CN115160681B - Low-odor high-carbon-black-content polyethylene color master batch and preparation method thereof - Google Patents

Low-odor high-carbon-black-content polyethylene color master batch and preparation method thereof Download PDF

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CN115160681B
CN115160681B CN202210825642.XA CN202210825642A CN115160681B CN 115160681 B CN115160681 B CN 115160681B CN 202210825642 A CN202210825642 A CN 202210825642A CN 115160681 B CN115160681 B CN 115160681B
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modified polyethylene
carbon black
polyethylene wax
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CN115160681A (en
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曹畅
林文丹
崔永哲
李刚
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Guangdong Jiucai New Material Co ltd
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Abstract

The invention discloses a low-odor high-carbon-black-content polyethylene color master batch and a preparation method thereof, and relates to the technical field of polyethylene color master batches. The polyethylene color master batch is prepared by adopting degradable modified polyethylene powder which is high in reaction activity, good in compatibility and slight in aromatic smell as carrier resin, adding heat-resistant modified polyethylene wax micropowder with slight aromatic smell, and matching low-structure carbon black, bis (beta-hydroxyethyl) cocoamine and an antioxidant, wherein the degradable modified polyethylene powder is well compatible with the modified polyethylene wax micropowder, and the bis (beta-hydroxyethyl) cocoamine is used as a wetting agent and an antistatic agent, so that the polyethylene color master batch is uniform in component, the smell is improved when the polyethylene color master batch is used for plastic products, and the heat resistance, the antistatic property and the degradation rate of the plastic products are improved.

Description

Low-odor high-carbon-black-content polyethylene color master batch and preparation method thereof
Technical Field
The invention relates to the technical field of polyethylene color master batches, in particular to a low-odor high-carbon-black-content polyethylene color master batch and a preparation method thereof.
Background
The color master batch is a resin coloring mixture with high efficiency and high concentration color, which is prepared by strictly processing and dispersing a large amount of pigment or pigment and carrier resin of one or more components, and the color master batch is generally added with auxiliary agents such as lubricant, brightener, antioxidant and the like and is generally prepared into granules, pills or powder. According to different purposes, the color master batches are divided into injection color master batches, blow molding color master batches, spinning color master batches and the like, and the color master batches are of different grades.
The patent of publication No. CN106046479B discloses a high carbon black dispersion polyethylene pellet which is prepared from the following raw materials, by weight, 100 parts of polyethylene resin pellets, 0.2-0.5 part of polyethylene wax, 0.2-0.5 part of a composite antioxidant, and 2-10 parts of black color master batches, wherein the black color master batches adopt medium and low structure carbon black, and the content of the carbon black is 40%; the pre-dispersion color master batch is prepared by adopting the strong shearing action of a double-screw extruder, and then is blended and extruded with polyethylene resin granules by adopting a single-screw extruder, so that the dispersion degree of the carbon black is improved and can reach more than 6 minutes. However, researches show that the conventional polyethylene color master batch with high carbon black content and the preparation method thereof have the following technical problems: the heat resistance, antistatic property and degradation rate of the polyethylene color master batch finished product need to be improved, and the polyethylene color master batch can volatilize unfriendly odor when the carbon black content is high, so that the improvement is needed.
Disclosure of Invention
The invention aims to provide a polyethylene color master batch with low odor and high carbon black content and a preparation method thereof, which are used for solving the technical problems that the heat resistance, the antistatic property and the degradation rate of a finished product of the polyethylene color master batch in the prior art need to be improved, and unfriendly odor can be volatilized when the carbon black content is high.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a low-odor high-carbon-black-content polyethylene color master batch which is prepared from the following components in parts by weight: 72 to 95 portions of degradable modified polyethylene powder, 3 to 10 portions of modified polyethylene wax micro powder, 18 to 32 portions of low-structure carbon black, 1 to 5 portions of bis (beta-hydroxyethyl) cocoamine and 0.1 to 0.6 portion of antioxidant; the degradable modified polyethylene powder is prepared by reacting 2-bromo-1,1-dimethoxyethane and 1,4-butanediol in the presence of toluene and potassium tert-butoxide as solvents for catalysis and performing aftertreatment to obtain an intermediate 1, and polymerizing the intermediate 1, N-vinyl caprolactam, an organic cobalt complexing agent and ethylene under the initiation of azobisisobutyronitrile and performing aftertreatment to obtain the degradable modified polyethylene powder; the modified polyethylene wax micro powder is obtained by polymerizing polyethylene wax, vinyl acrylate and maleic anhydride under the initiation of benzoyl peroxide and carrying out post-treatment.
