CN116715899A - Anti-yellowing agent, preparation method thereof and application thereof in polyester polymer material - Google Patents
Anti-yellowing agent, preparation method thereof and application thereof in polyester polymer material Download PDFInfo
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- CN116715899A CN116715899A CN202310653556.XA CN202310653556A CN116715899A CN 116715899 A CN116715899 A CN 116715899A CN 202310653556 A CN202310653556 A CN 202310653556A CN 116715899 A CN116715899 A CN 116715899A
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- titanium dioxide
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- 238000004383 yellowing Methods 0.000 title claims abstract description 77
- 229920000728 polyester Polymers 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002861 polymer material Substances 0.000 title abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 56
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 38
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 28
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 19
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 9
- 150000002989 phenols Chemical class 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 239000010963 304 stainless steel Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 claims description 4
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 12
- 230000032683 aging Effects 0.000 abstract description 9
- 238000003958 fumigation Methods 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 52
- 239000010408 film Substances 0.000 description 47
- 229920000139 polyethylene terephthalate Polymers 0.000 description 26
- 239000005020 polyethylene terephthalate Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000002457 bidirectional effect Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007977 PBT buffer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- -1 solar back plates Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 201000004569 Blindness Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 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 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic 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
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
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Abstract
The invention belongs to the technical field of special auxiliary agents, and discloses a yellow removing agent, a preparation method thereof and application thereof in polyester polymer materials. The anti-yellowing agent comprises the following components in percentage by mass: hindered phenols primary antioxidant: 0.1 to 30 percent of phosphite ester auxiliary antioxidant: 20% -90%, lipophilic nano titanium dioxide powder: 0.1 to 10 percent of superfine talcum powder, 0.1 to 10 percent of calcium stearate powder and 0.1 to 5 percent of superfine talcum powder. The anti-yellowing agent can simultaneously solve the problems of thermal oxidative aging yellowing of polyester polymer materials such as BOPET films and the like, processing yellowing of reclaimed materials and gas fumigation yellowing in the process of storage and transportation, and has the advantages of good anti-yellowing effect, strong universality, economy in cost, simple processing process, stable performance, convenient use and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of special auxiliary agents, and particularly relates to a yellow removing agent, a preparation method thereof and application thereof in polyester polymer materials.
Background
Polyester polymer material products such as BOPET films and the like belong to new material industries and are strategic emerging industries which are mainly supported and developed in China. The downstream industries of BOPET industry comprise a plurality of industrial application fields such as new energy, photoelectric display, electronics and electrics. In recent years, with the expansion of the downstream application field of BOPET in China, the BOPET film is widely applied in the industries of release protection films, solar back plates, optical films, window films, flame retardant films and the like, and is a functional film material with very broad prospects.
The BOPET film is often required to have high transparency in the downstream application field, and the BOPET film is required to be free from yellowing in the processing process and also free from yellowing in the storage process. Therefore, it is a very interesting work to study the yellowing phenomenon of BOPET during processing and storage and to propose a cost-effective technical solution.
The problem of yellowing of BOPET films during processing and storage is prone to occur, mainly due to the following reasons: (1) BOPET processing temperature is generally higher, and in many cases, the temperature exceeds 260 ℃, and under the conditions of high temperature, high pressure and high shearing, thermooxidative aging phenomenon is easy to occur, so that yellowing of materials occurs in the processing process; (2) In order to reduce the cost in a specific application field, some BOPET film processing factories often add PET reclaimed materials with a certain proportion in the production process, and the PET reclaimed materials contain more small molecules and chain breakage, so that the yellowing problem easily occurs in the processing process; (3) The BOPET film is easy to generate gas fumigation yellowing in the process of storage and transportation, so that the surface of a BOPET finished product is yellow.
