CN110563872B - Modified antioxidant for solving polypropylene phenol red, polypropylene composition, and preparation method and application thereof - Google Patents
Modified antioxidant for solving polypropylene phenol red, polypropylene composition, and preparation method and application thereof Download PDFInfo
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- CN110563872B CN110563872B CN201910781558.0A CN201910781558A CN110563872B CN 110563872 B CN110563872 B CN 110563872B CN 201910781558 A CN201910781558 A CN 201910781558A CN 110563872 B CN110563872 B CN 110563872B
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- -1 polypropylene phenol Polymers 0.000 title claims abstract description 159
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 148
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 148
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 119
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 115
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229960003531 phenolsulfonphthalein Drugs 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000004611 light stabiliser Substances 0.000 claims abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 12
- 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 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 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 claims description 9
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 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 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 150000008360 acrylonitriles Chemical class 0.000 claims description 3
- 150000001565 benzotriazoles Chemical class 0.000 claims description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- 150000003873 salicylate salts Chemical class 0.000 claims description 3
- 150000003918 triazines Chemical class 0.000 claims description 3
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 description 14
- 238000005266 casting Methods 0.000 description 9
- 238000013508 migration Methods 0.000 description 9
- 230000005012 migration Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000006081 fluorescent whitening agent Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000013799 ultramarine blue Nutrition 0.000 description 3
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 235000005811 Viola adunca Nutrition 0.000 description 2
- 240000009038 Viola odorata Species 0.000 description 2
- 235000013487 Viola odorata Nutrition 0.000 description 2
- 235000002254 Viola papilionacea Nutrition 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 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 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 244000172533 Viola sororia Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/14—Homopolymers or copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Abstract
The invention relates to the field of polypropylene film processing and forming, in particular to a modified antioxidant for solving polypropylene phenol red, a polypropylene composition, a preparation method and application thereof. The modified antioxidant is obtained by mixing and reacting styrene-acrylate copolymer and REVONOX 420. The polypropylene composition comprises: a polypropylene resin; the above-mentioned modified antioxidant; antioxidants and light stabilizers. The polypropylene film prepared by applying the modified antioxidant or the polypropylene composition has no phenol red phenomenon on the end surface after being rolled, and can prolong the service life of the polypropylene film.
Description
Technical Field
The invention relates to the field of polypropylene film processing and forming, in particular to a modified antioxidant for solving polypropylene phenol red, a polypropylene composition, a preparation method and application thereof, which are used for solving the problem of end face phenol red after the polypropylene film is rolled.
Background
The red color of the end face of the polypropylene film after molding and rolling is generally called phenol red. In order to solve the phenol red problem of the polypropylene film in the existing industrial production process, the problem can be solved by adding ultramarine inorganic pigment or fluorescent whitening agent organic auxiliary agent into the polypropylene. The mode of adding the inorganic pigment is to eliminate red light of the polypropylene film by the principle that ultramarine blue reflects blue light, but the mode often causes the opacity of the polypropylene film and influences the application of the film product. The mode of adding the fluorescent brightener organic auxiliary agent is that the fluorescent brightener can absorb ultraviolet light (the wavelength range is between 300 and 400 nm), and then emits blue-violet fluorescence (the wavelength range is between 420 and 480 nm) which can be seen by naked eyes, and the blue-violet fluorescence is complementary with red light on a polypropylene film substrate to have a whitening effect. This approach has no effect on the clarity of the polypropylene product, but often has migration and contamination problems.
Therefore, the development of the migration-resistant auxiliary agent for eliminating the phenol red phenomenon of the polypropylene film has important guiding significance for improving the quality of the polypropylene film.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a modified antioxidant for solving the problem of polypropylene phenol red, a polypropylene composition, a preparation method and application thereof.
The inventor finds out in the research process that: the end face of the polypropylene film material is easy to generate red phenomenon after molding and rolling, and the application of the polypropylene film material is influenced by the generation of the phenol red phenomenon. In the process of improving the phenol red phenomenon of the polypropylene film material, the problem cannot be well solved by simply adding some antioxidants or antioxidants. Some polypropylene films eliminate red light by adding ultramarine blue inorganic raw materials into the polypropylene and reflecting blue light through ultramarine blue, but the mode often causes the opacity of the polypropylene film and influences the variety of products. The fluorescent whitening agent is used as an organic auxiliary agent, absorbs ultraviolet light and emits bluish violet fluorescence visible to the naked eye, so that the fluorescent whitening agent is complementary with red light on the polypropylene film substrate and has a whitening effect. While this approach does not affect the clarity of the polypropylene film, it also creates contamination and migration problems.
