a mixture of antioxidant 1098 and antioxidant 9228 in a 3:1 mass ratio.
The preparation raw materials of the flexible hydrolysis-resistant extrusion polyamide material provided by the invention comprise 0.4-0.7% of lubricant; the lubricant is specifically used in an amount of 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, or 0.7%. The lubricant is selected from one or more of oxidized polyethylene wax, montan acid wax and pentaerythritol stearate.
In a specific embodiment of the invention, the flexible hydrolysis-resistant extruded polyamide material comprises the following raw materials in percentage by mass:
39% PA6, 31% PPO ZM035,4% maleic anhydride grafted polyphenylene sulfide, 12% toughener W1G,6% N-butylbenzenesulfonamide, 7% DINP,0.2% antioxidant 1098,0.2% antioxidant 9228, and 0.6% lubricant PETS;
Or comprises 35% of PA6, 35% of PPO ZM035,6% of maleic anhydride grafted polyphenylene sulfide, 7% of toughening agent A560,7% of toughening agent W1G,5% of plasticizer N-BBSA,5% of DINP,0.2% of antioxidant 1098,0.1% of antioxidant 9228 and 0.7% of lubricant PETS;
Or comprises 52% of PA612, 20% of PPO ZM035,3% of maleic anhydride grafted polyphenylene sulfide, 10% of toughening agent A560,4% of toughening agent W1G,7% of plasticizer N-BBSA,4% of DINP,0.3% of antioxidant 1098,0.3% of antioxidant 9228 and 0.4% of lubricant PETS;
Or 20% PA612, 50% PPO ZM045,5% maleic anhydride grafted polyphenylene sulfide, 11% toughener W1G,3% plasticizer N-BBSA,11% DINP,0.3% antioxidant 1098,0.3% antioxidant 9228,0.1% lubricant E wax, and 0.3% lubricant PETS;
Or comprises 20% of PA6, 20% of PA612, 35% of PPO ZM035,5% of maleic anhydride grafted polyphenylene sulfide, 4% of toughening agent A560,4% of toughening agent W1G,5% of plasticizer N-BBSA,7% of DINP,0.3% of antioxidant 1098,0.3% of antioxidant 9228,0.1% of lubricant E wax, and 0.3% of lubricant PETS;
or 29% PA612, 40% PPO ZM045,7% maleic anhydride grafted polyphenylene sulfide, 5% toughener a560,6% toughener W1G,4% plasticizer N-BBSA,8% DINP,0.2% antioxidant 1098,0.1% antioxidant 9228,0.5% lubricant E wax, and 0.2% lubricant PETS.
The invention also provides a preparation method of the flexible hydrolysis-resistant extrusion polyamide material, which comprises the following steps:
mixing polyamide resin, polyphenyl ether resin, compatilizer, toughening agent, antioxidant and lubricant to obtain a mixture;
mixing the mixture with a composite plasticizer, carrying out melt mixing, extruding, cooling, drying and granulating to obtain a flexible hydrolysis-resistant extruded polyamide material;
The composite plasticizer comprises a first plasticizer and a second plasticizer; the first plasticizer is selected from N-butyl benzene sulfonamide and/or N-ethyl p-toluene sulfonamide; the second plasticizer is selected from one or more of dioctyl terephthalate, diisooctyl terephthalate and dinonyl phthalate.
According to the invention, after the polyamide resin, the polyphenyl ether resin, the compatilizer, the toughening agent, the antioxidant and the lubricant are weighed according to the proportion, the polyamide resin, the polyphenyl ether resin, the compatilizer, the toughening agent and the lubricant are preferably added into a high-speed mixer to be mixed at a high speed for 3-5 minutes, so that a uniform mixture is obtained.
The method comprises the steps of adding the mixture through a main feed, and adding the composite plasticizer into a parallel double-screw extruder through a side feed pressure pump for smelting and mixing; the temperature of the heating area 1# to 10# and the temperature of the machine head are 220 ℃, 260 ℃ and 260 ℃ in sequence during extrusion 260 ℃, 255 ℃, 250 ℃ and 250 ℃.
The invention provides a nylon pipe which is prepared from the flexible hydrolysis-resistant extrusion polyamide material. The nylon pipe is applied to automobile and industrial pneumatic pipes, hydraulic oil pipes and multilayer composite pipes.
In order to further illustrate the present invention, a flexible hydrolysis-resistant extruded polyamide material, a method for preparing the same, and a nylon tube provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The starting materials used in the examples and comparative examples:
Polyamide resin: BE3335-F, jiangsu Hongsheng new material; PA 612I 2, new material of shandong xianglong;
Polyphenylene ether resin: ZM035 and ZM045, dalianzhong chemical industry;
and (3) a compatilizer: FB820, preferably Yi Rong (Shanghai) polymer;
and (3) a plasticizer: N-BBSA, zhejiang pranlame chemical; DINP, elkesen mobil chemical industry;
Toughening agent: a560, american dow chemical; W1G, xiamen Aisi chemical
An antioxidant: 1098. 9228, ji Linsong original technology;
And (3) a lubricant: e wax, crain, germany; PETS, italian method base
Examples and comparative examples
According to the formulas of tables 1 and 2, polyamide resin, polyphenyl ether resin, compatilizer, tackifier, antioxidant and lubricant are weighed according to the proportion, and then added into a high-speed mixer to be mixed for 4 minutes at a high speed, so as to obtain a uniform mixture;
And adding the mixture through a main feed, adding the plasticizer into a parallel double-screw extruder through a side feed pressure pump for melt mixing, and obtaining the flexible hydrolysis-resistant extrusion polyamide material after water cooling, air drying and granulating the extruded molten material.
