CN112175265A - Modified color master batch and preparation method thereof - Google Patents
Modified color master batch and preparation method thereof Download PDFInfo
- Publication number
- CN112175265A CN112175265A CN202011060463.9A CN202011060463A CN112175265A CN 112175265 A CN112175265 A CN 112175265A CN 202011060463 A CN202011060463 A CN 202011060463A CN 112175265 A CN112175265 A CN 112175265A
- Authority
- CN
- China
- Prior art keywords
- temperature
- parts
- prepared
- reacting
- antioxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a modified color master batch and a preparation method thereof, wherein the modified color master batch is prepared from the following raw materials in parts by weight: 80-100 parts of low-density polyethylene, 30-40 parts of pigment, 3-5 parts of antioxidant, 3-5 parts of dispersant, 3-5 parts of heat stabilizer, 3-5 parts of lubricant and 3-5 parts of plasticizer; and an antioxidant is prepared, after the antioxidant is illuminated, protons in the antioxidant rapidly move to nitrogen atoms to form isomers, the isomers are poor in stability and can safely convert redundant energy into heat energy and recover to a stable state, so that light energy is converted into heat energy to be consumed, the oxidation of a polymer is inhibited, the two sides of the other phenolic hydroxyl group are connected with tert-butyl groups, the phenolic hydroxyl group is subjected to space obstacle, and hydrogen atoms are easy to fall off from molecules and are combined with peroxide free radicals, alkoxy free radicals and hydroxyl free radicals to lose activity, so that the aging reaction is stopped.
Description
Technical Field
The invention belongs to the technical field of color master batch preparation, and particularly relates to a modified color master batch and a preparation method thereof.
Background
The colour master batch is mainly used on plastics, and is formed from three basic elements of pigment or dye, carrier and additive, and is an aggregate made up by uniformly loading excessive pigment into resin, and can be called pigment concentrate, so that its colouring power is higher than that of pigment itself, and when it is processed, it can be mixed with small quantity of colour master batch and uncoloured resin so as to obtain the coloured resin or product with designed pigment concentration.
The existing color master batch cannot avoid long-time illumination in the use process, and under the illumination condition, the color master batch can absorb light energy and further generate photochemical reaction, so that self chemical bonds are broken, and further the self performance is greatly reduced.
Disclosure of Invention
The invention aims to provide a modified color master batch and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
the existing color master batch cannot avoid long-time illumination in the use process, and under the illumination condition, the color master batch can absorb light energy and further generate photochemical reaction, so that self chemical bonds are broken, and further the self performance is greatly reduced.
The purpose of the invention can be realized by the following technical scheme:
a modified color master batch is prepared from the following raw materials in parts by weight: 80-100 parts of low-density polyethylene, 30-40 parts of pigment, 3-5 parts of antioxidant, 3-5 parts of dispersant, 3-5 parts of heat stabilizer, 3-5 parts of lubricant and 3-5 parts of plasticizer;
the modified color master batch is prepared by the following steps:
step S1: adding low-density polyethylene, pigment, antioxidant, dispersant, heat stabilizer, lubricant and plasticizer into a high-speed mixer, and mixing at normal temperature until the mixture is uniform to prepare a mixture;
step S2: and (4) adding the mixture prepared in the step S1 into a single-screw extruder, extruding, cooling and pelletizing at the temperature of 160-170 ℃ to prepare the modified color master batch.
Further, the dispersing agent is one or two of stearic acid monoglyceride and tristearin mixed at any proportion, the heat stabilizer is one or more of tribasic lead sulfate, dibasic lead stearate and dibasic lead phosphite mixed at any proportion, the lubricant is one or two of liquid paraffin and microcrystalline paraffin mixed at any proportion, and the plasticizer is one or two of dioctyl phthalate and dibutyl phthalate mixed at any proportion.
