CN114163812B - Low-temperature-resistant high-wear-resistant nylon material and preparation method and application thereof - Google Patents
Low-temperature-resistant high-wear-resistant nylon material and preparation method and application thereof Download PDFInfo
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- CN114163812B CN114163812B CN202111559289.7A CN202111559289A CN114163812B CN 114163812 B CN114163812 B CN 114163812B CN 202111559289 A CN202111559289 A CN 202111559289A CN 114163812 B CN114163812 B CN 114163812B
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- 239000000463 material Substances 0.000 title claims abstract description 99
- 229920001778 nylon Polymers 0.000 title claims abstract description 92
- 239000004677 Nylon Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 80
- 239000004952 Polyamide Substances 0.000 claims abstract description 29
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 29
- 229920002647 polyamide Polymers 0.000 claims abstract description 29
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000000314 lubricant Substances 0.000 claims abstract description 20
- 238000005299 abrasion Methods 0.000 claims description 50
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 35
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 23
- 125000000524 functional group Chemical group 0.000 claims description 19
- 238000001125 extrusion Methods 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- 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
- 229920001577 copolymer Polymers 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 13
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 13
- -1 PA614 Polymers 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000004014 plasticizer Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 2
- YNRCALZIDKRUIR-UHFFFAOYSA-N CCCCCCCCN.OS(CC1=CC=CC=C1)(=O)=O Chemical compound CCCCCCCCN.OS(CC1=CC=CC=C1)(=O)=O YNRCALZIDKRUIR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 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
- 229920006144 PA618 Polymers 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 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
- 239000000654 additive Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000008064 anhydrides Chemical group 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 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
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 2
- ACSJOJBMNBXQTG-UHFFFAOYSA-N n-(2-ethylhexyl)benzenesulfonamide Chemical compound CCCCC(CC)CNS(=O)(=O)C1=CC=CC=C1 ACSJOJBMNBXQTG-UHFFFAOYSA-N 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
- 239000002667 nucleating agent Substances 0.000 claims description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 claims 1
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 claims 1
- 229960002216 methylparaben Drugs 0.000 claims 1
- 238000005453 pelletization Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 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
- 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
- 150000001991 dicarboxylic acids 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
- 239000000843 powder Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- UEOXCHJYRKCZFF-UHFFFAOYSA-N O1C(CC2=C1C=CC=C2)=O.NO Chemical class O1C(CC2=C1C=CC=C2)=O.NO UEOXCHJYRKCZFF-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- 239000003365 glass fiber 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
- RIKCMEDSBFQFAL-UHFFFAOYSA-N octyl 4-hydroxybenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=C(O)C=C1 RIKCMEDSBFQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 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
- 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 description 1
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IGDWPXAOHHLWFK-UHFFFAOYSA-N benzenesulfonic acid;butan-1-amine Chemical compound CCCCN.OS(=O)(=O)C1=CC=CC=C1 IGDWPXAOHHLWFK-UHFFFAOYSA-N 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
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229960001617 ethyl hydroxybenzoate Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GYCKQBWUSACYIF-UHFFFAOYSA-N o-hydroxybenzoic acid ethyl ester Natural products CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 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
Abstract
The invention provides a low-temperature-resistant high-wear-resistant nylon material, and a preparation method and application thereof, wherein the preparation raw materials of the low-temperature-resistant high-wear-resistant nylon material comprise the following components in percentage by weight: 60-87% of polyamide; 12-38% of wear-resistant master batch; 0.2-0.8% 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 the 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-resistant nylon material, a preparation method and application thereof.
Background
Nylon materials are widely paid attention to as engineering plastics with high mechanical strength, excellent self-lubricating property and oil resistance, and have more application in the aspects of pipeline cables and bearings due to the remarkable performance, and the application in the field is gradually expanded along with the gradual expansion of the wind power industry.
