CN111704796B - Electroplating nylon material and preparation method thereof - Google Patents
Electroplating nylon material and preparation method thereof Download PDFInfo
- Publication number
- CN111704796B CN111704796B CN202010612262.9A CN202010612262A CN111704796B CN 111704796 B CN111704796 B CN 111704796B CN 202010612262 A CN202010612262 A CN 202010612262A CN 111704796 B CN111704796 B CN 111704796B
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- glass fiber
- nylon material
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- 239000000463 material Substances 0.000 title claims abstract description 86
- 239000004677 Nylon Substances 0.000 title claims abstract description 85
- 229920001778 nylon Polymers 0.000 title claims abstract description 85
- 238000009713 electroplating Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000003365 glass fiber Substances 0.000 claims abstract description 88
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 74
- 239000011707 mineral Substances 0.000 claims abstract description 73
- -1 rare earth ions Chemical class 0.000 claims abstract description 60
- 229920002647 polyamide Polymers 0.000 claims abstract description 50
- 239000004952 Polyamide Substances 0.000 claims abstract description 49
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 36
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims abstract description 9
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 150000004645 aluminates Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000013522 chelant Substances 0.000 claims description 4
- 239000012760 heat stabilizer Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 125000005822 ethenylethoxy group Chemical group [H]\[#6]([H])=[#6](\[H])C([H])([H])C([H])([H])[#8]-* 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- QOWUTEUEDJTSAX-UHFFFAOYSA-H C(CC)O[Zr+2]OCCC.C(C)C(C(=O)[O-])(C(O)(C(=O)[O-])CC(=O)[O-])CC.C(C)C(C(=O)[O-])(C(O)(C(=O)[O-])CC(=O)[O-])CC.C(CC)O[Zr+2]OCCC.C(CC)O[Zr+2]OCCC Chemical compound C(CC)O[Zr+2]OCCC.C(C)C(C(=O)[O-])(C(O)(C(=O)[O-])CC(=O)[O-])CC.C(C)C(C(=O)[O-])(C(O)(C(=O)[O-])CC(=O)[O-])CC.C(CC)O[Zr+2]OCCC.C(CC)O[Zr+2]OCCC QOWUTEUEDJTSAX-UHFFFAOYSA-H 0.000 claims description 2
- 229910021532 Calcite Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 235000019738 Limestone Nutrition 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229920006152 PA1010 Polymers 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 241001625808 Trona Species 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052626 biotite Inorganic materials 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- CXUJOBCFZQGUGO-UHFFFAOYSA-F calcium trimagnesium tetracarbonate Chemical compound [Mg++].[Mg++].[Mg++].[Ca++].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O CXUJOBCFZQGUGO-UHFFFAOYSA-F 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910001649 dickite Inorganic materials 0.000 claims description 2
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010459 dolomite Substances 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- RJOJUSXNYCILHH-UHFFFAOYSA-N gadolinium(3+) Chemical compound [Gd+3] RJOJUSXNYCILHH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 229910000515 huntite Inorganic materials 0.000 claims description 2
- 229910001449 indium ion Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006028 limestone Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052627 muscovite Inorganic materials 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010448 nahcolite Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229920006119 nylon 10T Polymers 0.000 claims description 2
- 229910052628 phlogopite Inorganic materials 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 claims description 2
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052611 pyroxene Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 229910052665 sodalite Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 229910052902 vermiculite Inorganic materials 0.000 claims description 2
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- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 2
- 241001595840 Margarites Species 0.000 claims 1
- 229940125717 barbiturate Drugs 0.000 claims 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 claims 1
- 229910052630 margarite Inorganic materials 0.000 claims 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical class O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 7
- DGLFSNZWRYADFC-UHFFFAOYSA-N chembl2334586 Chemical compound C1CCC2=CN=C(N)N=C2C2=C1NC1=CC=C(C#CC(C)(O)C)C=C12 DGLFSNZWRYADFC-UHFFFAOYSA-N 0.000 description 6
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- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- HVYLDJKDVOOTHV-UHFFFAOYSA-N acetic acid;2-iminoethanethiol Chemical compound CC(O)=O.CC(O)=O.SCC=N HVYLDJKDVOOTHV-UHFFFAOYSA-N 0.000 description 1
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- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
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- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
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- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
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- SNMVVAHJCCXTQR-UHFFFAOYSA-K thulium(3+);triacetate Chemical compound [Tm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SNMVVAHJCCXTQR-UHFFFAOYSA-K 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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Abstract
The invention provides an electroplating nylon material and a preparation method thereof. The electroplating nylon material comprises the following components in parts by weight: 40-80 parts of polyamide, 10-50 parts of modified mineral and 10-30 parts of modified glass fiber, wherein the total weight part of the polyamide, the modified mineral and the modified glass fiber is 100 parts; the modified mineral is a mineral with a silane coupling agent bonded on the surface and rare earth ions absorbed; the modified glass fiber is a glass fiber with the surface bridged with maleic anhydride grafted ultrahigh molecular weight polyethylene through a silane coupling agent and adsorbed with rare earth ions. The electroplating nylon material is prepared by mixing the components and then carrying out melt extrusion by using an extruder. The electroplating nylon material provided by the invention has good electroplating performance, rigidity, heat resistance and impact toughness through the synergistic cooperation of the modified minerals and the modified glass fibers.