Further, the antioxidant is prepared by the following steps:
step A1: adding phenol, aluminum powder and triphenoxy aluminum into a reaction kettle, preserving heat for 2-4h under the condition that the temperature is 140-150 ℃, introducing isobutene, reacting for 3-4h under the condition that the temperature is 120-130 ℃, adding a hydrochloric acid solution, standing for 30-40min, removing a water phase, adding p-methoxybenzyl ether and N-methylformamide into an organic phase, stirring uniformly under the condition that the rotation speed is 100-120r/min, adding sodium hydride, and reacting for 2-3h under the condition that the temperature is 25-30 ℃ to obtain an intermediate 1;
the reaction process is as follows:
step A2: dissolving the intermediate 1 prepared in the step A1 in ethanol to prepare an intermediate 1 solution, adding the intermediate 1 solution into a reaction kettle, dropwise adding mixed acid at the dropping speed of 0.8mL/min under the conditions of the rotation speed of 120-150r/min and the temperature of 50-55 ℃, stirring for 30-40min, adding tin powder and hydrochloric acid solution, stirring for 30-40min at the temperature of 90-95 ℃, adjusting the pH value to 9-10, distilling at the temperature of 110-120 ℃, adding a substrate and 2, 3-dichloro-5, 6-dicyan p-benzoquinone into a dichloromethane saturated aqueous solution, reacting for 3-5h at the temperature of 25-30 ℃, distilling at the temperature of 110-120 ℃ to remove the dichloromethane saturated aqueous solution, preparing an intermediate 2;
the reaction process is as follows:
step A3: adding o-nitroaniline, a hydrochloric acid solution and deionized water into a reaction kettle, stirring at the rotation speed of 120-150r/min and at the temperature of 3-5 ℃ for 30min, dropwise adding a sodium nitrate solution for 50-80min, reacting for 30-40min after dropwise adding, adding sulfamic acid, continuously stirring for 5-10min, and filtering to remove a filtrate to obtain an intermediate 3;
the reaction process is as follows:
step A4: dissolving p-cresol in chloroform, adding the intermediate 3 prepared in the step A3, stirring for 5-10min at the rotation speed of 100-120r/min and the temperature of 3-5 ℃, adjusting the pH value of a reaction solution to 8-10, reacting for 1-1.5h at the temperature of 8-10 ℃, filtering to remove filtrate, mixing a filter cake, sodium hydroxide, deionized water and absolute ethyl alcohol, adding hydrazine hydrate at the temperature of 80-85 ℃, refluxing for 1-1.5h, adjusting the pH value to 7-9, and filtering to remove the filtrate to prepare an intermediate 4;
the reaction process is as follows:
step A5: adding p-methoxybenzyl ether, methyl formamide and the intermediate 4 prepared in the step A4 into a reaction kettle, stirring at the rotation speed of 100-120r/min until the mixture is uniform, adding sodium hydride, reacting at the temperature of 25-30 ℃ for 2-3h, adding deionized water and potassium permanganate, and performing reflux reaction at the temperature of 110-120 ℃ for 4-5h to prepare an intermediate 6;
the reaction process is as follows:
step A6: adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone and the intermediate 6 prepared in the step A5 into a dichloromethane saturated aqueous solution, reacting for 3-5h at the temperature of 25-30 ℃, distilling to remove the dichloromethane saturated aqueous solution at the temperature of 110-120 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, reacting for 1-1.5h at the temperature of 25-30 ℃, filtering and drying to prepare the antioxidant.
The reaction process is as follows:
furthermore, the dosage ratio of the phenol, the aluminum powder, the triphenoxy aluminum, the isobutene and the hydrochloric acid solution in the step A1 is 20g:0.2g:0.1g:40g:0.8-1mL, the dosage mass ratio of the p-methoxybenzyl ether to the organic phase is 1:2, and the dosage of the sodium hydride is 10-20% of the mass of the organic phase.
Further, the intermediate 1, the mixed acid, the tin powder and the hydrochloric acid solution in the step A2 are mixed according to the dosage ratio of 1mL to 2mL to 2.5g to 5mL, the mixed acid is formed by mixing concentrated nitric acid and concentrated sulfuric acid according to the volume ratio of 1 to 0.8, the mass fraction of the concentrated nitric acid is 68-70%, the mass fraction of the concentrated sulfuric acid is 75-80%, the mass fraction of the hydrochloric acid solution is 36-40%, and the dosage of the 2, 3-dichloro-5, 6-dicyan p-benzoquinone is 5-10% of the mass of the substrate.
Further, the dosage of the o-nitroaniline, the hydrochloric acid solution, the deionized water and the sodium nitrate solution in the step A3 is 1g to 3mL to 5mL to 4mL, and the dosage of the sulfamic acid is 3-5% of the mass of the o-nitroaniline.
Further, the molar ratio of the p-cresol used in the step A4 to the intermediate 3 is 1:1, and the ratio of the filter cake to the sodium hydroxide to the deionized water to the absolute ethyl alcohol is 1g:5g:3mL:5 mL.
Further, the using amount ratio of the methoxybenzyl ether in the step A5 to the intermediate 4 is 1:1, the using amount of sodium hydride is 10-20% of the mass of the intermediate 4, and the using amount of potassium permanganate is 30-50% of the mass of the intermediate 4.
Further, the amount of the 2, 3-dichloro-5, 6-dicyan-p-benzoquinone in the step A6 is 5-10% of the mass of the intermediate 6, the molar ratio of the intermediate 6 to the intermediate 2 is 1:1, and the amount of dicyclohexylcarbodiimide is 30-50% of the sum of the mass of the intermediate 6 and the intermediate 2.
A preparation method of a modified color master batch specifically comprises the following steps:
step S1: adding low-density polyethylene, pigment, antioxidant, dispersant, heat stabilizer, lubricant and plasticizer into a high-speed mixer, and mixing at normal temperature until the mixture is uniform to prepare a mixture;
step S2: and (4) adding the mixture prepared in the step S1 into a single-screw extruder, extruding, cooling and pelletizing at the temperature of 160-170 ℃ to prepare the modified color master batch.
