CN114163812A - Low-temperature-resistant high-wear-resistance nylon material and preparation method and application thereof - Google Patents
Low-temperature-resistant high-wear-resistance nylon material and preparation method and application thereof Download PDFInfo
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- CN114163812A CN114163812A CN202111559289.7A CN202111559289A CN114163812A CN 114163812 A CN114163812 A CN 114163812A CN 202111559289 A CN202111559289 A CN 202111559289A CN 114163812 A CN114163812 A CN 114163812A
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- nylon material
- master batch
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- 239000000463 material Substances 0.000 title claims abstract description 75
- 229920001778 nylon Polymers 0.000 title claims abstract description 70
- 239000004677 Nylon Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 70
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 28
- 239000004952 Polyamide Substances 0.000 claims abstract description 26
- 229920002647 polyamide Polymers 0.000 claims abstract description 26
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 239000000314 lubricant Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 33
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 32
- 229920001296 polysiloxane Polymers 0.000 claims description 16
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 14
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 12
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 12
- 238000007710 freezing Methods 0.000 claims description 11
- 230000008014 freezing Effects 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000004014 plasticizer Substances 0.000 claims description 8
- -1 PA614 Polymers 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 claims description 4
- UEOXCHJYRKCZFF-UHFFFAOYSA-N O1C(CC2=C1C=CC=C2)=O.NO Chemical class O1C(CC2=C1C=CC=C2)=O.NO UEOXCHJYRKCZFF-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- ULRUJYWXKGJJOK-UHFFFAOYSA-N 2-(2-ethylhexyl)benzenesulfonamide Chemical compound CCCCC(CC)CC1=CC=CC=C1S(N)(=O)=O ULRUJYWXKGJJOK-UHFFFAOYSA-N 0.000 claims description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- YBZMSJMVWKKNCC-UHFFFAOYSA-K [K+].[Cu++].[I-].[I-].[I-] Chemical compound [K+].[Cu++].[I-].[I-].[I-] YBZMSJMVWKKNCC-UHFFFAOYSA-K 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000004018 acid anhydride group Chemical group 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229960001617 ethyl hydroxybenzoate Drugs 0.000 claims description 2
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 claims description 2
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 claims description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 2
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 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
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 claims description 2
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 claims description 2
- 229960002216 methylparaben Drugs 0.000 claims description 2
- SVDVKEBISAOWJT-UHFFFAOYSA-N n-methylbenzenesulfonamide Chemical compound CNS(=O)(=O)C1=CC=CC=C1 SVDVKEBISAOWJT-UHFFFAOYSA-N 0.000 claims description 2
- KFGDFRBWKQXPSH-UHFFFAOYSA-N n-octyl-1-phenylmethanesulfonamide Chemical compound CCCCCCCCNS(=O)(=O)CC1=CC=CC=C1 KFGDFRBWKQXPSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- RIKCMEDSBFQFAL-UHFFFAOYSA-N octyl 4-hydroxybenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=C(O)C=C1 RIKCMEDSBFQFAL-UHFFFAOYSA-N 0.000 claims description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229920006150 hyperbranched polyester Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a low-temperature-resistant high-wear-resistance nylon material and a preparation method and application thereof, wherein the low-temperature-resistant high-wear-resistance nylon material comprises the following raw materials in percentage by weight: 60-87% of polyamide; 12-38% of wear-resistant master batch; 0.2 to 0.8 percent of lubricant; 0.8 to 1.2 percent of antioxidant. The nylon material has excellent low temperature resistance, high wear resistance and self-lubricating effect, can keep natural color, and is suitable for wear-resistant sliding blocks, wear-resistant pipelines or cables and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis and processing of high polymer materials, and relates to a low-temperature-resistant high-wear-resistance nylon material, and a preparation method and application thereof.
Background
The nylon material has high mechanical strength, excellent self-lubricating property and oil resistance, is widely concerned as an engineering plastic, has more applications in the aspects of pipeline cables and bearings due to the obvious performance, and can be gradually expanded in the field along with the gradual expansion of the wind power industry.
The self-lubricity and low coefficient of friction of the nylon material itself make the abrasion resistance of the material suitable for most pipeline cable requirements. Among the nylon, short-chain nylon such as PA6 or PA66 nylon has excellent mechanical properties, temperature resistance, cold resistance, wear resistance and weather resistance, and is widely used for mechanical parts, but nylon is not suitable for manufacturing parts with high requirement on matching dimensional accuracy due to large hygroscopicity and poor dimensional stability. Long carbon chain nylons such as PA11 and PA12 have natural advantages in water absorption and density, and are receiving wide attention because they can maintain good dimensional stability and good solvent resistance.