Therefore, the red light of the polypropylene film material is eliminated or resisted by exogenously adding other materials or substances, and the phenol red phenomenon of the polypropylene film material cannot be fundamentally solved. The inventor finds out through long-term research that: the modified antioxidant is prepared by modifying the existing hydroxylamine antioxidant and reacting the antioxidant with the styrene-acrylate copolymer, so that the obtained modified antioxidant can keep the antioxidant property of the existing antioxidant on one hand, and has the property of a high-molecular auxiliary agent by combining with the styrene-acrylate copolymer, and the problem of end face phenol red after the product is rolled can be solved when the modified antioxidant is applied to plastic products such as polypropylene films and the like; and the service life of the polypropylene film material is further prolonged.
Specifically, the invention provides the following technical scheme:
according to a first aspect of the present invention, there is provided a modified antioxidant obtained by mixing and reacting a styrene-acrylate copolymer and REVONOX 420.
REVONOX420 is a phenol-free hydroxylamine antioxidant, has good color protection, high compatibility, low volatility and stable high temperature storage, can be used as a stabilizer in melt processing, and can inhibit discoloration and discoloration, and is more effective than conventional hindered phenol antioxidants. The inventor finds out in the research process that: the preparation method comprises the steps of carrying out mixed reaction on a styrene-acrylate copolymer with a side chain having a hydroxyl functional group and REVONOX420, carrying out etherification reaction on hydroxyl carried on the side chain of the styrene-acrylate copolymer and hydroxyl of oxidized bis (hydrogenated tallow alkyl) amine (REVONOX420) to prepare the modified antioxidant, wherein the obtained modified antioxidant keeps the antioxidant property of the antioxidant REVONOX420 on one hand, and realizes chemical combination with the styrene-acrylate copolymer on the other hand, so that the obtained modified antioxidant has the property of a high molecular auxiliary agent, improves the migration resistance in polypropylene, can be widely applied to plastic products such as polypropylene films and the like, and can solve the problem of phenol red on the end surface after product rolling.
The modified antioxidant provided by the invention is used for preparing the polypropylene composition, and the modified antioxidant is used as a high-molecular auxiliary agent, so that the compatibility with polypropylene resin is improved, and the antioxidant effect is improved; and on the premise of maintaining the oxidation resistance of the antioxidant (REVONOX420), the modified antioxidant can further effectively improve the migration resistance of the antioxidant, and the modified antioxidant is applied to a polypropylene composition and used for preparing a polypropylene film and can prolong the service life of the polypropylene film.
Further, the styrene-acrylate copolymer is prepared by utilizing toluene, styrene and hydroxyethyl acrylate, and the molar mass ratio of the hydroxyethyl acrylate to the REVONOX420 is 1: 1-1: 1.3. the styrene-acrylate copolymer can be obtained by polymerizing toluene, styrene and hydroxyethyl acrylate, for example, when the molar ratio of toluene, styrene and hydroxyethyl acrylate is 100:30:3, ammonium persulfate is used as an initiator, and the styrene-acrylate copolymer is generated by reaction at 60-80 ℃. And then mixed with REVONOX420 to react, the REVONOX420 itself acts as an antioxidant, even if the molar amount is slightly more than that of the hydroxyethyl acrylate, and the subsequent preparation of the polypropylene composition is not affected. The polypropylene composition and the polypropylene film material obtained by the method do not generate phenol red after being rolled.
Further, sulfuric acid is used as a catalyst, the reaction is carried out at the temperature of 60-80 ℃, and the reaction time is 2-4 hours. Thereby allowing rapid preparation of the modified antioxidant.
According to a second aspect of the present invention, there is provided a polypropylene composition comprising: a polypropylene resin; a modified antioxidant according to any one of the embodiments of the first aspect of the present invention; an antioxidant; light stabilizers.
