CN115785655A - Extra-black weather-resistant polyamide material and preparation method and application thereof - Google Patents
Extra-black weather-resistant polyamide material and preparation method and application thereof Download PDFInfo
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- CN115785655A CN115785655A CN202211622523.0A CN202211622523A CN115785655A CN 115785655 A CN115785655 A CN 115785655A CN 202211622523 A CN202211622523 A CN 202211622523A CN 115785655 A CN115785655 A CN 115785655A
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- polyamide
- black
- nigrosine
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 112
- 229920002647 polyamide Polymers 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 35
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 35
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 32
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 230000001050 lubricating effect Effects 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 16
- -1 polyethylene Polymers 0.000 claims description 15
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 claims description 11
- 229920000767 polyaniline Polymers 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000001993 wax Substances 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 2
- VOYADQIFGGIKAT-UHFFFAOYSA-N 1,3-dibutyl-4-hydroxy-2,6-dioxopyrimidine-5-carboximidamide Chemical compound CCCCn1c(O)c(C(N)=N)c(=O)n(CCCC)c1=O VOYADQIFGGIKAT-UHFFFAOYSA-N 0.000 claims description 2
- DEMUGIHCZXFUDI-UHFFFAOYSA-N 2-(3,5-dibutyl-4-hydroxyphenyl)propanoic acid Chemical compound CCCCC1=CC(C(C)C(O)=O)=CC(CCCC)=C1O DEMUGIHCZXFUDI-UHFFFAOYSA-N 0.000 claims description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003143 4-hydroxybenzyl group Chemical group [H]C([*])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000002193 fatty amides Chemical class 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims 2
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 claims 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims 1
- 229940037312 stearamide Drugs 0.000 claims 1
- 238000004040 coloring Methods 0.000 abstract description 4
- 238000004043 dyeing Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000047 product Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052582 BN Inorganic materials 0.000 description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 6
- 239000013065 commercial product Substances 0.000 description 6
- 239000004595 color masterbatch Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- YFCIFWOJYYFDQP-PTWZRHHISA-N 4-[3-amino-6-[(1S,3S,4S)-3-fluoro-4-hydroxycyclohexyl]pyrazin-2-yl]-N-[(1S)-1-(3-bromo-5-fluorophenyl)-2-(methylamino)ethyl]-2-fluorobenzamide Chemical compound CNC[C@@H](NC(=O)c1ccc(cc1F)-c1nc(cnc1N)[C@H]1CC[C@H](O)[C@@H](F)C1)c1cc(F)cc(Br)c1 YFCIFWOJYYFDQP-PTWZRHHISA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- FHSJASSJVNBPOX-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O FHSJASSJVNBPOX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a super-black weather-resistant polyamide material and a preparation method and application thereof, wherein the super-black weather-resistant polyamide material comprises a polyamide matrix, superfine crystalline silicon, nigrosine master batches and a lubricating dispersant, wherein the nigrosine master batches comprise a high polymer dye and polyamide resin, and the high polymer dye comprises polyamide, nigrosine and a first antioxidant; the polyamide material is prepared by preparing polyamide, nigrosine and a first antioxidant into a high-molecular dye, further preparing nigrosine master batches by matching the high-molecular dye with polyamide resin, and finally filling the nigrosine master batches into a polyamide matrix to serve as a dyeing component, so that the optimal coloring effect of the nigrosine is realized, the obtained polyamide material has high blackness and glossiness, and meanwhile, the superfine crystalline silicon is added in a matching manner, and the weather resistance and the wear resistance of the polyamide material are improved.
Description
Technical Field
The invention belongs to the technical field of polyamide resin, and particularly relates to an extra-black weather-resistant polyamide material, and a preparation method and application thereof.
Background
The polyamide resin has good comprehensive properties including mechanical property, heat resistance, abrasion resistance, chemical resistance and self-sliding property, has low friction coefficient and certain flame retardance, is easy to process, has wide application range, can be used for manufacturing dye screens, fuel filters, tanks, collectors, oil storage tanks, engine cylinder cover covers, radiator water cylinders and balance rotating shaft gears in the automobile manufacturing industry and can also be applied to external decoration parts.