Description
Technical Field
The invention belongs to the technical field of nylon materials, and relates to an electroplating nylon material and a preparation method thereof.
Background
Polyamide (PA), commonly known as nylon, is a linear polymer having an amide bond (-CONH-) as a repeating unit in the molecule, and can be prepared by polycondensation of dibasic acid and diamine, or by ring-opening polymerization of amino acid caprolactam. The polyamide is an engineering plastic with excellent performance, has the characteristics of good mechanical strength, self-lubricating performance, good wear resistance, shock absorption, noise reduction and the like, and is widely applied to the industries of machinery, automobiles, electric appliances and the like. However, polyamide materials also have some drawbacks: on one hand, polar amido bonds exist in PA molecules, so that the PA molecules easily absorb water, and the PA molecules have poor dimensional stability and reduced mechanical strength; on the other hand, the notch impact toughness of PA is poor, and the heat distortion temperature under the condition of 1.80MPa is low, so that the application range of PA is limited by the problems. The existing nylon materials are generally added with glass fibers to remarkably improve the strength and modulus, so the glass fibers become almost indispensable components of the nylon materials.
The plastic electroplating is to coat metal on the surface of the plastic, so that good metal texture can be realized, the plastic product can replace the metal product to reduce the weight, the appearance and the decoration of the plastic are effectively improved, and the performances of the plastic in the aspects of electricity, heat, corrosion resistance and the like are also improved. At present, a large number of plastic electroplating products are applied to the industries of electronics, automobiles, household appliances and the like.
The pure nylon material has poor dimensional stability and low bonding force with metal, is generally not easy to be electroplated and needs special modification treatment. CN 108219450A discloses a high-strength, high-modulus, low-shrinkage electroplated nylon material and a preparation method thereof, the electroplated nylon material comprises the following raw materials by weight percent: 23-75% of nylon resin, 5-10% of PA1335, 0-35% of glass fiber, 20-30% of filling mineral, 0-1% of lubricant and 0-1% of antioxidant; the crystallinity of the nylon material is reduced and the dimensional stability of the nylon material is improved by adding the PA1335 amorphous nylon; the nylon material is endowed with electroplating property by combining the filling minerals with special sizes and alkalescence, so that the nylon material has outstanding mechanical properties and excellent electroplating effect. However, the glass fiber often causes floating fiber on the surface of the nylon material, increases roughness, is not beneficial to the adhesion of an electroplated layer, and deteriorates electroplating effect; the inorganic mineral has poor compatibility with the high polymer material and poor dispersibility, so that the improvement of the platability of the nylon material is limited, and the impact resistance of the nylon material is possibly reduced.
Therefore, there is a need in the art to develop a nylon material with good platability, rigidity, heat resistance and impact toughness at low and normal temperatures to meet the application requirements
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an electroplating nylon material and a preparation method thereof. Compared with the common nylon material, the electroplating nylon material has better electroplating performance, rigidity, heat resistance and toughness through the synergistic cooperation of the modified minerals and the modified glass fibers.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an electroplated nylon material, which comprises the following components in parts by weight: 40-80 parts of polyamide, 10-50 parts of modified mineral and 10-30 parts of modified glass fiber, wherein the total weight part of the polyamide, the modified mineral and the modified glass fiber is 100 parts;
the modified mineral is a mineral with a silane coupling agent bonded on the surface and rare earth ions absorbed;
the modified glass fiber is a glass fiber with the surface bridged with maleic anhydride grafted ultrahigh molecular weight polyethylene through a silane coupling agent and adsorbed with rare earth ions.
In the invention, the surface modification is carried out on the minerals through the silane coupling agent and the rare earth ions, so that the compatibility of the minerals and a nylon matrix and the dispersity of the minerals in the nylon matrix are improved, and the improvement effect of the minerals on the electroplatability of a nylon material is improved. The surface modification is carried out on the glass fiber through maleic anhydride grafted ultra-high molecular weight polyethylene (UHMWPE-g-MAH) and rare earth ions, on one hand, the ultra-high molecular weight polyethylene has a self-lubricating effect and is beneficial to reducing the shear fracture of the glass fiber in the preparation process of the electroplated nylon material; on the other hand, the polar maleic anhydride group and the rare earth ions improve the compatibility of the glass fiber and the nylon matrix, improve the dispersibility of the glass fiber and reduce the adverse effect of the glass fiber on the electroplating performance of the nylon material. The modified mineral and the modified glass fiber are cooperatively matched, so that the electroplatability, rigidity, heat resistance and toughness of the nylon material are improved.
In the present invention, the polyamide may be used in an amount of 50 to 80 parts by weight, for example, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 78 parts or 80 parts.
The modified mineral can be 10-50 parts by weight, for example, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts.
The modified glass fiber is 10 to 30 parts by weight, for example, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts or 30 parts.
According to the invention, the electroplating performance of the nylon material can be obviously improved by the modified mineral in a proper addition amount, and the rigidity, heat resistance and toughness are improved to a certain extent; however, if the amount of the additive is too large, the processability is impaired, and the dispersion tends to be uneven, so that the plating property and toughness of the nylon material are lowered. The modified glass fiber can obviously improve the rigidity and heat resistance of the nylon material under the condition of proper addition amount, improves the toughness to a certain extent, but has certain adverse effect on the electroplating performance; if the amount of the additive is too large, the processability is also affected, and the dispersion is easily uneven, so that the electroplating performance and the toughness of the nylon material are reduced.
