CN114350022B - 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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- CN114350022B CN114350022B CN202111466504.9A CN202111466504A CN114350022B CN 114350022 B CN114350022 B CN 114350022B CN 202111466504 A CN202111466504 A CN 202111466504A CN 114350022 B CN114350022 B CN 114350022B
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- 238000004383 yellowing Methods 0.000 title claims abstract description 113
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 97
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 90
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 88
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims abstract description 27
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000006096 absorbing agent Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 12
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 9
- 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 7
- 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
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 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 27
- 238000007254 oxidation reaction Methods 0.000 abstract description 27
- 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 abstract description 3
- 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 16
- 229920001155 polypropylene Polymers 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 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 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 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 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 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
- 229920005633 polypropylene homopolymer resin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-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
- 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 description 1
- 230000004075 alteration Effects 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
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003287 optical effect Effects 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
- 238000006116 polymerization reaction Methods 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
- 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
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004753 textile Substances 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
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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, and a yellowing-resistant polyolefin and a preparation method and application thereof. The antioxidant comprises 0.02-0.045 part of main antioxidant I, 0.001-0.02 part of main antioxidant II, 0.045-0.1 part of auxiliary antioxidant and 0.02-0.05 part of acid absorber; the main antioxidant I is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the main antioxidant II is a propionate antioxidant; the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite and/or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite. The addition of 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, in particular to a yellowing-resistant antioxidant and application thereof, a yellowing-resistant polyolefin composition and application thereof, and a yellowing-resistant polyolefin and a preparation method and application thereof.
Background
As a thermoplastic synthetic resin with excellent performance, polypropylene has the characteristics of chemical resistance, heat resistance, electrical insulation, high strength mechanical property, good high wear resistance processing property and the like, and is widely applied to various fields of machinery, automobiles, electronic appliances, buildings, textiles, packaging, agriculture, forestry, fishery, food industry and the like. Because polypropylene belongs to a thermoplastic organic mixture with a long carbon chain, and is influenced by factors such as polymerization conditions, post-processing conditions and the like, the polypropylene product contains a large amount of free radicals, and is extremely easy to oxidize and degrade after being exposed in air, so that the performances such as melt index, yellow index and the like of the polypropylene product are reduced, and the subsequent processing application is seriously influenced.
CN111378228A discloses a yellowing-resistant polypropylene compound and a preparation method thereof, which is characterized in that the material has excellent yellowing resistance in high-temperature heat aging environment, and can be used for materials with high yellowing resistance requirements such as automobile kettles. 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 absorber. The product has excellent yellowing resistance in the high-temperature aging process, and after the severe thermo-oxidative aging test of 150 ℃/500h in the automobile industry, the color difference value change delta E of the material is less than 1.0, so that the yellowing resistance requirements of parts such as automobile washing kettles, expansion tank kettles and the like on the material can be met.
CN110577702a discloses a transparent rigid-tough balanced thermo-forming homo-polypropylene resin, which comprises polypropylene, a primary antioxidant 1010, an auxiliary antioxidant 168, an acid absorber calcium stearate and a nucleating agent. The preparation process of transparent rigid-tough balanced heat forming homo-polypropylene resin includes adding propylene and hydrogen to Unipol gas phase fluidizing reactor in the presence of main catalyst SHACTM 201, cocatalyst triethylaluminum and external electron donor n-propyl trimethoxysilane to polymerize and regulate the xylene soluble matter content of the powder to obtain polypropylene powder; then adding the main antioxidant 1010, the auxiliary antioxidant 168, the acid absorber calcium stearate and the nucleating agent, mixing, and carrying out twin-screw melt extrusion and granulation to obtain the resin.
The antioxidant effect of the antioxidant formula adopted by the polypropylene at present can only meet the basic antioxidant function requirement, the antioxidant capacity and yellowing resistance of the antioxidant are insufficient in the fields of high-end products such as films, and the like, and the existing antioxidant is large in addition amount, so that the production cost is increased intangibly. Therefore, 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, characterized in that the antioxidant comprises: 0.02-0.045 part of primary antioxidant I, 0.001-0.02 part of primary antioxidant II, 0.045-0.1 part of auxiliary antioxidant and 0.02-0.05 part of acid absorber;
wherein the main antioxidant I is selected from pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
the main antioxidant II is selected from propionate antioxidants;
the auxiliary antioxidant is selected from tri (2, 4-di-tert-butylphenyl) phosphite and/or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite.