The polyamide resin is generally colored by using common carbon black, but the poor dispersibility of the carbon black causes that pockmarks and white spots are easy to form on the surface of the polyamide product, and the addition of the carbon black causes that the gloss of the surface of the polyamide product is reduced.
At present, the color master batch is used as a common dyeing material and is very commonly applied in the production process of resin. CN104327499A discloses an organic black master batch for polyamide, which comprises the following components in percentage by mass: 50-70% of polyamide resin and 30-50% of nigrosine powder; the invention also discloses a preparation method of the organic black master batch for polyamide, which comprises the following steps: (1) metering and conveying of carrier and toner: the metering and conveying device comprises two independent material supplementing bins and two metering scales with feeding hoppers, and the polyamide resin and the nigrosine are fed into the respective material supplementing bins, then enter the feeding hoppers on the respective metering scales through the material supplementing bins, and are conveyed to the double-screw extruder in proportion; (2) preparing color master batches: feeding the polyamide resin and the nigrosine into a double-screw extruder in proportion for melt extrusion granulation, carrying out bracing and water-cooling granulation or underwater granulation, drying, weighing and packaging after granulation to obtain the product. The color master batch obtained by the invention has stable quality, and the product is very uniform in coloring and higher in glossiness after being applied to the polyamide material. CN106189209A discloses a polyamide composite material added with high thermal conductivity organic black master batch, which comprises the following components in parts by weight: 50-90 parts of polyamide resin, 0.01-2 parts of boron nitride nanosheets, 5-9 parts of boron nitride powder, 2-4 parts of nano silicon nitride, 3-6 parts of organic black master batch, 6-11 parts of carbon fibers, 1-3 parts of maleic anhydride grafted polypropylene wax, 0.5-1.2 parts of silane coupling agent, 2-5 parts of adhesive and 0.3-0.7 part of antioxidant; the invention also discloses a preparation method of the high-thermal-conductivity polyamide composite material, wherein the boron nitride nanosheet and the boron nitride powder are added into the polyamide resin, and the nano silicon nitride is added to form an independent thermal-conductivity network among the boron nitride nanosheet, the boron nitride powder, the nano silicon nitride and the polyamide resin, so that the thermal conductivity of the prepared composite material is effectively improved, and the wear resistance and the impact resistance of the composite material are greatly improved. However, the high-gloss spray-free product is not only attractive in high gloss and high black but also requires certain wear resistance and weather resistance, but the polyamide material prepared by the method of directly adding the color master batch has an L value of only 4-5, is difficult to achieve high gloss and high black, and is poor in wear resistance and high weather resistance.
Therefore, the development of a super black weather-resistant polyamide resin with high blackness and gloss and excellent weather resistance and wear resistance is a technical problem to be solved urgently in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an ultra-black weather-resistant polyamide material, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an ultra-black weather-resistant polyamide material, which comprises the following components in parts by weight:
the nigrosine master batch comprises the following components in parts by weight:
1-2 parts of macromolecular dye
94-96 parts by weight of polyamide resin;
the macromolecular dye comprises the following raw materials in parts by weight:
50-60 parts by weight of polyamide
30 to 40 portions of aniline black
10-20 parts of first antioxidant. .
Wherein the polyamide matrix may be 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, 86 parts by weight, 87 parts by weight, 88 parts by weight, 89 parts by weight, or the like.
The ultrafine crystalline silicon may be 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or the like.
The nigrosine masterbatch is 5.3 parts by weight, 5.6 parts by weight, 5.9 parts by weight, 6.2 parts by weight, 6.5 parts by weight, 6.8 parts by weight, 7.1 parts by weight, 7.4 parts by weight, 7.7 parts by weight, or the like.
The lubricating dispersant can be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9 parts by weight, or the like.
The polymeric dye may be 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, or 1.9 parts by weight, or the like.
The polyamide resin may be 94.2 parts by weight, 94.4 parts by weight, 94.6 parts by weight, 94.8 parts by weight, 95 parts by weight, 95.2 parts by weight, 95.4 parts by weight, 95.6 parts by weight, 95.8 parts by weight, or the like.