The existing wear-resistant materials are usually polytetrafluoroethylene micro powder, molybdenum disulfide, aramid powder, silicone master batch, graphite, ultra-high molecular weight polyethylene, wollastonite and the like, but many materials belong to inorganic fillers or non-polar materials, and the compatibility with nylon has certain problems, so that the defects in a system are more, the defects of the materials are easily amplified under the action of external force, the mechanical properties of the materials are poor, on the other hand, the compatibility of the system is poor, the phenomena of sharkskin, dark lines and the like are easily generated in the processing process, the appearance of the materials is poor, and therefore, the improvement of the compatibility of the system is beneficial to the improvement of the properties of the nylon materials.
CN112143242A discloses a high-strength wear-resistant nylon composite material, which is prepared from PA66, glass fiber, a wear-resistant agent (polytetrafluoroethylene, molybdenum disulfide and the like), and the like, wherein the prepared nylon composite material has low-temperature and wear-resistant properties, but the surface of the prepared material is rough due to the introduction of glass fiber, so that the application of the material is limited, and meanwhile, the compatibility of a system is reduced due to the added wear-resistant agent fluororesin. CN104788950A discloses a wear-resistant self-lubricating nylon composite material, which uses nylon, carbon fiber, a water repellent, molybdenum disulfide and a compatilizer, wherein the introduction of the carbon fiber and the molybdenum disulfide leads to that the material cannot be prepared into the natural color after being extruded, and the application of the material is limited.
Therefore, it is desired to develop a nylon material which has low temperature resistance, high wear resistance, good compatibility and can maintain the natural color.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-temperature-resistant high-wear-resistance nylon material, and a preparation method and application thereof. The nylon material has excellent low temperature resistance, high wear resistance and self-lubricating effect, can keep natural color, and is suitable for various parts requiring special performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a low-temperature-resistant high-wear-resistance nylon material, and the preparation raw materials of the low-temperature-resistant high-wear-resistance nylon material comprise the following components in percentage by weight:
in the invention, the wear-resistant master batch is added to improve the wear resistance of the nylon material; the wear-resistant master batch contains the groups, and can react with the polyamide, so that the compatibility of a nylon material system is improved.
In the invention, in the raw materials for preparing the low-temperature-resistant and high-wear-resistant nylon material, the dosage of polyamide can be 60%, 65%, 70%, 75%, 80%, 85% or 87%.
In the invention, in the raw materials for preparing the low-temperature-resistant and high-wear-resistant nylon material, the dosage of the wear-resistant master batch can be 12%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 35% or 38% and the like.
In the invention, in the raw materials for preparing the low-temperature-resistant and high-wear-resistant nylon material, the amount of the lubricant used can be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or the like.
In the invention, in the raw materials for preparing the low-temperature-resistant and high-wear-resistant nylon material, the dosage of the antioxidant can be 0.8%, 0.9%, 1.0%, 1.1% or 1.2% and the like.
Preferably, the polyamide has an average number of carbon atoms per nitrogen atom Nc of between 6 and 18 (for example 6, 8, 10, 13, 15 or 18, etc.), preferably between 9 and 16.
The polyamides used in the present invention may be prepared from diamines and dicarboxylic acids or from aminocarboxylic acids or the corresponding lactams. The resin prepared by lactam contains at least 6 carbon atoms per nitrogen atom, and in the case of the resin prepared by diamine and dicarboxylic acid, the arithmetic average of each carbon atom in the mixed components of diamine and dicarboxylic acid must be at least 6. Polyamides to which this rule applies are, for example: PA1012 is prepared from decamethylenediamine (10 carbon atoms) and dodecanedioic acid (12 carbon atoms), and PA11 is formed by the polycondensation of aminoundecanoic acid (11 carbon atoms).
Preferably, the polyamide comprises any one of PA612, PA614, PA1012, PA11, PA12, PA1212, PA616 or PA618 or a combination of at least two thereof.
Preferably, the lubricant comprises any one or a combination of at least two of zinc stearate, titanate, stearic acid, erucamide, oleamide, or silicone.
Preferably, the antioxidant comprises any one of or a combination of at least two of aromatic amines, sterically hindered phenols, phosphites, sulfur-containing synergists, hydroxylamine benzofuranone derivatives, or potassium iodide-copper iodide inorganic stabilizers.
Preferably, the wear-resistant master batch is prepared by the following preparation method:
mixing polar functional group modified ultrahigh molecular weight polyethylene, multi-active site polymer, modified fluororesin, lubricant and antioxidant, freezing and grinding to obtain the wear-resistant master batch.
Compared with the prior art that wear-resistant materials (polytetrafluoroethylene micro powder, molybdenum disulfide, aramid powder, silicone master batch, graphite and ultra-high molecular weight polyethylene) are directly mixed with polyamide, the invention firstly modifies the ultra-high molecular weight polyethylene and fluororesin, and then mixes polar functional group modified ultra-high molecular weight polyethylene, multi-active-site polymer, modified fluororesin and auxiliary agent to prepare the wear-resistant master batch with better compatibility.