Illustratively, the modified mineral of the present invention can be prepared by the following method:
(1) Dispersing minerals in an organic solvent, mixing with a silane coupling agent, reacting, and carrying out solid-liquid separation to obtain the minerals treated by the silane coupling agent;
(2) Dispersing the mineral treated by the silane coupling agent obtained in the step (1) in a rare earth salt aqueous solution, standing, and performing solid-liquid separation to obtain the modified mineral;
wherein, the organic solvent in the step (1) can be toluene;
the mass ratio of the mineral to the silane coupling agent in the step (1) can be 2-10;
the reaction temperature in the step (1) can be 80-105 ℃, and the reaction time can be 6-8h;
the rare earth salt in the step (2) can be acetate; the concentration of the rare earth salt water solution can be 0.5-2.0 wt%;
the standing time in the step (2) can be 24-48 h.
Illustratively, the modified glass fiber of the present invention can be prepared by the following method:
a. dispersing glass fiber in an organic solvent, mixing with a silane coupling agent, reacting, and carrying out solid-liquid separation to obtain glass fiber treated by the silane coupling agent;
b. dispersing the glass fiber treated by the silane coupling agent obtained in the step a in an organic solvent, mixing with the maleic anhydride grafted ultra-high molecular weight polyethylene, reacting, and carrying out solid-liquid separation to obtain the glass fiber grafted with UHMWPE-g-MAH;
c. dispersing the glass fiber grafted with UHMWPE-g-MAH obtained in the step b into a rare earth saline solution, standing, and carrying out solid-liquid separation to obtain the modified mineral;
wherein, the organic solvent in step a may be toluene;
the mass ratio of the glass fiber to the silane coupling agent in the step a can be 2-10;
the reaction temperature in the step a can be 80-105 ℃, and the reaction time can be 6-8h;
the organic solvent in step b may be decalin;
the reaction temperature in the step b can be 100-130 ℃, and the reaction time can be 8-12h;
the rare earth salt in the step c can be acetate; the concentration of the rare earth salt water solution can be 0.5-2.0 wt%;
the standing time in the step c can be 24-48 h.
As a preferable technical scheme of the invention, the weight average molecular weight of the polyamide is 10000-100000; for example, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, or the like may be used.
Preferably, the polyamide is selected from one or a combination of at least two of PA6, PA46, PA56, PA66, PA610, PA612, PA613, PA11, PA12, PA1010, PA1012, PA1111, PA1313, PA6T, PA9T, PA10T, PA6I and PA 6I/6T.
In a preferred embodiment of the present invention, the mineral in the modified mineral is selected from one or a combination of two or more of silicates, carbonates, borates, and metal oxides.
Preferably, the mineral in the modified mineral is selected from one or a combination of at least two of wollastonite, pyroxene, dickite, vermiculite, halloysite, sepiolite, montmorillonite, bentonite, kaolin, talc, nacrite, phlogopite, sericite, biotite, muscovite, limestone, nahcolite, potasite, calcite, dolomite, ankerite, huntite, sodalite, cerite, brucite, trona, monetite, hydromagnesite, boromagnesite, paigeite, alumina, iron oxide, magnesium oxide, zinc oxide, copper oxide and calcium oxide.
Preferably, the modificationD of minerals in minerals 50 The grain diameter is 0.1-20 μm; for example, it may be 0.1. Mu.m, 0.5. Mu.m, 1. Mu.m, 3. Mu.m, 5. Mu.m, 8. Mu.m, 10. Mu.m, 12. Mu.m, 15. Mu.m, 18. Mu.m, 20 μm, or the like.
In a preferred embodiment of the present invention, the silane coupling agent in the modified mineral and the modified glass fiber is independently selected from any one or a combination of two or more of a silane coupling agent, a phthalate coupling agent, an aluminate coupling agent and a zirconate coupling agent.
Preferably, the first and second liquid crystal display panels are, the coupling agent is selected from gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-ureidopropyltriethoxysilane, N-aminoethyl-gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, polyaminoalkyltrialkoxysilane, anilinomethyltrimethoxysilane, tri (dioctylphosphoryloxy) isopropyl titanate, isopropyl ester isopropyl triisostearate, isopropyldioleacyloxy (dioctylphosphonoyl) titanate, isopropyltris (dioctylphosphonoyl) titanate, isopropyltrioleate acyloxytitanate, isopropyltris (dioctylphosphonoyl) titanate, bis (dioctyloxypyrophosphate) ethylene titanate, the chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine, tetraisopropylbis (dioctylphosphonoyl) titanate, distearoyloxyisopropyl aluminate, isopropoxydistearoyloxyaluminate, trimethyl aluminate, triisopropyl aluminate, tribenzyl aluminate, alkoxytris (vinyl-ethoxy) zirconate, triisopropyl aluminate, triisopropyl gallate, alkoxytris (vinyl-ethoxy) zirconate, triisopropyl gallate, and the like, alkoxy tri (p-aminophenoxy) zirconate, bis (diethyl citrate) dipropoxy zirconium chelate and tetra (triethanolamine) zirconate.