The polyamide may be 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight, or the like.
The nigrosine may be 31, 32, 33, 34, 35, 36, 37, 38, 39, or the like.
The first antioxidant may be 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, or the like.
Preferably, the relative molecular weight of the polymeric dye is 20000 to 30000, such as 22000, 24000, 26000 or 28000.
The super-black weather-resistant polyamide resin provided by the invention comprises a polyamide matrix, superfine crystalline silicon, nigrosine master batches and a lubricating dispersant, wherein the nigrosine master batches comprise a combination of a high polymer dye and polyamide resin, and the high polymer dye comprises polyamide, nigrosine and a first antioxidant; according to the invention, firstly, polyamide, nigrosine and a first antioxidant are prepared into a high-molecular dye, in the process of preparing the high-molecular dye, an amide group in the polyamide can be combined with an amino group in the nigrosine to form a copolymer, then the obtained copolymer is mixed with the first antioxidant to obtain the high-molecular dye, and the high-molecular dye is further prepared into nigrosine master batches and then added into a polyurethane matrix, so that the most ideal coloring of the nigrosine on the polyurethane matrix can be realized, the finally obtained polyamide material has high blackness and high gloss, and the weather resistance of the finally obtained resin can be improved; and then, the superfine crystalline silicon and the lubricating dispersant are further added in a matched manner, and the lubricating dispersant is utilized to further disperse the aniline black master batch and the superfine crystalline silicon, so that the finally obtained polyamide material has high blackness and high glossiness, and also has excellent weather resistance and wear resistance.
The term "extra black" in the ultra black weather-resistant polyamide material of the invention means that the blackness of the polyamide material is 1.0-3.0.
Preferably, the ultrafine crystalline silicon has a particle size of 4 to 6 μm, for example, 4.2 μm, 4.4 μm, 4.6 μm, 4.8 μm, 5 μm, 5.2 μm, 5.4 μm, 5.6 μm, or 5.8 μm.
Preferably, the nigrosine masterbatch also comprises a lubricant.
Preferably, the content of the lubricant in the nigrosine base particle is 1 to 2 parts by weight, for example, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, or 1.9 parts by weight.
Preferably, the lubricant comprises polyethylene wax.
Preferably, the relative molecular weight of the polymeric dye is 20000 to 30000, such as 22000, 24000, 26000 or 28000.
Preferably, the molecular weight of the polyamide matrix, the polyamide resin and the polyamide each independently comprises 15000 to 20000, such as 16000, 17000, 18000 or 19000 and the like.
Preferably, the lubricating dispersant comprises any one or a combination of more than two of silane polymer, solid paraffin, liquid paraffin, fatty acid salt, calcium stearate, zinc stearate, fatty amide, methylene bis-stearic amide, oleic amide, stearic amide, ethylene bis-stearic amide or N, N-ethylene bis-stearic amide.
Preferably, the ultra-black weather-resistant polyamide material further comprises a second antioxidant and/or a stabilizer.
Preferably, the content of the second antioxidant in the ultra-black weather-resistant polyamide material is 0.1 to 1 part by weight, such as 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, or 0.9 part by weight.
Preferably, the first antioxidant and the second antioxidant each independently comprise tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N '-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (2, 4-di-tert-butyl) phosphite, octadecyl hindered phenol (3, 5-dibutyl-4-hydroxy-phenylpropionate), 1,3, 5-tris (3, 5-di-tert-butyl, 4-hydroxybenzyl) s-triazine, 2,4,6- (1h, 3h, 5h) trione, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, diethylene glycol bis [ β - (3-tert-butyl-4-hydroxyphenyl) propionate ] methyl or a combination of at least one or two of any of these.
Preferably, the stabilizer is contained in the ultra-black weather-resistant polyamide material in an amount of 0.1 to 1 part by weight, for example, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, or 0.9 part by weight.