The second aspect of the invention provides the application of the yellowing-resistant 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 by comprising polyolefin and the yellowing-resistant antioxidant;
wherein the yellowing-resistant antioxidant is used in an amount of 0.1 to 0.2 parts by weight relative to 100 parts by weight of the polyolefin.
According to a fourth aspect of the present invention, there is provided a process for producing a yellowing-resistant polyolefin, comprising:
s1, uniformly mixing all 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;
s3, granulating the melt to obtain the yellowing-resistant polyolefin.
In a fifth aspect, the present invention provides a yellowing-resistant polyolefin, which is characterized in that the yellowing-resistant polyolefin is produced by the above-mentioned production method.
The sixth aspect of the invention provides an application of the yellowing-resistant polyolefin composition or the yellowing-resistant polyolefin in a polyolefin film.
Through the technical scheme, the anti-yellowing antioxidant and application thereof, the anti-yellowing polyolefin composition, the anti-yellowing polyolefin, and the preparation method and application thereof provided by the invention have the following beneficial technical effects:
the yellowing-resistant antioxidant ensures that the antioxidant and the yellowing resistance of the polyolefin material are effectively improved on the premise that the mechanical properties of the polymer, particularly the polyolefin film, are not reduced by optimizing the type of the main antioxidant, and meanwhile, the production cost is reduced due to the small addition amount of the antioxidant.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a yellowing-resistant antioxidant, which is characterized by comprising: 0.02-0.045 part of primary antioxidant I, 0.001-0.02 part of primary antioxidant II, 0.045-0.1 part of auxiliary antioxidant and 0.02-0.05 part of acid absorber;
wherein the main antioxidant I is selected from pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
the main antioxidant II is selected from propionate antioxidants;
the auxiliary antioxidant is selected from tri (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 range, the components in the yellowing-resistant antioxidant can realize synergistic effect, so that the oxidation resistance and the yellowing resistance 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 a resin body, and a compound formed after absorbing the free radicals can not generate a compound such as quinone after absorbing the free radicals like hindered phenol antioxidants, so that optical chromatic aberration such as redness or yellowing is caused.
According to the invention, the antioxidant comprises: 0.025-0.03 part of primary antioxidant I, 0.005-0.015 part of primary antioxidant II, 0.06-0.09 part of auxiliary antioxidant and 0.025-0.045 part of acid absorber.
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 the group consisting of triethylene glycol ether-bis (3-laurylthiopropionate).
According to the present invention, the acid absorber is selected from at least one of calcium stearate, magnesium stearate, and magnesium aluminum hydrotalcite.
In a second aspect, the invention provides the use of the yellowing-resistant antioxidant in polyolefin, polymethyl methacrylate (PMMA) and Polycarbonate (PC).
The third aspect of the invention provides a yellowing-resistant polyolefin composition, which is characterized by comprising polyolefin and the yellowing-resistant antioxidant;
wherein the amount of the yellowing-resistant antioxidant is 0.1 to 0.2 parts by weight relative to 100 parts by weight of the polyolefin.
According to the invention, the main antioxidant II is used for cooperating with the auxiliary antioxidant, so that the free radical in the polyolefin product is preferentially reduced to a certain concentration, and then the free radical in the polyolefin is stabilized at a lower concentration through the main antioxidant I, thereby reducing the chain degradation of the polyolefin caused by the free radical and realizing the stability of the 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 yellowing-resistant antioxidant is 0.12-0.18 parts by weight.
According to a fourth aspect of the present invention, there is provided a process for producing a yellowing-resistant polyolefin, comprising:
s1, uniformly mixing all 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;
s3, granulating the melt to obtain the yellowing-resistant polyolefin.
According to the invention, the polyolefin may be a polyolefin conventional in the art, such as polypropylene and/or polyethylene, preferably a homo-polypropylene.