Further, the preparation method of the degradable modified polyethylene powder comprises the following steps:
step one, sequentially adding 2-bromo-1,1-dimethoxyethane, 1,4-butanediol, p-toluenesulfonic acid and a solvent toluene into a three-neck flask, heating to 115-130 ℃, preserving heat, refluxing, stirring, reacting for 16-18 hours, washing with ethyl acetate, carrying out reduced pressure distillation to obtain 2-bromo-1,3-dioxepane, adding tetrahydrofuran and potassium tert-butoxide, carrying out stirring reaction for 60-80 min, cooling to room temperature, continuing stirring, reacting for 10-12 hours, adding diethyl ether, filtering, washing with diethyl ether, filtering, and carrying out reduced pressure distillation on the filtrate to obtain an intermediate 1;
and step two, adding the intermediate 1, N-vinyl caprolactam and a solvent toluene into a three-neck flask, adding an organic cobalt coordination agent and azodiisobutyronitrile, introducing ethylene under the protection of nitrogen, heating to 68-80 ℃, keeping the temperature, stirring, reacting for 20-24 hours, carrying out reduced pressure distillation to remove the solvent, filtering, washing a filter cake with toluene for three times, drying at 65-78 ℃ for 16-20 hours to obtain a crude product, crushing the crude product, and sieving with a 10-20-mesh sieve to obtain the degradable modified polyethylene powder.
The synthetic reaction formula of the degradable modified polyethylene powder is as follows:
Figure BDA0003743863110000031
when the degradable modified polyethylene powder is prepared, 2-bromo-1,1-dimethoxyethane and 1,4-butanediol are used as raw materials, hydrogen ions are combined with oxygen on methoxyl groups under the catalysis of p-toluenesulfonic acid to protonate the raw materials, the electropositivity of methoxyl carbon is enhanced, the attack of 1,4-butanediol is facilitated to generate 2-bromo-1,3-dioxepane, hydrogen bromide of the 2-bromo-1,3-dioxepane is removed under the catalysis of potassium tert-butoxide to generate double bonds, and the intermediate 1 is obtained after ether washing and reduced pressure distillation; the intermediate 1, ethylene, N-vinyl caprolactam and an organic cobalt complexing agent generate a multi-polymer under the initiation action of free radicals of azodiisobutyronitrile, the organic cobalt complexing agent is selected from a Co (II) ammonia complex, can capture the free radicals, catalyzes the ring opening homopolymerization of the intermediate 1 under mild conditions, and simultaneously introduces the organic cobalt into a main chain section of the polymer. Toluene is used as a solvent in the first step and the second step, and a small part of the toluene is reacted or remained after distillation, so that the degradable modified polyethylene powder has slight aromatic odor. The chain segment of the degradable modified polyethylene powder contains a hydrophilic and easily degradable caprolactam structure, and the introduction of organic cobalt improves the reactivity and the strength, facilitates the processing and the forming, is beneficial to the compatibility with various additives in an aqueous solvent, and improves the degradation rate of a processed product.
Further, in the first step, the molar ratio of the 2-bromine-1,1-dimethoxyethane to 1,4-butanediol, p-toluenesulfonic acid and potassium tert-butoxide is 1:1.1 to 1.3:0.01 to 0.03: 1.2-1.4,1,4-butanediol, solvent toluene and tetrahydrofuran in a dosage ratio of 9g:40mL of: 30mL.
Further, in the second step, the introduction pressure of ethylene is 20-30 bar, and the molar ratio of the intermediate 1 to the N-vinyl caprolactam is 1.5-2.2: 1, the dosage of the organic cobalt coordination agent, the dosage of the azodiisobutyronitrile and the dosage of the solvent toluene are respectively 0.4 to 0.8 time, 0.01 to 0.03 time and 2 to 6 times of the weight of the N-vinyl caprolactam.
Further, the preparation method of the modified polyethylene wax micropowder comprises the following steps:
step one, adding polyethylene wax and toluene into a three-neck flask, uniformly mixing and stirring, blowing nitrogen for protection, heating in an oil bath to 115-130 ℃, adding vinyl acrylate, maleic anhydride and benzoyl peroxide, and carrying out heat preservation reflux reaction for 2-4 hours to obtain a mixed reaction solution;
filtering the mixed reaction solution, washing with ethyl acetate for 3-5 times, decompressing and concentrating the filtrate to remove the solvent, recrystallizing the mixed solvent of ethyl acetate and petroleum ether to obtain a modified polyethylene wax crude product, drying the modified polyethylene wax crude product at 45-60 ℃, and crushing to obtain modified polyethylene wax micropowder; wherein the volume ratio of the ethyl acetate to the petroleum ether in the mixed solvent is 1:3 to 6, and the recrystallization temperature is 3 to 15 ℃.
When the modified polyethylene wax micro powder is prepared, polyethylene wax, vinyl acrylate and maleic anhydride are grafted under the initiation action of free radicals of benzoyl peroxide to obtain a terpolymer; the vinyl acrylate has high reactive activity of active double bonds, the maleic anhydride has high reactive activity of double bonds and an anhydride structure, the molecular weight of the polyethylene wax is increased after grafting, the thermal motion of a polyethylene wax molecular chain is blocked, the modified polyethylene wax with long carbon chains has good heat resistance and rigidity, is not easy to decompose and volatilize, has an ester group structure in the modified polyethylene wax, is washed by ethyl acetate, has slight aromatic odor, improves the heat resistance and the rigidity when preparing the color master batch, and improves the unfriendly odor.