The invention has the beneficial effects that: the invention prepares an antioxidant in the process of preparing a modified color master batch, the antioxidant takes phenol as a raw material, firstly reacts with isobutene to insert tert-butyl into the ortho position of phenolic hydroxyl, the phenolic hydroxyl is protected by p-methoxybenzyl ether to prepare an intermediate 1, the intermediate 1 reacts with nitric acid solution to ensure that the original para position of the phenolic hydroxyl is inserted with nitro, then the nitro is reduced to amino, the phenolic hydroxyl is deprotected to prepare an intermediate 2, then diazotization reaction is carried out by taking o-nitroaniline as a raw material to prepare an intermediate 3, after coupling reaction of the intermediate 3 and p-cresol, reduction ring closure is carried out to prepare an intermediate 4, the phenolic hydroxyl of the intermediate 4 is protected by p-methoxybenzyl ether, methyl on a benzene ring is oxidized to carboxyl by potassium permanganate to prepare an intermediate 5, the phenolic hydroxyl of the intermediate 5 is deprotected, and the intermediate 2 is condensed, the amino group on the intermediate 2 and the carboxyl group on the intermediate 5 after deprotection are subjected to dehydration condensation to prepare the antioxidant, the phenolic hydroxyl group close to the triazole ring nitrogen in the antioxidant is far higher than the electron density on the triazole ring nitrogen because the electron density on the oxygen atom is higher than that on the triazole ring nitrogen atom, after the antioxidant is irradiated by light, protons rapidly move to the nitrogen atom to form an isomer, the isomer has poor stability and can safely convert redundant energy into heat energy and recover to a stable state, further, the light energy is converted into heat energy to be consumed, the oxidation of a polymer is inhibited, two sides of the other phenolic hydroxyl group are connected with tert-butyl groups, the phenolic hydroxyl group is subjected to space obstacle, hydrogen atoms are easy to fall off from molecules and are combined with peroxide radicals, alkoxy radicals and hydroxyl radicals to lose activity, and the aging reaction is.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A modified color master batch is prepared from the following raw materials in parts by weight: 80 parts of low-density polyethylene, 30 parts of pigment, 3 parts of antioxidant, 3 parts of dispersant, 3 parts of heat stabilizer, 3 parts of lubricant and 3 parts of plasticizer;
the modified color master batch is prepared by the following steps:
step S1: adding low-density polyethylene, pigment, antioxidant, dispersant, heat stabilizer, lubricant and plasticizer into a high-speed mixer, and mixing at normal temperature until the mixture is uniform to prepare a mixture;
step S2: and (4) adding the mixture prepared in the step S1 into a single-screw extruder, extruding at the temperature of 160 ℃, cooling and granulating to obtain the modified color master batch.
The antioxidant is prepared by the following steps:
step A1: adding phenol, aluminum powder and triphenoxy aluminum into a reaction kettle, preserving heat for 2 hours at the temperature of 140 ℃, introducing isobutene, reacting for 3 hours at the temperature of 120 ℃, adding a hydrochloric acid solution, standing for 30 minutes, removing a water phase, adding p-methoxybenzyl ether and methyl formamide into an organic phase, stirring uniformly at the rotation speed of 100r/min, adding sodium hydride, and reacting for 2 hours at the temperature of 25 ℃ to obtain an intermediate 1;
step A2: dissolving the intermediate 1 prepared in the step A1 in ethanol to prepare an intermediate 1 solution, adding the intermediate 1 solution into a reaction kettle, dropwise adding mixed acid at the rotation speed of 120r/min and the temperature of 50 ℃, stirring for 30min at the dropping speed of 0.8mL/min, adding tin powder and a hydrochloric acid solution, stirring for 30min at the temperature of 90 ℃, adjusting the pH value to 9, distilling at the temperature of 110 ℃, adding a substrate and 2, 3-dichloro-5, 6-dicyan p-benzoquinone into a dichloromethane saturated aqueous solution, reacting for 3h at the temperature of 25 ℃, and distilling at the temperature of 110 ℃ to remove the dichloromethane saturated aqueous solution to prepare an intermediate 2;
step A3: adding o-nitroaniline, a hydrochloric acid solution and deionized water into a reaction kettle, stirring for 30min at the rotation speed of 120r/min and the temperature of 3 ℃, dropwise adding a sodium nitrate solution for 50min, reacting for 30min after dropwise adding, adding sulfamic acid, continuously stirring for 5min, and filtering to remove a filtrate to obtain an intermediate 3;
step A4: dissolving p-cresol in chloroform, adding the intermediate 3 prepared in the step A3, stirring for 5min at the rotation speed of 100r/min and the temperature of 3 ℃, adjusting the pH value of a reaction solution to 8, reacting for 1h at the temperature of 8 ℃, filtering to remove filtrate, mixing a filter cake, sodium hydroxide, deionized water and absolute ethyl alcohol, adding hydrazine hydrate at the temperature of 80 ℃, refluxing for 1h, adjusting the pH value to 7, and filtering to remove the filtrate to prepare an intermediate 4;
step A5: adding p-methoxybenzyl ether, methyl formamide and the intermediate 4 prepared in the step A4 into a reaction kettle, stirring uniformly at the rotation speed of 100r/min, adding sodium hydride, reacting for 2 hours at the temperature of 25 ℃, adding deionized water and potassium permanganate, and performing reflux reaction for 4 hours at the temperature of 110 ℃ to prepare an intermediate 6;
step A6: adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone and the intermediate 6 prepared in the step A5 into a dichloromethane saturated aqueous solution, reacting for 3 hours at the temperature of 25 ℃, distilling to remove the dichloromethane saturated aqueous solution at the temperature of 110 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, reacting for 1 hour at the temperature of 25 ℃, filtering and drying to prepare the antioxidant.
