CN114350022A - Anti-yellowing antioxidant and application thereof, anti-yellowing polyolefin composition and application thereof, anti-yellowing polyolefin and preparation method and application thereof - Google Patents
Anti-yellowing antioxidant and application thereof, anti-yellowing polyolefin composition and application thereof, anti-yellowing polyolefin and preparation method and application thereof Download PDFInfo
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- CN114350022A CN114350022A CN202111466504.9A CN202111466504A CN114350022A CN 114350022 A CN114350022 A CN 114350022A CN 202111466504 A CN202111466504 A CN 202111466504A CN 114350022 A CN114350022 A CN 114350022A
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- yellowing
- antioxidant
- polyolefin
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- 238000004383 yellowing Methods 0.000 title claims abstract description 116
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 99
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 92
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims abstract description 30
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 14
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group 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 abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- 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 abstract description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- BGHBLQKNCVRIKV-UHFFFAOYSA-N OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O BGHBLQKNCVRIKV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 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 abstract description 4
- 239000000155 melt Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 26
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 7
- 235000013539 calcium stearate Nutrition 0.000 claims description 7
- 239000008116 calcium stearate Substances 0.000 claims description 7
- LGOPTUPXVVNJFH-UHFFFAOYSA-N pentadecanethioic s-acid Chemical compound CCCCCCCCCCCCCCC(O)=S LGOPTUPXVVNJFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- SBKRBXBQFDKYSO-UHFFFAOYSA-N (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C)=C(O)C(C(C)(C)C)=C1 SBKRBXBQFDKYSO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 25
- 238000007254 oxidation reaction Methods 0.000 abstract description 25
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000006698 induction Effects 0.000 description 22
- 239000004743 Polypropylene Substances 0.000 description 19
- 229920001155 polypropylene Polymers 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical group CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of high polymer materials, and relates to a yellowing-resistant antioxidant and application thereof, a yellowing-resistant polyolefin composition and application thereof, a yellowing-resistant polyolefin and a preparation method and application thereof. The antioxidant comprises 0.02-0.045 parts of main antioxidant I, 0.001-0.02 parts of main antioxidant II, 0.045-0.1 parts of auxiliary antioxidant and 0.02-0.05 parts of acid acceptor; the main antioxidant I is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the main antioxidant II is propionate antioxidant; the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite and/or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite. The antioxidant ensures that the mechanical property of the polymer is not reduced, improves the oxidation resistance and yellowing resistance, has small addition amount and reduces the production cost.
Description
Technical Field
The invention relates to the field of high polymer materials, and particularly relates to a yellowing-resistant antioxidant and application thereof, a yellowing-resistant polyolefin composition and application thereof, a yellowing-resistant polyolefin and a preparation method and application thereof.
Background
Polypropylene, as a thermoplastic synthetic resin with excellent performance, has the characteristics of chemical resistance, heat resistance, electrical insulation, high-strength mechanical performance, good high-wear-resistance processing performance and the like, and is widely applied to various fields of machinery, automobiles, electronic and electric appliances, buildings, textiles, packaging, agriculture, forestry, fishery, food industry and the like. Because polypropylene belongs to a long-carbon-chain thermoplastic organic mixture and is influenced by factors such as polymerization conditions, post-processing conditions and the like, the product contains a large number of free radicals, and is easily oxidized and degraded after being exposed in air, so that the performance of the polypropylene product such as melt index, yellow index and the like is reduced, and the subsequent processing application of the polypropylene product is seriously influenced.
CN111378228A discloses a yellowing-resistant polypropylene compound and a preparation method thereof, and is characterized in that the material has excellent yellowing resistance in a high-temperature thermal aging environment, and can be used for materials with high requirements on yellowing resistance, such as automobile kettles and the like. The yellowing-resistant polypropylene compound comprises the following components in percentage by weight: 99.58 to 96.9 percent of polypropylene, 0.1 to 0.5 percent of main antioxidant, 0.1 to 0.5 percent of auxiliary antioxidant, 0.02 to 0.1 percent of hindered benzoate, 0.1 to 1 percent of nucleating agent and 0.1 to 1 percent of acid acceptor. The product of the invention has excellent yellowing resistance in the high-temperature aging process, and the color difference value change delta E of the material is less than 1.0 after 150 ℃/500h harsh thermo-oxidative aging test in the automobile industry, so that the requirement of parts such as automobile wash kettles, expansion tank kettles and the like on yellowing resistance of the material can be met.