<xnotran> , 4- -2,2,6,6- , (1,2,2,6,6- ) , 2,2,6,6- , 4- -2,2,6,6- -1- , (2,2,6,6- -4- ) [ [6- [ (1,1,3,3- ) ] -1,3,5- -2,4- ] [2- (2,2,6,6- ) - - - [4- (2,2,6,6- ) - ] ] . </xnotran>
In a second aspect, the present invention provides a preparation method of the ultra-black weather-resistant polyamide material according to the first aspect, wherein the preparation method comprises the following steps:
(1) Reacting polyamide with nigrosine, adding a first antioxidant, and mixing to obtain a macromolecular dye;
(2) Mixing the high-molecular dye obtained in the step (1), polyamide resin and a lubricant, and extruding to obtain nigrosine master batches;
(3) And (3) mixing the aniline black master batches obtained in the step (2), a polyamide matrix, superfine crystalline silicon, a lubricating dispersant, an optional second antioxidant and an optional stabilizer, and extruding to obtain the ultra-black weather-resistant polyamide material.
Preferably, the temperature of the reaction in step (1) is 50 to 60 ℃, such as 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃ or 59 ℃ and the like.
Preferably, the reaction time in step (1) is 4 to 6 hours, such as 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours, and the like.
Preferably, the mixing in step (2) and step (3) is carried out in a high mixing machine.
Preferably, the mixing time in step (2) and step (3) is independently 3-10 min, such as 4min, 5min, 6min, 7min, 8min or 9 min.
Preferably, the extrusion in step (2) and step (3) is carried out in a twin screw extruder.
Preferably, the temperature of each working zone of the twin-screw extrusion zone is as follows: one region is 180 to 220 ℃ (for example 184 ℃, 188 ℃, 192 ℃, 196 ℃, 200 ℃, 204 ℃, 208 ℃, 212 ℃ or 216 ℃ and the like), the second region is 190 to 230 ℃ (for example 194 ℃, 198 ℃, 202 ℃, 206 ℃, 210 ℃, 214 ℃, 218 ℃, 222 ℃ or 226 ℃ and the like), the third region is 200 to 250 ℃ (for example 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃ or 245 ℃ and the like), the fourth region is 200 to 250 ℃ (for example 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃ or 245 ℃ and the like), the fifth region is 200 to 250 ℃ (for example 205 ℃, 210 ℃, 215 ℃, 220 ℃, 230 ℃, 235 ℃, 240 ℃ or 245 ℃ and the like), the six regions are 200 to 250 ℃ (e.g., 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃ or 245 ℃, etc.), the seven regions are 200 to 250 ℃ (e.g., 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃ or 245 ℃, etc.), the eight regions are 200 to 250 ℃ (e.g., 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃ or 245 ℃, etc.), the nine regions are 200 to 250 ℃ (e.g., 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃ or 245 ℃, etc.), and the head is 190 to 240 ℃ (e.g., 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃ or 235 ℃, etc.).
Preferably, the twin-screw extruder has a rotation speed of 300 to 500rpm, for example 320rpm, 340rpm, 360rpm, 380rpm, 400rpm, 420rpm, 440rpm, 460rpm or 480rpm, and the like.
In a third aspect, the invention provides a use of the ultra-black weather-resistant polyamide resin material as described in the first aspect in automobiles or exterior trim parts.
