阅读说明：本技术 一种高炭黑含量高熔体流动速率通用型色母及制备方法 (Universal color master batch with high carbon black content and high melt flow rate and preparation method thereof ) 是由 张军 苏克顺 毛泽鹏 贾宇 杨帆 杨张滨 杨念新 杨气鹏 高玉巧 宋金萍 杨正花 于 2020-12-08 设计创作，主要内容包括：本发明公开了一种高炭黑含量高熔体流动速率通用型色母及制备方法。该通用型色母中炭黑质量含量高达50～60％时仍然具有较高熔体流动速率,易于在不同粘度的的聚合物熔体中分散,尤其是在高温下熔体具有较低粘度的PA、PET体系。同时,该通用型炭黑色母粒既适用于PE、PP、PS等非极性或弱极性聚合物体系,也适用于PA、PVC、PET、ABS等极性聚合物体系,是一种真正意义上的通用型炭黑母粒。本发明的高炭黑含量高熔体流动速率通用型色母,其是由以下质量配比的原料制成：氧化聚乙烯蜡15～30份、聚烯烃树脂10～20份、氯化聚乙烯3～5份、高结构度炭黑50～60份、稳定剂0.5～1.0份。(The invention discloses a general color master batch with high carbon black content and high melt flow rate and a preparation method thereof. The universal color master batch still has a high melt flow rate when the mass content of the carbon black reaches 50-60%, is easy to disperse in polymer melts with different viscosities, and particularly has a PA and PET system with low viscosity at high temperature. Meanwhile, the universal carbon black master batch is suitable for non-polar or weakly polar polymer systems such as PE, PP, PS and the like, is also suitable for polar polymer systems such as PA, PVC, PET, ABS and the like, and is a real universal carbon black master batch. The general color master batch with high carbon black content and high melt flow rate is prepared from the following raw materials in parts by mass: 15-30 parts of oxidized polyethylene wax, 10-20 parts of polyolefin resin, 3-5 parts of chlorinated polyethylene, 50-60 parts of high-structure-degree carbon black and 0.5-1.0 part of stabilizer.)

1. The general color master batch with high carbon black content and high melt flow rate is characterized by being prepared from the following raw materials in parts by mass:

2. the high-carbon-black-content high-melt-flow-rate universal color master batch as claimed in claim 1, wherein the oxidized polyethylene wax is one or a combination of powdery products obtained by high-temperature oxidation of high-density polyethylene and having a viscosity of 4000-8000 mPa.s at 140 ℃ and an acid value of 10-40 mg KOH/g.

3. The high carbon black content high melt flow rate universal color masterbatch according to claim 1, wherein the polyolefin resin is one or a combination of three different polyethylene products selected from the group consisting of powdered low density polyethylene, linear low density polyethylene, high density polyethylene, and homo-polypropylene.

4. The high carbon black content high melt flow rate universal color masterbatch according to claim 3, wherein the powdered polyethylene is a resin with a melt mass flow rate of 100-200 g/10min under a load of 2160g and a test temperature of 190 ℃; the powdery polypropylene is resin with melt mass flow rate of 100-200 g/10min under the conditions of 2160g of load and 230 ℃ of test temperature.

5. The universal color master batch with high carbon black content and high melt flow rate according to claim 1, wherein the chlorinated polyethylene is prepared from powdery high-density polyethylene and chlorine gas by an aqueous phase suspension process, and is a chlorinated polyethylene resin with a random structure, wherein the mass fraction of chlorine atoms is 33-38%, the Mooney viscosity is 45-55, and the residual melting enthalpy is 0-5J/g.

6. The universal color master batch with high carbon black content and high melt flow rate as claimed in claim 1, wherein the high-structure-degree carbon black has an original particle size of 15-20 nm and a specific surface area of 100-120 m²(iv) carbon black having an oil absorption value of 105 to 125mL/g and a coloring strength of not less than 100.

7. The high carbon black content high melt flow rate universal color masterbatch of claim 1 wherein the stabilizer is a combination of a metal soap heat stabilizer for stabilizing the chlorinated polyethylene resin and an antioxidant for preventing the polyolefin resin from oxidative degradation.