As a preferred embodiment of the present invention, the rare earth ions in the modified mineral and the modified glass fiber are each independently selected from one or a combination of at least two of zirconium ion, cobalt ion, lanthanum ion, praseodymium ion, samarium ion, europium ion, gadolinium ion, holmium ion, erbium ion, ytterbium ion, lutetium ion, scandium ion, indium ion, neodymium ion, cerium ion, yttrium ion, thulium ion, dysprosium ion, and terbium ion.
Preferably, the length of the glass fiber in the modified glass fiber is 3mm to 20mm, for example, 3mm, 5mm, 8mm, 10mm, 12mm, 15mm, 18mm or 20mm, etc.; the aspect ratio is 300 to 2000, and may be, for example, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, or the like.
The longer the glass fiber in the matrix, the better the reinforcing effect on the material, but if the glass fiber is too long, floating fiber is easily generated on the surface of the nylon material, and the electroplating effect is deteriorated. Therefore, the length of the glass fiber in the present invention is preferably within the above range.
As a preferred technical solution of the present invention, the electroplating nylon material further includes 0.1 to 5 parts of hyperbranched polyamide, and preferably further includes 0.3 to 2 parts (for example, 0.3 part, 0.5 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, or 3 parts, etc.) of hyperbranched polyamide, based on 100 parts of the total weight of the polyamide, the modified mineral, and the modified glass fiber.
The hyperbranched polyamide can improve the overall fluidity of the material by adding a small amount of the hyperbranched polyamide, and further improve the dispersibility of the modified glass fiber, so that the electroplating qualification rate, the rigidity, the heat resistance and the toughness of the electroplated nylon material are further improved. However, if the amount of the additive is too large, the interaction between nylon substrates is weakened due to the special structure thereof, and mechanical properties such as rigidity and toughness of the material are deteriorated.
Preferably, the number average molecular weight of the hyperbranched polyamide is 1000 to 5000; for example, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, or the like may be used.
As a preferred technical scheme of the invention, the electroplating nylon material also comprises 0.1-1 part (such as 0.1 part, 0.2 part, 0.3 part, 0.5 part, 0.6 part, 0.8 part or 1 part and the like) of antioxidant, wherein the total weight part of the polyamide, the modified mineral and the modified glass fiber is 100 parts.
Preferably, the electroplated nylon material further comprises 0.1-1 part (e.g., 0.1 part, 0.2 part, 0.3 part, 0.5 part, 0.6 part, 0.8 part, or 1 part, etc.) of an ultraviolet absorber, based on 100 parts of the total weight of the polyamide, modified mineral, and modified glass fiber.
Preferably, the electroplated nylon material further comprises 0.1-1 part (e.g., 0.1 part, 0.2 part, 0.3 part, 0.5 part, 0.6 part, 0.8 part or 1 part, etc.) of a heat stabilizer, based on 100 parts of the total weight of the polyamide, the modified mineral and the modified glass fiber.
Preferably, the electroplated nylon material further comprises 0.1-1 part (e.g., 0.1 part, 0.2 part, 0.3 part, 0.5 part, 0.6 part, 0.8 part, or 1 part, etc.) of a lubricant, based on 100 parts of the total weight of the polyamide, modified mineral, and modified glass fiber.
As a preferred technical scheme of the invention, the electroplating nylon material comprises the following components in parts by weight: 40-80 parts of polyamide, 10-50 parts of modified mineral, 10-30 parts of modified glass fiber, 0.1-5 parts of hyperbranched polyamide, 0.1-1 part of antioxidant, 0.1-1 part of ultraviolet absorbent, 0.1-1 part of heat stabilizer and 0.1-1 part of lubricant, wherein the total weight parts of the polyamide, the modified mineral and the modified glass fiber are 100 parts.
In a second aspect, the present invention provides a method for preparing the electroplating nylon material according to the first aspect, wherein the method comprises the following steps: and mixing the components, and then melting and extruding the mixture by an extruder to obtain the electroplating nylon material.
In a preferred embodiment of the present invention, the mixing is performed in a high-speed mixer.
Preferably, the rotating speed of the high-speed mixer is 300-1000 r/min, such as 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min or 1000 r/min; the mixing time is 5-10min, such as 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min or 10 min.
Preferably, the extruder is a twin screw extruder.
Preferably, the double-screw extruder comprises a first zone, a second zone, a third zone, a fourth zone, a fifth zone, a sixth zone, a seventh zone, an eighth zone, a ninth zone, a tenth zone and an eleventh zone which are connected in sequence from a feed inlet to a machine head, wherein the mixed material of the components passes through the zones in sequence, and the temperature of the first zone is 210-300 ℃, and can be 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃ or the like;
the temperature of the second zone is 220-310 deg.C, such as 220 deg.C, 230 deg.C, 240 deg.C, 250 deg.C, 260 deg.C, 270 deg.C, 280 deg.C, 290 deg.C, 300 deg.C or 310 deg.C;
the temperature of the three zones is 230-320 ℃, for example 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃ or 320 ℃ and the like;
the temperature of the four zones is 240-330 ℃, for example 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃ or 330 ℃ and the like;
the temperature of the five zones is 240-330 ℃, for example 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃ or 330 ℃ and the like;
the temperature of the six zones is 240-330 ℃, for example 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃ or 330 ℃ and the like;
the temperature of the seven zones is 240-330 ℃, for example, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃ or 330 ℃ and the like;
the temperature of the eight zones is 240-330 ℃, for example 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃ or 330 ℃ and the like;
the temperature of the nine zones is 240-330 ℃, for example 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃ or 330 ℃ and the like;
the temperature of the ten zones is 240-330 ℃, for example 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃ or 330 ℃ and the like;
the temperature of the eleventh zone is 235 to 325 ℃, and may be, for example, 235 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃ or 325 ℃, etc.