In the invention, the polymer with multiple active sites and the modified fluororesin are matched with each other, so that the prepared wear-resistant master batch has better compatibility with polyamide; meanwhile, the ultra-high molecular weight polyethylene has polar functional groups after surface treatment, takes reaction activity into consideration, can better ensure the dispersion and dispersion size of the wear-resistant master batch in a system, and better exerts the wear resistance of the material; in addition, the polar functional group modified ultra-high molecular weight polyethylene has better low-temperature toughness, and the low-temperature toughness of the nylon material can be realized without additionally adding a toughening agent.
In addition, the wear-resistant master batch disclosed by the invention enables the color of the nylon material to be unlimited, and different colors can be matched according to actual application in the later stage.
Preferably, the polar functional group-modified ultrahigh molecular weight polyethylene is present in an amount of 80 to 95% (e.g., 80%, 83%, 85%, 88%, 90%, 93%, or 95%, etc.), the multi-site polymer is present in an amount of 0.1 to 5% (e.g., 0.1%, 0.3%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, or 5%, etc.), the modified fluororesin is present in an amount of 5 to 20% (e.g., 5%, 8%, 10%, 13%, 15%, 18%, or 20%, etc.), the lubricant is present in an amount of 0.6 to 2.5% (e.g., 0.6%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, or 2.5%, etc.), and the antioxidant is present in an amount of 0.2 to 0.6% (e.g., 0.2%, 0.3%, 0.4%, 0.5%, or 0.6%, etc.), based on 100% by weight of the wear-resistant master batch.
Preferably, the polar functional group in the polar functional group-modified ultrahigh molecular weight polyethylene includes any one or a combination of at least two of an acid anhydride group, an epoxy group, a halogen, a carboxyl group, an amino group, a hydroxyl group, and a derivative thereof. These polar functional groups can react with nylon materials.
Preferably, the polar functional group-modified ultrahigh molecular weight polyethylene has a molecular weight of 30 to 500 ten thousand, for example 30, 50, 80, 100, 200, 300, 400 or 500 ten thousand, etc., preferably 50 to 200 ten thousand.
Preferably, the polar functional group-modified ultrahigh molecular weight polyethylene has a density of 0.90 to 1.70g/cm3E.g. 0.90g/cm3、1.00g/cm3、1.10g/cm3、1.20g/cm3、1.30g/cm3、1.40g/cm3、1.50g/cm3、1.60g/cm3Or 1.70g/cm3Etc., preferably 0.93 to 1.50g/cm3。
Preferably, the multi-site polymer comprises any one of or a combination of at least two of an ethylene-maleic anhydride copolymer, a branched polymer, or a polyethyleneimine.
For example, the ethylene-maleic anhydride copolymer may have the formula
The branched polymer may have the formula
Wherein the hydroxyl group may be replaced with a carboxyl group; the polyethyleneimine may have the formula
Preferably, the copolymerization molar ratio of the ethylene-maleic anhydride copolymer is 1:1-1:5 (e.g., 1:1, 1:2, 1:3, 1:4, 1:5, etc.), wherein the mass ratio of ethylene is less than 25%, and the mass ratio of maleic anhydride is greater than 75%.
Preferably, the molecular weight of the ethylene-maleic anhydride copolymer is 10000-400000, such as 10000, 50000, 100000, 200000, 300000 or 400000, preferably 10000-150000, and the physical property state can be solid powder or particles.
Preferably, the branched polymer may be selected from polyesters of different degrees of branching, wherein the active groups contained therein may be selected from carboxyl, hydroxyl, and epoxy, etc., and have a melting point of 120-180 deg.C, such as 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, or 180 deg.C, etc.
Preferably, the modified fluororesin includes an alkane coupling agent-modified fluororesin and/or a titanate coupling agent-modified fluororesin.
Preferably, the fluororesin in the modified fluororesin includes any one or a combination of at least two of FEP, PTFE, ETFE, or PVDF.
Preferably, the fluororesin in the modified fluororesin has a molecular weight of 3000-15000, for example 3000, 5000, 8000, 10000, 13000 or 15000, etc., preferably 3500-12000.
Preferably, the fluororesin in the modified fluororesin has a particle size of 0.02 to 1.2. mu.m, for example, 0.02. mu.m, 0.05. mu.m, 0.08. mu.m, 0.1. mu.m, 0.3. mu.m, 0.5. mu.m, 0.8. mu.m, 1.0. mu.m or 1.2. mu.m, and the like, preferably 0.05 to 0.8. mu.m.
The modified fluororesin of the present invention may be prepared by itself or may be purchased. For example, the modified fluororesin may be obtained by directly mixing the fluororesin with the alkyl coupling agent-modified fluororesin and/or the titanate coupling agent.