8. The high carbon black content high melt flow rate universal color masterbatch of claim 7, wherein the mass ratio of the metal soap heat stabilizer to the antioxidant is 1:1, wherein the metal soap heat stabilizer is barium stearate or calcium stearate; the antioxidant is the combination of hindered phenol main antioxidant and phosphite ester auxiliary antioxidant.

9. A process for preparing a high carbon black content high melt flow rate universal color masterbatch according to any of claims 1-8 comprising the steps of:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin and a stabilizer in the raw materials of the formula for 2min at a low speed (below 500 rpm) in a high-speed mixer, starting the high speed (above 1000 rpm) to stir the materials to 55 +/-5 ℃, discharging the materials to the mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliary agent to a diluting auxiliary agent bin when the temperature is reduced to 40 +/-5 ℃;

preparing a carbon black master batch:

blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey polyolefin resin, oxidized polyethylene wax and high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing mill for blending, wherein the rotating speed of the double-rotor continuous mixing mill is controlled to be 500-550 rpm, the temperature of the mixing mill is 190-210 ℃ when the polyolefin resin is powdery homopolymerized polypropylene, and the temperature of the mixing mill is 150-180 ℃ when the polyolefin resin is powdery polyethylene;

granulating by a single-screw extruder: and (3) mixing the materials after blending in the double-rotor continuous mixing roll, chlorinated polyethylene resin and a stabilizer by a single-screw extruder with side feeding, uniformly mixing, and finally obtaining the universal color master batch with high carbon black content and high melt flow rate by an underwater granulation process of a granulator.

10. The preparation method of the universal color master batch with high carbon black content and high melt flow rate according to claim 9, wherein the screw rotation speed of the single screw extruder is 70-80 rpm, wherein when the polyolefin resin is powdery homo-polypropylene, the temperature of the conveying section of the single screw extruder is controlled to be 120-130 ℃, and the temperature of the plasticizing section and the head of the single screw extruder are controlled to be 210-220 ℃; when the polyolefin resin is polyethylene, the temperature of the conveying section of the single-screw extruder is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head are controlled to be 160-190 ℃.

Technical Field

The invention relates to a carbon black master batch and a preparation method thereof, in particular to a high-carbon-black-content general-purpose master batch with high melt flow rate and a preparation method thereof.

Background

Carbon black is an important functional filler, and has wide application in the processing and application fields of polymer materials such as synthetic rubber, synthetic resin, synthetic fiber, paint, adhesive and the like, and simultaneously, the carbon black has various varieties and large performance difference, and the requirements and the functions of the carbon black are different in different materials and application fields. For example, in the formulation of rubber materials, carbon black is mainly used as a reinforcing filler, and high wear-resistant carbon black, semi-reinforcing carbon black, spray carbon black, fast extrusion carbon black, and the like can be selected according to rubber performance requirements and use conditions. The using amount of the carbon black in the rubber composition is larger, and in a general rubber formula, the mass of the carbon black can reach 50% of the using amount of the rubber, and even exceeds the using amount of the rubber. However, carbon black is mainly used as an ultraviolet light shielding agent and a black coloring agent in the industries of plastics, fibers and the like, and with the economic development and the technical progress in recent years, the demand for carbon black is remarkably increased, and the application field of the carbon black is also continuously expanded. When the carbon black is used in a plastic and fiber formula, the using amount of the carbon black is far lower than that of a rubber material formula, the mass of the carbon black is usually only 0.5-5% of that of a plastic or fiber matrix resin, and the low using amount of the carbon black can be conveniently added into the plastic or fiber matrix resin at a low cost and uniformly dispersed, so that the problem of continuous exploration and improvement in the industry is continuously sought.