Further, the polypropylene resin can be homo-polypropylene or co-polypropylene, and the melt index of the polypropylene resin is 2.0-35g/10min, preferably 3.0-10g/10 min. The melt index is a value representing the flowability of a thermoplastic material during processing. The melt index may be specified by the American society for testing standards (ASTM) according to the method commonly used by DuPont, USA for characterizing plastic materials, by melting the plastic material into a fluid for a period of time (10 minutes) at a temperature and pressure, and then passing the fluid through a 2.095 mm diameter cylinder in grams (g). The larger the value of the melt index, the better the processing flowability of the plastic material, and vice versa. Selecting polypropylene resin with a melt index of 2.0-35g/10min, such as 3-25g/10min, or 3-20g/10min, 3-15g/10min, preferably 3-10g/10min, can be used for preparing a proper polypropylene composition with modified antioxidant, antioxidant and light stabilizer to prepare a polypropylene film, and can obtain a polypropylene film material with good hardness and processability.
Further, the modified antioxidant accounts for 0.05 to 1.5 percent of the polypropylene resin, preferably 0.5 to 1.0 percent of the polypropylene resin. The addition amount of the modified antioxidant accounts for 0.05-1.5 percent of the addition amount of the polypropylene resin, for example, 0.05-1.3 percent, 0.1-1.3 percent, 0.2-1.2 percent, 0.3-1.1 percent and 0.4-1.0 percent, so that the modified antioxidant can be matched with other antioxidants and light stabilizers to obtain a polypropylene composition, the modified antioxidant has good compatibility with the polypropylene resin, the oxidation resistance and the migration resistance of the polypropylene composition are improved, the modified antioxidant can be widely applied to plastic products such as polypropylene films and the like, and the problem of end face phenol red after the products are rolled can be solved.
Further, the antioxidant comprises hindered phenol compounds and phosphite ester compounds. Meanwhile, the antioxidant containing the hindered phenol compound and the phosphite ester compound can further improve the oxidation resistance and the migration resistance of the polypropylene composition, is applied to plastic products such as polypropylene films and the like, and can solve the problem of phenol red on the end face of the rolled product.
Further, the antioxidant comprises at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076) and tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168). Preferably, the antioxidant comprises at least two of the antioxidant 1010, the antioxidant 1076 and the antioxidant 168, for example, the antioxidant comprises the antioxidant 1010 and the antioxidant 168, so that the antioxidant performance and the migration resistance of the polypropylene composition can be further improved, and the problem of phenol red on the end surface after the product is rolled can be solved when the polypropylene composition is applied to plastic products such as polypropylene films.
Further, the antioxidant accounts for 0.1-0.5% of the polypropylene resin, for example, the antioxidant accounts for 0.1-0.3% of the polypropylene resin, and for example, the antioxidant accounts for 0.1-0.2% of the polypropylene resin.
Further, the light stabilizer is at least one selected from benzophenone compounds, benzotriazole compounds, salicylate compounds, substituted acrylonitrile compounds and triazine compounds, and the light stabilizer is preferably o-hydroxybenzophenone. The benzophenone compound, the benzotriazole compound, the salicylate compound, the substituted acrylonitrile compound or the triazine compound can inhibit or slow down the photooxidation degradation process, can be used for prolonging the service life of a polymer material, and helps to solve the problem of phenol red on the end surface of a rolled polypropylene film material.
Further, the light stabilizer accounts for 0.05 to 0.3 percent of the polypropylene resin, and preferably accounts for 0.2 percent of the polypropylene resin.
According to a third aspect of the present invention, there is provided a process for producing a polypropylene composition, which is the polypropylene composition according to the second aspect of the present invention, comprising: and mixing the polypropylene resin, the modified antioxidant, the antioxidant and the light stabilizer, and performing melt extrusion processing to obtain the polypropylene composition.
Further, the temperature of the melt extrusion processing is 180-210 ℃, and the rotating speed of the melt extrusion processing is 200-300 rpm.
According to a fourth aspect of the present invention, there is provided a polypropylene film prepared from the polypropylene composition according to any one of the embodiments of the second aspect of the present invention;
furthermore, the polypropylene film prepared from the polypropylene composition provided by the invention has no phenol red phenomenon on the end surface after being rolled.