The self-lubricity of the nylon material itself and its low coefficient of friction allow the wear resistance of the material to be adapted to most conduit cable requirements. Among many nylons, short-chain nylons such as PA6 or PA66 nylon have excellent mechanical properties, heat and cold resistance, abrasion resistance and weather resistance, and are widely used for mechanical parts, but nylon is not suitable for manufacturing parts requiring high dimensional accuracy due to its large hygroscopicity and poor dimensional stability. Long carbon chain nylons such as PA11 and PA12 have natural advantages in terms of water absorption and density, and are widely focused on maintaining good dimensional stability and good solvent resistance.
The existing wear-resistant materials are usually polytetrafluoroethylene micropowder, molybdenum disulfide, aramid powder, silicone master batch, graphite, ultra-high molecular weight polyethylene, wollastonite and the like, but many materials belong to inorganic filler or nonpolar materials, and have certain problems in compatibility with nylon, so that the defects in a system are more, the defects of the materials are easily amplified under the action of external force, and the mechanical properties of the materials are easily deteriorated, on the other hand, the system compatibility is poorer, and phenomena such as shark skin, dark lines and the like are easily generated in the processing process, so that the appearance of the materials is deteriorated, and the improvement of the system compatibility is favorable for improving the performance of the nylon materials.
CN112143242a discloses a high-strength wear-resistant nylon composite material, which is prepared from PA66, glass fiber, wear-resistant agent (polytetrafluoroethylene, molybdenum disulfide, etc.), etc., the nylon composite material prepared by the invention has low temperature and wear-resistant properties, but the surface of the prepared material is rough due to the introduction of the glass fiber, thus restricting the application of the material, and meanwhile, the compatibility of the 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 causes that the material cannot prepare natural color after extrusion, and limits the application of the material.
Therefore, development of a nylon material which is resistant to low temperature and abrasion, has good compatibility and can maintain natural color is desired in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-temperature-resistant high-wear-resistant 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 the natural color, and is suitable for various parts requiring special performance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a low-temperature-resistant high-wear-resistant nylon material, which is prepared from the following raw materials in percentage by weight:
in the invention, the wear-resistant master batch is added to improve the wear resistance of the nylon material; the polyamide belongs to polar materials, and the tail end of the polyamide is provided with amino and carboxyl, which can react with most groups, such as maleic anhydride, epoxy, carboxyl, hydroxyl, esters and the like, which are common in general.
In the invention, the polyamide can be used in an amount of 60%, 65%, 70%, 75%, 80%, 85% or 87% in the raw materials for preparing the low-temperature-resistant and high-wear-resistant nylon material.
In the invention, the wear-resistant master batch can be used in the amount of 12%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 35% or 38% in the raw materials for preparing the low-temperature-resistant high-wear-resistant nylon material.
In the invention, the lubricant can be used in an amount of 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.8% in the preparation raw materials of the low-temperature-resistant and high-wear-resistant nylon material.
In the preparation raw materials of the low-temperature-resistant 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 Nc per nitrogen atom of between 6 and 18 (for example 6, 8, 10, 13, 15 or 18, etc.), preferably 9 to 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 resins prepared by lactams have at least 6 carbon atoms per nitrogen atom and in the case of the resins prepared by diamines and dicarboxylic acids the arithmetic average of each carbon atom in the mixed components of diamines and dicarboxylic acids must be at least 6. Polyamides for which the present rule applies are, for example: PA1012 is prepared from decanediamine (10 carbon atoms) and dodecanedioic acid (12 carbon atoms), and PA11 is prepared by polycondensation of aminoundecanoic acid (11 carbon atoms).
Preferably, the polyamide comprises any one or a combination of at least two of PA612, PA614, PA1012, PA11, PA12, PA1212, PA616 or PA 618.
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 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 ultra-high 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 the wear-resistant material (polytetrafluoroethylene micropowder, molybdenum disulfide, aramid powder, silicone master batch, graphite and ultra-high molecular weight polyethylene) is directly mixed with polyamide, the wear-resistant master batch prepared by modifying the ultra-high molecular weight polyethylene and the fluororesin and then mixing the polar functional group modified ultra-high molecular weight polyethylene, the multi-active site polymer, the modified fluororesin and the auxiliary agent has better compatibility.