Preferably, the screw rotating speed of the double-screw extruder is 350-850r/min; for example, 350r/min, 400r/min, 450r/min, 500r/min, 550r/min, 600r/min, 650r/min, 700r/min, 750r/min, 800r/min, 850r/min, or the like may be used.
Preferably, the residence time of the mixed materials of the components in the double-screw extruder is 1-3min; for example, the time period may be 1min, 1.2min, 1.5min, 1.8min, 2min, 2.2min, 2.5min, 2.8min or 3 min.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the mineral and the glass fiber are modified, so that the dispersibility of the mineral and the glass fiber in a nylon matrix is improved, and the platability, rigidity, heat resistance and toughness of the nylon material are improved through the synergistic cooperation of the modified mineral and the modified glass fiber under a specific addition amount; and the hyperbranched polyamide is combined, so that the performance is further improved.
The electroplating qualified rate of the electroplating nylon material provided by the invention is 80-88%, the tensile strength is 114.5-181.4MPa, the thermal deformation temperature is 194.2-208.4 ℃, and the notch impact strength of the simply supported beam at 23 ℃ is 6.7-10.8kJ/m 2 The notch impact strength of the simple beam at the temperature of minus 30 ℃ is 6.2 to 10.1kJ/m 2 The alloy has good electroplating performance, rigidity, heat resistance and toughness, and can be used in the fields of automobile interior and exterior materials or communication equipment shells and the like.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. 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 limitation of the present invention.
The sources of the raw materials used in the examples of the invention are as follows:
PA: m2400 of Meida of New Congress, and the molecular weight is 50000-60000 g/mol;
UHMWPE-g-MAH: the self-made molecular weight is 2000000g/mol, the grafting rate is 1.5 percent, and the preparation method comprises the following steps:
placing a three-neck flask in an oil bath kettle at 120 ℃, adding 100mL of dimethylbenzene and 20g of UHMWPE, heating to fully dissolve the UHMWPE, adding 0.5g of initiator Dibenzoyl peroxide (BPO) and 10g of Maleic Anhydride (MAH), introducing nitrogen for protection, fully reacting for 4-8h, cooling to room temperature, and filtering to obtain UHMWPE-g-MAH; packing 5g of UHMWPE-g-MAH with filter paper, putting the packed UHMWPE-g-MAH into a Soxhlet extractor, extracting the packed UHMWPE-g-MAH with acetone for 36h to fully remove unreacted initiator, grafting monomer and MAH homopolymer possibly generated, drying the extracted UHMWPE-g-MAH in an oven at 60 ℃ for 10h, then drying the dried UHMWPE-g-MAH in a vacuum drying oven to constant weight, and storing the dried UHMWPE-g-MAH for later use. The molecular weight of UHMWPE-g-MAH is 2000000g/mol measured by GPC method, and the grafting ratio is 1.5% measured by chemical titration (phenolphthalein as indicator) with KOH ethanol solution.
Hyperbranched polyamide: hyPer N103 from wuhan hyperbranched resin technology ltd;
thermal stabilizer: polyad HS-03, altana.
Preparation example 1
Preparation of modified montmorillonite
(1) Firstly, 100 parts by mass of montmorillonite (D) 50 Particle size of 0.2 μm) is dried under vacuum at 100 ℃ for 6 hours and then cooled to normal temperature under vacuum condition;
(2) Adding 0.8g of dried montmorillonite into 20mL of toluene, and ultrasonically dispersing for 30min at normal temperature to obtain a uniform suspension; adding 0.364gKH-550 into the suspension, and ultrasonically mixing for 10min; reacting for 6 hours in a constant temperature tank at 90 ℃; centrifuging reaction liquid at normal temperature of 12000r/min, washing the separated solid product with absolute ethyl alcohol for 3 times, and drying in vacuum for 8 hours to obtain montmorillonite treated by the silane coupling agent;
(3) Adding 10g of montmorillonite treated by the silane coupling agent obtained in the step (2) into deionized water, stirring, filtering, adding into absolute ethyl alcohol, stirring, standing for 20 hours, filtering, and drying for later use; preparing 500ml of 1wt% thulium acetate deionized water solution, standing for 24h, then adding the montmorillonite treated by the cleaned silane coupling agent, ultrasonically dispersing for 2h, standing for 36h, filtering, and drying in vacuum to constant weight to obtain the modified montmorillonite.
Preparation example 2
Preparation of montmorillonite treated by silane coupling agent
The preparation method was the same as in step (1) and step (2) of preparation example 1.
Preparation example 3
Preparation of rare earth ion treated montmorillonite
According to the method of preparation example 1, the montmorillonite dried in step (1) is directly used in step (4) to adsorb rare earth ions, and the montmorillonite treated by rare earth ions is obtained.