Further, in the step one, the weight ratio of the polyethylene wax, the toluene, the vinyl acrylate, the maleic anhydride and the benzoyl peroxide is 6-10: 22 to 30:1 to 3: 0.4-0.8: 0.2 to 0.5; the polyethylene wax has an average particle diameter of 5-15 μm and a density of 0.98g/cm 3 The melting point was 138 ℃.
Further, the low-structure carbon black has an oil absorption value of 56cm 3 100g, particle diameter of 20nm, tinting strength of 115% and pH of 9; the antioxidant is prepared from antioxidant 264, antioxidant 168 and antioxidant 1010 according to the weight ratio of 1:2:2, mixing the components.
The invention also provides a preparation method of the polyethylene color master batch with low odor and high carbon black content, which comprises the following steps:
s1, adding degradable modified polyethylene powder, modified polyethylene wax micro powder and low-structure carbon black into a high-speed mixer, stirring at the rotating speed of 200-400 rpm for 20-30 min, and then stirring at the rotating speed of 650-800 rpm for 10-20 min to obtain a dispersed master batch;
s2, uniformly mixing the dispersed master batch, bis (beta-hydroxyethyl) cocoamine and an antioxidant, adding the mixture into an internal mixer, carrying out internal mixing at 160-180 ℃ for 25-40 min to obtain an internal mixed material, adding the internal mixed material into a double-screw extruder, and extruding at 145-170 ℃ to obtain an extruded material;
and S3, carrying out water cooling and grain cutting on the extruded material to obtain the polyethylene color master batch.
The preparation method of the polyethylene color master batch adopts the processing modes of stirring and mixing, banburying, screw extrusion, water cooling and grain cutting to obtain the polyethylene color master batch with reliable quality and uniform components, and the processing method is simple and controllable and is suitable for industrial application.
The invention has the following beneficial effects:
1. the polyethylene color master batch disclosed by the invention is prepared by adopting degradable modified polyethylene powder which is high in reaction activity, good in compatibility and slight in aromatic smell as carrier resin, adding heat-resistant modified polyethylene wax micropowder with slight aromatic smell, and matching with low-structure carbon black, bis (beta-hydroxyethyl) cocoamine and an antioxidant, wherein the degradable modified polyethylene powder is well compatible with the modified polyethylene wax micropowder, and the bis (beta-hydroxyethyl) cocoamine is used as a wetting agent and an antistatic agent, so that the low-structure carbon black which is easy to disperse and has small particle size is favorably dispersed in the degradable modified polyethylene powder in a flowing manner, and the polyethylene color master batch is uniform in component by combining the antioxidant effect of the antioxidant, so that the unfriendly smell is improved when the polyethylene color master batch is used for plastic products, and the heat resistance, the antistatic property and the degradation rate of the plastic products are improved.
2. When the degradable modified polyethylene powder is prepared, methylbenzene is used as a solvent, and a small part of methylbenzene participates in reaction or remains after distillation, so that the degradable modified polyethylene powder has slight aromatic odor; the molecular chain segment contains a hydrophilic easily degradable caprolactam structure, and the introduction of organic cobalt improves the reactivity and the strength, facilitates the processing and the forming and improves the degradation rate of processed products.
3. The modified polyethylene wax micro powder improves the molecular weight of polyethylene wax through graft copolymerization grafting, blocks the thermal motion of a polyethylene wax molecular chain, has good heat resistance and rigidity, is not easy to decompose and volatilize, has an ester group structure in the modified polyethylene wax micro powder, is washed by ethyl acetate, and has slight aromatic smell.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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
The polyethylene color master batch with low odor and high carbon black content is prepared from the following components in parts by weight: 87g of degradable modified polyethylene powder, 5.8g of modified polyethylene wax micro powder, 26g of low-structure carbon black, 1.7g of bis (beta-hydroxyethyl) cocoamine and 0.4g of antioxidant; wherein the oil absorption value of the low-structure carbon black is 56cm 3 100g, particle diameter of 20nm, tinting strength of 115% and pH of 9; the antioxidant is prepared from antioxidant 264, antioxidant 168 and antioxidant 1010 according to the weight ratio of 1:2:2, mixing the components.