In the invention, the multi-active-site polymer and the modified fluororesin are mutually matched, so that the prepared wear-resistant master batch has better compatibility with polyamide; meanwhile, the ultra-high molecular weight polyethylene is provided with polar functional groups after surface treatment, and the reactivity is considered, so that the dispersion and the dispersion size 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 can be realized without adding a toughening agent.
In addition, the wear-resistant master batch provided by the invention ensures that the color of the nylon material is not limited, and the color matching of different colors can be carried out according to practical application in the later period.
Preferably, the polar functional group modified ultra high molecular weight polyethylene is present in an amount of 80-95% (e.g., 80%, 83%, 85%, 88%, 90%, 93%, or 95%, etc.), the multi-active site polymer is present in an amount of 0.1-5% (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 5-20% (e.g., 5%, 8%, 10%, 13%, 15%, 18%, or 20%, etc.), the lubricant is present in an amount of 0.6-2.5% (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 0.2-0.6% (e.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 groups in the polar functional group-modified ultra-high molecular weight polyethylene include anhydride groups, epoxy groups, halogens, carboxyl groups, amino groups, hydroxyl groups, and derivatives of any one or a combination of at least two of the foregoing groups. These polar functional groups may react with the nylon material.
Preferably, the polar functional group modified ultra high molecular weight polyethylene has a molecular weight of 30 to 500 tens of thousands, for example 30, 50, 80, 100, 200, 300, 400 or 500 tens of thousands, preferably 50 to 200 tens of thousands.
Preferably, the polar functional group-modified ultra-high molecular weight polyethylene has a density of 0.90 to 1.70g/cm 3 For example 0.90g/cm 3 、1.00g/cm 3 、1.10g/cm 3 、1.20g/cm 3 、1.30g/cm 3 、1.40g/cm 3 、1.50g/cm 3 、1.60g/cm 3 Or 1.70g/cm 3 Etc., preferably 0.93-1.50g/cm 3 。
Preferably, the multi-active site polymer comprises any one 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 formulaThe branched polymer may have the formula +.>Wherein the hydroxyl group may be replaced with a carboxyl group; the structural formula of the polyethyleneimine can be +.>
Preferably, the ethylene-maleic anhydride copolymer has a copolymerization molar ratio of 1:1 to 1:5 (e.g., 1:1, 1:2, 1:3, 1:4, or 1:5, etc.), wherein the mass ratio of ethylene is < 25%, and the mass ratio of maleic anhydride is > 75%.
Preferably, the molecular weight of the ethylene-maleic anhydride copolymer is 10000-400000, such as 10000, 50000, 100000, 200000, 300000 or 400000, and preferably 10000-150000, and the physical state thereof may be solid powder, granule.
Preferably, the branched polymer may be selected from polyesters of varying degrees of branching, wherein the reactive groups contained therein may be selected from carboxyl, hydroxyl, and epoxy groups and the like, having a melting point of 120-180 ℃, such as 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ or the like.
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 comprises 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 to 15000, for example 3000, 5000, 8000, 10000, 13000 or 15000, etc., preferably 3500 to 12000.
Preferably, the particle size of the fluororesin in the modified fluororesin is 0.02 to 1.2 μm, for example 0.02 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1.0 μm or 1.2 μm, etc., preferably 0.05 to 0.8 μm.
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 an alkane coupling agent modified fluororesin and/or a titanate coupling agent.
Preferably, the lubricant comprises any one 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 masterbatch is preferred.
Preferably, the zinc stearate is present in an amount of 0.2 to 0.4% (e.g., 0.2%, 0.3%, or 0.4%, etc.), the erucamide 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.), and the silicone masterbatch is present in an amount of 0.2 to 1.5% (e.g., 0.2%, 0.5%, 0.8%, 1%, 1.3%, or 1.5%, etc.), based on 100% by weight of the abrasion resistant masterbatch.