Detailed Description
The present invention is further described below in conjunction with specific examples, which are representative of, but not limiting of, the scope of the invention.
According to one aspect of the present invention, there is provided a modified antioxidant prepared by mixing and reacting a styrene-acrylate copolymer and REVONOX 420. The modified antioxidant is prepared by taking oxidized bis (hydrogenated tallow alkyl) amine (REVONOX420) as a matrix, taking a styrene-acrylate copolymer with a side chain having a hydroxyl group as a high molecular main chain, carrying out etherification reaction on the hydroxyl group suspended on the main chain and the hydroxyl group in the antioxidant matrix molecule, and reacting for 2 hours at 60 ℃ by taking sulfuric acid as a catalyst. The prepared modified antioxidant not only effectively maintains the antioxidant property of the antioxidant, but also is chemically combined with a macromolecular chain covalent bond, so that the dispersion of the antioxidant in polypropylene is improved, and the migration phenomenon is inhibited.
In at least some embodiments, the modified antioxidant is prepared by adding an antioxidant (REVONOX420) in an equimolar amount to a hydroxyethyl acrylate monomer to a styrene-acrylate copolymer, using sulfuric acid as a catalyst, reacting at 60-80 ℃ for 2 hours, pouring the obtained product into ethanol, precipitating, filtering, and drying. For example, the modified antioxidant can be obtained by reacting at 60 ℃ for 2 hours.
The modified antioxidant can be combined with an antioxidant and a light stabilizer to prepare a polypropylene composition, and the polypropylene composition can be used for preparing a polypropylene film and can solve the problem of the generation of the phenol red phenomenon on the end surface of the rolled polypropylene film.
In at least some embodiments of the present invention, the present invention provides a polypropylene composition comprising: a polypropylene resin; the above-mentioned modified antioxidant; an antioxidant; and a light stabilizer.
The polypropylene resin can be homo-polypropylene or co-polypropylene, and has a melt index of 2.0-35g/10min, preferably 3.0-10g/10 min.
The styrene-acrylate copolymer used in the invention can be directly purchased and prepared, and can also be synthesized by itself. For example, the catalyst can be prepared by toluene, styrene and hydroxyethyl acrylate under the action of an initiator. In at least some embodiments, the molar ratio of toluene, styrene, and hydroxyethyl acrylate is 100:30: and 3, at the temperature of 80 ℃, the initiator is ammonium persulfate, the dosage of the initiator is 0.8-2% of the dosage of all monomers, for example, the dosage of the initiator can be 1% (wt%) of the total amount of toluene, styrene and hydroxyethyl acrylate, and the reaction is carried out for 6 hours to prepare the catalyst. Thus, a styrene-acrylate copolymer can be rapidly prepared.
The antioxidant in the polypropylene composition can be one antioxidant or two or more antioxidants, and the usable antioxidant can be at least one of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010), n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076) and tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168).
The light stabilizer can be benzophenone compounds, benzotriazole compounds, salicylate compounds, substituted acrylonitrile compounds and triazine compounds, and is preferably o-hydroxybenzophenone. As a light stabilizer, the substances can effectively help to avoid the oxidation of the polypropylene composition or the polypropylene film material and the generation of phenol red.
In at least some embodiments, the instant invention provides a polypropylene composition comprising the following components: 100 parts of polypropylene resin; 0.1-0.3 part of modified antioxidant; 0.2 part of antioxidant 1010; 0.1 part of antioxidant 168; 0.2 part of o-hydroxybenzophenone light stabilizer. The modified antioxidant and the antioxidant thereof are added into the polypropylene resin, so that the phenol red phenomenon of an extruded or blown film can be effectively solved.
Further, when the polypropylene composition is prepared, the polypropylene resin, the modified antioxidant, the antioxidant and the light stabilizer are uniformly mixed in proportion and then extruded and granulated by a double-screw extruder. In at least some embodiments, the granulation is melt extruded through a twin screw extruder at an extrusion temperature of 180 ℃ and a screw speed of 200 ℃ and 300 rpm.
The scheme of the present invention will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Embodiment 1 provides a modified antioxidant and a preparation method thereof, comprising:
92g of toluene, 31.2g of styrene, 3.5g of hydroxyethyl acrylate and 1.2g of ammonium persulfate serving as an initiator are prepared and reacted at the temperature of 80 ℃ for 6 hours to obtain the styrene-acrylate copolymer.