The preparation method of the degradable modified polyethylene powder comprises the following steps:
step one, adding 16.9g of 2-bromo-1,1-dimethoxyethane, 10.6g of 1, 4-butanediol, 0.34g of p-toluenesulfonic acid and 47mL of solvent toluene into a three-neck flask in sequence, heating to 122 ℃, carrying out heat preservation, reflux, stirring and reaction for 17 hours, washing with ethyl acetate, carrying out reduced pressure distillation to obtain 2-bromo-1,3-dioxepane, adding 35mL of tetrahydrofuran and 14.1g of potassium tert-butoxide, carrying out stirring reaction for 72 minutes, cooling to room temperature, carrying out continuous stirring reaction for 11 hours, adding diethyl ether, filtering, washing and filtering the diethyl ether, and carrying out reduced pressure distillation on the filtrate to obtain an intermediate 1;
the nuclear magnetic detection results of intermediate 1 are as follows: 1 H NMR(400MHz，CDCl 3 )：δ＝1.73ppm(m，4H，CH 2 CH 2 )，3.42ppm(s，2H，CCH 2 )，3.90ppm(m，4H，CH 2 OCOCH 2 )；
step two, adding 20.5g of the intermediate 1, 13.9g N-vinyl caprolactam and 69.5g of solvent toluene into a three-neck flask, adding 8.34g of organic cobalt coordination agent and 0.28g of azobisisobutyronitrile, introducing ethylene under the protection of nitrogen, heating to 75 ℃, keeping the temperature, stirring for reaction for 23 hours, carrying out reduced pressure distillation to remove the solvent, filtering, washing a filter cake with toluene for three times, drying at 68 ℃ for 19 hours to obtain a crude product, crushing the crude product, and sieving with a 10-mesh sieve to obtain degradable modified polyethylene powder; the pressure at which ethylene was passed was 28bar.
The preparation method of the modified polyethylene wax micro powder comprises the following steps:
adding 8.5g of polyethylene wax and 28g of toluene into a three-neck flask, uniformly mixing and stirring, blowing nitrogen for protection, heating an oil bath to 123 ℃, adding 1.8g of vinyl acrylate, 0.6g of maleic anhydride and 0.3g of benzoyl peroxide, and carrying out heat preservation reflux reaction for 2.5 hours to obtain a mixed reaction solution; wherein the polyethylene wax has an average particle diameter of 10 μm and a density of 0.98g/cm 3 The melting point is 138 ℃;
filtering the mixed reaction solution, washing with ethyl acetate for 4 times, concentrating the filtrate under reduced pressure to remove the solvent, recrystallizing the mixed solvent of ethyl acetate and petroleum ether to obtain a modified polyethylene wax crude product, and drying and crushing the modified polyethylene wax crude product at 52 ℃ to obtain modified polyethylene wax micropowder; wherein the volume ratio of the ethyl acetate to the petroleum ether in the mixed solvent is 1:5, the recrystallization temperature is 8 ℃.
The preparation method of the polyethylene color masterbatch with low odor and high carbon black content comprises the following steps:
s1, adding degradable modified polyethylene powder, modified polyethylene wax micro powder and low-structure carbon black into a high-speed mixer, stirring at a rotating speed of 350rpm for 26min, and then stirring at a rotating speed of 760rpm for 16min to obtain a dispersed master batch;
s2, uniformly mixing the dispersion master batch, bis (beta-hydroxyethyl) cocoamine and an antioxidant, then putting the mixture into an internal mixer, carrying out internal mixing for 32min at 170 ℃ to obtain an internal mixed material, putting the internal mixed material into a double-screw extruder, and extruding at 155 ℃ to obtain an extruded material;
and S3, carrying out water cooling and grain cutting on the extruded material to obtain the polyethylene color master batch.
Example 2
The polyethylene color master batch with low odor and high carbon black content is prepared from the following components in parts by weight: 86g of degradable modified polyethylene powder, 7g of modified polyethylene wax micro powder, 27g of low-structure carbon black, 3.6g of bis (beta-hydroxyethyl) cocoamine and 0.5g of antioxidant; wherein the oil absorption value of the low-structure carbon black is 56cm 3 100g, particle diameter of 20nm, tinting strength of 115% and pH of 9; the antioxidant is prepared from antioxidant 264, antioxidant 168 and antioxidant 1010 according to the weight ratio of 1:2:2, mixing the components.
The preparation method of the degradable modified polyethylene powder comprises the following steps:
step one, adding 16.9g of 2-bromo-1,1-dimethoxyethane, 10.8g of 1, 4-butanediol, 0.45g of p-toluenesulfonic acid and 48mL of solvent toluene into a three-neck flask in sequence, heating to 126 ℃, carrying out heat preservation reflux stirring reaction for 17.5 hours, washing with ethyl acetate, carrying out reduced pressure distillation to obtain 2-bromo-1,3-dioxepane, adding 36mL of tetrahydrofuran and 14.8g of potassium tert-butoxide, carrying out stirring reaction for 78 minutes, cooling to room temperature, continuing stirring reaction for 11.5 hours, adding diethyl ether, filtering, washing with diethyl ether, filtering, and carrying out reduced pressure distillation on the filtrate to obtain an intermediate 1;
step two, adding 21.7g of the intermediate 1, 13.9g N-vinyl caprolactam and 69.5g of solvent toluene into a three-neck flask, adding 8.3g of organic cobalt coordination agent and 0.35g of azobisisobutyronitrile, introducing ethylene under the protection of nitrogen, heating to 76 ℃, keeping the temperature, stirring for reaction for 23 hours, carrying out reduced pressure distillation to remove the solvent, filtering, washing a filter cake with toluene for three times, drying at 71 ℃ for 19 hours to obtain a crude product, crushing the crude product, and sieving with a 20-mesh sieve to obtain degradable modified polyethylene powder; the pressure at which ethylene was passed was 23bar.