Preferably, the lubricant comprises any one of or a combination of at least two of zinc stearate, titanate, stearic acid, erucamide, oleamide, or silicone master batch; a combination of zinc stearate, erucamide and silicone master batch is preferred.
Preferably, the zinc stearate is present in an amount of 0.2-0.4% (e.g., 0.2%, 0.3%, 0.4%, etc.), the erucamide is present in an amount of 0.2-0.6% (e.g., 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, etc.), and the silicone masterbatch is present in an amount of 0.2-1.5% (e.g., 0.2%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, etc.), based on 100% by weight of the abrasion resistant masterbatch.
Preferably, the antioxidant comprises any one of or a combination of at least two of an aromatic amine, a sterically hindered phenol, a phosphite, a thiosynergist, or a hydroxylamine benzofuranone derivative.
Preferably, the mixing is performed by a torque rheometer.
Preferably, the temperature of the mixing is 250-270 ℃, such as 250 ℃, 255 ℃, 260 ℃, 265 ℃ or 270 ℃ and the like, and the time is 5-15min, such as 5min, 10min or 15min and the like.
Preferably, the freezing is performed in a liquid nitrogen environment, and the freezing time is 5-10min, such as 5min, 10min or 15 min.
Preferably, the length of the wear resistant masterbatch is 2-5 μm, such as 2 μm, 3 μm, 4 μm or 5 μm.
Preferably, the raw materials for preparing the low-temperature-resistant and high-wear-resistant nylon material also comprise a plasticizer.
Preferably, the plasticizer is contained in an amount of 0.1 to 10%, for example, 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., based on 100% by weight of the low temperature-resistant and high abrasion-resistant nylon material.
Preferably, the plasticizer comprises an ester of p-hydroxybenzoic acid having 2 to 20 (e.g., 2, 3, 5, 8, 10, 13, 15, 18, or 20, etc.) carbon atoms and/or an amide of an arylsulfonic acid having 2 to 12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, etc.) carbon atoms; preferably any one or a combination of at least two of P-benzenesulfonamide, N-butylbenzenesulfonamide, methylparaben, N-methylbenzenesulfonamide, ethylparaben, octylparaben, isocetyl paraben, N-octyltoluensulfonic acid amide, N-butylanilic acid amide or 2-ethylhexylbenzenesulfonamide.
Preferably, the raw materials for preparing the low-temperature-resistant and high-wear-resistant nylon material also comprise other auxiliaries.
Preferably, the content of the other auxiliary agent is 0.1-5%, such as 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4% or 5% by weight of the low temperature resistant and high abrasion resistant nylon material as 100%.
Preferably, the other auxiliary agent comprises any one or a combination of at least two of an ultraviolet stabilizer, a nucleating agent, a flame retardant, a pigment, a leveling agent, a heat conducting agent or an electric conducting additive.
In a second aspect, the invention provides a preparation method of the low-temperature-resistant high-wear-resistance nylon material in the first aspect, and the preparation method comprises the following steps:
mixing the polyamide, the wear-resistant master batch, the lubricant, the antioxidant, the optional plasticizer and the optional other auxiliary agents according to the formula ratio, extruding and granulating, cooling, granulating and drying to obtain the low-temperature-resistant high-wear-resistance nylon material.
Preferably, the extrusion granulation is performed by a twin-screw extruder.
Preferably, the twin-screw extruder has an extrusion temperature of 240 ℃ to 260 ℃, such as 240 ℃, 245 ℃, 250 ℃, 255 ℃ or 260 ℃ and the like, and an extrusion rate of 25 to 35kg/h, such as 25kg/h, 30kg/h or 35kg/h and the like.
Preferably, the melt temperature of the extrusion process is 250-270 ℃, such as 250 ℃, 255 ℃, 260 ℃, 265 ℃ or 270 ℃ and the like, and the vacuum degree is-0.05 MPa to-0.08 MPa, such as-0.05 MPa, -0.06MPa, -0.07MPa or-0.08 MPa and the like.
In a third aspect, the invention provides the application of the low-temperature-resistant and high-wear-resistant nylon material in wear-resistant sliding blocks, wear-resistant pipelines or cables. The low-temperature-resistant and high-wear-resistant nylon material of the first aspect can be used for extrusion or injection molding processing.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) in the invention, the wear-resistant performance (friction coefficient: 0.15-0.27) of the nylon material is improved by adding the wear-resistant master batch, and the wear-resistant master batch has better compatibility with polyamide;
(2) in the invention, the polymer with multiple active sites and the modified fluororesin are matched with each other, so that the prepared wear-resistant master batch has better compatibility with polyamide; meanwhile, the ultra-high molecular weight polyethylene has polar functional groups after surface treatment, and has reaction activity, so that the dispersion of the wear-resistant master batch in a system can be better ensured, and the wear resistance of the material can be better exerted; in addition, the polar functional group modified ultra-high molecular weight polyethylene has better low-temperature toughness, and the low-temperature toughness of the nylon material (the notch impact strength of a simply supported beam at the temperature of minus 30 ℃) is 7.2-25.4KJ/m without adding a toughening agent additionally2)。
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The raw material grades and supplier information used in the preparation examples and examples of the present invention are as follows:
the preparation method of the modified fluororesin used in the preparation example of the invention comprises the following steps: fluororesin (F201 and AT-3000) and silane coupling agent (KH550) were mixed in a mass ratio of 100:0.8 to obtain modified fluororesin A and modified fluororesin B, respectively.