Example 2
A modified color master batch is prepared from the following raw materials in parts by weight: 85 parts of low-density polyethylene, 35 parts of pigment, 4 parts of antioxidant, 4 parts of dispersant, 4 parts of heat stabilizer, 4 parts of lubricant and 4 parts of plasticizer;
the modified color master batch is prepared by the following steps:
step S1: adding low-density polyethylene, pigment, antioxidant, dispersant, heat stabilizer, lubricant and plasticizer into a high-speed mixer, and mixing at normal temperature until the mixture is uniform to prepare a mixture;
step S2: and (4) adding the mixture prepared in the step S1 into a single-screw extruder, extruding at the temperature of 160 ℃, cooling and granulating to obtain the modified color master batch.
The antioxidant is prepared by the following steps:
step A1: adding phenol, aluminum powder and triphenoxy aluminum into a reaction kettle, preserving heat for 3 hours at the temperature of 140 ℃, introducing isobutene, reacting for 3 hours at the temperature of 120 ℃, adding a hydrochloric acid solution, standing for 40 minutes, removing a water phase, adding p-methoxybenzyl ether and methyl formamide into an organic phase, stirring uniformly at the rotation speed of 100r/min, adding sodium hydride, and reacting for 2 hours at the temperature of 30 ℃ to obtain an intermediate 1;
step A2: dissolving the intermediate 1 prepared in the step A1 in ethanol to prepare an intermediate 1 solution, adding the intermediate 1 solution into a reaction kettle, dropwise adding mixed acid at the rotation speed of 120r/min and the temperature of 55 ℃, stirring for 40min at the dropping speed of 0.8mL/min, adding tin powder and a hydrochloric acid solution, stirring for 30min at the temperature of 95 ℃, adjusting the pH value to 9, distilling at the temperature of 120 ℃, adding a substrate and 2, 3-dichloro-5, 6-dicyan p-benzoquinone into a dichloromethane saturated aqueous solution, reacting for 4h at the temperature of 25 ℃, and distilling at the temperature of 120 ℃ to remove the dichloromethane saturated aqueous solution to prepare an intermediate 2;
step A3: adding o-nitroaniline, a hydrochloric acid solution and deionized water into a reaction kettle, stirring for 30min under the conditions that the rotation speed is 150r/min and the temperature is 4 ℃, dropwise adding a sodium nitrate solution for 80min, reacting for 40min after dropwise adding, adding sulfamic acid, continuously stirring for 10min, and filtering to remove a filtrate to obtain an intermediate 3;
step A4: dissolving p-cresol in chloroform, adding the intermediate 3 prepared in the step A3, stirring for 8min at the rotation speed of 100r/min and the temperature of 4 ℃, adjusting the pH value of a reaction solution to 9, reacting for 1.3h at the temperature of 9 ℃, filtering to remove filtrate, mixing a filter cake, sodium hydroxide, deionized water and absolute ethyl alcohol, adding hydrazine hydrate at the temperature of 83 ℃, refluxing for 1.3h, adjusting the pH value to 8, and filtering to remove the filtrate to prepare an intermediate 4;
step A5: adding p-methoxybenzyl ether, methyl formamide and the intermediate 4 prepared in the step A4 into a reaction kettle, stirring uniformly at the rotation speed of 110r/min, adding sodium hydride, reacting for 2.5 hours at the temperature of 28 ℃, adding deionized water and potassium permanganate, and performing reflux reaction for 4 hours at the temperature of 120 ℃ to prepare an intermediate 6;
step A6: adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone and the intermediate 6 prepared in the step A5 into a dichloromethane saturated aqueous solution, reacting for 4 hours at the temperature of 28 ℃, distilling to remove the dichloromethane saturated aqueous solution at the temperature of 115 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, reacting for 1.3 hours at the temperature of 28 ℃, filtering and drying to prepare the antioxidant.
Example 3
A modified color master batch is prepared from the following raw materials in parts by weight: 90 parts of low-density polyethylene, 38 parts of pigment, 4 parts of antioxidant, 4 parts of dispersant, 4 parts of heat stabilizer, 4 parts of lubricant and 4 parts of plasticizer;
the modified color master batch is prepared by the following steps:
step S1: adding low-density polyethylene, pigment, antioxidant, dispersant, heat stabilizer, lubricant and plasticizer into a high-speed mixer, and mixing at normal temperature until the mixture is uniform to prepare a mixture;
step S2: and (4) adding the mixture prepared in the step S1 into a single-screw extruder, extruding at the temperature of 170 ℃, cooling and granulating to obtain the modified color master batch.