Aiming at the yellowing problem of BOPET in the processing and storage processes, the main technical solutions currently existing in the industry are as follows: (1) Aiming at the application fields of middle and low ends, a plurality of BOPET manufacturers can directly mix blue or purple toner with PET in a certain proportion, so as to reduce the yellowing problem generated in the BOPET film processing process; (2) Aiming at the thermo-oxidative aging of BOPET caused by high temperature, high pressure, high shear and the like in the processing process, some BOPET film manufacturers can add some main antioxidants and auxiliary antioxidants, such as 1010, 1076 and 168, and the cases can be found in a plurality of patents and documents; (3) Aiming at the yellowing problem possibly generated in the storage and transportation processes, most BOPET manufacturers can make articles on good sealing, and some manufacturers can even cover a plurality of layers of sealing packages on the BOPET finished product, so that the problem of gas fumigation yellowing in the BOPET film storage process is avoided.
The technical scheme mainly solves the problems that: (1) The toner is used for solving the yellowing problem in the BOPET film processing process, each production corresponds to a specific color matching scheme, the technical scheme has no universality, has the defects of complicated process, imperfect yellowing effect and the like in actual production operation, and is a technical scheme for treating both symptoms and root causes. (2) The antioxidant is used for solving the problem of thermal oxidative aging in the BOPET film processing process, so that the industry tends to have great blindness in the selection of the antioxidant, for example, the use of 1010 and 168, which are mentioned in a plurality of patents and documents, solves the problem of thermal oxidative aging in the BOPET film processing process, and the problem of thermal oxidative aging in the BOPET film processing process cannot have a good effect in the actual production process. For example, many of the companies mentioned above have selected antioxidants 1010 and 168 to prevent thermo-oxidative degradation during BOPET processing, and have not substantially improved the yellowing problem during actual production. The main reason is that 1010 is an antioxidant which is easy to generate phenolic yellowing, and 168 has a common effect of maintaining the color in the practical application process. (3) The problem of the smoky yellowing of the BOPET film easily generated in the storage process in the technical thought is not realized by most companies in the industry at present, so that most schemes for strengthening and storing the BOPET film in a sealing manner are adopted to treat the symptoms but not the root cause.
The patent CN 109972411A prepares nano zinc oxide serving as an anti-yellowing agent by taking sodium hydroxide and zinc chloride as raw materials, combines a compound of an ester-based quaternary ammonium salt softener and N-dodecyl dimethyl amine oxide, a phosphite antioxidant and an ultraviolet absorber UV-531, and prepares the anti-yellowing master batch through extrusion granulation. The patent mainly utilizes nano zinc oxide to have the function of absorbing ultraviolet rays; in addition, the nano particles can scatter the ultraviolet rays acted on the nano particles in all directions, so that the ultraviolet ray intensity in the irradiation direction is reduced; the compound of the ester-based quaternary ammonium salt softener and the N-dodecyl dimethyl amine oxide can improve the yellowing property of the fabric. Patent CN 114276671a discloses a TPU anti-yellowing masterbatch, which comprises the following raw materials: TPU, antioxidant and ultraviolet absorber, wherein the weight portions of the raw materials are as follows: 85-90% of TPU, 3-5% of antioxidant and 7-10% of ultraviolet absorber; the TPU anti-yellowing master batch has excellent precipitation resistance, does not influence the performance of the TPU, and has the yellowing resistance grade of more than 4.5 grade.
Although the prior art can achieve certain yellowing resistance, the prior art has the advantages of narrow application range, no universality, and certain effect on ultraviolet yellowing resistance and thermal oxidation aging yellowing resistance, and is not ideal for the yellowing resistance of the gas fumigation and the yellowing resistance of the reclaimed materials in the processing process.
Disclosure of Invention
In view of the above drawbacks and shortcomings of the prior art, a primary object of the present invention is to provide a yellowing agent. The anti-yellowing agent adopts a specific hindered phenol main antioxidant and a phosphite ester auxiliary antioxidant, and combines a specific lipophilic nano titanium dioxide powder, a superfine talcum powder and a calcium stearate powder, so that the anti-yellowing agent can simultaneously solve the problems of thermal oxidative aging yellowing, reclaimed material processing yellowing and gas fumigation yellowing in the storage and transportation processes of polyester polymer materials such as BOPET films, and has the advantages of good anti-yellowing effect, strong universality, economy, simple processing process, stable performance, convenience in use and wide application prospect.
Another object of the present invention is to provide a method for preparing the above-mentioned anti-yellowing agent.
It is still another object of the present invention to provide an application of the above-mentioned anti-yellowing agent to polyester-based polymer materials such as BOPET film.