Preferably, the antioxidant comprises any one or a combination of at least two of an aromatic amine, a sterically hindered phenol, a phosphite, a sulphur-containing synergist or a hydroxylamine benzofuranone derivative.
Preferably, the mixing is performed by a torque rheometer.
Preferably, the temperature of the mixing is 250-270 ℃, e.g. 250 ℃, 255 ℃, 260 ℃, 265 ℃ or 270 ℃, etc., for a period of 5-15min, e.g. 5min, 10min or 15min, etc.
Preferably, the freezing is performed in a liquid nitrogen environment for a period of time ranging from 5 to 10 minutes, such as 5 minutes, 10 minutes, 15 minutes, etc.
Preferably, the wear resistant master batch has a length of 2-5 μm, e.g. 2 μm, 3 μm, 4 μm or 5 μm etc.
Preferably, the preparation raw materials of the low-temperature-resistant high-wear-resistant nylon material further comprise a plasticizer.
Preferably, the plasticizer is present in an amount of 0.1 to 10%, such as 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc., based on 100% by weight of the low temperature resistant, 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 aryl sulfonic 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, methyl P-hydroxybenzoate, N-methylbenzenesulfonamide, ethyl hydroxybenzoate, octyl P-hydroxybenzoate, isocetyl P-hydroxybenzoate, N-octylamide toluene sulfonic acid, N-butylamide benzene sulfonic acid or 2-ethylhexyl benzenesulfonamide.
Preferably, the preparation raw materials of the low-temperature-resistant high-wear-resistant nylon material also comprise other auxiliary agents.
Preferably, the content of the other auxiliary agent is 0.1-5%, for example 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4% or 5% based on 100% by weight of the low temperature resistant and high abrasion resistant nylon material.
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 a conductive performance additive.
In a second aspect, the invention provides a preparation method of the low-temperature-resistant high-wear-resistant nylon material in the first aspect, which 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, extruding and granulating, cooling, granulating and drying to obtain the low-temperature-resistant high-wear-resistant 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℃260℃or the like and an extrusion speed of 25 to 35kg/h such as 25kg/h, 30kg/h or 35kg/h or the like.
Preferably, the melt temperature of the extrusion process is from 250℃to 270℃such as 250℃255℃260℃265℃270℃or the like, and the vacuum is from-0.05 MPa to-0.08 MPa such as-0.05 MPa, -0.06MPa, -0.07MPa or-0.08 MPa or the like.
In a third aspect, the invention provides an application of the low-temperature-resistant high-wear-resistant nylon material in a wear-resistant sliding block, a wear-resistant pipeline or a cable. The low temperature resistant and high wear resistant nylon material of the first aspect can be used for extrusion or injection molding.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) In the invention, the addition of the wear-resistant master batch improves the wear resistance (friction coefficient: 0.15-0.27) of the nylon material, and the wear-resistant master batch has better compatibility with polyamide;
(2) In the invention, the multi-active-site polymer and the modified fluororesin are mutually matched, so that the prepared wear-resistant master batch has better compatibility with polyamide; meanwhile, the ultra-high molecular weight polyethylene is provided with polar functional groups after surface treatment, and the reactivity is considered, so that the dispersion of the wear-resistant master batch in the 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 nylon material can be realized without adding a toughening agent (-30 ℃ simple beam notch impact strength: 7.2-25.4 KJ/m) 2 )。
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The raw material brands 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: the fluorine resins (F201 and AT-3000) were mixed with a silane coupling agent (KH 550) in a mass ratio of 100:0.8, respectively, to obtain a modified fluorine resin A and a modified fluorine resin B.
