CN118063961A - Flexible barrier extrusion polyamide material, preparation method thereof and nylon tube - Google Patents
Flexible barrier extrusion polyamide material, preparation method thereof and nylon tube Download PDFInfo
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- 230000004888 barrier function Effects 0.000 title claims abstract description 49
- 239000004952 Polyamide Substances 0.000 title claims abstract description 46
- 229920002647 polyamide Polymers 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000001125 extrusion Methods 0.000 title claims abstract description 36
- 239000004677 Nylon Substances 0.000 title claims abstract description 26
- 229920001778 nylon Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 8
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 41
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 39
- 239000004014 plasticizer Substances 0.000 claims abstract description 31
- 239000000314 lubricant Substances 0.000 claims abstract description 29
- 229920001470 polyketone Polymers 0.000 claims abstract description 29
- 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 20
- 239000002994 raw material Substances 0.000 claims abstract description 8
- ZGHZSTWONPNWHV-UHFFFAOYSA-N 2-(oxiran-2-yl)ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCC1CO1 ZGHZSTWONPNWHV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims abstract description 7
- DJDSLBVSSOQSLW-UHFFFAOYSA-N mono(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(O)=O DJDSLBVSSOQSLW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 30
- 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 17
- -1 dioctyl (2-ethylhexyl) 4, 5-epoxytetrahydrophthalate Chemical compound 0.000 claims description 13
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 3
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- FIBARIGPBPUBHC-UHFFFAOYSA-N octyl 8-(3-octyloxiran-2-yl)octanoate Chemical compound CCCCCCCCOC(=O)CCCCCCCC1OC1CCCCCCCC FIBARIGPBPUBHC-UHFFFAOYSA-N 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 229920006228 ethylene acrylate copolymer Polymers 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 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 15
- FEXXLIKDYGCVGJ-UHFFFAOYSA-N butyl 8-(3-octyloxiran-2-yl)octanoate Chemical compound CCCCCCCCC1OC1CCCCCCCC(=O)OCCCC FEXXLIKDYGCVGJ-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 2
- 239000000956 alloy Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- WDPPKHWPTVDXNU-UHFFFAOYSA-N dioctyl 7-oxabicyclo[4.1.0]hept-1-ene-3,4-dicarboxylate Chemical compound C(CCCCCCC)OC(C1C(C(=O)OCCCCCCCC)CC2C(=C1)O2)=O WDPPKHWPTVDXNU-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920006152 PA1010 Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical group C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a flexible barrier extrusion polyamide material, a preparation method thereof and a nylon pipe, wherein the polyamide material comprises the following raw materials in percentage by mass: 30-50% of polyamide resin, 26-47% of polyketone resin, 10-15% of compatilizer, 9-12% of plasticizer, 0.3-0.6% of antioxidant and 0.3-0.6% of lubricant; the plasticizer is selected from at least two of N-butyl benzene sulfonamide, epoxy butyl stearate and 4, 5-epoxy tetrahydrodioctyl phthalate (2-ethyl hexyl) ester. The polyamide material has excellent comprehensive properties of barrier property, tensile modulus and notch impact strength by adopting the compound of the specific plasticizer and coacting with the polyketone resin.
Description
Technical Field
The invention belongs to the technical field of modified polyamide materials, and particularly relates to a flexible barrier extrusion polyamide material, a preparation method thereof and a nylon tube.
Background
The long carbon chain nylon refers to nylon with the number of methylene between adjacent amide bonds in a molecular chain being more than 10, such as PA610, PA612, PA1010, PA11, PA12, PA1212 and the like. The long carbon chain nylon has the advantages of light specific gravity, good flexibility, hydrolysis resistance, oil resistance, acid and alkali resistance, corrosion resistance and the like, and can be widely applied to automobile system pipelines such as fuel oil pipes, cooling pipes, brake oil pipes and the like after being processed and modified, and can also be applied to pneumatic pipes, hydraulic oil pipes and wire harness sleeves in various mechanical industries.
With the stricter emission regulations and the wide use of ethanol-containing mixed gasoline, the original nylon pipeline has hardly met the use requirement of a fuel pipe, mainly because the long carbon chain nylon has weaker barrier property to hydrocarbon and ethanol. The existing OEM generally adopts to add a blocking layer in the original pipeline system, and meets the emission requirement through a multi-layer structure design. EVOH and PVDF are generally used as the barrier layers, but the complex multilayer structure has higher requirements on extrusion equipment and process, and how to improve the barrier property of the long carbon chain nylon on the basis of ensuring the performance of the long carbon chain nylon can reduce the use of high-cost barrier materials and can also improve the design freedom of the pipeline.