The invention aims at realizing the following technical scheme:
a yellow removing agent comprises the following components in percentage by mass: hindered phenols primary antioxidant: 0.1 to 30 percent of phosphite ester auxiliary antioxidant: 20% -90%, lipophilic nano titanium dioxide powder: 0.1 to 10 percent of superfine talcum powder, 0.1 to 10 percent of calcium stearate powder and 0.1 to 5 percent of superfine talcum powder.
Preferably, the anti-yellowing agent comprises the following components in percentage by mass: hindered phenols primary antioxidant: 5% -10% of phosphite ester auxiliary antioxidant: 75% -80%, lipophilic nano titanium dioxide powder: 5 to 10 percent, 2 to 4 percent of superfine talcum powder and 1 to 3 percent of calcium stearate powder.
Further, the hindered phenol type main antioxidant is one or two of an antioxidant 1790 (Tianjin Li Anlong, hereinafter, not repeated), and an antioxidant 3114 (Tianjin Li Anlong, hereinafter, not repeated).
Further, the phosphite ester auxiliary antioxidant is one or more of an antioxidant P-EPQ, an antioxidant PEP-36 and an antioxidant 9228.
Further, the lipophilic nano titanium dioxide powder is a self-made product, and is prepared by the following method:
adding deionized water and absolute ethyl alcohol into the nano titanium dioxide powder, stirring and mixing uniformly to prepare titanium dioxide slurry, then sequentially adding tetraethoxysilane and acid for hydrolysis and condensation reaction, and washing and drying after the reaction is finished to obtain the lipophilic nano titanium dioxide powder.
Preferably, the nano titanium dioxide powder is selected from titanium dioxide powder with the particle size of 20-100 nm (such as nano titanium dioxide powder product with the particle size of 50nm manufactured by Ningbo very micro nano new materials technology Co., ltd.).
Preferably, the stirring and uniformly mixing means stirring at a constant speed for 15-20 min at a rotation speed of 400-800 rpm.
Preferably, the addition amount of the tetraethoxysilane is 5-20% of the mass of the nano titanium dioxide powder.
Further, the superfine talcum powder body is AC-320 produced by science and technology.
Further, the calcium stearate powder is superfine calcium stearate BS-3818 produced by Zhongshan Huaming Tai company.
The preparation method of the anti-yellowing agent comprises the following preparation steps:
(1) Weighing hindered phenol main antioxidants and phosphite auxiliary antioxidants according to the proportion, and then placing the weighed hindered phenol main antioxidants and phosphite auxiliary antioxidants in a 304 stainless steel barrel for stirring and mixing by a stirrer for standby;
(2) Sequentially adding lipophilic nano titanium dioxide powder, superfine talcum powder and calcium stearate powder into the mixture obtained in the step (1), and then fully and uniformly stirring to obtain the yellow-removing agent product.
Further, the stirring and mixing in the step (1) means stirring at a stirring speed of 400-600 rpm for 10-15 min.
Further, the stirring in the step (2) means stirring at a stirring speed of 400 to 600rpm for 15 to 20 minutes.
The application of the anti-yellowing agent in polyester polymer materials comprises PET, PC, PMMA, TPU or PBT.
The application of the anti-yellowing agent in BOPET film comprises the following steps: adding the anti-yellowing agent into PET resin according to the mass percentage of 0.01-0.5%, and uniformly stirring, and then applying the anti-yellowing agent to BOPET film processing.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the selection of the antioxidant, the main antioxidant with good anti-gas fumigation effect and larger molecular weight and the auxiliary antioxidant with higher phosphorus content are adopted, so that the color stability can be effectively maintained in the processing process, and the good anti-gas fumigation performance of the anti-yellowing agent product can be further endowed.
(2) The self-made lipophilic nano titanium dioxide can serve as a white pigment to cover a part of yellowing materials. In addition, the nano titanium dioxide particles with specific size can generate Rayleigh scattering effect in the high polymer material, so that the BOPET film has blue visual effect, and the use amount of the nano titanium dioxide is reduced by utilizing the characteristic. After the nano titanium dioxide is subjected to oleophylic treatment, the dispersion of the nano titanium dioxide in the PET substrate is enhanced. In addition, the nano titanium dioxide is an excellent light stabilizer, so that the problem of photo-aging of the BOPET film in the use process can be effectively avoided.