CN110577702A discloses a transparent rigidity-toughness balanced thermoforming homopolymerized polypropylene resin, which comprises polypropylene, a main antioxidant 1010, an auxiliary antioxidant 168, an acid-absorbing agent calcium stearate and a nucleating agent. Adding propylene and hydrogen into a Unipol gas-phase fluidized reactor for polymerization reaction in the presence of a main catalyst SHACTM 201, a cocatalyst triethylaluminum and an external electron donor n-propyltrimethoxysilane, and adjusting the content of xylene soluble substances of powder to obtain polypropylene powder; then adding the main antioxidant 1010, the auxiliary antioxidant 168, the acid-absorbing agent calcium stearate and the nucleating agent, mixing, and carrying out melt extrusion and granulation by a double screw to obtain the resin.
The antioxidant effect of the antioxidant formula adopted by the existing polypropylene can only meet the requirement of basic antioxidant function, the antioxidant capacity and yellowing resistance of the polypropylene are insufficient in the fields of high-end products such as films, and the existing antioxidant is added in a large amount, so that the production cost is increased invisibly. Therefore, the development of efficient anti-yellowing antioxidants is urgent and important.
Disclosure of Invention
The invention aims to solve the problems of poor oxidation resistance and yellowing resistance and high cost in the prior art, and provides a yellowing-resistant antioxidant and application thereof, a yellowing-resistant polyolefin composition, a yellowing-resistant polyolefin and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a yellowing-resistant antioxidant, comprising: 0.02-0.045 parts of primary antioxidant I, 0.001-0.02 parts of primary antioxidant II, 0.045-0.1 parts of auxiliary antioxidant and 0.02-0.05 parts of acid acceptor;
wherein the primary antioxidant I is selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
the main antioxidant II is selected from propionate antioxidants;
the auxiliary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite and/or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite.
The second aspect of the invention provides an application of the anti-yellowing antioxidant in at least one of polyolefin, polymethyl methacrylate and polycarbonate.
The third aspect of the invention provides a yellowing-resistant polyolefin composition, which is characterized in that the yellowing-resistant polyolefin composition comprises polyolefin and the yellowing-resistant antioxidant;
wherein the dosage of the yellowing-resistant antioxidant is 0.1-0.2 weight part relative to 100 weight parts of polyolefin.
The fourth aspect of the present invention provides a preparation method of a yellowing-resistant polyolefin, which is characterized in that the preparation method comprises:
s1, uniformly mixing the components in the yellowing-resistant polyolefin composition to obtain a mixture;
s2, adding the mixture into a double-screw extruder for melting and mixing, and extruding to obtain a melt;
and S3, granulating the melt to obtain the yellowing-resistant polyolefin.
The fifth aspect of the invention provides yellowing-resistant polyolefin, which is characterized in that the yellowing-resistant polyolefin is prepared by the preparation method.
The sixth aspect of the present invention provides an application of the yellowing-resistant polyolefin composition or the yellowing-resistant polyolefin in a polyolefin film.
Through the technical scheme, the yellowing-resistant antioxidant and the application thereof, the yellowing-resistant polyolefin composition, the yellowing-resistant polyolefin and the preparation method and the application thereof provided by the invention have the following beneficial technical effects:
the yellowing-resistant antioxidant ensures that the oxygen resistance and yellowing resistance of the polyolefin material are effectively improved on the premise that the mechanical property of a polymer, particularly a polyolefin film, is not reduced by optimizing the type of the main antioxidant, and simultaneously, the production cost is reduced due to the small addition amount of the antioxidant.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a yellowing-resistant antioxidant, which is characterized by comprising the following components in part by weight: 0.02-0.045 parts of primary antioxidant I, 0.001-0.02 parts of primary antioxidant II, 0.045-0.1 parts of auxiliary antioxidant and 0.02-0.05 parts of acid acceptor;
wherein the primary antioxidant I is selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
the main antioxidant II is selected from propionate antioxidants;
the auxiliary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite and/or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite.
In the invention, when the components of the antioxidant meet the above ranges, the components in the yellowing-resistant antioxidant can realize synergistic interaction, so that the antioxidant and yellowing-resistant performances of the resin composition containing the yellowing-resistant antioxidant are further improved.
In the invention, the main antioxidant II is selected from propionate antioxidants, can effectively absorb free radicals in the resin body, and the compound formed after absorbing the free radicals can not generate quinone compounds and other compounds like hindered phenol antioxidants which absorb the free radicals, so that optical chromatic aberration, such as redness or yellowing, is caused.
According to the present invention, the antioxidant comprises: 0.025-0.03 part of main antioxidant I, 0.005-0.015 part of main antioxidant II, 0.06-0.09 part of auxiliary antioxidant and 0.025-0.045 part of acid acceptor.