Polyketone is a novel polymer material synthesized from carbon monoxide and olefin (ethylene and propylene), and the molecular chain of polyketone is a compact crystal structure formed by high crystallization of hydrocarbon, and the structure endows polyketone with the characteristics of excellent chemical resistance, hydrolysis resistance, abrasion resistance, high barrier property and the like. The alloying of nylon and polyketone is easy to realize, but how to combine the respective characteristics of the two materials, and simultaneously improve the flexibility, the extrusion processability and the like of the alloy material, and the alloy material is applied to flexible nylon pipeline products, and no patent or article is studied.
Disclosure of Invention
In view of the above, the present invention aims to provide a flexible barrier extrusion polyamide material, a preparation method thereof and a nylon tube, wherein the polyamide material has excellent barrier property, tensile modulus and notch impact strength.
The invention provides a flexible barrier extrusion polyamide material, which comprises the following raw materials in percentage by mass:
30-50% of polyamide resin, 26-47% of polyketone resin, 10-15% of compatilizer, 9-12% of plasticizer, 0.3-0.6% of antioxidant and 0.3-0.6% of lubricant;
The plasticizer is selected from at least two of N-butyl benzene sulfonamide, epoxy butyl stearate and 4, 5-epoxy tetrahydrodioctyl phthalate (2-ethyl hexyl) ester.
Preferably, the plasticizer is selected from the group consisting of a mixture of N-butylbenzenesulfonamide and octyl epoxy stearate;
or a mixture of N-butylbenzenesulfonamide and dioctyl (2-ethylhexyl) 4, 5-epoxytetrahydrophthalate.
Preferably, the compatibilizer is selected from one or more of a maleic anhydride grafted ethylene octene copolymer, a glycidyl methacrylate grafted ethylene octene copolymer, an ethylene acrylate copolymer, and an ethylene acrylate maleic anhydride copolymer.
Preferably, 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.
Preferably, the polyamide resin is aliphatic polyamide, and the relative viscosity of the polyamide resin is 2.2-3.5.
Preferably, the antioxidant comprises a hindered phenolic antioxidant and/or a phosphite antioxidant.
Preferably, the lubricant is selected from ethylene bis stearamide and/or pentaerythritol stearate.
The invention provides a preparation method of the flexible barrier extrusion polyamide material, which comprises the following steps:
Mixing polyamide resin, polyketone resin, compatilizer, antioxidant and lubricant to obtain a mixture;
and (3) carrying out melt mixing on the mixture and the plasticizer, and carrying out water cooling, air drying and granulating after extrusion to obtain the flexible barrier extrusion polyamide.
Preferably, the temperatures of the heating zones 1# to 10# and the head at the time of extrusion are 220 ℃,240 ℃, 235 ℃, 230 ℃ and 240 ℃ in order.
The invention provides a nylon pipe which is prepared from the flexible barrier extrusion polyamide material.
The invention provides a flexible barrier extrusion polyamide material, which comprises the following raw materials in percentage by mass: 30-50% of polyamide resin, 26-47% of polyketone resin, 10-15% of compatilizer, 9-12% of plasticizer, 0.3-0.6% of antioxidant and 0.3-0.6% of lubricant; the plasticizer is selected from at least two of N-butyl benzene sulfonamide, epoxy butyl stearate and 4, 5-epoxy tetrahydrodioctyl phthalate (2-ethyl hexyl) ester. The polyamide material has excellent comprehensive properties of barrier property, tensile modulus and notch impact strength by adopting the compound of the specific plasticizer and coacting with the polyketone resin.
Detailed Description
The invention provides a flexible barrier extrusion polyamide material, which comprises the following raw materials in percentage by mass:
30-50% of polyamide resin, 26-47% of polyketone resin, 10-15% of compatilizer, 9-12% of plasticizer, 0.3-0.6% of antioxidant and 0.3-0.6% of lubricant;
The plasticizer is selected from at least two of N-butyl benzene sulfonamide, epoxy butyl stearate and 4, 5-epoxy tetrahydrodioctyl phthalate (2-ethyl hexyl) ester.
The polyamide material has excellent comprehensive properties of barrier property, tensile modulus and notch impact strength by adopting the combination of the specific plasticizer and the polyketone resin.