Compared with the prior art, the invention has the following beneficial effects:
the super-black weather-resistant polyamide material provided by the invention comprises a polyamide matrix, superfine crystalline silicon, nigrosine master batches and a lubricating dispersant, wherein the nigrosine master batches comprise a high-molecular dye and polyamide resin, and the high-molecular dye comprises polyamide, nigrosine and a first antioxidant; the polyamide, the nigrosine and the first antioxidant are prepared into the high-molecular dye, the high-molecular dye is matched with the polyamide resin to further prepare nigrosine master batches, and the nigrosine master batches are filled into a polyamide matrix to serve as a dyeing component, so that the most ideal coloring effect of the nigrosine is realized, the obtained polyamide material has high blackness and glossiness, and meanwhile, the superfine crystalline silicon is added in a matching mode, and the weather resistance and the wear resistance of the polyamide material are improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The super-black weather-resistant polyamide material comprises the following components in parts by weight:
the nigrosine master batch comprises the following components in parts by weight:
macromolecular dye 1.5 weight portions
Polyamide resin 95 parts by weight
Polyethylene wax 1.5 parts by weight;
the macromolecular dye comprises the following raw materials in parts by weight:
polyamide 55 parts by weight
35 parts by weight of nigrosine
15 parts of a first antioxidant;
the preparation method of the extra-black weather-resistant polyamide material provided by the embodiment comprises the following steps:
(1) Reacting polyamide (a commercial product, with the molecular weight of 18200) and aniline black for 250min at 55 ℃, adding a first antioxidant (tris (2, 4-di-tert-butylphenyl) phosphite), and mixing to obtain a polymer dye;
(2) Mixing the macromolecular dye obtained in the step (1), polyamide resin (a commercial product with the molecular weight of 18200) and polyethylene wax in a high-speed mixer for 5min, and extruding in a double-screw extruder with the rotating speed of 500rpm, wherein the temperature of each working area in the double-screw extrusion area is as follows: the first zone is 220 ℃, the second zone is 225 ℃, the third zone is 230 ℃, the fourth zone is 235 ℃, the fifth zone is 240 ℃, the sixth zone is 240 ℃, the seventh zone is 245 ℃, the eighth zone is 250 ℃, the ninth zone is 250 ℃ and the machine head is 245 ℃ to obtain aniline black master batch;
(3) Mixing the nigrosine master batch obtained in the step (2), a polyamide matrix (a commercial product, the molecular weight of which is 18200), superfine crystalline silicon (the particle size of which is 5 microns), a lubricating dispersant (EBS), a second antioxidant (tris (2, 4-di-tert-butylphenyl) phosphite) and a heat stabilizer (4-benzoyloxy-2, 6-tetramethylpiperidine) in a high-speed mixer for 5 minutes, and extruding the mixture in a double-screw extruder at the rotating speed of 500rpm, wherein the temperature of each working area of the double-screw extrusion area is as follows: 220 ℃ in the first region, 225 ℃ in the second region, 230 ℃ in the third region, 235 ℃ in the fourth region, 240 ℃ in the fifth region, 245 ℃ in the sixth region, 250 ℃ in the seventh region, 250 ℃ in the eighth region, 255 ℃ in the ninth region and 250 ℃ in the head to obtain the ultra-black weather-resistant polyamide resin.
Example 2
The super-black weather-resistant polyamide material comprises the following components in parts by weight:
the nigrosine master batch comprises the following components in parts by weight:
1 part by weight of macromolecular dye
Polyamide resin 94 parts by weight
1 part by weight of polyethylene wax;
the macromolecular dye comprises the following components in parts by weight:
50 parts by weight of polyamide
Nigrosine 30 parts by weight
10 parts of a first antioxidant;
the preparation method and all the raw materials of the ultra-black weather-resistant polyamide material provided by the embodiment are the same as those of the embodiment 1.
Example 3
The super-black weather-resistant polyamide material comprises the following components in parts by weight:
the nigrosine master batch comprises the following components in parts by weight:
2 parts by weight of macromolecular dye
Polyamide resin 96 parts by weight
2 parts of polyethylene wax;
the macromolecular dye comprises the following components in parts by weight:
polyamide 60 parts by weight
Nigrosine 40 parts by weight
20 parts of a first antioxidant;
the preparation method and all the raw materials of the ultra-black weather-resistant polyamide material provided by the embodiment are the same as those of the embodiment 1.
Example 4
An ultra-black weather-resistant polyamide material is different from the polyamide material in the embodiment 1 only in that polyethylene wax is not added into aniline black master batches, and other components, the using amount and the preparation method are the same as those in the embodiment 1.