As is known, carbon black can exert excellent ultraviolet light shielding, coloring and other properties only by being well and uniformly dispersed in a high polymer material, and simultaneously, the mechanical properties of a matrix material cannot be obviously reduced. If a small amount of carbon black powder is simply mixed with the granular resin and then the carbon black can not be well dispersed in the matrix resin through common plastic and fiber processing and forming methods such as extrusion, injection, blow molding, calendering, spinning and the like, the product performance is poor, the use requirement can not be met, and the product is serious and even difficult to form; in the carbon black processing process, dust flies to pollute equipment and environment, and the conductivity of part of carbon black varieties even damages the equipment. Similarly, if a small amount of carbon black powder (0.5-5%) is mixed with the granular resin and then pelletized by a common double-screw extruder for plastic modification, the carbon black still cannot be well dispersed in the matrix resin, and the pelletizing process also causes the increase of processing cost. This is because carbon black, which is an inorganic material, has low adhesion to the surface of an organic polymer matrix, and because carbon black has a small apparent density and a large specific surface area, it is difficult to directly uniformly disperse carbon black by processing equipment for general plastic products. This phenomenon is more remarkable for high-structure carbon black having a small particle diameter in the as-formed state and a large specific surface area. The method for solving the problem of the dispersibility of the carbon black in the products such as plastics, fibers and the like usually adopts special equipment and a special formula to prepare the carbon black master batch firstly, and the carbon black can be uniformly dispersed in matrix resin in the processing engineering of the plastics or the fiber products by adding the master batch containing the pre-dispersed carbon black. The method helps to keep the performance of the plastic or fiber stable, does not cause the performance of the product to be remarkably reduced due to the addition of the carbon black, and simultaneously avoids the processing cost increase caused by the granulation of the matrix resin and the carbon black.

In the prior art, a formula for preparing color master batches usually comprises polymer matrix resin, pigments (carbon black and the like), a lubricant, a dispersant, a stabilizer, an antioxidant and the like. For example, patent publication No. CN 102206272a discloses a method for preparing carbon black masterbatch by compounding carbon black, a dispersant, an antioxidant, a processing aid, etc. with a polyolefin carrier resin composed of 15-80 parts of High Density Polyethylene (HDPE), 0-20 parts of Linear Low Density Polyethylene (LLDPE) and 0-10 parts of ethylene-vinyl acetate copolymer (EVA), which can be widely applied to HDPE gas pipelines, polypropylene (PP) purified water delivery pipelines, etc. as an ultraviolet shielding agent and a black colorant. The patent publication No. CN 85105419 discloses a polyvinyl chloride (PVC) plastic coloring master batch, which is characterized in that the basic formula is as follows: 100 parts of PVC, 1-60 parts of a diffusion lubricant, 1-15 parts of a stabilizer, 20-100 parts of a plasticizer and a proper amount of pigment, wherein the PVC is used as a carrier coloring master batch and is suitable for coloring PVC wires and cables and can also be used for coloring other PVC products. The patent publication No. CN 103881330A, CN 109836785A and other patents disclose a polyethylene terephthalate (PET) color master batch and a preparation method thereof, the PET color master batch mainly comprises auxiliary agents such as PET matrix resin, slipping agent, dispersing agent, antistatic agent, pigment, antioxidant and the like, and the color master batch is mainly used for processing and using performance requirements of sheets such as PET and the like. The publication No. CN108329648A discloses a preparation method of an acrylonitrile-butadiene-styrene terpolymer resin (ABS) weather-resistant color master batch, which mainly comprises 25-35% of ABS resin, 50-60% of titanium dioxide, 2-3% of a dispersing agent, 1.5-2.5% of polyethylene wax, 2-3% of an ultraviolet absorbent, 5-9% of an antioxidant and 0.5-1.5% of a hindered amine light stabilizer, and the ABS color master batch can be mainly used for coloring ABS plastics and can also obviously improve the weather resistance of the ABS plastic materials. In the preparation process of the color master batch (carbon black master batch), the selection of the type of the matrix resin determines the polymer system suitable for the later period, for example, the color master batch (carbon black master batch) prepared by selecting polyolefin as the matrix resin is mainly suitable for the formulation and processing of polyolefin plastic products such as polyethylene, polypropylene and the like, and similarly, if the color master batch (carbon black master batch) prepared by selecting PVC, PET, ABS and acrylonitrile-styrene-acrylate terpolymer (ASA) as the matrix resin is mainly respectively corresponding to the formulation and processing of the plastic products such as PVC, PET, ABS, ASA and the like.