The flexible barrier extrusion polyamide material provided by the invention comprises 30-50% of polyamide resin; the polyamide resin is specifically used in an amount of 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49% or 50%. The polyamide resin is an aliphatic polyamide, preferably selected from one or more of PA66, PA6, PA610, PA612, PA1012 and PA 12. The viscosity of the polyamide resin is 2.2-3.5.
The flexible barrier extrusion polyamide material provided by the invention comprises 26-47% of polyketone resin; the polyketone resin is specifically used in an amount of 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, or 47%. 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 flexible barrier extrusion polyamide material provided by the invention comprises 10-15% of a compatilizer; the specific amount of the compatilizer is 10%, 11%, 12%, 13%, 14% or 15%. The compatibilizer is selected from ethylene acrylic acid ester maleic anhydride copolymers.
The flexible barrier extrusion polyamide provided by the invention comprises 9-12% of plasticizer, wherein the plasticizer is a composite plasticizer, and the plasticizer and the polyketone resin are combined to improve the barrier property, tensile modulus and notch impact strength of the polyamide material. The plasticizer is used in an amount of in particular 9%, 9.5%, 10%, 10.5%, 11%, 11.5% or 12%. The plasticizer is at least two selected from N-butyl benzene sulfonamide (N-BBSA), epoxy butyl stearate and 4, 5-epoxy tetrahydrodioctyl phthalate (2-ethylhexyl) ester; preferably selected from the group consisting of N-butylbenzenesulfonamide and octyl epoxy stearate; or a mixture of N-butylbenzenesulfonamide and dioctyl (2-ethylhexyl) 4, 5-epoxytetrahydrophthalate. In a specific embodiment, the plasticizer is a mixture of N-butylbenzenesulfonamide and butyl epoxystearate in a mass ratio of 6:3; or a mixture of N-butylbenzenesulfonamide and butyl epoxystearate in a mass ratio of 7:4; or a mixture of N-butylbenzenesulfonamide and butyl epoxystearate in a mass ratio of 5:5; or a mixture of N-butylbenzenesulfonamide and dioctyl (2-ethylhexyl) 4, 5-epoxytetrahydrophthalate in a mass ratio of 4:8; or a mixture of N-butylbenzenesulfonamide and butyl epoxystearate in a mass ratio of 6:6; or a mixture of N-butylbenzenesulfonamide and dioctyl (2-ethylhexyl) 4, 5-epoxytetrahydrophthalate in a mass ratio of 5:6.
The flexible barrier extrusion polyamide material provided by the invention comprises 0.3-0.6% of antioxidant; the specific amount of the antioxidant is 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, or 0.6%. The antioxidant comprises hindered phenol antioxidants and/or phosphite antioxidants; preferably one or more of an antioxidant 1098, an antioxidant 1010, an antioxidant 626 and an antioxidant 9228, more preferably at least two of an antioxidant 1098, an antioxidant 1010, an antioxidant 626 and an antioxidant 9228; more selected from the group consisting of a combination of antioxidant 1098 and antioxidant 626; in a specific embodiment, the antioxidant is selected from a mixture of antioxidant 1098 and antioxidant 626 in a mass ratio of 0.3:0.1, or a mixture of antioxidant 1098 and antioxidant 626 in a mass ratio of 0.4:0.2, or a mixture of antioxidant 1098 and antioxidant 626 in a mass ratio of 0.3:0.2, or a mixture of antioxidant 1098 and antioxidant 626 in a mass ratio of 0.5:0.2, or a mixture of antioxidant 1098 and antioxidant 626 in a mass ratio of 0.2:0.1, or a mixture of antioxidant 1098 and antioxidant 626 in a mass ratio of 0.2:0.2.
The flexible barrier extrusion polyamide material provided by the invention comprises 0.3-0.6% of lubricant; the lubricant is specifically used in an amount of 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, or 0.60%. The lubricant is preferably one or more selected from Ethylene Bis Stearamide (EBS), pentaerythritol stearate (PETS) and calcium stearate, more preferably ethylene bis stearamide and/or pentaerythritol stearate. In a specific embodiment, the lubricant is selected from a mixture of ethylene bis-stearamide and pentaerythritol stearate in a mass ratio of 0.3:0.3, or pentaerythritol stearate, or a mixture of ethylene bis-stearamide and pentaerythritol stearate in a mass ratio of 0.2:0.3, or a mixture of ethylene bis-stearamide and pentaerythritol stearate in a mass ratio of 0.2:0.5.