(3) According to the invention, components such as hydrotalcite and calcium stearate are introduced in the formula, so that the dispersion of the anti-yellowing agent in polyester polymer materials such as PET (polyethylene terephthalate) can be enhanced, and the anti-yellowing effect can be improved; the material also has the advantages of absorbing halogen, inhibiting hydrolysis of polyester polymer materials such as PET and the like.
(4) The invention has wider application range, can be applied to BOPET films, PET spinning, sheets and other PET products, and has good yellowing effect on the polymer materials of other polyesters such as PC, PMMA, TPU, PBT and the like in various molding processes such as injection molding, extrusion, blow molding, bidirectional pulling and the like. The yellow-removing agent has the advantages of simple addition, low cost, excellent effect and the like, and is an unobtainable yellow-removing agent product.
Drawings
FIGS. 1-2 are SEM images of the yellow stain remover product obtained in example 1.
FIG. 3 is a graph comparing the color of a PET injection molded panel (left) with 0.05% of the yellow eliminator product of example 1 added to a PET injection molded panel (right) without added yellow eliminator product.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The lipophilic nano titanium dioxide used in the following examples was self-prepared by the following method:
adding deionized water and absolute ethyl alcohol into nano titanium dioxide powder (particle size is 50nm, which is produced by Ningbo very micro nano new material technology Co., ltd.), stirring at a constant speed of 15min at a rotating speed of 600rpm to prepare titanium dioxide slurry, sequentially adding ethyl orthosilicate with the mass of 10% of the nano titanium dioxide powder and a proper amount of hydrochloric acid to carry out hydrolytic condensation reaction for 2h, and washing and drying a solid product sequentially by the deionized water and the ethanol after the reaction is finished to obtain the lipophilic nano titanium dioxide powder.
Example 1
The embodiment is a yellow removing agent product applied to BOPET films, and comprises the following components in percentage by mass:
the yellow removing agent product is prepared by the following method:
(1) The hindered phenol main antioxidant 1790 and the phosphite ester auxiliary antioxidant P-EPQ are weighed according to the proportion, and then are placed in a 304 stainless steel barrel to be stirred and mixed for standby use by a stirrer;
(2) Sequentially adding lipophilic nano titanium dioxide powder, superfine talcum powder AC-320 and calcium stearate powder BS-3818 into the mixture obtained in the step (1), and then fully and uniformly stirring to obtain a yellow-removing agent product.
SEM images of the yellow eliminator product obtained in this example are shown in fig. 1 and 2.
The yellow-removing agent product prepared in the example is added into PET resin (common PET injection molding grade resin is added with 10 percent (wt.%) of colorless transparent PET reclaimed materials) according to the addition amount of 0.05 percent (wt.%) to obtain a 2mm color plate by injection molding; and after 10% of PET colorless transparent return material is added into the same PET injection molding grade resin, directly injecting to obtain a 2mm color plate, wherein the color comparison result is shown in figure 3 (the left graph is the color plate added with the anti-yellowing agent product, and the right graph is the color plate not added with the anti-yellowing agent product).
As can be seen from the results of fig. 3, the inventive yellow eliminator product exhibits excellent yellow eliminating effect with the addition of a certain proportion of PET reclaimed material.
Example 2
The embodiment is a yellow removing agent product applied to BOPET films, and comprises the following components in percentage by mass:
the yellow removing agent product is prepared by the following method:
(1) The hindered phenol main antioxidant 1790 and the phosphite auxiliary antioxidant 9228 are weighed according to the proportion, and then are placed in a 304 stainless steel barrel to be stirred and mixed for standby use by a stirrer;
(2) Sequentially adding lipophilic nano titanium dioxide powder, superfine talcum powder AC-320 and calcium stearate powder BS-3818 into the mixture obtained in the step (1), and then fully and uniformly stirring to obtain a yellow-removing agent product.