According to the invention, special type blending granulation equipment and a compound blending forming mode are adopted, such as different granulation equipment, such as different length-diameter ratios, and the length difference between a melting section and a mixing section, and the temperature difference is regulated to realize effective blending, so that the antioxidant and polyolefin molecules are fully and uniformly mixed, the antioxidant can exert high-efficiency stable antioxidant property and yellowing resistance in the polyolefin, and the prepared yellowing-resistant polyolefin can have high antioxidant property and yellowing resistance 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 rotating speed of the screw is 100-300rpm.
According to the invention, the melting section temperature of the double-screw extruder is 150-180 ℃, the mixing section temperature is 190-210 ℃, the extrusion section temperature is 180-185 ℃, and the pressure of the extruder is 1.6-2.5MPa.
According to the invention, the mixing sections are 6 mixing sections; wherein the temperature of the first mixing section is 190-200 ℃, the temperature of the second mixing section is 200-210 ℃, the temperature of the third mixing section is 200-210 ℃, the temperature of the fourth mixing section is 195-200 ℃, the temperature of the fifth mixing section is 190-195 ℃, and the temperature of the sixth mixing section is 190-195 ℃.
In the invention, the mixing section meets the temperature, so that the antioxidant can be ensured to be more uniformly dispersed in the polyolefin, the oxidation induction period of the prepared polyolefin is obviously improved, the corresponding yellow index and melt index are obviously reduced, and the comprehensive performance is further improved.
In a fifth aspect, the present invention provides a yellowing-resistant polyolefin, which is characterized in that the yellowing-resistant polyolefin is produced by the above-mentioned production 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 10min.
The sixth aspect of the 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 by examples. In the following examples of the present invention,
melt index was measured by GB/T3682-2000 method;
the yellow index was measured by HG/T3862-2006 method;
the oxidation induction period was measured by the method of GB/T19466.2-2004;
impact strength was measured by GB/T1043.1-2008 method;
tensile strength was measured by GB/T1040.2-2006 method;
elongation at break is measured by GB/T1040.2-2006 method;
polypropylene pellet, grade 1102K, number average molecular weight 3.3X10 4 Melt index 2.5g/10min;
the other raw materials used in the examples and comparative examples are all commercially available.
Preparation example 1
0.025 parts by weight of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 0.01 parts by weight of triethylene glycol ether-di (3-laurylthiopropionate), 0.09 parts by weight of tris (2, 4-di-tert-butylphenyl) phosphite and 0.045 parts by weight of calcium stearate are weighed and uniformly mixed to obtain a yellowing-resistant antioxidant, which is named as 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 are weighed. The anti-yellowing antioxidant is obtained by uniformly mixing the components, and is named as A2.
Preparation example 3
In accordance with preparation 1, except that 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 production example 1, except that 0.045 parts by weight of pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 0.09 parts by weight of tris (2, 4-di-t-butylphenyl) phosphite and 0.045 parts by weight of calcium stearate were obtained as D1.
Comparative preparation example 2
In accordance with production example 1, except that pentaerythritol tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] was 0.046 parts by weight, D2 was obtained.
Comparative preparation example 3
In the same manner as in preparation example 1, except that pentaerythritol tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] was not contained, D3 was obtained.
Comparative preparation example 4
In accordance with preparation 1, except that triethylene glycol ether-bis (3-laurylthiopropionate) was replaced with 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-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 the screw is 48:1, the rotating speed is 200rpm, carrying out two-section melting at 150 ℃ and 180 ℃, then sequentially carrying out 6-section mixing at 190 ℃,200 ℃,200 ℃,200 ℃,195 ℃ and 190 ℃ respectively, and extruding at the pressure of 1.6MPa and the temperature of 185 ℃ after the mixing is finished 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, step S2 is cycled 2 times, except. Obtaining the yellowing resistant polyolefin P2. 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 example 1, except that step S2 is: placing the mixture into a 35-stage double-screw extruder, wherein the length-diameter ratio of the screw is 42:1, the rotating speed is 150rpm, performing two-stage melting at 170 ℃ and 190 ℃, sequentially performing 5-stage mixing at 200 ℃,210 ℃,210 ℃,210 ℃,200 ℃ and 190 ℃, and extruding the melt at the pressure of 1.8MPa and the temperature of 180 ℃ after the mixing is finished to obtain the melt. 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 repeated 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
Step S2 of example 3 was cycled 3 times to obtain a 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
In agreement with example 1, except that A1 was replaced by A2, a yellowing resistant polyolefin P6 was obtained.