Preparation example 1
In the preparation example, a wear-resistant master batch is provided, and the wear-resistant master batch is prepared by the following preparation method:
88.4% of polar group modified ultra-high molecular weight polyethylene, 0.4% of ethylene-maleic anhydride copolymer, 10% of modified fluororesin, 0.2% of zinc stearate, 0.2% of erucamide, 0.4% of silicone master batch and 0.4% of phosphite antioxidant are mixed by a torque rheometer, the mixing temperature is 250 ℃ for 5min, and after the mixing is completed, the mixture is frozen for 10min in a liquid nitrogen environment and ground, so that the wear-resistant master batch A with the length of 2-5 mu m is obtained.
Wherein the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; the ethylene-maleic anhydride copolymer is marked as E60P; the brand of the modified fluororesin is modified fluororesin A; the phosphite antioxidant is Irganox 168.
Preparation example 2
In the preparation example, a wear-resistant master batch is provided, and the wear-resistant master batch is prepared by the following preparation method:
93.7% of polar group modified ultra-high molecular weight polyethylene, 0.3% of polyethylenimine, 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 are mixed by a torque rheometer, the mixing temperature is 250 ℃ for 5min, and after the mixing is completed, the mixture is frozen for 10min in a liquid nitrogen environment and ground, so that the wear-resistant master batch B with the length of 2-5 mu m is obtained.
Wherein the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; the brand of the polyethyleneimine is P1050; the brand of the modified fluororesin is modified fluororesin B; the phosphite antioxidant is Irganox 168.
Preparation example 3
In the preparation example, a wear-resistant master batch is provided, and the wear-resistant master batch is prepared by the following preparation method:
79% of polar group modified ultra-high 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 are mixed by a torque rheometer, the mixing temperature is 250 ℃ for 5min, and after the mixing is completed, the mixture is frozen for 10min in a liquid nitrogen environment and ground, so that the wear-resistant master batch C with the length of 2-5 mu m is obtained.
Wherein the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; the brand of the hyperbranched polyester is Hyper C181; the brand of the modified fluororesin is modified fluororesin A; the phosphite antioxidant is Irganox 168.
Preparation example 4
In the preparation example, a wear-resistant master batch is provided, and the wear-resistant master batch is prepared by the following preparation method:
93.7% of polar group modified ultra-high 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 are mixed by a torque rheometer, the mixing temperature is 250 ℃ for 5min, and after the mixing is completed, the mixture is frozen for 10min in a liquid nitrogen environment and ground, so that the wear-resistant master batch D with the length of 2-5 mu m is obtained.
Wherein the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; the brand of the hyperbranched polyester is Hyper C181; the brand of the modified fluororesin is modified fluororesin B; the phosphite antioxidant is Irganox 168.
Preparation example 5
In the preparation example, a wear-resistant master batch is provided, and the wear-resistant master batch is prepared by the following preparation method:
79.5% of polar group modified ultra-high molecular weight polyethylene, 1.5% of ethylene-maleic anhydride copolymer, 17.8% of modified fluororesin, 0.2% of zinc stearate, 0.4% of erucic acid amide, 0.2% of silicone master batch and 0.4% of phosphite antioxidant are mixed by a torque rheometer, the mixing temperature is 250 ℃ and the time is 5min, and after the mixing is completed, the mixture is frozen for 10min in a liquid nitrogen environment and ground, so that the wear-resistant master batch E with the length of 2-5 mu m is obtained.
Wherein the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; the ethylene-maleic anhydride copolymer is identified by the trademark E400; the brand of the modified fluororesin is modified fluororesin B; the phosphite antioxidant is Irganox 168.
Preparation example 6
The present preparation example differs from preparation example 1 only in that the polar group-modified ultra-high molecular weight polyethylene was replaced with an unmodified ultra-high molecular weight polyethylene (brand G015T), and the other conditions were the same as those of preparation example 1, to obtain master batch F.
Preparation example 7
The preparation example differs from preparation example 1 only in that the ethylene-maleic anhydride copolymer was not included in the preparation raw material, and the other conditions were the same as those of preparation example 1, to obtain a master batch G.