Adding 16.1g of antioxidant (REVONOX420) and 0.2g of sulfuric acid into the obtained styrene-acrylate copolymer, reacting for 2 hours at 60 ℃, pouring into ethanol for precipitation, filtering and drying to obtain the modified antioxidant.
Example 2
Example 2 provides a polypropylene composition comprising:
adding 1g of modified antioxidant, 10102 g of antioxidant and 2g of benzophenone light stabilizer into 1000g of polypropylene resin, wherein the modified antioxidant is the modified antioxidant obtained in the embodiment 1, uniformly mixing, extruding and granulating by a double-screw extruder, and obtaining the polypropylene composition, wherein the temperature of the extruder is 180 ℃, and the rotating speed of the screw is 200 rpm.
The prepared polypropylene composition is used for producing a casting film, and the film is accompanied with slight phenol red phenomenon after being rolled and can be accepted in production and application.
Example 3
Example 3 provides a polypropylene composition comprising:
adding 3g of modified antioxidant, 1681 g of antioxidant and 2g of benzophenone light stabilizer into 1000g of polypropylene resin, wherein the modified antioxidant is the modified antioxidant obtained in example 1, uniformly mixing, extruding and granulating by a double-screw extruder, and obtaining the polypropylene composition, wherein the temperature of the extruder is 210 ℃, and the rotating speed of the screw is 300 rpm.
The prepared polypropylene composition is used for producing a casting film, and the phenol red phenomenon does not occur after the film is rolled.
Example 4
Example 4 provides a polypropylene composition comprising:
adding 2g of modified antioxidant, 10102 g of antioxidant, 1681 g of antioxidant and 2g of o-hydroxybenzophenone light stabilizer into 1000g of polypropylene resin, uniformly mixing the modified antioxidant obtained in the embodiment 1, and extruding and granulating the mixture by a double-screw extruder at the temperature of 200 ℃ and the rotation speed of a screw of 260rpm to obtain the polypropylene composition.
The prepared polypropylene composition is used for producing a casting film, and the phenol red phenomenon does not occur after the film is rolled.
Comparative example 1
Comparative example 1 provides a polypropylene composition comprising:
adding 10102 g of antioxidant, 1681 g of antioxidant and 1g of o-hydroxybenzophenone light stabilizer into 1000g of polypropylene resin, uniformly mixing, extruding and granulating by a double-screw extruder, wherein the temperature of the extruder is 180 ℃, and the rotating speed of a screw is 200rpm, and thus obtaining the polypropylene composition.
The prepared polypropylene composition is used for producing a casting film, and the obvious phenol red phenomenon appears after the film is rolled.
Comparative example 2
Comparative example 2 provides a polypropylene composition comprising:
1000g of polypropylene resin is added with 4205 g of antioxidant REVONOX, 10102 g of antioxidant, 1681 g of antioxidant and 1g of o-hydroxybenzophenone light stabilizer, and the mixture is uniformly mixed and extruded by a double-screw extruder for granulation, wherein the temperature of the extruder is 180 ℃, and the rotating speed of the screw is 200rpm, so that the polypropylene composition is obtained.
The prepared polypropylene composition is used for producing a casting film, and the obvious phenol red phenomenon appears after the film is rolled. Experimental results show that the styrene-acrylate copolymer is not adopted to react with the antioxidant REVONOX420, the antioxidant 1010, the antioxidant 168 and the o-hydroxybenzophenone are directly added into the polypropylene resin for mixing, extruding and granulating, the obtained polypropylene composition is used for producing a casting film, and the film is still accompanied with an obvious phenol red phenomenon after being rolled.
Comparative example 3
Comparative example 3 provides a polypropylene composition comprising:
and adding 20g of modified antioxidant and 2g of benzophenone light stabilizer into 1000g of polypropylene resin, wherein the modified antioxidant is the modified antioxidant obtained in the example 1, uniformly mixing, extruding and granulating by a double-screw extruder, and obtaining the polypropylene composition, wherein the temperature of the extruder is 180 ℃, and the rotating speed of the screw is 200 rpm.