Comparative example 1
The polyamide material comprises the following components in parts by weight:
the nigrosine master batch comprises the following components in parts by weight:
the preparation method of the polyamide material provided by the comparative example comprises the following steps:
(1) Nigrosine, a polyamide resin (commercially available product, having a molecular weight of 18200), polyethylene wax and a first antioxidant (tris (2, 4-di-tert-butylphenyl) phosphite) were mixed for 5min and extruded in a twin-screw extruder at a speed of 500rpm, the temperature in each working zone of the twin-screw extrusion zone being as follows: the first zone is 220 ℃, the second zone is 225 ℃, the third zone is 230 ℃, the fourth zone is 235 ℃, the fifth zone is 240 ℃, the sixth zone is 240 ℃, the seventh zone is 245 ℃, the eighth zone is 250 ℃, the ninth zone is 250 ℃ and the head is 245 ℃ to obtain nigrosine master batches;
(2) Mixing the nigrosine masterbatch obtained in the step (1), a polyamide matrix (a commercial product with the molecular weight of 18200), superfine crystalline silicon (the particle size is 5 mu m), a lubricating dispersant (EBS), a second antioxidant (tris (2, 4-di-tert-butylphenyl) phosphite) and a heat stabilizer (4-benzoyloxy-2, 6-tetramethylpiperidine) for 5min, extruding the mixture in a double-screw extruder with the rotating speed of 500rpm, wherein the temperature of each working area in the double-screw extrusion area is as follows: 220 ℃ in the first region, 225 ℃ in the second region, 230 ℃ in the third region, 235 ℃ in the fourth region, 240 ℃ in the fifth region, 245 ℃ in the sixth region, 250 ℃ in the seventh region, 250 ℃ in the eighth region, 255 ℃ in the ninth region and 250 ℃ in the head to obtain the polyamide material.
Comparative example 2
The polyamide material comprises the following components in parts by weight:
the macromolecular dye comprises the following components in parts by weight:
polyamide material 55 parts by weight
35 parts by weight of nigrosine
15 parts of a first antioxidant;
the preparation method of the extra-black weather-resistant polyamide resin provided by the embodiment comprises the following steps:
(1) Reacting polyamide (a commercial product, with the molecular weight of 18200) and aniline black for 250min at 55 ℃, adding a first antioxidant (tris (2, 4-di-tert-butylphenyl) phosphite), and mixing to obtain a polymer dye;
(2) Mixing the macromolecular dye obtained in the step (1), a polyamide matrix (a commercial product with the molecular weight of 18200), superfine crystalline silicon (the particle size is 5 microns), a lubricating dispersant (EBS), a second antioxidant (tris (2, 4-di-tert-butylphenyl) phosphite), a heat stabilizer (4-benzoyloxy-2, 6-tetramethylpiperidine) and polyethylene wax for 5min, extruding the mixture in a double-screw extruder with the rotating speed of 500rpm, wherein the temperature of each working area in the double-screw extrusion area is as follows: 220 ℃ in the first region, 225 ℃ in the second region, 230 ℃ in the third region, 235 ℃ in the fourth region, 240 ℃ in the fifth region, 245 ℃ in the sixth region, 250 ℃ in the seventh region, 250 ℃ in the eighth region, 255 ℃ in the ninth region and 250 ℃ in the head to obtain the polyamide material.
Comparative example 3
A polyamide material is different from the polyamide material in the embodiment 1 only in that a first antioxidant is not added in the raw materials of the high molecular dye, and other components, the using amount and the preparation method are the same as those in the embodiment 1.
Comparative example 4
A polyamide material which differs from example 1 only in that no ultra fine crystalline silicon is added and the other components, amounts and preparation methods are the same as example 1.
Comparative example 5
A polyamide material which differs from example 1 only in that no lubricating dispersant is added and the other components, amounts and preparation method are the same as in example 1.
Comparative example 6
An ultra-black weather-resistant polyamide material is different from the polyamide material in the embodiment 1 only in that the addition amount of the macromolecular dye in the nigrosine master batch is 3 parts by weight, and other components, the use amount and the preparation method are the same as those in the embodiment 1.
Comparative example 7
An ultra-black weather-resistant polyamide material is different from the polyamide material in the embodiment 1 only in that 0.5 part by weight of macromolecular dye is in aniline black master batch, and other components, the using amount and the preparation method are the same as those in the embodiment 1.