Table 1 kinds and amounts of raw materials used in examples
TABLE 2 types and amounts of raw materials used in comparative examples
The hydrolysis-resistant extrusion polyamide materials prepared in the examples and the comparative examples are dried, and then injection molding standard sample bars according to ISO standards are carried out, and mechanical property tests are carried out; the tensile strength of the product after 1000 hours of hydrolysis and aging of ethylene glycol at 120 ℃ and the impact strength of the product after 1000 hours of aging of salt spray test are tested. And extruding the dried material into nylon pipes with the size of phi 8mm 1mm by a single screw extruder, and observing whether the extrusion process and the product quality are stable or not. The specific test results are shown in tables 3 and 4:
table 3 results of Performance test of Polyamide materials prepared in examples
Table 4 results of Performance test of Polyamide materials prepared in comparative examples
From the above examples, the present invention provides a flexible hydrolysis-resistant extruded polyamide material comprising, in mass fraction, the following raw materials: 20-52% of polyamide resin, 20-50% of polyphenyl ether resin, 3-7% of compatilizer, 8-14% of toughening agent, 10-14% of composite plasticizer, 0.3-0.6% of antioxidant and 0.4-0.7% of lubricant; the composite plasticizer includes a first plasticizer and a second plasticizer; the first plasticizer is selected from N-butyl benzene sulfonamide and/or N-ethyl p-toluene sulfonamide; the second plasticizer is selected from one or more of dioctyl terephthalate, diisooctyl terephthalate and dinonyl phthalate. The polyamide resin is modified by adopting the specific type of composite plasticizer and the polyphenyl ether resin, so that the polyamide material has the comprehensive properties of good flexibility, high impact strength, strong hydrolysis resistance and the like. In addition, the modified polypropylene has excellent 120 ℃ hydrolysis resistance tensile strength and salt (ZnCl 2) post impact strength. The test results show that: the tensile strength of the polyamide material is 53.6-57.4 MPa, the tensile modulus is 530-690 MPa, the notch impact strength is 72.9-86.7 KJ/m 2, the tensile strength after hydrolysis resistance is 47.3-50.3 MPa, and the impact strength after salt resistance is 60.8-68.8 KJ/m 2.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The flexible hydrolysis-resistant extrusion polyamide material comprises the following raw materials in percentage by mass:
20-52% of polyamide resin, 20-50% of polyphenyl ether resin, 3-7% of compatilizer, 8-14% of toughening agent, 10-14% of composite plasticizer, 0.3-0.6% of antioxidant and 0.4-0.7% of lubricant;
The composite plasticizer includes a first plasticizer and a second plasticizer; the first plasticizer is selected from N-butyl benzene sulfonamide; the second plasticizer is selected from diisononyl phthalate; the mass ratio of the first plasticizer to the second plasticizer is 2:1-1:4;
the polyamide resin is selected from PA6 or PA612.
2. The flexible hydrolysis-resistant extruded polyamide material of claim 1, wherein the polyphenylene ether resin has a viscosity of 0.35 to 0.45dl/g;
The compatilizer is selected from maleic anhydride grafted polyphenylene sulfide, and the grafting rate is 0.2-1.2wt%.
3. The flexible hydrolysis resistant extruded polyamide material of claim 1, wherein the toughening agent is selected from one or more of ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, maleic anhydride grafted ethylene octene copolymer, and maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer.
4. The flexible hydrolysis resistant extruded polyamide material of claim 1, wherein the antioxidant comprises one or more of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1 h,3h,5 h) -trione, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
5. The flexible hydrolysis resistant extruded polyamide material of claim 1, wherein the lubricant is selected from one or more of oxidized polyethylene wax, montan acid wax, and pentaerythritol stearate.
6. A method for preparing the flexible hydrolysis-resistant extruded polyamide material according to any one of claims 1 to 5, comprising the steps of:
mixing polyamide resin, polyphenyl ether resin, compatilizer, toughening agent, antioxidant and lubricant to obtain a mixture;
And mixing the mixture with the composite plasticizer, carrying out melt mixing, extruding, cooling, drying and granulating to obtain the flexible hydrolysis-resistant extruded polyamide material.
7. The method according to claim 6, wherein, the temperature of the heating area 1# to 10# and the temperature of the machine head are 220 ℃, 260 ℃ and 260 ℃ in sequence during extrusion 260 ℃, 255 ℃, 250 ℃ and 250 ℃.
8. A nylon tube made from the flexible hydrolysis-resistant extruded polyamide material of any one of claims 1-5.
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| CN106280430A (en) * | 2016-08-25 | 2017-01-04 | 深圳市高科塑化有限公司 | A kind of food stage hydrolysis PA66/PPO composite and preparation method thereof |
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| CN113337106A (en) * | 2021-05-17 | 2021-09-03 | 福建中锦新材料有限公司 | High-temperature hydrolysis resistant PA6 and PPO alloy material and preparation method and device thereof |
| CN113861671A (en) * | 2021-10-09 | 2021-12-31 | 中山市捷德新材料科技有限公司 | High-fluidity glass fiber reinforced polyphenyl ether polyamide composite material and preparation method thereof |
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| CN101370648A (en) * | 2006-01-20 | 2009-02-18 | 阿克马法国公司 | Polyamide hose for compressed air |
| CN106280430A (en) * | 2016-08-25 | 2017-01-04 | 深圳市高科塑化有限公司 | A kind of food stage hydrolysis PA66/PPO composite and preparation method thereof |
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