The preparation method of the modified polyethylene wax micro powder comprises the following steps:
step one, adding 7.5g of polyethylene wax and 24g of toluene into a three-neck flask, uniformly mixing and stirring, blowing nitrogen for protection, and raising in oil bathHeating to 128 ℃, adding 1.7g of vinyl acrylate, 0.5g of maleic anhydride and 0.4g of benzoyl peroxide, and carrying out heat preservation reflux reaction for 3.5 hours to obtain a mixed reaction solution; wherein the polyethylene wax has an average particle diameter of 12 μm and a density of 0.98g/cm 3 The melting point is 138 ℃;
filtering the mixed reaction solution, washing with ethyl acetate for 5 times, concentrating the filtrate under reduced pressure to remove the solvent, recrystallizing the mixed solvent of ethyl acetate and petroleum ether to obtain a modified polyethylene wax crude product, and drying and crushing the modified polyethylene wax crude product at 52 ℃ to obtain modified polyethylene wax micropowder; wherein the volume ratio of the ethyl acetate to the petroleum ether in the mixed solvent is 1:4, the recrystallization temperature is 5 ℃.
The preparation method of the polyethylene color masterbatch with low odor and high carbon black content comprises the following steps:
s1, adding degradable modified polyethylene powder, modified polyethylene wax micro powder and low-structure carbon black into a high-speed mixer, stirring at 380rpm for 23min, and then at 780rpm for 20min to obtain a dispersed master batch;
s2, uniformly mixing the dispersed master batch, bis (beta-hydroxyethyl) cocoamine and an antioxidant, putting the mixture into an internal mixer, carrying out internal mixing at 167 ℃ for 38min to obtain an internal mixed material, putting the internal mixed material into a double-screw extruder, and extruding at 160 ℃ to obtain an extruded material;
and S3, carrying out water cooling and grain cutting on the extruded material to obtain the polyethylene color master batch.
Example 3
The polyethylene color master batch with low odor and high carbon black content is prepared from the following components in parts by weight: 83g of degradable modified polyethylene powder, 8g of modified polyethylene wax micro powder, 24g of low-structure carbon black, 2g of bis (beta-hydroxyethyl) cocoamine and 0.5g of antioxidant; wherein the oil absorption value of the low-structure carbon black is 56cm 3 100g, particle size of 20nm, tinting strength of 115% and pH of 9; the antioxidant is prepared from antioxidant 264, antioxidant 168 and antioxidant 1010 according to the weight ratio of 1:2:2, mixing the components.
The preparation method of the degradable modified polyethylene powder comprises the following steps:
step one, sequentially adding 16.9g 2-bromo-1,1-dimethoxyethane, 11.4g 1, 4-butanediol, 0.48g p-toluenesulfonic acid and 51mL solvent toluene into a three-neck flask, heating to 123 ℃, carrying out heat preservation, reflux, stirring and reaction for 17 hours, washing with ethyl acetate, carrying out reduced pressure distillation to obtain 2-bromo-1,3-dioxepane, adding 38mL tetrahydrofuran and 15.5g potassium tert-butoxide, carrying out stirring reaction for 78 minutes, cooling to room temperature, continuing stirring and reaction for 11.5 hours, adding diethyl ether, filtering, washing and filtering diethyl ether, and carrying out reduced pressure distillation on filtrate to obtain an intermediate 1;
step two, adding 23.9g of the intermediate 1, 13.9g N-vinyl caprolactam and 63mL of solvent toluene into a three-neck flask, adding 9.7g of organic cobalt coordination agent and 0.31g of azobisisobutyronitrile, introducing ethylene under the protection of nitrogen, heating to 76 ℃, keeping the temperature, stirring for reaction for 23 hours, carrying out reduced pressure distillation to remove the solvent, filtering, washing a filter cake with toluene for three times, drying at 76 ℃ for 19 hours to obtain a crude product, crushing the crude product, and sieving with a 10-mesh sieve to obtain degradable modified polyethylene powder; the ethylene was passed under a pressure of 30bar.
The preparation method of the modified polyethylene wax micro powder comprises the following steps:
adding 8.6g of polyethylene wax and 23g of toluene into a three-neck flask, uniformly mixing and stirring, blowing nitrogen for protection, heating an oil bath to 124 ℃, adding 2.6g of vinyl acrylate, 0.7g of maleic anhydride and 0.6g of benzoyl peroxide, and carrying out heat preservation reflux reaction for 3.5 hours to obtain a mixed reaction solution; wherein the polyethylene wax has an average particle diameter of 15 μm and a density of 0.98g/cm 3 The melting point is 138 ℃;
filtering the mixed reaction solution, washing with ethyl acetate for 3 times, concentrating the filtrate under reduced pressure to remove the solvent, recrystallizing the mixed solvent of ethyl acetate and petroleum ether to obtain a modified polyethylene wax crude product, and drying and crushing the modified polyethylene wax crude product at 58 ℃ to obtain modified polyethylene wax micropowder; wherein the volume ratio of the ethyl acetate to the petroleum ether in the mixed solvent is 1:4, the recrystallization temperature is 10 ℃.