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
In accordance with example 6, except that step S2 was repeated 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
In agreement 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 the same manner as in example 1 except for the step S1, 0.1 parts by weight of A1 was weighed. 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 the same manner as in example 1, except that in step S2, the temperature of the kneading blocks was 180℃and 190℃and 185℃and 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
In accordance 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 accordance with comparative example 1, except that step S2 was cycled 2 times. Obtaining the yellowing resistant polyolefin DP2.
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
In agreement with example 1, except that A1 was replaced by 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
In agreement with example 1, except that A1 was replaced by D3, a yellowing resistant polyolefin DP4 was obtained.
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
In agreement with example 1, except that A1 was replaced by 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 repeated 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 repeated 3 times, 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
As can be seen from the results in Table 1, the polypropylene prepared by the method has better oxidation resistance and yellowing resistance on the premise of keeping higher mechanical properties, and the oxidation induction period, impact strength, tensile strength and elongation at break are all kept at higher levels. The elongation at break of the polypropylene is not less than 500%, the yellow index is not more than 8, under the condition of the preferable dosage, the minimum yellow index of the polymer is 0.75, the polypropylene prepared by melt extrusion for two times still has a lower yellow index, only 1.24, still has a longer oxidation induction period and higher mechanical property, further shows excellent ageing resistance, and the dosage of each component in the antioxidant is greatly reduced compared with that of the antioxidant in the prior art, so that the production cost is reduced.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A yellowing-resistant antioxidant, wherein the antioxidant comprises: 0.02-0.045 part of primary antioxidant I, 0.001-0.02 part of primary antioxidant II, 0.045-0.1 part of auxiliary antioxidant and 0.02-0.05 part of acid absorber;
wherein the main antioxidant I is selected from pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
the main antioxidant II is selected from triethylene glycol ether-bis (3-laurylthiopropionate);
the auxiliary antioxidant is selected from tri (2, 4-di-tert-butylphenyl) phosphite.
2. The antioxidant of claim 1, wherein the antioxidant comprises: 0.025-0.03 part of primary antioxidant I, 0.005-0.015 part of primary antioxidant II, 0.06-0.09 part of auxiliary antioxidant and 0.025-0.045 part of acid absorber.
3. The antioxidant according to claim 1 or 2, wherein the acid absorber is selected from at least one of calcium stearate, magnesium stearate and magnesium aluminum hydrotalcite.
4. Use of the yellowing-resistant antioxidant of any one of claims 1 to 3 in at least one of polyolefin, polymethyl methacrylate and polycarbonate.
5. A yellowing-resistant polyolefin composition comprising a polyolefin and the yellowing-resistant antioxidant of any one of claims 1-3;
wherein the yellowing-resistant antioxidant is used in an amount of 0.1 to 0.2 parts by weight relative to 100 parts by weight of the polyolefin.
6. A process for the preparation of a yellowing-resistant polyolefin, the process comprising:
s1, uniformly mixing all the components in the yellowing-resistant polyolefin composition of 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;
s3, granulating the melt to obtain the yellowing-resistant polyolefin.
7. The production method according to claim 6, wherein the twin-screw extruder has a screw aspect ratio of 42-48:1 and a screw rotation speed of 100-300rpm;
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 1.6-2.5MPa.
8. The method according to claim 6 or 7, wherein the kneading blocks are 3 to 6 kneading blocks.
9. The production method according to claim 6 or 7, wherein the kneading blocks are 6 kneading blocks, the first kneading block has a temperature of 190 to 200 ℃, the second kneading block has a temperature of 200 to 210 ℃, the third kneading block has a temperature of 200 to 210 ℃, the fourth kneading block has a temperature of 195 to 200 ℃, the fifth kneading block has a temperature of 190 to 195 ℃, and the sixth kneading block has a temperature of 190 to 195 ℃.