The antioxidant is prepared by the following steps:
step A1: adding phenol, aluminum powder and triphenoxy aluminum into a reaction kettle, preserving heat for 3 hours at the temperature of 150 ℃, introducing isobutene, reacting for 4 hours at the temperature of 130 ℃, adding a hydrochloric acid solution, standing for 35 minutes, removing a water phase, adding p-methoxybenzyl ether and methyl formamide into an organic phase, stirring uniformly at the rotation speed of 120r/min, adding sodium hydride, and reacting for 3 hours at the temperature of 30 ℃ to obtain an intermediate 1;
step A2: dissolving the intermediate 1 prepared in the step A1 in ethanol to prepare an intermediate 1 solution, adding the intermediate 1 solution into a reaction kettle, dropwise adding mixed acid at the rotation speed of 150r/min and the temperature of 55 ℃, stirring for 40min at the dropping speed of 0.8mL/min, adding tin powder and a hydrochloric acid solution, stirring for 40min at the temperature of 95 ℃, adjusting the pH value to 10, distilling at the temperature of 120 ℃, adding a substrate and 2, 3-dichloro-5, 6-dicyan p-benzoquinone into a dichloromethane saturated aqueous solution, reacting for 4h at the temperature of 30 ℃, and distilling at the temperature of 120 ℃ to remove the dichloromethane saturated aqueous solution to prepare an intermediate 2;
step A3: adding o-nitroaniline, a hydrochloric acid solution and deionized water into a reaction kettle, stirring for 30min under the conditions that the rotation speed is 150r/min and the temperature is 4 ℃, dropwise adding a sodium nitrate solution for 80min, reacting for 40min after dropwise adding, adding sulfamic acid, continuously stirring for 10min, and filtering to remove a filtrate to obtain an intermediate 3;
step A4: dissolving p-cresol in chloroform, adding the intermediate 3 prepared in the step A3, stirring for 10min at the rotation speed of 120r/min and the temperature of 5 ℃, adjusting the pH value of a reaction solution to 10, reacting for 1.5h at the temperature of 10 ℃, filtering to remove filtrate, mixing a filter cake, sodium hydroxide, deionized water and absolute ethyl alcohol, adding hydrazine hydrate at the temperature of 85 ℃, refluxing for 1.5h, adjusting the pH value to 9, and filtering to remove the filtrate to prepare an intermediate 4;
step A5: adding p-methoxybenzyl ether, methyl formamide and the intermediate 4 prepared in the step A4 into a reaction kettle, stirring uniformly at the rotation speed of 120r/min, adding sodium hydride, reacting for 3 hours at the temperature of 30 ℃, adding deionized water and potassium permanganate, and performing reflux reaction for 4.5 hours at the temperature of 120 ℃ to prepare an intermediate 6;
step A6: adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone and the intermediate 6 prepared in the step A5 into a dichloromethane saturated aqueous solution, reacting for 4 hours at the temperature of 30 ℃, distilling to remove the dichloromethane saturated aqueous solution at the temperature of 115 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, reacting for 1.5 hours at the temperature of 30 ℃, filtering and drying to prepare the antioxidant.
Example 4
A modified color master batch is prepared from the following raw materials in parts by weight: 100 parts of low-density polyethylene, 40 parts of pigment, 5 parts of antioxidant, 5 parts of dispersant, 5 parts of heat stabilizer, 5 parts of lubricant and 5 parts of plasticizer;
the modified color master batch is prepared by the following steps:
step S1: adding low-density polyethylene, pigment, antioxidant, dispersant, heat stabilizer, lubricant and plasticizer into a high-speed mixer, and mixing at normal temperature until the mixture is uniform to prepare a mixture;
step S2: and (4) adding the mixture prepared in the step S1 into a single-screw extruder, extruding at the temperature of 170 ℃, cooling and granulating to obtain the modified color master batch.