According to the invention, the primary antioxidant II is selected from at least one of triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, pentaerythritol tetrakis (3-laurylthiopropionate) and triethylene glycol ether-bis (3-laurylthiopropionate).
Further, the primary antioxidant II is selected from triethylene glycol ether-bis (3-laurylthiopropionate).
According to the invention, the acid acceptor is selected from at least one of calcium stearate, magnesium stearate and magnesium aluminum hydrotalcite.
The second aspect of the invention provides an application of the anti-yellowing antioxidant in polyolefin, polymethyl methacrylate (PMMA) and Polycarbonate (PC).
The third aspect of the invention provides a yellowing-resistant polyolefin composition, which is characterized in that the yellowing-resistant polyolefin composition comprises polyolefin and the yellowing-resistant antioxidant;
wherein, the dosage of the yellowing-resistant antioxidant is 0.1 to 0.2 part relative to 100 parts by weight of polyolefin.
According to the invention, the main antioxidant II is cooperated with the auxiliary antioxidant, so that the free radicals in the polyolefin product are preferentially reduced to a certain concentration, and then the free radicals in the polyolefin are stabilized at a lower concentration through the main antioxidant I, thereby reducing the chain degradation of the polyolefin initiated by the free radicals and realizing the stable comprehensive performance of the polyolefin.
In the invention, the yellowing-resistant polyolefin composition has high mechanical property, high oxidation resistance and yellowing resistance.
Further, the dosage of the anti-yellowing antioxidant is 0.12-0.18 weight part.
The fourth aspect of the present invention provides a preparation method of a yellowing-resistant polyolefin, which is characterized in that the preparation method comprises:
s1, uniformly mixing the components in the yellowing-resistant polyolefin composition to obtain a mixture;
s2, adding the mixture into a double-screw extruder for melting and mixing, and extruding to obtain a melt;
and S3, granulating the melt to obtain the yellowing-resistant polyolefin.
According to the present invention, the polyolefin may be a polyolefin conventional in the art, such as polypropylene and/or polyethylene, preferably homopolypropylene.
According to the invention, special type of blending granulation equipment and a compound blending molding mode are adopted, for example, different granulation equipment such as different length-diameter ratios, different lengths of a melting section and a mixing section and temperature difference regulation are adopted to realize effective blending, so that the antioxidant and polyolefin molecules are fully and uniformly mixed, the antioxidant can exert high-efficiency and stable antioxidant performance and yellowing resistance performance in polyolefin, and the prepared yellowing-resistant polyolefin has high antioxidant performance and yellowing resistance performance on the premise of keeping high mechanical property, and the stability of the comprehensive performance of the polyolefin is ensured.
According to the invention, the length-diameter ratio of the screw of the double-screw extruder is (42-48):1, and the rotation speed of the screw is 100-300 rpm.
According to the invention, the temperature of the melting section of the double-screw extruder is 150-180 ℃, the temperature of the mixing section is 190-210 ℃, the temperature of the extrusion section is 180-185 ℃, and the pressure of the extruder is 1.6-2.5 MPa.
According to the invention, the mixing sections are 6 mixing sections; wherein the temperature of the first mixing section is 190-.
In the invention, the mixing section meets the temperature, so that the antioxidant can be more uniformly dispersed in the polyolefin, the oxidation induction period of the prepared polyolefin is obviously prolonged, the corresponding yellow index and melt index are obviously reduced, and the comprehensive performance is further improved.
The fifth aspect of the invention provides yellowing-resistant polyolefin, which is characterized in that the yellowing-resistant polyolefin is prepared by the preparation method.
In the invention, the elongation at break of the yellowing-resistant polyolefin is not less than 500%, the melt index is 4.5-11g/10min, the yellow index is not more than 10, and the oxidation induction period is not less than 10 min.
The sixth aspect of the present invention provides an application of the yellowing-resistant polyolefin composition or the yellowing-resistant polyolefin in a polyolefin film.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
the melt index is measured by the method of GB/T3682-;
the yellow index is measured by the method HG/T3862-2006;
the oxidative induction period is measured by the GB/T19466.2-2004 method;
the impact strength is measured by the method of GB/T1043.1-2008;
the tensile strength is measured by the method GB/T1040.2-2006;
the elongation at break is measured by the method GB/T1040.2-2006;
polypropylene pellets, No. 1102K, number average molecular weight 3.3X 104Melt index 2.5g/10 min;
other raw materials used in examples and comparative examples are all commercially available products.