Example 3
The embodiment is a yellow removing agent product applied to BOPET films, and comprises the following components in percentage by mass:
the yellow removing agent product is prepared by the following method:
(1) Weighing hindered phenol main antioxidant 3114 and phosphite auxiliary antioxidant PEP-36 according to the proportion, and then placing the weighed hindered phenol main antioxidant 3114 and phosphite auxiliary antioxidant PEP-36 in a 304 stainless steel barrel for stirring and mixing by a stirrer for standby;
(2) Sequentially adding lipophilic nano titanium dioxide powder, superfine talcum powder AC-320 and calcium stearate powder BS-3818 into the mixture obtained in the step (1), and then fully and uniformly stirring to obtain a yellow-removing agent product.
Example 4
The embodiment is a yellow removing agent product applied to BOPET films, and comprises the following components in percentage by mass:
the yellow removing agent product is prepared by the following method:
(1) Weighing the hindered phenol main antioxidant 3114 and the phosphite auxiliary antioxidant 9228 according to the proportion, and placing the weighed hindered phenol main antioxidant and phosphite auxiliary antioxidant in a 304 stainless steel barrel for stirring and mixing by a stirrer for standby;
(2) Sequentially adding lipophilic nano titanium dioxide powder, superfine talcum powder AC-320 and calcium stearate powder BS-3818 into the mixture obtained in the step (1), and then fully and uniformly stirring to obtain a yellow-removing agent product.
The yellow-removing agent product applied to the BOPET film prepared in the embodiment is added into PET resin (film grade PET resin produced by chemical fiber and FG 600) according to the adding proportion of 0.05% (wt.%), and after being stirred uniformly, the BOPET film with the thickness of 50 micrometers is prepared on a bidirectional pull-up tester, and whether the BOPET film has a yellowing phenomenon or not is observed.
In order to verify that the inventive anti-yellowing agent product has excellent anti-yellowing effect, two comparative BOPET products were provided.
Comparative example 1
Directly adopts PET pure resin (film grade PET resin produced by instrumentation chemical fiber, model FG 600), does not add any auxiliary agent, and directly prepares the BOPET film product with the thickness of 50 micrometers on a bidirectional pull-up tester.
Comparative example 2
10% (wt.%) of PET transparent recycle material is added into film grade PET resin FG600 produced by instrumentation chemical fiber, and then a BOPET film product with the thickness of 50 micrometers is prepared on a bidirectional pull-up tester.
All examples (added to the BOPET film product of comparative example 2 in an amount of 0.05% (wt.%)) and BOPET film products produced in comparative example were observed for the color just produced and recorded, respectively, and the film products were exposed on a warehouse desk and left for one month for the color observation and recorded, and the experimental results are shown in table 1 below.
TABLE 1
| Project | Color of the product just produced | Product color after one month placed on warehouse desk |
| Example 1 | Colorless and transparent | Colorless and transparent |
| Example 2 | Colorless and transparent | Colorless and transparent |
| Example 3 | Colorless and transparent | Colorless and transparent |
| Example 4 | Colorless and transparent | Colorless and transparent |
| Comparative example 1 | Colorless and transparent | Slightly yellow |
| Comparative example 2 | Yellowing of | Severe yellowing of |
From the results, after the yellow-removing agent product is added, the BOPET film can well ensure the colorless transparency of the BOPET in the processing process or the storage and transportation process. The invention shows that the product of the anti-yellowing agent can well solve the thermal oxidative aging yellowing of polyester polymer materials such as BOPET films and the like, the processing yellowing of reclaimed materials and the gas fumigation yellowing in the process of storage and transportation.
Comparative example 3
Compared with the example 1, the yellow-removing agent product is not added with lipophilic nano titanium dioxide and comprises the following components in percentage by mass:
the process for preparing the anti-yellowing agent product is the same as in example 1.
Comparative example 4
Compared with the example 1, the yellow-removing agent product does not contain superfine talcum powder and calcium stearate powder, and comprises the following components in percentage by mass:
1790 10% of hindered phenol primary antioxidant;
phosphite ester auxiliary antioxidant P-EPQ 80%;
10% of lipophilic nano titanium dioxide;
the process for preparing the anti-yellowing agent product is the same as in example 1.