Preparation example 1
In the present preparation example, a wear-resistant master batch is provided, which is prepared by the following preparation method:
mixing 88.4% polar group modified ultrahigh molecular weight polyethylene, 0.4% ethylene-maleic anhydride copolymer, 10% modified fluororesin, 0.2% zinc stearate, 0.2% erucamide, 0.4% silicone master batch and 0.4% phosphite antioxidant by a torque rheometer, wherein the mixing temperature is 250 ℃ and the mixing time is 5min, freezing for 10min in a liquid nitrogen environment after the mixing is finished, and grinding to obtain the wear-resistant master batch A with the length of 2-5 mu m.
Wherein the polar group modified ultra-high molecular weight polyethylene is LY 1040; the ethylene-maleic anhydride copolymer has the trade name E60P; the grade of the modified fluororesin is modified fluororesin A; the phosphite antioxidant is Irgonox 168.
Preparation example 2
In the present preparation example, a wear-resistant master batch is provided, which is prepared by the following preparation method:
mixing 93.7% polar group modified ultrahigh molecular weight polyethylene, 0.3% polyethyleneimine, 5% modified fluororesin, 0.2% zinc stearate, 0.2% erucamide, 0.2% silicone master batch and 0.4% phosphite antioxidant by a torque rheometer, wherein the mixing temperature is 250 ℃ and the mixing time is 5min, freezing for 10min in a liquid nitrogen environment after mixing is finished, and grinding to obtain the wear-resistant master batch B with the length of 2-5 mu m.
Wherein the polar group modified ultra-high molecular weight polyethylene is LY 1040; the polyethyleneimine has a mark of P1050; the grade of the modified fluororesin is modified fluororesin B; the phosphite antioxidant is Irgonox 168.
Preparation example 3
In the present preparation example, a wear-resistant master batch is provided, which is prepared by the following preparation method:
mixing 79% of polar group modified ultrahigh molecular weight polyethylene, 0.4% of hyperbranched polyester, 18.6% of modified fluororesin, 0.2% of zinc stearate, 0.2% of erucamide, 1.2% of silicone master batch and 0.4% of phosphite antioxidant by a torque rheometer, wherein the mixing temperature is 250 ℃ and the mixing time is 5min, freezing for 10min in a liquid nitrogen environment after mixing, and grinding to obtain the wear-resistant master batch C with the length of 2-5 mu m.
Wherein the polar group modified ultra-high molecular weight polyethylene is LY 1040; the grade of the hyperbranched polyester is Hyper C181; the grade of the modified fluororesin is modified fluororesin A; the phosphite antioxidant is Irgonox 168.
Preparation example 4
In the present preparation example, a wear-resistant master batch is provided, which is prepared by the following preparation method:
mixing 93.7% of polar group modified ultrahigh molecular weight polyethylene, 0.3% of hyperbranched polyester, 5% of modified fluororesin, 0.2% of zinc stearate, 0.2% of erucamide, 0.2% of silicone master batch and 0.4% of phosphite antioxidant by a torque rheometer, wherein the mixing temperature is 250 ℃ and the mixing time is 5min, freezing for 10min in a liquid nitrogen environment after mixing, and grinding to obtain the wear-resistant master batch D with the length of 2-5 mu m.
Wherein the polar group modified ultra-high molecular weight polyethylene is LY 1040; the grade of the hyperbranched polyester is Hyper C181; the grade of the modified fluororesin is modified fluororesin B; the phosphite antioxidant is Irgonox 168.
Preparation example 5
In the present preparation example, a wear-resistant master batch is provided, which is prepared by the following preparation method:
mixing 79.5% polar group modified ultrahigh molecular weight polyethylene, 1.5% ethylene-maleic anhydride copolymer, 17.8% modified fluororesin, 0.2% zinc stearate, 0.4% erucamide, 0.2% silicone master batch and 0.4% phosphite antioxidant by a torque rheometer, wherein the mixing temperature is 250 ℃ and the mixing time is 5min, freezing for 10min in a liquid nitrogen environment after mixing is finished, and grinding to obtain the wear-resistant master batch E with the length of 2-5 mu m.