Preparation example 4
Preparation of modified talc powder
(1) Firstly, 100 parts by mass of talcum powder (D) 50 Particle size of 0.5 μm) is dried under vacuum at 100 ℃ for 6 hours and then cooled to normal temperature under vacuum condition;
(2) Adding 0.8g of dried talcum powder into 50mL of methylbenzene, and performing ultrasonic dispersion at normal temperature for 30min to obtain a uniform suspension; adding 0.5g KH-550 into the suspension, and ultrasonically mixing for 10min; reacting for 6 hours in a constant temperature tank at 90 ℃; centrifuging the reaction solution at normal temperature of 12000r/min, washing the separated solid product with absolute ethyl alcohol for 3 times, and drying in vacuum for 8 hours to obtain the talcum powder treated by the silane coupling agent;
(3) Adding 10g of the talcum powder treated by the silane coupling agent obtained in the step (2) into deionized water, stirring, filtering, adding into absolute ethyl alcohol, stirring, standing for 20 hours, filtering, and drying for later use; preparing 500mL of 1wt% neodymium nitrate deionized water solution, standing for 24h, adding the cleaned talcum powder treated by the silane coupling agent, ultrasonically dispersing for 2h, standing for 36h, filtering, and drying in vacuum to constant weight to obtain the modified talcum powder.
Preparation example 5
Preparation of modified glass fibers
a. Firstly, 100 parts by mass of glass fiber (with the length of 20mm and the diameter of 10 μm) is vacuumized and dried for 6 hours at the temperature of 100 ℃, and then is cooled to the normal temperature under the vacuum condition;
b. adding 0.8g of dried glass fiber into 20mL of toluene, and performing ultrasonic dispersion at normal temperature for 30min to obtain a uniform suspension; adding 0.4g KH-560 into the suspension, and ultrasonically mixing for 10min; reacting for 6 hours in a constant temperature tank at 90 ℃; centrifuging the reaction solution at normal temperature of 12000r/min, washing the separated solid product with absolute ethyl alcohol for 3 times, and drying in vacuum for 8 hours to obtain glass fiber treated by the silane coupling agent;
c. b, adding 1g of the glass fiber treated by the silane coupling agent obtained in the step b into 100g of decahydronaphthalene, and performing ultrasonic dispersion at normal temperature for 60min to obtain a uniform suspension; then 5g of UHMWPE-g-MAH is added into the suspension liquid, and ultrasonic mixing is carried out for 20min; reacting for 8 hours in a constant temperature tank at 130 ℃; centrifuging the reaction solution at normal temperature of 12000r/min, washing the separated solid product with absolute ethyl alcohol for 3 times, and drying in vacuum for 8 hours to obtain the glass fiber grafted with UHMWPE-g-MAH;
d. adding 10g of the glass fiber grafted with UHMWPE-g-MAH obtained in the step c into absolute ethyl alcohol, stirring, standing for 20h, filtering, and drying for later use; preparing 500mL of 1wt% cerium sulfate deionized water solution, standing for 24h, adding the cleaned glass fiber grafted with UHMWPE-g-MAH, performing ultrasonic dispersion for 2h, standing for 36h, filtering, and performing vacuum drying to constant weight to obtain the modified glass fiber.
Preparation example 6
Preparation of silane coupling agent treated glass fiber
The preparation method was the same as in step a and step b of preparation example 5.
Preparation example 7
Preparation of UHMWPE-g-MAH treated glass fibers
According to the method of preparation example 5, the glass fiber dried in the step a is directly used in the step c to react with UHMWPE-g-MAH, so as to obtain the UHMWPE-g-MAH treated glass fiber.
Preparation example 8
Preparation of rare earth ion treated glass fibers
According to the method of preparation example 5, the glass fiber dried in the step a is directly used in the step d to adsorb rare earth ions, and the glass fiber treated by the rare earth ions is obtained.
Examples 1 to 11 and comparative examples 1 to 21
Examples 1-11 and comparative examples 1-21 each provide an electroplated nylon material prepared as follows:
adding the raw materials into a high-speed mixer according to a ratio, uniformly mixing for 10min at the rotating speed of 500r/min, adding the mixture into a double-screw extruder, carrying out melt blending, controlling the temperature of a first zone to be 250 ℃, the temperature of a second zone to be 260 ℃, the temperature of a third zone to be 260 ℃, the temperature of a fourth zone to be 260 ℃, the temperature of a fifth zone to be 260 ℃, the temperature of a sixth zone to be 260 ℃, the temperature of a seventh zone to be 260 ℃, the temperature of an eighth zone to be 260 ℃, the temperature of a ninth zone to be 260 ℃, the temperature of a tenth zone to be 260 ℃, the temperature of an eleventh zone to be 265 ℃, the rotating speed of a screw to be 500r/min, and keeping the time to be 2min, cooling, drying and dicing after extrusion, so as to obtain the electroplating nylon material.
The kinds and amounts (parts by weight) of raw materials and the properties of the plated nylon materials prepared in examples 1 to 11 and comparative examples 1 to 21 are shown in the following tables 1 to 4.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
The test methods for the properties in tables 1 to 4 are as follows:
the qualified rate of electroplating: according to the appearance standard of the Benz electroplated part, whether the electroplating appearance is qualified or not is evaluated by observing the type, the number, the spacing and the size of surface flaws (such as pits, pinholes, pits, burrs and the like) of an electroplated product;
tensile strength: ISO 527;
heat distortion temperature: ISO 75-2/A;
impact strength of the simply supported beam notch: ISO 179-1/eA.