The prepared polypropylene composition is used for producing a casting film, and the film is still accompanied with a little phenol red phenomenon after being rolled. The experimental results show that even if the amount of the modified antioxidant is increased, when the polypropylene composition is prepared without adding other antioxidants, the film obtained by casting is generated, and the generation of phenol red phenomenon is still unavoidable after rolling. Without being limited by theory, it is hypothesized that different antioxidants have slightly different antioxidant functions, and the antioxidant properties of various substance components can be exerted as much as possible by using the modified antioxidant provided by the application in combination with other antioxidants and a light stabilizer.
Comparative example 4
Comparative example 4 provides a polypropylene composition prepared according to the method of example 3, except that, in example 3, the modified antioxidant was not added, but REVONOX420 and the styrene-acrylate copolymer were physically mixed in an amount equivalent to the modified antioxidant of example 3.
The prepared polypropylene composition is used for producing a casting film, and the film has an obvious phenol red phenomenon after being rolled.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (8)
1. The modified antioxidant is characterized in that the modified antioxidant is obtained by mixing and reacting a styrene-acrylate copolymer and REVONOX420, wherein the styrene-acrylate copolymer is prepared from toluene, styrene and hydroxyethyl acrylate, and the molar ratio of the hydroxyethyl acrylate to the REVONOX420 is 1: 1-1: 1.3; and (3) carrying out the mixing reaction at the temperature of 60-80 ℃ by using sulfuric acid as a catalyst, wherein the mixing reaction time is 2-4 hours.
2. A polypropylene composition, comprising:
a polypropylene resin;
a modified antioxidant according to claim 1; an antioxidant;
a light stabilizer;
the modified antioxidant accounts for 0.05 to 1.5 percent of the polypropylene resin in percentage by weight; the antioxidant comprises hindered phenol compounds and phosphite compounds;
the antioxidant accounts for 0.1 to 0.5 percent of the polypropylene resin in percentage by weight;
the light stabilizer accounts for 0.05 to 0.3 percent of the polypropylene resin in percentage by weight;
the polypropylene resin is homo-polypropylene or co-polypropylene, and the melt index of the polypropylene resin is 2.0-35g/10 min.
3. The polypropylene composition according to claim 2, wherein the polypropylene resin has a melt index of 3.0 to 10g/10 min;
the modified antioxidant accounts for 0.5 to 1.0 percent of the polypropylene resin in percentage by weight.
4. The polypropylene composition of claim 2, wherein the antioxidant comprises at least two of antioxidant 1010, antioxidant 1076, and antioxidant 168.
5. The polypropylene composition according to claim 2, wherein the light stabilizer is at least one selected from the group consisting of benzophenone compounds, benzotriazole compounds, salicylate compounds, substituted acrylonitrile compounds and triazine compounds;
the light stabilizer accounts for 0.2 percent of the polypropylene resin in percentage by weight.
6. The polypropylene composition according to claim 2, wherein the polypropylene composition comprises, in parts by weight:
100 parts of polypropylene resin;
0.1-0.3 part of modified antioxidant;
0.2 part of antioxidant 1010, wherein the weight of the antioxidant 1010 is;
0.1 part of antioxidant 168, wherein the antioxidant 168 is;
0.2 part of o-hydroxybenzophenone as a light stabilizer.
7. A process for the preparation of a polypropylene composition according to any one of claims 2 to 6, comprising: mixing the polypropylene resin, the modified antioxidant, the antioxidant and the light stabilizer, and performing melt extrusion processing and granulation to obtain the polypropylene composition;
the temperature of the melt extrusion processing granulation is 180-210 ℃, and the rotating speed of the melt extrusion processing granulation is 200-300 rpm.
8. A polypropylene film, which is prepared from the polypropylene composition according to any one of claims 2 to 6;
the end face of the rolled polypropylene film is free from phenol red.
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Denomination of invention: Solution to Modified Antioxidants, Polypropylene Compositions, Preparation Methods and Applications of Polypropylene Phenol Red Granted publication date: 20201027 Pledgee: Agricultural Bank of China Limited Zhuozhou City Sub-branch Pledgor: ZHUOZHOU JUANCHENG CHEMICAL Co.,Ltd. Registration number: Y2024980004106 |