Wherein the polar group modified ultra-high molecular weight polyethylene is LY 1040; the ethylene-maleic anhydride copolymer has the designation E400; the grade of the modified fluororesin is modified fluororesin B; the phosphite antioxidant is Irgonox 168.
Preparation example 6
This production example differs from production example 1 only in that the polar group-modified ultrahigh-molecular weight polyethylene was replaced with unmodified ultrahigh-molecular weight polyethylene (brand G015T), and the master batch F was obtained under the same conditions as in production example 1.
Preparation example 7
This production example differs from production example 1 only in that the ethylene-maleic anhydride copolymer was not included in the raw materials for production, and master batch G was obtained under the same conditions as in production example 1.
Preparation example 8
This production example differs from production example 1 only in that the modified fluororesin was replaced with an unmodified fluororesin (reference numeral F201), and the master batch H was obtained under the same conditions as in production example 1.
Example 1
In this embodiment, a low-temperature-resistant and high-wear-resistant nylon material is provided, and the raw materials for preparing the low-temperature-resistant and high-wear-resistant nylon material comprise the following components in percentage by weight:
wherein the polyamide is PA12 resin; the wear-resistant master batch is a wear-resistant master batch A; the lubricant is zinc stearate; antioxidants were 1098 (0.4%), 168 (0.2%) and DSTDP (0.2%).
The preparation method comprises the following steps:
mixing the polyamide, the wear-resistant master batch, the lubricant and the antioxidant in a formula ratio for 5min by a high-speed mixer, and then granulating by a double-screw extruder, wherein the extrusion temperature is 250 ℃, the extrusion speed is 30kg/h, the melt temperature is 255 ℃, and the vacuum degree is-0.08 MPa to obtain the low-temperature-resistant high-wear-resistant nylon material natural-color granules.
Example 2
This example differs from example 1 only in that the abrasion resistant master batch a was replaced with abrasion resistant master batch B, the addition amount was adjusted to 35%, and the polyamide ratio was adjusted to 64%, and the preparation method was the same.
Example 3
In this embodiment, a low-temperature-resistant and high-wear-resistant nylon material is provided, and the raw materials for preparing the low-temperature-resistant and high-wear-resistant nylon material comprise the following components in percentage by weight:
wherein, the polyamide is PA612 resin; the wear-resistant master batch is wear-resistant master batch C; the lubricant is zinc stearate; antioxidants were 1098 (0.4%), 168 (0.2%) and DSTDP (0.2%).
The preparation method comprises the following steps:
mixing the polyamide, the wear-resistant master batch, the lubricant and the antioxidant in a formula ratio for 5min by a high-speed mixer, and then granulating by a double-screw extruder, wherein the extrusion temperature is 260 ℃, the extrusion speed is 30kg/h, the melt temperature is 265 ℃, and the vacuum degree is-0.08 MPa to obtain the low-temperature-resistant high-wear-resistant nylon material natural-color granules.
Example 4
This example differs from example 1 only in that the abrasion resistant master batch a was replaced with abrasion resistant master batch E, the addition amount was adjusted to 28%, and the polyamide ratio was adjusted to 71%, and the preparation method was the same.
Example 5
The present example is different from example 1 only in that the abrasion resistant master batch a was replaced with the abrasion resistant master batch D, the addition amount was adjusted to 19%, the polyamide ratio was adjusted to 80%, and the preparation method was the same.
Example 6
The present example is different from example 3 only in that the wear-resistant mother particle C was replaced with the wear-resistant mother particle B, the addition amount was adjusted to 16%, the polyamide ratio was adjusted to 83%, and the preparation method was the same.
Comparative example 1
This comparative example is different from example 1 only in that the abrasion resistant master batch a was replaced with the same amount of master batch F, and the other conditions were the same as example 1.
Comparative example 2
This comparative example is different from example 1 only in that the abrasion resistant master batch a was replaced with the same amount of master batch G, and the other conditions were the same as example 1.
Comparative example 3
This comparative example is different from example 1 only in that the abrasion resistant master batch a was replaced with the same amount of master batch H, and the other conditions were the same as example 1.
Comparative example 4
The comparative example is different from example 1 only in that the weight percentage of the wear-resistant master batch A is 8%, the weight percentage of the polyamide is 91.1%, and other conditions are the same as example 1.
Comparative example 5
In this embodiment, a low-temperature-resistant and high-wear-resistant nylon material is provided, and the raw materials for preparing the low-temperature-resistant and high-wear-resistant nylon material comprise the following components in percentage by weight:
wherein the polyamide is PA12 resin; the polar group modified ultra-high molecular weight polyethylene is of the mark LY 1040; the ethylene-maleic anhydride copolymer is E60P, and the modified fluororesin is modified fluororesin A; the lubricant is zinc stearate (0.23%), erucamide (0.03%), silicone master batch (0.05%); antioxidants were 1098 (0.4%), 168 (0.25%) and DSTDP (0.2%).