Comparative example 8
A super black weather-resistant polyamide material is different from the polyamide material in the embodiment 1 only in that nigrosine in a high molecular dye is added in an amount of 50 parts by weight, and other components, the amount and the preparation method are the same as those in the embodiment 1.
Comparative example 9
A super black weather-resistant polyamide material is different from the polyamide material in the embodiment 1 only in that the nigrosine in the high molecular dye is added in 20 parts by weight, and other components, the using amount and the preparation method are the same as those in the embodiment 1.
And (3) performance testing:
(1) Blackness: measurements were performed using minolta CM-2500C;
(2) Gloss: testing with a BYK glossmeter;
(3) Grey card rating: testing by adopting a xenon lamp aging box;
(4) Gloss retention rate: the test was carried out according to the method provided in PV 3987.
The polyamide materials provided in examples 1 to 4 and comparative examples 1 to 9 were tested according to the test methods described above, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in table 1: the ultra-black weather-resistant polyamide materials obtained in examples 1 to 4 had a blackness of 1.0, a gloss of 80 to 95, a gray card rating of 4 to 5, and a gloss retention of 50 to 60%.
Comparing the data of example 1 and comparative example, it can be seen that:
(1) Comparative example 1 is a polyamide material prepared by directly adding nigrosine into a polyamide matrix after preparing the nigrosine into the master batch without preparing a high molecular dye, comparative example 2 is a polyamide material prepared by directly adding a high molecular dye into a polyamide matrix without preparing a nigrosine master batch, and comparative example 5 is a polyamide material prepared by adding no lubricating dispersant, wherein the blackness test value of the obtained polyamide material is high;
(2) The absence of the first antioxidant (comparative example 3) in the polymeric dye also affects the jetness of the polyamide material produced.
(3) The polyamide material obtained without adding the ultrafine crystalline silicon (comparative example 4) had poor gloss retention;
(4) The higher addition amount of the high molecular dye in the nigrosine master batch (comparative example 6) and the higher addition amount of the nigrosine in the high molecular dye (comparative example 8) can both cause the poor glossiness of the obtained polyamide material;
(5) The lower addition amount of the high molecular dye in the nigrosine master batch (comparative example 7) and the higher addition amount of the nigrosine in the high molecular dye (comparative example 9) can both result in higher blackness test values of the obtained polyamide material.
The applicant states that the present invention is illustrated by the above examples to a super black weather resistant polyamide material and its preparation method and application, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The ultra-black weather-resistant polyamide material is characterized by comprising the following components in parts by weight:
the nigrosine master batch comprises the following raw materials in parts by weight:
1-2 parts of macromolecular dye
94-96 parts by weight of polyamide resin;
the macromolecular dye comprises the following raw materials in parts by weight:
50-60 parts by weight of polyamide
30 to 40 portions of aniline black
10-20 parts of first antioxidant.
2. The ultra black weather-resistant polyamide material as claimed in claim 1, wherein the ultra fine crystalline silicon has a particle size of 4 to 6 μm.
3. The ultra-black weather-resistant polyamide material as claimed in claim 1 or 2, wherein the raw material of the nigrosine masterbatch further comprises a lubricant;
preferably, the content of the lubricant in the raw material of the nigrosine master batch is 1 to 2 parts by weight;
preferably, the lubricant comprises polyethylene wax.
4. The ultra black weather-resistant polyamide material according to any one of claims 1 to 3, wherein the relative molecular weight of the polymeric dye is 20000 to 30000;
preferably, the polyamide matrix, the polyamide resin and the polyamide each independently have a molecular weight of 15000 to 20000.
5. The ultra black weatherable polyamide material according to any one of claims 1 to 4, wherein the lubricating dispersant comprises any one or a combination of at least two of silane polymer, solid paraffin, liquid paraffin, fatty acid salt, calcium stearate, zinc stearate, fatty amide, methylene bis stearamide, oleamide, stearamide, ethylene bis stearamide or N, N-ethylene bis stearamide.