The preparation raw materials of the flexible barrier extrusion polyamide material provided by the invention comprise:
50% PA12, 30% POK730R, 10% compatibilizer 4700, 6% N-BBSA, 3% butyl epoxystearate, 0.3% antioxidant 1098, 0.1% antioxidant 626, 0.3% lubricant EBS, 0.3% lubricant PETS;
Or 50% PA12, 28% POK730R, 10% compatibilizer 4700, 7% N-BBSA, 4% butyl epoxy stearate, 0.4% antioxidant 1098, 0.2% antioxidant 626, 0.4% lubricant PETS;
Or comprises 40% of PA12, 39% of POK730R, 10% of compatilizer 4700, 5% of N-BBSA, 5% of butyl epoxy stearate, 0.3% of antioxidant 1098,0.2% of antioxidant 626, 0.2% of lubricant EBS and 0.3% of lubricant PETS;
Or 30% PA12, 47% POK730R, 10% compatibilizer 4700, 4% N-BBSA, 8% dioctyl 4, 5-epoxytetrahydrophthalate (2-ethylhexyl) ester, 0.3% antioxidant 1098, 0.2% antioxidant 626, 0.2% lubricant EBS, 0.3% lubricant PETS;
Or comprises 36% of PA610, 36% of POK730R, 15% of compatilizer 4700, 6% of N-BBSA, 6% of butyl epoxy stearate, 0.5% of antioxidant 1098, 0.2% of antioxidant 626 and 0.3% of lubricant PETS;
Or comprises 25% of PA610, 25% of PA12, 27% of POK730R, 11% of compatilizer 4700, 7% of N-BBSA, 4% of butyl epoxy stearate, 0.2% of antioxidant 1098, 0.1% of antioxidant 626, 0.2% of lubricant EBS and 0.5% of lubricant PETS;
Or comprises 38% PA610, 38% POK630A, 12% compatibilizer 4700, 5% N-BBSA, 6% dioctyl 4, 5-epoxytetrahydrophthalate (2-ethylhexyl) ester, 0.2% antioxidant 1098, 0.2% antioxidant 626, and 0.6% lubricant PETS.
The invention provides a preparation method of the flexible barrier extrusion polyamide material, which comprises the following steps:
Mixing polyamide resin, polyketone resin, compatilizer, antioxidant and lubricant to obtain a mixture;
and (3) carrying out melt mixing on the mixture and the plasticizer, and carrying out water cooling, air drying and granulating after extrusion to obtain the flexible barrier extrusion polyamide material.
The invention preferably comprises the steps of weighing polyamide resin, polyketone resin, compatilizer, antioxidant and lubricant according to a proportion, and adding the mixture into a high-speed mixer for mixing.
The invention preferably adds the mixture through a main feed, and the plasticizer is added into a parallel double-screw extruder through a side feed pressure pump for melt mixing.
The temperature of the heating zone 1# to 10# and the temperature of the machine head are 220 ℃, 240 ℃, 235 ℃, 230 ℃ and 240 ℃ in sequence during extrusion. The rotating speed of the host machine is set to 400-600 rpm.
The invention also provides a nylon tube which is prepared from the flexible barrier extrusion polyamide material. The nylon pipe provided by the invention can be applied to pipeline industries such as fuel oil pipes, hydraulic oil pipes and the like.
In order to further illustrate the present invention, a flexible barrier extruded polyamide material, a method of 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: PA 610I 2, shandong xianglong; PA 12L 3000, vancomic chemistry;
polyketone resin: 630A, 730R, korea phosphor;
And (3) a compatilizer: 4700, korea SK chemistry;
And (3) a plasticizer: N-BBSA, zhejiang pranlame chemical; butyl epoxy stearate, chemical industry in tung country; dioctyl (2-ethylhexyl) 4, 5-epoxytetrahydrophthalate, WU Han Kang Qiong organism;
An antioxidant: 1098. 626, tianjin Li Anlong;
And (3) a lubricant: EBS, japan flower king; PETS, italian method base;
Examples and comparative examples
1) According to the formula proportion in tables 1 and 2, polyamide resin, polyketone resin, compatilizer, antioxidant and lubricant are weighed according to the proportion, and then added into a high-speed mixer for high-speed mixing to obtain a uniform mixture;
2) The mixture was fed by main feed and the plasticizer was fed by side feed pressure pump to a parallel twin screw extruder for melt compounding. And (3) carrying out water cooling, air drying and granulating on the extruded molten material to obtain the flexible barrier extrusion polyamide material.