The yellow eliminator products of comparative examples 3 and 4 were added to the BOPET film product of comparative example 2 in an amount of 0.05% (wt.%) and the color immediately after production was observed and recorded, respectively, and the film product was exposed on a desk of a warehouse and left for one month to observe the color and record, and the experimental results are shown in table 2 below.
TABLE 2
| Project | Color of the product just produced | Product color after one month placed on warehouse desk |
| Comparative example 3 | Slightly yellow | Slightly yellow |
| Comparative example 4 | Slightly yellow | Slightly yellow |
As can be seen from the results in Table 2, the addition of the lipophilic nano titanium dioxide, the superfine talcum powder and the calcium stearate powder in the yellow removing agent product has good synergistic effect on the yellow removing performance of the BOPET film product added with the PET reclaimed material.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The anti-yellowing agent is characterized by comprising the following components in percentage by mass: hindered phenols primary antioxidant: 0.1 to 30 percent of phosphite ester auxiliary antioxidant: 20% -90%, lipophilic nano titanium dioxide powder: 0.1 to 10 percent of superfine talcum powder, 0.1 to 10 percent of calcium stearate powder and 0.1 to 5 percent of superfine talcum powder.
2. The anti-yellowing agent according to claim 1, wherein the anti-yellowing agent comprises the following components in percentage by mass: hindered phenols primary antioxidant: 5% -10% of phosphite ester auxiliary antioxidant: 75% -80%, lipophilic nano titanium dioxide powder: 5 to 10 percent, 2 to 4 percent of superfine talcum powder and 1 to 3 percent of calcium stearate powder.
3. A yellowing agent according to claim 1 or 2, wherein said hindered phenol based primary antioxidant is one or both of antioxidant 1790 and antioxidant 3114; the phosphite auxiliary antioxidant is one or more of antioxidant P-EPQ, antioxidant PEP-36 and antioxidant 9228.
4. The yellow removing agent according to claim 1 or 2, wherein the lipophilic nano titanium dioxide powder is prepared by the following method:
adding deionized water and absolute ethyl alcohol into the nano titanium dioxide powder, stirring and mixing uniformly to prepare titanium dioxide slurry, then sequentially adding tetraethoxysilane and acid for hydrolysis and condensation reaction, and washing and drying after the reaction is finished to obtain the lipophilic nano titanium dioxide powder.
5. The yellow removing agent according to claim 4, wherein the nano titanium dioxide powder is selected from titanium dioxide powder with particle size of 20-100 nm; the stirring and mixing are carried out uniformly at the rotation speed of 400-800 rpm for 15-20 min; the addition amount of the tetraethoxysilane is 5-20% of the mass of the nano titanium dioxide powder.
6. A yellowing agent according to claim 1 or 2, wherein said superfine talc powder is AC-320 produced in sum technology; the calcium stearate powder is superfine calcium stearate BS-3818 produced by Zhongshan Huaming Tai company.
7. A process for the preparation of a yellow-removing agent according to any one of claims 1 to 6, comprising the following steps:
(1) Weighing hindered phenol main antioxidants and phosphite auxiliary antioxidants according to the proportion, and then placing the weighed hindered phenol main antioxidants and phosphite auxiliary antioxidants in a 304 stainless steel barrel for stirring and mixing by a stirrer for standby;
(2) Sequentially adding lipophilic nano titanium dioxide powder, superfine talcum powder and calcium stearate powder into the mixture obtained in the step (1), and then fully and uniformly stirring to obtain the yellow-removing agent product.
8. The method for preparing a yellow removing agent according to claim 7, wherein the stirring and mixing in the step (1) means stirring at a stirring speed of 400 to 600rpm for 10 to 15 minutes; the stirring in the step (2) means stirring at a stirring speed of 400-600 rpm for 15-20 min.
9. Use of a yellowing agent according to any one of claims 1 to 6 in a polyester-based polymeric material comprising PET, PC, PMMA, TPU or PBT.
10. The use of a yellowing agent according to any one of claims 1 to 6 in BOPET films, wherein the use is as follows: adding the anti-yellowing agent into PET resin according to the mass percentage of 0.01-0.5%, and uniformly stirring, and then applying the anti-yellowing agent to BOPET film processing.
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