The antioxidant is prepared by the following steps:
step A1: adding phenol, aluminum powder and triphenoxy aluminum into a reaction kettle, keeping the temperature at 150 ℃ for 4 hours, introducing isobutylene, reacting at 130 ℃ for 4 hours, adding a hydrochloric acid solution, standing for 40 minutes, removing a water phase, adding p-methoxybenzyl ether and methyl formamide into an organic phase, stirring uniformly at a rotation speed of 120r/min, adding sodium hydride, and reacting at 30 ℃ for 3 hours to obtain an intermediate 1;
step A2: dissolving the intermediate 1 prepared in the step A1 in ethanol to prepare an intermediate 1 solution, adding the intermediate 1 solution into a reaction kettle, dropwise adding mixed acid at the rotation speed of 150r/min and the temperature of 55 ℃, stirring for 40min at the dropping speed of 0.8mL/min, adding tin powder and a hydrochloric acid solution, stirring for 40min at the temperature of 95 ℃, adjusting the pH value to 10, distilling at the temperature of 120 ℃, adding a substrate and 2, 3-dichloro-5, 6-dicyan p-benzoquinone into a dichloromethane saturated aqueous solution, reacting for 5h at the temperature of 30 ℃, and distilling at the temperature of 120 ℃ to remove the dichloromethane saturated aqueous solution to prepare an intermediate 2;
step A3: adding o-nitroaniline, a hydrochloric acid solution and deionized water into a reaction kettle, stirring for 30min at the rotation speed of 150r/min and the temperature of 5 ℃, dropwise adding a sodium nitrate solution for 80min, reacting for 40min after dropwise adding, adding sulfamic acid, continuously stirring for 10min, and filtering to remove a filtrate to obtain an intermediate 3;
step A4: dissolving p-cresol in chloroform, adding the intermediate 3 prepared in the step A3, stirring for 10min at the rotation speed of 120r/min and the temperature of 5 ℃, adjusting the pH value of a reaction solution to 10, reacting for 1.5h at the temperature of 10 ℃, filtering to remove filtrate, mixing a filter cake, sodium hydroxide, deionized water and absolute ethyl alcohol, adding hydrazine hydrate at the temperature of 85 ℃, refluxing for 1.5h, adjusting the pH value to 9, and filtering to remove the filtrate to prepare an intermediate 4;
step A5: adding p-methoxybenzyl ether, methyl formamide and the intermediate 4 prepared in the step A4 into a reaction kettle, stirring uniformly at the rotation speed of 120r/min, adding sodium hydride, reacting for 3 hours at the temperature of 30 ℃, adding deionized water and potassium permanganate, and performing reflux reaction for 5 hours at the temperature of 120 ℃ to prepare an intermediate 6;
step A6: adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone and the intermediate 6 prepared in the step A5 into a dichloromethane saturated aqueous solution, reacting for 5 hours at the temperature of 30 ℃, distilling to remove the dichloromethane saturated aqueous solution at the temperature of 120 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, reacting for 1.5 hours at the temperature of 30 ℃, filtering and drying to prepare the antioxidant.
Comparative example
The comparative example is a common color master batch in the market.
The color masterbatches prepared in examples 1 to 3 and comparative example were subjected to performance tests, and the test results are shown in table 1 below;
TABLE 1
From the above table 1, it can be seen that the color master batches prepared in examples 1-3 have no abnormality when irradiated under 6000Lux illumination intensity for 1800 hours, while the color master batches prepared in comparative examples have no abnormality when irradiated under 6000Lux illumination intensity for 800 hours, and the color master batches crack when irradiated under 900 hours, which indicates that the antioxidant effect of the present invention is very good.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (10)
1. A modified color master batch is characterized in that: the feed is prepared from the following raw materials in parts by weight: 80-100 parts of low-density polyethylene, 30-40 parts of pigment, 3-5 parts of antioxidant, 3-5 parts of dispersant, 3-5 parts of heat stabilizer, 3-5 parts of lubricant and 3-5 parts of plasticizer;
the modified color master batch is prepared by the following steps:
step S1: adding low-density polyethylene, pigment, antioxidant, dispersant, heat stabilizer, lubricant and plasticizer into a high-speed mixer, and mixing at normal temperature until the mixture is uniform to prepare a mixture;
step S2: and (4) adding the mixture prepared in the step S1 into a single-screw extruder, extruding, cooling and pelletizing at the temperature of 160-170 ℃ to prepare the modified color master batch.
2. The modified color masterbatch of claim 1, wherein: the dispersing agent is one or two of stearic acid monoglyceride and tristearin mixed in any proportion, the heat stabilizer is one or more of tribasic lead sulfate, dibasic lead stearate and dibasic lead phosphite mixed in any proportion, the lubricating agent is one or two of liquid paraffin and microcrystalline paraffin mixed in any proportion, and the plasticizer is one or two of dioctyl phthalate and dibutyl phthalate mixed in any proportion.