Preparation example 1
Weighing 0.025 parts by weight of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 0.01 parts by weight of triethylene glycol ether-bis (3-lauryl thiopropionate), 0.09 parts by weight of tris (2, 4-di-tert-butylphenyl) phosphite and 0.045 parts by weight of calcium stearate, and uniformly mixing to obtain the yellowing-resistant antioxidant, wherein the name of the yellowing-resistant antioxidant is A1.
Preparation example 2
0.03 part by weight of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 0.005 part by weight of triethylene glycol ether-bis (3-laurylthiopropionate), 0.09 part by weight of tris (2, 4-di-tert-butylphenyl) phosphite and 0.045 part by weight of calcium stearate were weighed. The components are uniformly mixed to obtain the yellowing-resistant antioxidant which is named as A2.
Preparation example 3
In accordance with preparation example 1, except that the triethylene glycol ether-bis (3-laurylthiopropionate) was replaced with triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, A3 was obtained.
Comparative preparation example 1
In accordance with preparation example 1, except that 0.045 parts by weight of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 0.09 parts by weight of tris (2, 4-di-tert-butylphenyl) phosphite and 0.045 parts by weight of calcium stearate, D1 was obtained.
Comparative preparation example 2
In accordance with preparation example 1, except that the tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester was 0.046 parts by weight, D2 was obtained.
Comparative preparation example 3
In accordance with preparation example 1, except that pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] was not included, D3 was obtained.
Comparative preparation example 4
In accordance with preparation example 1, except that the triethylene glycol ether-bis (3-laurylthiopropionate) was replaced with 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, D4 was obtained.
Example 1
S1, weighing 0.17 part by weight of A1 and 100 parts by weight of polypropylene, adding into a container, and fully mixing to obtain a mixture;
s2, placing the mixture into a 50-level double-screw extruder, wherein the length-diameter ratio of a screw is 48:1, the rotating speed is 200rpm, carrying out two-stage melting at the temperatures of 150 ℃ and 180 ℃, then sequentially carrying out 6-stage mixing at the temperatures of 190 ℃, 200 ℃, 200 ℃, 200 ℃, 195 ℃ and 190 ℃, and after mixing is finished, extruding at the pressure of 1.6MPa and the temperature of 185 ℃ to obtain a melt;
s3, granulating the melt to obtain the yellowing-resistant polyolefin P1.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin P1 are shown in table 1.
Example 2
In accordance with example 1, except that step S2 was cycled 2 times. The yellowing-resistant polyolefin P2 is obtained. The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin P2 are shown in table 1.
Example 3
In accordance with embodiment 1, except that step S2 is: putting the mixture into a 35-grade double-screw extruder, melting the mixture in two stages at 170 ℃ and 190 ℃ at the rotation speed of 150rpm with the length-diameter ratio of 42:1, sequentially mixing 5 stages at 200 ℃, 210 ℃, 210 ℃, 200 ℃ and 190 ℃, and extruding the melt under the pressure of 1.8MPa and the temperature of 180 ℃ to obtain the melt after mixing. And granulating the melt to obtain the yellowing-resistant polyolefin P3.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin P3 are shown in table 1.
Example 4
In accordance with example 3, except that step S2 was cycled 2 times, a yellowing resistant polyolefin P4 was obtained. The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin P4 are shown in table 1.
Example 5
In example 3, step S2 was repeated 3 times to obtain yellowing-resistant polyolefin P5. The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin P5 are shown in table 1.
Example 6
Consistent with example 1, except that replacing a1 with a2 gave a yellowing resistant polyolefin P6.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin P6 are shown in table 1.
Example 7
Consistent with example 6, except that step S2 was cycled 2 times, a yellowing resistant polyolefin P7 was obtained. The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin P7 are shown in table 1.
Example 8
Consistent with example 1, except that a1 was replaced by A3, a yellowing resistant polyolefin P8 was obtained.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin P8 are shown in table 1.
Example 9
In step S1, 0.1 part by weight of A1 was weighed in accordance with example 1. The yellowing-resistant polyolefin P9 is obtained.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin P9 are shown in table 1.
Example 10
In accordance with example 1, except that the temperatures of the kneading sections in step S2 were 180 ℃, 190 ℃, 190 ℃, 190 ℃, 185 ℃, 185 ℃, 185 ℃, respectively. The yellowing-resistant polyolefin P10 is obtained.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin P10 are shown in table 1.
Comparative example 1
Consistent with example 1, except that a1 was replaced with D1, a yellowing resistant polyolefin DP1 was obtained.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin DP1 are shown in table 1.