Preparation example 8
The present preparation example differs from preparation example 1 only in that the modified fluororesin was replaced with an unmodified fluororesin (trade name: F201), and the other conditions were the same as those of preparation example 1, to obtain a master batch H.
Example 1
The embodiment provides a low-temperature-resistant high-wear-resistant nylon material, which is prepared from the following raw materials in percentage by weight:
wherein the polyamide is PA12 resin; the wear-resistant master batch is 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 polyamide, wear-resistant master batch, lubricant and antioxidant in a formula amount for 5min by a high-speed mixer, 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 natural-color particles.
Example 2
The difference between this example and example 1 is only that the abrasion resistant master batch A was replaced with the abrasion resistant master batch B, the addition was adjusted to 35%, the polyamide ratio was adjusted to 64%, and the preparation method was the same.
Example 3
The embodiment provides a low-temperature-resistant high-wear-resistant nylon material, which is prepared from the following raw materials in percentage by weight:
wherein the polyamide is PA612 resin; the wear-resistant master batch is a 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 polyamide, wear-resistant master batch, lubricant and antioxidant in the formula amount for 5min by a high-speed mixer, 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, so as to obtain the low-temperature-resistant high-wear-resistant nylon material natural-color particles.
Example 4
The difference between this example and example 1 is only that the abrasion resistant master batch A was replaced with the abrasion resistant master batch E, the addition was adjusted to 28%, the polyamide ratio was adjusted to 71%, and the preparation method was the same.
Example 5
The difference between this example and example 1 is only that the abrasion resistant master batch A was replaced with the abrasion resistant master batch D, the addition was adjusted to 19%, the polyamide ratio was adjusted to 80%, and the preparation method was the same.
Example 6
The difference between this example and example 3 is that the abrasion resistant master batch C was replaced with the abrasion resistant master batch B, the addition was adjusted to 16%, the polyamide ratio was adjusted to 83%, and the preparation method was the same.
Comparative example 1
This comparative example differs from example 1 only in that the wear-resistant master batch a was replaced with an equal amount of master batch F, with the other conditions being the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that the abrasion resistant master batch a was replaced with an equal amount of master batch G, with the other conditions being the same as in example 1.
Comparative example 3
This comparative example differs from example 1 only in that the abrasion resistant master batch a was replaced with an equal amount of master batch H, with the other conditions being the same as in example 1.
Comparative example 4
This comparative example differs from example 1 only in that the weight percentage of the abrasion resistant masterbatch A is 8%, the weight percentage of the polyamide is 91.1% and the other conditions are the same as in example 1.
Comparative example 5
The embodiment provides a low-temperature-resistant high-wear-resistant nylon material, which is prepared from the following raw materials in percentage by weight:
wherein the polyamide is PA12 resin; the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; 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 amount for 5min by a high-speed mixer, 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 natural-color particles.
The nylon materials of examples 1-6 and comparative examples 1-5 were tested for performance as follows:
(1) Coefficient of friction: testing according to GB/T3960 standard;
(2) Notched impact strength of simply supported beams: testing according to ISO179 standard;
(3) Gloss level: the test was performed according to the method of ASTM D523.
The results of the performance test are shown in Table 1.
TABLE 1
As can be seen from Table 1, the low temperature resistant and high abrasion resistant nylon materials prepared in examples 1 to 6 of the present invention are excellent in low temperature impact properties, all being more than 6KJ/m 2 The modified fluororesin and the ultrahigh molecular weight polyethylene have better compatibility, are intuitively embodied on the glossiness and the low-temperature toughness of the material, and simultaneously, have certain improvement on the performances of the material in all aspects through premixing treatment.