The preparation method of the polyethylene color master batch with low odor and high carbon black content comprises the following steps:
s1, adding degradable modified polyethylene powder, modified polyethylene wax micro powder and low-structure carbon black into a high-speed mixer, stirring for 28min at the rotating speed of 340rpm, and then stirring for 16min at the rotating speed of 760rpm to obtain a dispersed master batch;
s2, uniformly mixing the dispersed master batch, bis (beta-hydroxyethyl) cocoamine and an antioxidant, putting the mixture into an internal mixer, carrying out internal mixing at 172 ℃ for 36min to obtain an internal mixed material, putting the internal mixed material into a double-screw extruder, and extruding at 166 ℃ to obtain an extruded material;
and S3, carrying out water cooling and grain cutting on the extruded material to obtain the polyethylene color master batch.
Example 4
The polyethylene color master batch with low odor and high carbon black content is prepared from the following components in parts by weight: 92g of degradable modified polyethylene powder, 10g of modified polyethylene wax micro powder, 30g of low-structure carbon black, 4.5g of bis (beta-hydroxyethyl) cocoamine and 0.5g of antioxidant; wherein the oil absorption value of the low-structure carbon black is 56cm 3 100g, particle diameter of 20nm, tinting strength of 115% and pH of 9; the antioxidant is prepared from antioxidant 264, antioxidant 168 and antioxidant 1010 according to the weight ratio of 1:2:2, mixing the components.
The preparation method of the degradable modified polyethylene powder comprises the following steps:
step one, adding 16.9g of 2-bromo-1,1-dimethoxyethane, 10.6g of 1, 4-butanediol, 0.52g of p-toluenesulfonic acid and 47mL of solvent toluene into a three-neck flask in sequence, heating to 127 ℃, preserving heat, refluxing, stirring, reacting for 18 hours, washing with ethyl acetate, carrying out reduced pressure distillation to obtain 2-bromo-1,3-dioxepane, adding 35mL of tetrahydrofuran and 14.6g of potassium tert-butoxide, carrying out stirring reaction for 76 minutes, cooling to room temperature, continuing stirring, reacting for 12 hours, adding diethyl ether, filtering, washing and filtering the diethyl ether, and carrying out reduced pressure distillation on the filtrate to obtain an intermediate 1;
step two, adding 24.0g of intermediate 1, 13.9g N-vinyl caprolactam and 75mL of solvent toluene into a three-neck flask, adding 10g of organic cobalt coordination agent and 0.39g of azobisisobutyronitrile, introducing ethylene under the protection of nitrogen, heating to 78 ℃, keeping the temperature, stirring and reacting for 23.5 hours, carrying out reduced pressure distillation to remove the solvent, filtering, washing a filter cake with toluene for three times, drying at 76 ℃ for 19 hours to obtain a crude product, crushing the crude product, and sieving with a 20-mesh sieve to obtain degradable modified polyethylene powder; the pressure at which ethylene was passed was 30bar.
The preparation method of the modified polyethylene wax micro powder comprises the following steps:
adding 7.6g of polyethylene wax and 28g of toluene into a three-neck flask, uniformly mixing and stirring, blowing nitrogen for protection, heating an oil bath to 128 ℃, adding 2.8g of vinyl acrylate, 0.8g of maleic anhydride and 0.5g of benzoyl peroxide, and carrying out heat preservation reflux reaction for 4 hours to obtain a mixed reaction solution; wherein the polyethylene wax has an average particle diameter of 10 μm and a density of 0.98g/cm 3 The melting point is 138 ℃;
filtering the mixed reaction solution, washing with ethyl acetate for 5 times, concentrating the filtrate under reduced pressure to remove the solvent, recrystallizing the mixed solvent of ethyl acetate and petroleum ether to obtain a modified polyethylene wax crude product, and drying and crushing the modified polyethylene wax crude product at 58 ℃ to obtain modified polyethylene wax micropowder; wherein the volume ratio of the ethyl acetate to the petroleum ether in the mixed solvent is 1:6, the recrystallization temperature is 13 ℃.
The preparation method of the polyethylene color masterbatch with low odor and high carbon black content comprises the following steps:
s1, adding degradable modified polyethylene powder, modified polyethylene wax micro powder and low-structure carbon black into a high-speed mixer, stirring at a rotating speed of 400rpm for 30min, and then stirring at a rotating speed of 730rpm for 20min to obtain a dispersed master batch;
s2, uniformly mixing the dispersed master batch, bis (beta-hydroxyethyl) cocoamine and an antioxidant, adding the mixture into an internal mixer, carrying out internal mixing at 176 ℃ for 38min to obtain an internal mixed material, adding the internal mixed material into a double-screw extruder, and extruding at 165 ℃ to obtain an extruded material;
and S3, carrying out water cooling and grain cutting on the extruded material to obtain the polyethylene color master batch.