Comparative example 2
In agreement with comparative example 1, except that step S2 was cycled 2 times. The yellowing resistant polyolefin DP2 was obtained.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin DP2 are shown in table 1.
Comparative example 3
Consistent with example 1, except that a1 was replaced with D2, a yellowing resistant polyolefin DP3 was obtained.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin DP3 are shown in table 1.
Comparative example 4
Consistent with example 1, except that replacing a1 with D3 gave a yellowing resistant polyolefin DP 4.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin DP4 are shown in table 1.
Comparative example 5
Consistent with example 1, except that a1 was replaced with D4, a yellowing resistant polyolefin DP5 was obtained.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin DP5 are shown in table 1.
Comparative example 6
In accordance with comparative example 5, except that step S2 was cycled 2 times, a yellowing resistant polyolefin DP6 was obtained.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin DP6 are shown in table 1.
Comparative example 7
In accordance with comparative example 5, except that step S2 was cycled 3 times, a yellowing resistant polyolefin DP7 was obtained.
The melt index, yellowness index, oxidation induction period, impact strength, tensile strength and elongation at break of the yellowing resistant polyolefin DP7 are shown in table 1.
TABLE 1
The results in table 1 show that the polypropylene prepared by the embodiment of the present invention has good oxidation resistance and yellowing resistance on the premise of maintaining high mechanical properties, and the oxidation induction period, impact strength, tensile strength and elongation at break of the polypropylene are all maintained at high levels. The elongation at break of the polypropylene is not less than 500%, the yellow index is not more than 8, the lowest yellow index of the polymer is 0.75 under the condition of the optimal dosage, the polypropylene prepared after twice melt extrusion still has a lower yellow index which is only 1.24, and still has a longer oxidation induction period and higher mechanical properties, further explaining that the ageing resistance is excellent, and the dosage of each component in the antioxidant is greatly reduced compared with the dosage of the antioxidant in the prior art, so that the production cost is reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. An anti-yellowing antioxidant, comprising: 0.02-0.045 parts of primary antioxidant I, 0.001-0.02 parts of primary antioxidant II, 0.045-0.1 parts of auxiliary antioxidant and 0.02-0.05 parts of acid acceptor;
wherein the primary antioxidant I is selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
the main antioxidant II is selected from propionate antioxidants;
the auxiliary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite and/or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite.
2. The antioxidant of claim 1, wherein the antioxidant comprises: 0.025-0.03 part of main antioxidant I, 0.005-0.015 part of main antioxidant II, 0.06-0.09 part of auxiliary antioxidant and 0.025-0.045 part of acid acceptor.
3. The antioxidant according to claim 1 or 2, wherein the primary antioxidant II is selected from at least one of triethylene glycol ether-bis (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, pentaerythritol tetrakis (3-laurylthiopropionate) and triethylene glycol ether-bis (3-laurylthiopropionate);
preferably, the acid acceptor is selected from at least one of calcium stearate, magnesium stearate and magnesium aluminum hydrotalcite.
4. Use of the yellowing-resistant antioxidant according to any one of claims 1 to 3 in at least one of polyolefin, polymethylmethacrylate, and polycarbonate.
5. An anti-yellowing polyolefin composition, comprising a polyolefin and the anti-yellowing antioxidant according to any one of claims 1 to 3;
wherein the dosage of the yellowing-resistant antioxidant is 0.1-0.2 weight part relative to 100 weight parts of polyolefin.
6. A preparation method of yellowing-resistant polyolefin is characterized by comprising the following steps:
s1, uniformly mixing the components in the yellowing-resistant polyolefin composition according to claim 5 to obtain a mixture;
s2, adding the mixture into a double-screw extruder for melting and mixing, and extruding to obtain a melt;
and S3, granulating the melt to obtain the yellowing-resistant polyolefin.
7. The preparation method according to claim 6, wherein the screw length-diameter ratio of the twin-screw extruder is 42-48:1, the screw rotation speed is 100-300 rpm;
the temperature of the melting section of the double-screw extruder is 150-180 ℃, the temperature of the mixing section is 190-210 ℃, the temperature of the extrusion section is 180-185 ℃, and the pressure of the extruder is 1.6-2.5 MPa.
8. The production method according to claim 6 or 7, wherein the kneading sections are 3 to 6 kneading sections;
preferably, the mixing section is 6 mixing sections, the temperature of the first mixing section is 190-.
9. An anti-yellowing polyolefin, which is prepared by the preparation method of any one of claims 6 to 8.
10. Use of the yellowing-resistant polyolefin composition of claim 5 or the yellowing-resistant polyolefin of claim 9 in a polyolefin film.
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