The applicant states that the low temperature resistant and high abrasion resistant nylon material of the present invention and the preparation method and application thereof are described by the above examples, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (38)
1. The low-temperature-resistant high-wear-resistant nylon material is characterized by comprising the following raw materials in percentage by weight:
60-87% of polyamide;
12-38% of wear-resistant master batch;
0.2-0.8% of lubricant;
0.8-1.2% of antioxidant;
the wear-resistant master batch is prepared by the following preparation method:
mixing polar functional group modified ultra-high molecular weight polyethylene, multi-active site polymer, modified fluororesin, lubricant and antioxidant, freezing and grinding to obtain the wear-resistant master batch;
the weight of the wear-resistant master batch is 100%, the content of the polar functional group modified ultra-high 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%;
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 anhydride group, an epoxy group, a carboxyl group, an amino group and a hydroxyl group;
the multi-active site polymer comprises any one or a combination of at least two of ethylene-maleic anhydride copolymer, branched polymer or polyethyleneimine;
the branched polymer is selected from polyesters with different branching degrees, wherein active groups contained in the branched polymer are selected from carboxyl, hydroxyl or epoxy, and the melting point of the branched polymer is 120-180 ℃;
the modified fluororesin comprises silane coupling agent modified fluororesin and/or titanate coupling agent modified fluororesin.
2. The low temperature and high abrasion resistant nylon material according to claim 1, wherein said polyamide has an average number of carbon atoms Nc per nitrogen atom comprised between 6 and 18.
3. The low temperature and high abrasion resistant nylon material according to claim 2, wherein said polyamide has an average number of carbon atoms Nc per nitrogen atom of between 9 and 16.
4. The low temperature and high abrasion resistant nylon material according to claim 1, wherein said polyamide comprises any one or a combination of at least two of PA612, PA614, PA1012, PA11, PA12, PA1212, PA616 or PA 618.
5. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the lubricant in the raw materials for preparing the low temperature and high abrasion resistant nylon material comprises any one or a combination of at least two of zinc stearate, titanate, stearic acid, erucamide, oleamide or silicone.
6. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the antioxidant in the raw material for preparing the low temperature and high abrasion resistant nylon material comprises any one or a combination of at least two of aromatic amine, sterically hindered phenol, phosphite, sulfur-containing synergist or potassium iodide-copper iodide inorganic stabilizer.
7. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the polar functional group modified ultra-high molecular weight polyethylene has a molecular weight of 30 to 500 tens of thousands.
8. The low temperature resistant and high abrasion resistant nylon material according to claim 7, wherein the polar functional group modified ultra-high molecular weight polyethylene has a molecular weight of 50 to 200 tens of thousands.
9. The nylon material of claim 1, wherein the polar functional group modified ultra-high molecular weight polyethylene has a density of 0.90-1.70g/cm 3 。
10. The nylon material of claim 9, wherein the polar functional group modified ultra-high molecular weight polyethylene has a density of 0.93-1.50g/cm 3 。
11. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the copolymerization mole ratio of the ethylene-maleic anhydride copolymer is 1:1-1:5, wherein the mass ratio of ethylene is < 25%, and the mass ratio of maleic anhydride is > 75%.
12. The low temperature and high abrasion resistant nylon material according to claim 1, wherein said ethylene-maleic anhydride copolymer has a molecular weight of 10000 to 400000.
13. The low temperature and high abrasion resistant nylon material according to claim 12, wherein said ethylene-maleic anhydride copolymer has a molecular weight of 10000 to 150000.
14. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the fluororesin in the modified fluororesin comprises any one of FEP, PTFE, ETFE or PVDF or a combination of at least two thereof.
15. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the molecular weight of the fluororesin in the modified fluororesin is 3000 to 15000.
16. The low temperature and high abrasion resistant nylon material according to claim 15, wherein the molecular weight of the fluororesin in the modified fluororesin is 3500 to 12000.
17. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the particle size of the fluororesin in the modified fluororesin is 0.02 to 1.2 μm.
18. The low temperature resistant and high abrasion resistant nylon material according to claim 17, wherein the particle size of the fluororesin in the modified fluororesin is 0.05 to 0.8 μm.
19. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the lubricant in the abrasion resistant master batch preparation raw material comprises any one or a combination of at least two of zinc stearate, titanate, stearic acid, erucamide, oleamide or silicone master batch.
20. The low temperature and high abrasion resistant nylon material according to claim 19, wherein the lubricant in the abrasion resistant master batch preparation raw material comprises a combination of zinc stearate, erucamide and silicone master batch.
21. The nylon material of claim 20, wherein the zinc stearate is 0.2-0.4%, the erucamide is 0.2-0.6%, and the silicone masterbatch is 0.2-1.5% by weight of the wear-resistant masterbatch is 100%.
22. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the antioxidant in the abrasion resistant masterbatch preparation raw material comprises any one or a combination of at least two of aromatic amine, sterically hindered phenol, phosphite or sulfur-containing synergist.
23. The low temperature and high abrasion resistant nylon material according to claim 1, wherein said mixing is performed by a torque rheometer.
24. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the temperature of the mixing is 250-270 ℃ for 5-15min.
25. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the freezing is performed in a liquid nitrogen environment for 5-10 min.
26. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the length of the abrasion resistant master batch is 2-5 μm.
27. The low temperature-resistant and high wear-resistant nylon material according to claim 1, wherein the low temperature-resistant and high wear-resistant nylon material further comprises a plasticizer.
28. The nylon material of claim 27, wherein the plasticizer is present in an amount of 0.1 to 10% based on 100% by weight of the nylon material.
29. The low temperature and high abrasion resistant nylon material according to claim 27, wherein said plasticizer comprises an ester of p-hydroxybenzoic acid having 2 to 20 carbon atoms and/or an amide of aryl sulfonic acid having 2 to 12 carbon atoms.
30. The low temperature and high abrasion resistant nylon material according to claim 29, wherein said plasticizer comprises any one or a combination of at least two of P-benzenesulfonamide, N-butylbenzenesulfonamide, methyl parahydroxybenzoate, N-methylbenzenesulfonamide, ethyl parahydroxybenzoate, octyl parahydroxybenzoate, isohexadecyl parahydroxybenzoate, N-octylamide toluene sulfonic acid, N-butylbenzenesulfonamide, or 2-ethylhexyl benzenesulfonamide.
31. The low-temperature-resistant and high-wear-resistant nylon material according to claim 1, wherein the preparation raw materials of the low-temperature-resistant and high-wear-resistant nylon material further comprise other auxiliary agents.
32. The nylon material of claim 31, wherein the other auxiliary agent is present in an amount of 0.1-5% based on 100% by weight of the nylon material.
33. The low temperature and high abrasion resistant nylon material according to claim 31, wherein said other auxiliary agents comprise any one or a combination of at least two of ultraviolet stabilizers, nucleating agents, flame retardants, pigments, leveling agents, heat conductive agents or conductive performance additives.
34. The method for preparing a low temperature resistant and high abrasion resistant nylon material according to any one of claims 1 to 33, wherein said method comprises the steps of:
and 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 amount, extruding and granulating to obtain the low-temperature-resistant high-wear-resistant nylon material.
35. The method of claim 34, wherein the extrusion pelletization is performed by a twin screw extruder.
36. The process of claim 35, wherein the twin screw extruder has an extrusion temperature of 240 ℃ to 260 ℃ and an extrusion speed of 25 to 35 kg/h.
37. The method according to claim 34, wherein the melt temperature during extrusion is 250 ℃ to 270 ℃ and the vacuum degree is-0.05 MPa to-0.08 MPa.
38. Use of a low temperature resistant high wear resistant nylon material according to any one of claims 1-33 in a wear resistant slider, a wear resistant pipe or a cable.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111559289.7A CN114163812B (en) | 2021-12-20 | 2021-12-20 | Low-temperature-resistant high-wear-resistant nylon material and preparation method and application thereof |
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