Comparative example 1
This comparative example differs from example 1 in that the degradable modified polyethylene powder was replaced with a linear low density polyethylene resin.
Comparative example 2
This comparative example differs from example 1 in that the modified polyethylene wax micropowder is replaced with polyethylene wax.
Comparative example 3
This comparative example differs from example 1 in that no bis (. Beta. -hydroxyethyl) cocoamine was added.
Performance testing
The polyethylene color master batches prepared in examples 1 to 4 and comparative examples 1 to 3 were tested for heat resistance, tensile strength and antistatic property; the heat resistance and tensile strength retention rate are respectively tested according to standard QB/T4885-2015, the antistatic performance is tested according to standard GB/T1410-2006, and the specific test results are shown in the following table:
test item Heat resistance (. Degree. C.) Tensile Strength Retention (%) Surface resistivity (omega)
Example 1 218 91.8 0.96×10 3
Example 2 214 91.6 0.94×10 3
Example 3 211 90.9 0.92×10 3
Example 4 208 90.7 0.91×10 3
Comparative example 1 176 82.4 0.89×10 3
Comparative example 2 183 83.7 0.87×10 3
Comparative example 3 207 88.4 0.82×10 3
As can be seen from the above table, the polyethylene color masterbatch particles prepared by the example of the method are superior to the comparative example in heat resistance, tensile strength retention rate and surface resistivity, which shows that the heat resistance, tensile strength and antistatic property are superior to the comparative example. Comparative example 1 because the degradable modified polyethylene powder is replaced by the linear low density polyethylene resin, the degradable modified polyethylene powder has no aromatic odor and cannot exert good degradability, processability and compatibility, and the comprehensive performance of the prepared polyethylene color master batch is obviously reduced; compared with the prior art, the modified polyethylene wax micropowder is replaced by the polyethylene wax, so that the molecular weight is reduced, an ester group structure is not formed, and the heat resistance and the strength are reduced to a certain extent; in the comparative example 3, as the bis (beta-hydroxyethyl) cocoamine is not added, the wetting and antistatic effects are reduced, the dispersion of the low-structure carbon black is not facilitated, and the comprehensive performance is reduced to some extent.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the following claims.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (8)

1. The polyethylene color master batch with low odor and high carbon black content is characterized by being prepared from the following components in parts by weight: 72-95 parts of degradable modified polyethylene powder, 3-10 parts of modified polyethylene wax micro powder, 18-32 parts of low-structure carbon black, 1-5 parts of bis (beta-hydroxyethyl) cocoamine and 0.1-0.6 part of antioxidant; the degradable modified polyethylene powder is prepared by reacting 2-bromo-1,1-dimethoxyethane and 1,4-butanediol in the presence of toluene and potassium tert-butoxide as solvents for catalysis and post-processing to obtain an intermediate 1, and polymerizing the intermediate 1, N-vinyl caprolactam, an organic cobalt complexing agent and ethylene under the initiation of azobisisobutyronitrile and performing post-processing; the modified polyethylene wax micropowder is obtained by polymerizing polyethylene wax, vinyl acrylate and maleic anhydride under the initiation of benzoyl peroxide and carrying out post-treatment.
2. The polyethylene color masterbatch with low odor and high carbon black content according to claim 1, wherein the preparation method of the degradable modified polyethylene powder comprises the following steps:
step one, sequentially adding 2-bromo-1,1-dimethoxyethane, 1,4-butanediol, p-toluenesulfonic acid and a solvent toluene into a three-neck flask, heating to 115-130 ℃, preserving heat, refluxing, stirring, reacting for 16-18 hours, washing with ethyl acetate, carrying out reduced pressure distillation to obtain 2-bromo-1,3-dioxepane, adding tetrahydrofuran and potassium tert-butoxide, carrying out stirring reaction for 60-80 min, cooling to room temperature, continuing stirring, reacting for 10-12 hours, adding diethyl ether, filtering, washing with diethyl ether, filtering, and carrying out reduced pressure distillation on the filtrate to obtain an intermediate 1;
and step two, adding the intermediate 1, N-vinyl caprolactam and a solvent toluene into a three-neck flask, adding an organic cobalt coordination agent and azodiisobutyronitrile, introducing ethylene under the protection of nitrogen, heating to 68-80 ℃, keeping the temperature, stirring, reacting for 20-24 hours, carrying out reduced pressure distillation to remove the solvent, filtering, washing a filter cake with toluene for three times, drying at 65-78 ℃ for 16-20 hours to obtain a crude product, crushing the crude product, and sieving with a 10-20-mesh sieve to obtain the degradable modified polyethylene powder.