As can be seen from the performance data in tables 1 to 4, the electroplating yield of the electroplated nylon material provided by the embodiment of the invention is 80 to 88 percent, the tensile strength is 114.5 to 181.4MPa, the thermal deformation temperature is 194.2 to 208.4 ℃, and the notch impact strength of the simple beam at 23 ℃ is 6.7 to 10.8kJ/m 2 The notch impact strength of the simple beam at minus 30 ℃ is 6.2-10.1kJ/m 2 Has good electroplating performance, rigidity, heat resistance and toughness.
Comparing example 1 with example 6, it can be seen that the plating yield, tensile strength, heat distortion temperature and impact strength of the plated nylon material with hyperbranched polyamide (example 1) are further improved compared to the plated nylon material without hyperbranched polyamide (example 6) because hyperbranched polyamide contributes to further improving the dispersibility of the modified glass fibers.
It can be seen from comparing examples 7 to 11 with comparative example 21 that the plating yield, tensile strength, heat distortion temperature and impact strength of the plated nylon material increase first and then decrease as the amount of the modified mineral increases, mainly because the modified mineral contributes to the improvement of the plating property, rigidity, heat resistance and toughness of the nylon material, but when it is added in a large amount, it is liable to be unevenly dispersed, rather causing the above-mentioned property to be degraded.
Comparing comparative examples 1-5, comparative examples 10, comparative examples 12-14 and example 6, it can be seen that the minerals and the treated minerals can significantly improve the plating yield of nylon materials. Wherein, the mineral which is not treated and only treated by the silane coupling agent or the rare earth ions is easy to agglomerate due to poor dispersibility, so that the impact strength of the nylon material is reduced; the modified mineral has good dispersibility, has the best effect of improving the electroplating performance of the nylon material, and can improve the rigidity, the heat resistance and the toughness to a certain extent.
Comparing comparative example 1 and comparative examples 6 to 10, and comparative example 5, comparative examples 15 to 18 and example 6, it can be seen that the glass fiber and the treated glass fiber can significantly improve the tensile strength and heat distortion temperature of the nylon material, and increase the impact strength to some extent, but reduce the plating performance. The modified glass fiber has the best improvement effect on the rigidity, heat resistance and toughness of the nylon material, and has the smallest influence on the electroplating performance.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (23)
1. The electroplating nylon material is characterized by comprising the following components in parts by weight: 40-80 parts of polyamide, 10-50 parts of modified mineral and 10-30 parts of modified glass fiber, wherein the total weight part of the polyamide, the modified mineral and the modified glass fiber is 100 parts; the electroplating nylon material also comprises 0.1-5 parts of hyperbranched polyamide;
the modified mineral is a mineral with a silane coupling agent bonded on the surface and rare earth ions absorbed; d of a mineral of the modified minerals 50 The particle size is 0.1-20 μm;
the modified mineral is prepared by the following method:
(1) Dispersing minerals in an organic solvent, mixing with a silane coupling agent, reacting, and carrying out solid-liquid separation to obtain the minerals treated by the silane coupling agent;
(2) Dispersing the mineral treated by the silane coupling agent obtained in the step (1) in a rare earth salt aqueous solution, standing, and performing solid-liquid separation to obtain the modified mineral;
the modified glass fiber is a glass fiber with the surface bridged with maleic anhydride grafted ultra-high molecular weight polyethylene through a silane coupling agent and adsorbed with rare earth ions;
the modified glass fiber is prepared by the following method:
a. dispersing glass fiber in an organic solvent, mixing with a silane coupling agent, reacting, and carrying out solid-liquid separation to obtain glass fiber treated by the silane coupling agent;
b. dispersing the glass fiber treated by the silane coupling agent obtained in the step a in an organic solvent, mixing with the maleic anhydride grafted ultra-high molecular weight polyethylene, reacting, and carrying out solid-liquid separation to obtain the glass fiber grafted with UHMWPE-g-MAH;
c. and c, dispersing the glass fiber grafted with the UHMWPE-g-MAH obtained in the step b into a rare earth salt aqueous solution, standing, and carrying out solid-liquid separation.
2. The electroplated nylon material of claim 1, wherein the weight average molecular weight of the polyamide is 10000 to 100000.
3. Plated nylon material according to claim 1, c h a r a c T e r I z e d in that the polyamide is selected from one or a combination of at least two of PA6, PA46, PA56, PA66, PA610, PA612, PA613, PA11, PA12, PA1010, PA1012, PA1111, PA1313, PA6T, PA9T, PA10T, PA6I and PA 6I/6T.
4. The electroplated nylon material of claim 1, wherein the modified minerals are selected from the group consisting of silicates, carbonates, borates, and metal oxides.
5. The electroplated nylon material of claim 4, wherein the minerals in the modified minerals are selected from one or a combination of at least two of wollastonite, pyroxene, dickite, vermiculite, halloysite, sepiolite, montmorillonite, bentonite, kaolin, talc, margarite, phlogopite, sericite, biotite, muscovite, limestone, nahcolite, barbiturate, calcite, dolomite, ankite, huntite, sodalite, nesquehonite, trona, gazeite, hydromagnesite, boromagnesite, paigecite, alumina, iron oxide, magnesium oxide, zinc oxide, copper oxide and calcium oxide.