10. A yellowing-resistant polyolefin prepared by the preparation method according to any one of claims 6 to 9.
11. Use of the yellowing-resistant polyolefin composition of claim 5 or the yellowing-resistant polyolefin of claim 10 in a polyolefin film.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0247146A (en) * | 1988-08-10 | 1990-02-16 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
| CN101597384A (en) * | 2009-07-03 | 2009-12-09 | 迪比喜化学贸易(上海)有限公司 | The composite antioxidant that is used for polyoxymethylene |
| CN103788598A (en) * | 2014-01-29 | 2014-05-14 | 厦门市天宇塑料工业有限公司 | Anti-yellowing anti-separation flame-retardant enhanced PBT composition and use thereof |
| WO2015032033A1 (en) * | 2013-09-03 | 2015-03-12 | 中国科学院化学研究所 | Composition providing heat stability for polymer and application thereof |
| CN107200866A (en) * | 2016-11-24 | 2017-09-26 | 汕头市八隅新材料有限公司 | A kind of resistance to yellow agent of soft polyurethane foam |
| CN107987401A (en) * | 2017-12-19 | 2018-05-04 | 会通新材料股份有限公司 | A kind of heat oxygen aging resistance vegetable fiber reinforced polypropylene composite material and preparation method thereof |
| CN108047493A (en) * | 2017-12-29 | 2018-05-18 | 天津利安隆新材料股份有限公司 | A kind of anti-oxidant compositions for nylon |
| CN110272563A (en) * | 2019-06-27 | 2019-09-24 | 江苏极易新材料有限公司 | A kind of composite antioxidant preparation method to turn yellow with more preferable improvement Polymer Processing and long-term ageing |
| CN111892769A (en) * | 2020-07-15 | 2020-11-06 | 国家能源集团宁夏煤业有限责任公司 | Ultraviolet-resistant polypropylene composite material composition, application thereof and preparation method of ultraviolet-resistant polypropylene composite material |
| CN112321934A (en) * | 2020-11-08 | 2021-02-05 | 江苏北化新橡新材料科技有限公司 | Irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin material for 150 ℃ American standard electronic wire and preparation method thereof |
| CN112409636A (en) * | 2020-11-23 | 2021-02-26 | 广东众和高新科技有限公司 | Antioxidant composition and preparation method and application thereof |
-
2021
- 2021-12-03 CN CN202111466504.9A patent/CN114350022B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0247146A (en) * | 1988-08-10 | 1990-02-16 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
| CN101597384A (en) * | 2009-07-03 | 2009-12-09 | 迪比喜化学贸易(上海)有限公司 | The composite antioxidant that is used for polyoxymethylene |
| WO2015032033A1 (en) * | 2013-09-03 | 2015-03-12 | 中国科学院化学研究所 | Composition providing heat stability for polymer and application thereof |
| CN103788598A (en) * | 2014-01-29 | 2014-05-14 | 厦门市天宇塑料工业有限公司 | Anti-yellowing anti-separation flame-retardant enhanced PBT composition and use thereof |
| CN107200866A (en) * | 2016-11-24 | 2017-09-26 | 汕头市八隅新材料有限公司 | A kind of resistance to yellow agent of soft polyurethane foam |
| CN107987401A (en) * | 2017-12-19 | 2018-05-04 | 会通新材料股份有限公司 | A kind of heat oxygen aging resistance vegetable fiber reinforced polypropylene composite material and preparation method thereof |
| CN108047493A (en) * | 2017-12-29 | 2018-05-18 | 天津利安隆新材料股份有限公司 | A kind of anti-oxidant compositions for nylon |
| CN110272563A (en) * | 2019-06-27 | 2019-09-24 | 江苏极易新材料有限公司 | A kind of composite antioxidant preparation method to turn yellow with more preferable improvement Polymer Processing and long-term ageing |
| CN111892769A (en) * | 2020-07-15 | 2020-11-06 | 国家能源集团宁夏煤业有限责任公司 | Ultraviolet-resistant polypropylene composite material composition, application thereof and preparation method of ultraviolet-resistant polypropylene composite material |
| CN112321934A (en) * | 2020-11-08 | 2021-02-05 | 江苏北化新橡新材料科技有限公司 | Irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin material for 150 ℃ American standard electronic wire and preparation method thereof |
| CN112409636A (en) * | 2020-11-23 | 2021-02-26 | 广东众和高新科技有限公司 | Antioxidant composition and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 硫代酯抗氧剂412S对聚丙烯加工稳定化的影响;谭卓华;李世昌;敖晓娟;杨育农;王浩江;王飞;雷祖碧;;合成材料老化与应用(02) * |
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