3. The polyethylene color masterbatch with low odor and high carbon black content as claimed in claim 2, wherein the molar ratio of 2-bromo-1,1-dimethoxyethane to 1,4-butanediol, p-toluenesulfonic acid, potassium tert-butoxide in step one is 1:1.1 to 1.3:0.01 to 0.03: 1.2-1.4,1,4-butanediol, solvent toluene and tetrahydrofuran in a dosage ratio of 9g:40mL of: 30mL.
4. The polyethylene color masterbatch with low odor and high carbon black content according to claim 2, wherein the ethylene inlet pressure in the second step is 20-30 bar, and the molar ratio of the intermediate 1 to the N-vinyl caprolactam is 1.5-2.2: 1, the dosage of the organic cobalt coordination agent, the azodiisobutyronitrile and the solvent toluene is 0.4 to 0.8 time, 0.01 to 0.03 time and 2 to 6 times of the weight of the N-vinyl caprolactam respectively.
5. The polyethylene color masterbatch with low odor and high carbon black content according to claim 1, wherein the preparation method of the modified polyethylene wax micropowder comprises the following steps:
step one, adding polyethylene wax and toluene into a three-neck flask, uniformly mixing and stirring, blowing nitrogen for protection, heating in an oil bath to 115-130 ℃, adding vinyl acrylate, maleic anhydride and benzoyl peroxide, and carrying out heat preservation reflux reaction for 2-4 hours to obtain a mixed reaction solution;
filtering the mixed reaction liquid, washing with ethyl acetate for 3-5 times, concentrating the filtrate under reduced pressure to remove the solvent, recrystallizing the mixed solvent of ethyl acetate and petroleum ether to obtain a modified polyethylene wax crude product, and drying and crushing the modified polyethylene wax crude product at 45-60 ℃ to obtain modified polyethylene wax micropowder; wherein the volume ratio of the ethyl acetate to the petroleum ether in the mixed solvent is 1:3 to 6, and the recrystallization temperature is 3 to 15 ℃.
6. The polyethylene color masterbatch with low odor and high carbon black content according to claim 5, wherein the weight ratio of polyethylene wax, toluene, vinyl acrylate, maleic anhydride and benzoyl peroxide in the first step is 6-10: 22 to 30:1 to 3: 0.4-0.8: 0.2 to 0.5; the polyethylene wax has an average particle diameter of 5-15 μm and a density of 0.98g/cm 3 The melting point was 138 ℃.
7. The low odor high carbon black containing polyethylene color masterbatch of claim 1, wherein said low structure carbon black has an oil absorption of 56cm 3 100g, particle diameter of 20nm, tinting strength of 115% and pH of 9; the antioxidant is prepared from antioxidant 264, antioxidant 168 and antioxidant 1010 according to the weight ratio of 1:2:2, mixing the components.
8. A method for preparing the low odor high carbon black content polyethylene color masterbatch according to any one of claims 1-7, comprising the steps of:
s1, adding degradable modified polyethylene powder, modified polyethylene wax micro powder and low-structure carbon black into a high-speed mixer, stirring at the rotating speed of 200-400 rpm for 20-30 min, and then stirring at the rotating speed of 650-800 rpm for 10-20 min to obtain a dispersed master batch;
s2, uniformly mixing the dispersed master batch, bis (beta-hydroxyethyl) cocoamine and an antioxidant, adding the mixture into an internal mixer, carrying out internal mixing at 160-180 ℃ for 25-40 min to obtain an internal mixed material, adding the internal mixed material into a double-screw extruder, and extruding at 145-170 ℃ to obtain an extruded material;
and S3, carrying out water cooling and grain cutting on the extruded material to obtain the polyethylene color master batch.
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JPS6320337A (en) * 1986-07-11 1988-01-28 Nippon Petrochem Co Ltd Resin composition for crosslinking/expansion
CN106046479A (en) * 2016-06-14 2016-10-26 中广核拓普（四川）新材料有限公司 High carbon black dispersity polyethylene aggregates and preparation method thereof
CN112143184A (en) * 2020-09-29 2020-12-29 青岛周氏塑料包装有限公司 Biodegradable color master batch and preparation method thereof
WO2021205123A1 (en) * 2020-04-09 2021-10-14 Centre National De La Recherche Scientifique Process for the free radical polymerization of thionolactones or thionocarbonates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6320337A (en) * 1986-07-11 1988-01-28 Nippon Petrochem Co Ltd Resin composition for crosslinking/expansion
CN106046479A (en) * 2016-06-14 2016-10-26 中广核拓普（四川）新材料有限公司 High carbon black dispersity polyethylene aggregates and preparation method thereof
WO2021205123A1 (en) * 2020-04-09 2021-10-14 Centre National De La Recherche Scientifique Process for the free radical polymerization of thionolactones or thionocarbonates
CN112143184A (en) * 2020-09-29 2020-12-29 青岛周氏塑料包装有限公司 Biodegradable color master batch and preparation method thereof

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