The preparation method comprises the following steps:
mixing polyamide, polar functional group modified ultra-high molecular weight polyethylene, ethylene-maleic anhydride copolymer, modified fluororesin, lubricant and antioxidant in a formula ratio for 5min by a high-speed mixer, and then granulating by a double-screw extruder, wherein the extrusion temperature is 250 ℃, the extrusion speed is 30kg/h, the melt temperature is 255 ℃, and the vacuum degree is-0.08 MPa, so as to obtain the low-temperature-resistant high-wear-resistant nylon material true-color particles.
The nylon materials of examples 1-6 and comparative examples 1-5 were tested for performance by the following methods:
(1) coefficient of friction: testing according to the GB/T3960 standard;
(2) impact strength of the simply supported beam notch: testing according to ISO179 standard;
(3) gloss: the test was carried out according to the method of ASTM D523.
The results of the performance tests are shown in table 1.
TABLE 1
As can be seen from Table 1, the low temperature impact resistance and high wear resistance nylon materials prepared in the embodiments 1-6 of the present invention have excellent low temperature impact property, which is more than 6KJ/m2The modified fluororesin and the ultrahigh molecular weight polyethylene have better compatibility, are intuitively reflected on the glossiness and the low-temperature toughness of the material, and simultaneously have improved performances in all aspects to a certain degree through premixing treatment.
The applicant states that the invention is illustrated by the above examples to the low temperature resistant and high wear resistant nylon material of the invention, the preparation method and the application thereof, but the invention is not limited to the above examples, that is, the invention is not meant to be implemented only by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The low-temperature-resistant high-wear-resistance nylon material is characterized by comprising the following raw materials in percentage by weight:
2. the nylon material of claim 1, characterized in that the polyamide has an average number of carbon atoms per nitrogen atom Nc comprised between 6 and 18, preferably between 9 and 16;
preferably, the polyamide comprises any one of PA612, PA614, PA1012, PA11, PA12, PA1212, PA616 or PA618 or a combination of at least two thereof.
3. The nylon material of claim 1 or 2, wherein the lubricant comprises any one or a combination of at least two of zinc stearate, titanate, stearic acid, erucamide, oleamide, or silicone;
preferably, the antioxidant comprises any one of or a combination of at least two of aromatic amines, sterically hindered phenols, phosphites, sulfur-containing synergists, hydroxylamine benzofuranone derivatives, or potassium iodide-copper iodide inorganic stabilizers.
4. The nylon material with low temperature resistance and high wear resistance according to any one of claims 1 to 3, wherein the wear-resistant master batch is prepared by the following preparation method:
mixing polar functional group modified ultrahigh molecular weight polyethylene, multi-active site polymer, modified fluororesin, lubricant and antioxidant, freezing and grinding to obtain the wear-resistant master batch;
preferably, the content of the polar functional group modified ultrahigh molecular weight polyethylene is 80-95%, the content of the multi-active site polymer is 0.1-5%, the content of the modified fluororesin is 5-20%, the content of the lubricant is 0.6-2.5%, and the content of the antioxidant is 0.2-0.6%, based on 100% by weight of the wear-resistant master batch.
5. The nylon material of claim 4, wherein the polar functional group in the polar functional group-modified ultra-high molecular weight polyethylene comprises any one or a combination of at least two of an acid anhydride group, an epoxy group, a halogen, a carboxyl group, an amino group or a hydroxyl group;
preferably, the molecular weight of the polar functional group-modified ultrahigh molecular weight polyethylene is 30 to 500 ten thousand, preferably 50 to 200 ten thousand;
preferably, the polar functional group-modified ultrahigh molecular weight polyethylene has a density of 0.90 to 1.70g/cm3Preferably 0.93 to 1.50g/cm3；
Preferably, the multi-site polymer comprises any one of or a combination of at least two of an ethylene-maleic anhydride copolymer, a branched polymer, or a polyethyleneimine;
preferably, the copolymerization molar ratio of the ethylene-maleic anhydride copolymer is 1:1-1:5, wherein the mass ratio of ethylene is less than 25%, and the mass ratio of maleic anhydride is more than 75%;
preferably, the ethylene-maleic anhydride copolymer has a molecular weight of 10000-400000, preferably 10000-150000;
preferably, the modified fluororesin includes a silane coupling agent-modified fluororesin and/or a titanate coupling agent-modified fluororesin;
preferably, the fluororesin in the modified fluororesin includes any one or a combination of at least two of FEP, PTFE, ETFE, or PVDF;
preferably, the molecular weight of the fluororesin in the modified fluororesin is 3000-15000, preferably 3500-12000;
preferably, the fluororesin in the modified fluororesin has a particle size of 0.02 to 1.2 μm, preferably 0.05 to 0.8 μm;
preferably, the lubricant comprises any one of or a combination of at least two of zinc stearate, titanate, stearic acid, erucamide, oleamide, or silicone master batch; preferably a combination of zinc stearate, erucamide and silicone master batch;
preferably, the content of the zinc stearate is 0.2-0.4%, the content of the erucamide is 0.2-0.6%, and the content of the silicone master batch is 0.2-1.5% by weight of the wear-resistant master batch of 100%;
preferably, the antioxidant comprises any one of or a combination of at least two of an aromatic amine, a sterically hindered phenol, a phosphite, a thiosynergist, or a hydroxylamine benzofuranone derivative.