Table 1 kinds and amounts of raw materials used in examples 1 to 7
TABLE 2 types and amounts of raw materials used in comparative examples 1 to 7
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; extruding the dried material into nylon pipes with the size of phi 8mm 1mm by a single screw extruder, and observing the dimensional stability during extrusion and whether precipitates exist on the surfaces of the nylon pipes; taking two nylon pipes with certain length, after one end is sealed, filling ethanol and alcohol-free gasoline respectively, then sealing the other end, placing the nylon pipe filled with the solution into a baking oven with the temperature of 60 ℃ for 24 hours, weighing the front and rear weights of the lower sealed nylon pipe, and calculating the permeability of the nylon pipe. The specific test results are shown in tables 3 and 4:
TABLE 3 Performance test results of Flexible Barrier extruded Polyamide materials prepared by examples 1-7
TABLE 4 Performance test results of Flexible Barrier extruded Polyamide materials prepared with comparative examples 1-7
From the above examples, the present invention provides a flexible barrier extruded polyamide material comprising, in mass fraction: 30-50% of polyamide resin, 26-47% of polyketone resin, 10-15% of compatilizer, 9-12% of plasticizer, 0.3-0.6% of antioxidant and 0.3-0.6% of lubricant; the plasticizer is selected from at least two of N-butyl benzene sulfonamide, epoxy butyl stearate and 4, 5-epoxy tetrahydrodioctyl phthalate (2-ethyl hexyl) ester. The polyamide material has excellent comprehensive properties of barrier property, tensile modulus and notch impact strength by adopting the compound of the specific plasticizer and coacting with the polyketone resin. The experimental results show that: the tensile modulus of the nylon pipe prepared from the polyamide material is 540-720 MPa, the notch impact strength is 65-85 KJ/m < 2 >, the ethanol barrier property is 1.27-1.85 g.mm/(m 2.24 h), and the hydrocarbon barrier property is 0.34-0.86 g.mm/(m 2.24 h).
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 (10)
1. The flexible barrier extrusion polyamide material comprises the following raw materials in percentage by mass:
30-50% of polyamide resin, 26-47% of polyketone resin, 10-15% of compatilizer, 9-12% of plasticizer, 0.3-0.6% of antioxidant and 0.3-0.6% of lubricant;
The plasticizer is selected from at least two of N-butyl benzene sulfonamide, epoxy butyl stearate and 4, 5-epoxy tetrahydrodioctyl phthalate (2-ethyl hexyl) ester.
2. The flexible barrier extruded polyamide material of claim 1 wherein the plasticizer is selected from the group consisting of a mixture of N-butylbenzenesulfonamide and octyl epoxy stearate;
or a mixture of N-butylbenzenesulfonamide and dioctyl (2-ethylhexyl) 4, 5-epoxytetrahydrophthalate.
3. The flexible barrier extruded polyamide material of claim 1, wherein the compatibilizing agent is selected from one or more of a maleic anhydride grafted ethylene octene copolymer, a glycidyl methacrylate grafted ethylene octene copolymer, an ethylene acrylate copolymer, and an ethylene acrylate maleic anhydride copolymer.
4. The flexible barrier extrusion polyamide material of claim 1, wherein the polyketone resin is a copolymer of carbon monoxide, ethylene and propylene, and the polyketone resin has a melt index of 3-6 g/10min.
5. The flexible barrier extrusion polyamide of claim 1 wherein the polyamide resin is an aliphatic polyamide and the polyamide resin has a relative viscosity of 2.2 to 3.5.
6. The flexible barrier extruded polyamide material of claim 1, wherein the antioxidant comprises a hindered phenolic antioxidant and/or a phosphite antioxidant.
7. A flexible barrier extruded polyamide material according to claim 1, wherein the lubricant is selected from ethylene bis stearamide and/or pentaerythritol stearate.
8. A method for preparing the flexible barrier extruded polyamide material according to any one of claims 1 to 7, comprising the steps of:
Mixing polyamide resin, polyketone resin, compatilizer, antioxidant and lubricant to obtain a mixture;
and (3) carrying out melt mixing on the mixture and the plasticizer, and carrying out water cooling, air drying and granulating after extrusion to obtain the flexible barrier extrusion polyamide.
9. The method according to claim 8, wherein, the temperature of the heating area 1# to 10# and the temperature of the machine head are 220 ℃, 240 ℃ and 240 ℃ in sequence during extrusion 240 ℃, 235 ℃, 230 ℃ and 240 ℃.
10. A nylon tube made from the flexible barrier extruded polyamide material of any one of claims 1-7.
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