3. The modified color masterbatch of claim 1, wherein: the antioxidant is prepared by the following steps:
step A1: adding phenol, aluminum powder and triphenoxy aluminum into a reaction kettle, preserving heat for 2-4h under the condition that the temperature is 140-150 ℃, introducing isobutene, reacting for 3-4h under the condition that the temperature is 120-130 ℃, adding a hydrochloric acid solution, standing for 30-40min, removing a water phase, adding p-methoxybenzyl ether and N-methylformamide into an organic phase, stirring uniformly under the condition that the rotation speed is 100-120r/min, adding sodium hydride, and reacting for 2-3h under the condition that the temperature is 25-30 ℃ to obtain an intermediate 1;
step A2: dissolving the intermediate 1 prepared in the step A1 in ethanol to prepare an intermediate 1 solution, adding the intermediate 1 solution into a reaction kettle, dropwise adding mixed acid at the dropping speed of 0.8mL/min under the conditions of the rotation speed of 120-150r/min and the temperature of 50-55 ℃, stirring for 30-40min, adding tin powder and hydrochloric acid solution, stirring for 30-40min at the temperature of 90-95 ℃, adjusting the pH value to 9-10, distilling at the temperature of 110-120 ℃, adding a substrate and 2, 3-dichloro-5, 6-dicyan p-benzoquinone into a dichloromethane saturated aqueous solution, reacting for 3-5h at the temperature of 25-30 ℃, distilling at the temperature of 110-120 ℃ to remove the dichloromethane saturated aqueous solution, preparing an intermediate 2;
step A3: adding o-nitroaniline, a hydrochloric acid solution and deionized water into a reaction kettle, stirring at the rotation speed of 120-150r/min and at the temperature of 3-5 ℃ for 30min, dropwise adding a sodium nitrate solution for 50-80min, reacting for 30-40min after dropwise adding, adding sulfamic acid, continuously stirring for 5-10min, and filtering to remove a filtrate to obtain an intermediate 3;
step A4: dissolving p-cresol in chloroform, adding the intermediate 3 prepared in the step A3, stirring for 5-10min at the rotation speed of 100-120r/min and the temperature of 3-5 ℃, adjusting the pH value of a reaction solution to 8-10, reacting for 1-1.5h at the temperature of 8-10 ℃, filtering to remove filtrate, mixing a filter cake, sodium hydroxide, deionized water and absolute ethyl alcohol, adding hydrazine hydrate at the temperature of 80-85 ℃, refluxing for 1-1.5h, adjusting the pH value to 7-9, and filtering to remove the filtrate to prepare an intermediate 4;
step A5: adding p-methoxybenzyl ether, methyl formamide and the intermediate 4 prepared in the step A4 into a reaction kettle, stirring at the rotation speed of 100-120r/min until the mixture is uniform, adding sodium hydride, reacting at the temperature of 25-30 ℃ for 2-3h, adding deionized water and potassium permanganate, and performing reflux reaction at the temperature of 110-120 ℃ for 4-5h to prepare an intermediate 6;
step A6: adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone and the intermediate 6 prepared in the step A5 into a dichloromethane saturated aqueous solution, reacting for 3-5h at the temperature of 25-30 ℃, distilling to remove the dichloromethane saturated aqueous solution at the temperature of 110-120 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, reacting for 1-1.5h at the temperature of 25-30 ℃, filtering and drying to prepare the antioxidant.
4. A modified masterbatch according to claim 3, wherein: the dosage ratio of the phenol, the aluminum powder, the triphenoxy aluminum, the isobutene and the hydrochloric acid solution in the step A1 is 20g:0.2g:0.1g:40g:0.8-1mL, the dosage mass ratio of the p-methoxybenzyl ether to the organic phase is 1:2, and the dosage of the sodium hydride is 10-20% of the organic phase.
5. A modified masterbatch according to claim 3, wherein: the dosage ratio of the intermediate 1, the mixed acid, the tin powder and the hydrochloric acid solution in the step A2 is 1mL:2mL:2.5g:5mL, the mixed acid is prepared by mixing concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:0.8, the mass fraction of the concentrated nitric acid is 68-70%, the mass fraction of the concentrated sulfuric acid is 75-80%, the mass fraction of the hydrochloric acid solution is 36-40%, and the dosage of the 2, 3-dichloro-5, 6-dicyan p-benzoquinone is 5-10% of the mass of the substrate.
6. A modified masterbatch according to claim 3, wherein: the dosage of the o-nitroaniline, the hydrochloric acid solution, the deionized water and the sodium nitrate solution in the step A3 is 1g to 3mL to 5mL to 4mL, and the dosage of the sulfamic acid is 3-5% of the mass of the o-nitroaniline.
7. A modified masterbatch according to claim 3, wherein: the molar ratio of the p-cresol in the step A4 to the intermediate 3 is 1:1, and the ratio of the filter cake to the sodium hydroxide to the deionized water to the absolute ethyl alcohol is 1g:5g:3mL:5 mL.
8. A modified masterbatch according to claim 3, wherein: the using amount ratio of the methoxybenzyl ether in the step A5 to the intermediate 4 is 1:1, the using amount of sodium hydride is 10-20% of the mass of the intermediate 4, and the using amount of potassium permanganate is 30-50% of the mass of the intermediate 4.
9. A modified masterbatch according to claim 3, wherein: the dosage of the 2, 3-dichloro-5, 6-dicyan p-benzoquinone in the step A6 is 5-10% of the mass of the intermediate 6, the molar ratio of the dosages of the intermediate 6 and the intermediate 2 is 1:1, and the dosage of the dicyclohexyl carbodiimide is 30-50% of the sum of the masses of the intermediate 6 and the intermediate 2.