6. The electroplated nylon material of claim 1, wherein the silane coupling agents in the modified mineral and the modified glass fiber are each independently selected from any one of silane coupling agents, phthalate coupling agents, aluminate coupling agents and zirconate coupling agents or a combination of two or more thereof.
7. The electroplated nylon material of claim 6, wherein the coupling agent is selected from the group consisting of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane,N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane,N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-ureidopropyltriethoxysilane,N-aminoethyl-gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane,N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, polyaminoalkyltrialkoxysilane, anilinomethyltrimethoxysilane, tris (dioctylphosphoryloxy) isopropyl titanate, triisostearic isopropyl titanate, isopropyldioleacyloxy (dioctylphosphoyloxy) titanate, isopropyltris (dioctylphosphoyloxy) titanate, isopropyltrioleyloxy titanate, isopropyltris (dioctylphosphonoyl) titanate, bis (dioctyloxypyrophosphate) titanateAny one or a combination of more than two of ester group) ethylene titanate, bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine chelate, tetraisopropylbis (dioctylphosphite acyloxy) titanate, distearoyloxyisopropyl aluminate, isopropoxydistearoyloxyacyloxy aluminate, trimethyl aluminate, triisopropyl aluminate, tribenzyl aluminate, alkoxy tri (vinyl-ethoxy) zirconate, alkoxy tri (p-aminophenoxy) zirconate, bis (diethyl citrate) dipropyloxy zirconium chelate and tetra (triethanolamine) zirconate.
8. The electroplated nylon material of claim 1, wherein the rare earth ions in the modified mineral and the modified glass fibers are each independently selected from one or a combination of at least two of zirconium ion, cobalt ion, lanthanum ion, praseodymium ion, samarium ion, europium ion, gadolinium ion, holmium ion, erbium ion, ytterbium ion, lutetium ion, scandium ion, indium ion, neodymium ion, cerium ion, yttrium ion, thulium ion, dysprosium ion, and terbium ion.
9. The electroplated nylon material of claim 1, wherein the length of the glass fiber in the modified glass fiber is from 3mm to 2mm, and the length-diameter ratio is from 300 to 2000.
10. The electroplated nylon material of claim 1, which is characterized by further comprising 0.3 to 2 parts of hyperbranched polyamide based on 100 parts of the total weight of the polyamide, the modified mineral and the modified glass fiber.
11. The electroplated nylon material of claim 1, wherein the hyperbranched polyamide has a number average molecular weight of 1000 to 5000.
12. The electroplated nylon material of claim 1, further comprising 0.1-1 part of an antioxidant, based on 100 parts of the polyamide, the modified mineral and the modified glass fiber.
13. The electroplated nylon material of claim 1, further comprising 0.1-1 parts of an ultraviolet absorber, based on 100 parts of the total weight of the polyamide, the modified mineral, and the modified glass fiber.
14. The electroplated nylon material of claim 1, further comprising 0.1-1 part of a heat stabilizer, based on 100 parts of the polyamide, the modified mineral and the modified glass fiber.
15. The electroplated nylon material of claim 1, further comprising 0.1-1 parts of a lubricant, based on 100 parts of the total weight of the polyamide, the modified mineral, and the modified glass fiber.
16. The electroplated nylon material of claim 1, comprising the following components in parts by weight: 40-80 parts of polyamide, 10-50 parts of modified mineral, 10-30 parts of modified glass fiber, 0.1-5 parts of hyperbranched polyamide, 0.1-1 part of antioxidant, 0.1-1 part of ultraviolet absorbent, 0.1-1 part of heat stabilizer and 0.1-1 part of lubricant, wherein the total weight of the polyamide, the modified mineral and the modified glass fiber is 100 parts.
17. A method of preparing an electroplated nylon material as claimed in any of claims 1 to 16, comprising the steps of: and mixing the components, and then melting and extruding the mixture by an extruder to obtain the electroplating nylon material.
18. The method of claim 17, wherein the mixing is performed in a high speed mixer.
19. The preparation method of the rubber composition, wherein the rotating speed of the high-speed mixer is 300 to 1000r/min, and the mixing time is 5 to 10 min.
20. The method of claim 17, wherein the extruder is a twin screw extruder.
21. The preparation method of claim 20, wherein the twin-screw extruder comprises a first zone, a second zone, a third zone, a fourth zone, a fifth zone, a sixth zone, a seventh zone, an eighth zone, a ninth zone, a tenth zone and an eleventh zone which are connected in sequence from a feed inlet to a head, the mixed materials of the components pass through the zones in sequence, the temperature of the first zone is 210-300 ℃, the temperature of the second zone is 220-310 ℃, the temperature of the third zone is 230-320 ℃, the temperature of the fourth zone is 240-330 ℃, the temperature of the fifth zone is 240-330 ℃, the temperature of the sixth zone is 240-330 ℃, the temperature of the seventh zone is 240-330 ℃, the temperature of the eighth zone is 240-330 ℃, the temperature of the ninth zone is 240-330 ℃, the temperature of the tenth zone is 240-330 ℃ and the temperature of the eleventh zone is 235-325 ℃.
22. The method as claimed in claim 20, wherein the twin-screw extruder has a screw rotation speed of 350 to 850 r/min.
23. The method as claimed in claim 20, wherein the residence time of the mixed material of the components in the twin-screw extruder is 1-3 min.
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