6. The ultra black weatherable polyamide material according to any one of claims 1 to 5, wherein the ultra black weatherable polyamide material further comprises a second antioxidant and/or a stabilizer;
preferably, the content of the second antioxidant in the ultra-black weather-resistant polyamide material is 0.1-1 part by weight;
preferably, the first antioxidant and the second antioxidant each independently comprise tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N '-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (2, 4-di-tert-butyl) phosphite, octadecyl hindered phenol (3, 5-dibutyl-4-hydroxy-phenylpropionate), 1,3, 5-tris (3, 5-di-tert-butyl, 4-hydroxybenzyl) s-triazine, 2,4,6- (1 h,3h, 5h) trione, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, diethylene glycol bis [ β - (3-tert-butyl-4-hydroxyphenyl) propionate ] methyl or a combination of at least one or two of any of the foregoing;
preferably, the content of the stabilizer in the ultra-black weather-resistant polyamide material is 0.1 to 1 part by weight;
<xnotran> , 4- -2,2,6,6- , (1,2,2,6,6- ) , 2,2,6,6- , 4- -2,2,6,6- -1- , (2,2,6,6- -4- ) [ [6- [ (1,1,3,3- ) ] -1,3,5- -2,4- ] [2- (2,2,6,6- ) - - - [4- (2,2,6,6- ) - ] ] . </xnotran>
7. A process for preparing the ultra-black weather-resistant polyamide material as claimed in any one of claims 1 to 6, which comprises the following steps:
(1) Polyamide and aniline black are reacted, and a first antioxidant is added and mixed to obtain a high-molecular dye;
(2) Mixing the high-molecular dye obtained in the step (1), polyamide resin and a lubricant, and extruding to obtain nigrosine master batches;
(3) And (3) mixing the aniline black master batches obtained in the step (2), a polyamide matrix, superfine crystalline silicon, a lubricating dispersant, an optional second antioxidant and an optional stabilizer, and extruding to obtain the ultra-black weather-resistant polyamide material.
8. The method according to claim 7, wherein the temperature of the reaction in the step (1) is 50 to 60 ℃;
preferably, the reaction time of the step (1) is 4-6 h.
9. The method according to claim 7 or 8, wherein the mixing in step (2) and step (3) is carried out in a high-speed mixer;
preferably, the mixing time of step (2) and step (3) is 3-10 min independently;
preferably, the extrusion of step (2) and step (3) is performed in a twin screw extruder;
preferably, the temperature of each working zone of the twin-screw extrusion zone is as follows: the first area is 180-220 ℃, the second area is 190-230 ℃, the third area is 200-250 ℃, the fourth area is 200-250 ℃, the fifth area is 200-250 ℃, the sixth area is 200-250 ℃, the seventh area is 200-250 ℃, the eighth area is 200-250 ℃, the ninth area is 200-250 ℃, and the head is 190-240 ℃;
preferably, the rotation speed of the twin-screw extruder is 300 to 500rpm.
10. Use of the extra black weather resistant polyamide resin according to any one of claims 1 to 6 in automobiles or exterior parts.
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| CN106189209A (en) * | 2016-08-24 | 2016-12-07 | 浙江佳华精化股份有限公司 | Polyamide compoiste material that a kind of high heat conduction Organic Black Masterbatch adds and preparation method thereof |
| CN111138848A (en) * | 2019-12-30 | 2020-05-12 | 上海中镭新材料科技有限公司 | Extra-black high-gloss wear-resistant polyamide resin and preparation method and application thereof |
| CN112812550A (en) * | 2021-01-05 | 2021-05-18 | 上海中镭新材料科技有限公司 | High-glossiness glass fiber reinforced polyamide composite material and preparation method thereof |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189209A (en) * | 2016-08-24 | 2016-12-07 | 浙江佳华精化股份有限公司 | Polyamide compoiste material that a kind of high heat conduction Organic Black Masterbatch adds and preparation method thereof |
| CN111138848A (en) * | 2019-12-30 | 2020-05-12 | 上海中镭新材料科技有限公司 | Extra-black high-gloss wear-resistant polyamide resin and preparation method and application thereof |
| CN112812550A (en) * | 2021-01-05 | 2021-05-18 | 上海中镭新材料科技有限公司 | High-glossiness glass fiber reinforced polyamide composite material and preparation method thereof |
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