10. The preparation method of the modified color master batch according to claim 1, wherein the preparation method comprises the following steps: the method specifically comprises the following steps:
step S1: adding low-density polyethylene, pigment, antioxidant, dispersant, heat stabilizer, lubricant and plasticizer into a high-speed mixer, and mixing at normal temperature until the mixture is uniform to prepare a mixture;
step S2: and (4) adding the mixture prepared in the step S1 into a single-screw extruder, extruding, cooling and pelletizing at the temperature of 160-170 ℃ to prepare the modified color master batch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011060463.9A CN112175265A (en) | 2020-09-30 | 2020-09-30 | Modified color master batch and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011060463.9A CN112175265A (en) | 2020-09-30 | 2020-09-30 | Modified color master batch and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112175265A true CN112175265A (en) | 2021-01-05 |
Family
ID=73946296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011060463.9A Pending CN112175265A (en) | 2020-09-30 | 2020-09-30 | Modified color master batch and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112175265A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429592A (en) * | 2021-07-06 | 2021-09-24 | 安徽卡洛塑业科技有限公司 | Preparation method of modified color master batch |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101187076A (en) * | 2007-11-13 | 2008-05-28 | 华东理工大学 | Color master batch for polyolefin grass fiber and its preparation method |
| CN103172928A (en) * | 2013-04-19 | 2013-06-26 | 常州一诺塑料科技有限公司 | Color master batch special for polyethylene lawn silk and preparation method thereof |
| CN103289184A (en) * | 2012-02-27 | 2013-09-11 | 上海蓉新化工有限公司 | Anti-oxidative color masterbatch and preparation method and application thereof |
| CN111690218A (en) * | 2020-07-30 | 2020-09-22 | 李坤 | Environment-friendly rat-proof and termite-proof plastic insulated control cable |
-
2020
- 2020-09-30 CN CN202011060463.9A patent/CN112175265A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101187076A (en) * | 2007-11-13 | 2008-05-28 | 华东理工大学 | Color master batch for polyolefin grass fiber and its preparation method |
| CN103289184A (en) * | 2012-02-27 | 2013-09-11 | 上海蓉新化工有限公司 | Anti-oxidative color masterbatch and preparation method and application thereof |
| CN103172928A (en) * | 2013-04-19 | 2013-06-26 | 常州一诺塑料科技有限公司 | Color master batch special for polyethylene lawn silk and preparation method thereof |
| CN111690218A (en) * | 2020-07-30 | 2020-09-22 | 李坤 | Environment-friendly rat-proof and termite-proof plastic insulated control cable |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429592A (en) * | 2021-07-06 | 2021-09-24 | 安徽卡洛塑业科技有限公司 | Preparation method of modified color master batch |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3238163A (en) | Dye receptive polyolefin compositions comprising a magnesium or zinc compound and a hydroxy substituted benzophenone | |
| CN112175265A (en) | Modified color master batch and preparation method thereof | |
| CN112321969B (en) | Anti-aging plastic packaging film and preparation method thereof | |
| CN111909364B (en) | Preparation method of silver-series antibacterial masterbatch | |
| CN101503343A (en) | Method for synthesizing acetylacetone metallic compound | |
| CN112011231A (en) | High-weather-resistance water-based paint and preparation method thereof | |
| CN109046328B (en) | Photo-thermal catalytic hydrogenation catalyst, preparation thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction | |
| CN110776688A (en) | Antioxidant and anti-UV color master batch and preparation method thereof | |
| CN113897079B (en) | Anti-aging green carbon black for tires and preparation method thereof | |
| CN112500589A (en) | Carrier-free carbon black master batch with high content of pigment | |
| CN111939958A (en) | g-C3N4/Bi2WO6/CuS ternary composite photocatalyst and preparation method thereof | |
| CN111333979B (en) | Antique bamboo joint resin tile and preparation method thereof | |
| CN112852018A (en) | Water-soluble methyl silane environment-friendly asphalt separant | |
| CN112210219A (en) | Silicon rubber with wide temperature range and long storage life and preparation method thereof | |
| CN112210167A (en) | Artemisia argyi PP functional master batch and application thereof in plastic products | |
| CN104045751A (en) | Preparation method of polyvinyl butyral | |
| CN113402736A (en) | Antibacterial color master batch and preparation method thereof | |
| CN113462057A (en) | Environment-friendly color master batch and preparation method thereof | |
| CN108164880A (en) | A kind of automotive wire cable and preparation method thereof | |
| CN111961302A (en) | High-temperature water-soluble PVA master batch composition and preparation method thereof | |
| CN112920628A (en) | Vehicle paint maintenance coating agent and preparation method thereof | |
| US4377650A (en) | Process for the preparation of colored powders of hydrolyzed ethylene-vinyl acetate copolymer | |
| CN113881121B (en) | High-coloring high-aging-resistance polyethylene color master batch and preparation method thereof | |
| CN108996502A (en) | The method that 4-Hydroxyphenyl hydantoin production waste liquor prepares high performance active carbon | |
| US2668804A (en) | Pigments and molding powders comprising polyvinyl acetal resins dyed with azo dyes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210105 |