6. The nylon material with low temperature resistance and high wear resistance according to claim 4 or 5, wherein the mixing is performed by a torque rheometer;
preferably, the temperature of the mixing is 250-270 ℃, and the time is 5-15 min;
preferably, the freezing is carried out in a liquid nitrogen environment, and the freezing time is 5-10 min;
preferably, the length of the wear-resistant master batch is 2-5 μm.
7. The nylon material with low temperature resistance and high wear resistance as claimed in any one of claims 1 to 6, wherein the raw materials for preparing the nylon material with low temperature resistance and high wear resistance further comprise a plasticizer;
preferably, the content of the plasticizer is 0.1-10% by weight of the low-temperature-resistant and high-wear-resistant nylon material as 100%;
preferably, the plasticizer comprises an ester of p-hydroxybenzoic acid having 2 to 20 carbon atoms and/or an amide of arylsulfonic acid having 2 to 12 carbon atoms; preferably any one or a combination of at least two of P-benzenesulfonamide, N-butylbenzenesulfonamide, methylparaben, N-methylbenzenesulfonamide, ethylparaben, octylparaben, isocetyl paraben, N-octyltoluensulfonic acid amide, N-butylanilic acid amide or 2-ethylhexylbenzenesulfonamide.
8. The nylon material with low temperature resistance and high wear resistance as claimed in any one of claims 1 to 7, wherein the raw materials for preparing the nylon material with low temperature resistance and high wear resistance further comprise other auxiliary agents;
preferably, the content of the other auxiliary agents is 0.1-5% by weight of the low-temperature-resistant and high-wear-resistant nylon material as 100%;
preferably, the other auxiliary agent comprises any one or a combination of at least two of an ultraviolet stabilizer, a nucleating agent, a flame retardant, a pigment, a leveling agent, a heat conducting agent or an electric conducting additive.
9. The preparation method of the nylon material with low temperature resistance and high wear resistance according to any one of claims 1 to 8, characterized by comprising the following steps:
mixing the polyamide, the wear-resistant master batch, the lubricant, the antioxidant, the optional plasticizer and the optional other auxiliary agents according to the formula ratio, and extruding and granulating to obtain the low-temperature-resistant high-wear-resistant nylon material;
preferably, the extrusion granulation is performed by a twin-screw extruder;
preferably, the extrusion temperature of the double-screw extruder is 240-260 ℃, and the extrusion speed is 25-35 kg/h;
preferably, the melt temperature in the extrusion process is 250-270 ℃, and the vacuum degree is-0.05 MPa-0.08 MPa.
10. Use of the low temperature resistant high wear resistant nylon material of any one of claims 1-8 in wear resistant sliders, wear resistant pipes or cables.
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| CN114685985A (en) * | 2022-04-11 | 2022-07-01 | 海信（山东）冰箱有限公司 | High-strength high-wear-resistance easy-to-mold PA66 material, preparation method thereof and refrigerator door hinge |
| CN114990729A (en) * | 2022-06-15 | 2022-09-02 | 广州明晖新材料有限公司 | Wear-resistant nylon yarn and preparation method thereof |
| CN115594966A (en) * | 2022-09-30 | 2023-01-13 | 上海金发科技发展有限公司（Cn） | Polyamide composite material and preparation method and application thereof |
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| CN114685985A (en) * | 2022-04-11 | 2022-07-01 | 海信（山东）冰箱有限公司 | High-strength high-wear-resistance easy-to-mold PA66 material, preparation method thereof and refrigerator door hinge |
| CN114685985B (en) * | 2022-04-11 | 2024-01-23 | 海信冰箱有限公司 | High-strength high-wear-resistance easy-forming PA66 material, preparation method thereof and refrigerator door hinge |
| CN114990729A (en) * | 2022-06-15 | 2022-09-02 | 广州明晖新材料有限公司 | Wear-resistant nylon yarn and preparation method thereof |
| CN115594966A (en) * | 2022-09-30 | 2023-01-13 | 上海金发科技发展有限公司（Cn） | Polyamide composite material and preparation method and application thereof |
| CN115594966B (en) * | 2022-09-30 | 2024-01-02 | 上海金发科技发展有限公司 | Polyamide composite material and preparation method and application thereof |
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