Because the color master batch (carbon black master batch) prepared by adopting the nonpolar polyolefin as the matrix resin is mainly suitable for nonpolar or weakly polar polymer systems such as PE, PP and the like, if the color master batch (carbon black master batch) is used for polar polymer systems such as Polyamide (PA), PVC, PET, ABS and the like, the color master batch (carbon black master batch) has poor dispersion and poor coloring effect, and even the mechanical properties such as the tensile strength, the elongation at break, the impact strength and the like of the polymer are reduced; or the color master batch (carbon black master batch) prepared by adopting polar polymer matrix resins such as PA, PVC, PET, ABS and the like is used for non-polar or weakly polar polymer systems such as PE, PP and the like and faces the same problem. In order to solve the problems commonly existing in the industry, the concept of universal color master batches is provided. The universal color master batch is also called universal color master batch, namely the prepared color master batch is suitable for non-polar or weakly-polar polymer systems such as PE, PP, Polystyrene (PS) and the like, and is also suitable for polar polymer systems such as PA, PVC, PET, ABS, ASA and the like. Therefore, the selection and use of the base material and the functional auxiliary agent of the universal color master batch (carbon black master batch) are very important, the early universal color master batch (carbon black master batch) is prepared by mixing turpentine serving as a carrier with a pigment (black body), and the universal color master batch (carbon black master batch) can be used in PE, PP, PS, PA, PVC, PET and ABS plastic products by utilizing certain miscibility of small-molecule turpentine and polar and nonpolar polymers. However, the universal color master batch (carbon black master batch) prepared from turpentine is eliminated due to a series of problems that special smell is generated due to volatile turpentine, the strength of the master batch particles is low, and the later use is influenced due to fragility. In order to further improve the performance of universal color masterbatch (carbon black masterbatch), the publication No. CN 111040458A discloses a universal modified rosin liquid color masterbatch composition and a preparation method thereof, the main components of the universal modified rosin liquid color masterbatch composition comprise 30-70% of modified rosin thickening liquid carrier and 30-70% of plastic additive, and the universal modified rosin liquid color masterbatch composition has good fluidity in a conduit during storage, and can be used for various liquid polymer systems such as coating, adhesives and the like. Because the final product is not in a regular particle form, the universal modified rosin liquid color master batch composition is not suitable for being used in conventional plastic molding processes such as extrusion, injection, calendering and the like. Publication No. CN108485245A also discloses a universal black master batch and a preparation method thereof, wherein the black master batch comprises the following components in percentage by weight: 40-50% of carbon black, 46-56% of linear low-density polyethylene powder, 1-3% of vinyl bis-stearamide and 1-3% of zinc stearate. Obviously, the universal black master batch carrier resin is linear low-density polyethylene, is mainly suitable for systems such as PE, PP and the like, and is not suitable for systems such as PA, PVC, PET, ABS and the like. Publication No. CN 107828169A discloses a formula of a high-capacity universal plastic color master batch and a production process thereof, wherein the formula comprises the following raw materials in parts by weight: 48-72 parts of acrylic resin, 36-48 parts of polyvinyl chloride resin, 2-5 parts of a pigment A, 3-8 parts of a pigment B, 5-12 parts of diatomite, 1-2 parts of stearic acid monoglyceride, 1-2 parts of fatty alcohol-polyoxyethylene ether, 3-6 parts of polyethylene glycol, 0.1-0.3 part of an ultraviolet absorbent and 0.6-1.6 parts of an antioxidant. The carrier resin of the universal color master batch adopts polar acrylic resin and PVC resin, is not suitable for PE and PP systems, but can be suitable for polar polymer systems such as PVC, ABS and the like. The analysis of the above situation shows that the universal color master batch used in the existing market is not a universal color master batch in the true sense, and can not completely meet the use requirements of non-polar polymers and polar polymer systems.

In summary, in the preparation process of the universal color master batch, especially the universal color master batch with high carbon black content and high melt flow rate, the products prepared by the prior art have certain limitations, and no universal color master batch which can truly meet the use requirements of a non-polar polymer and a polar polymer system simultaneously exists in the market. Meanwhile, when the mass content of carbon black reaches 40% or more, the melt flow rate of the conventional color masterbatch is low, for example, the publication of patent No. CN 102206272a discloses that the MFR of a carbon masterbatch with polyethylene as a carrier carbon black content of 40% is 30-50 g/10min at a temperature of 190 ℃ under a load of 21.6kg, and the carbon masterbatch with the low melt flow rate is not suitable for being used in low-melt polymers such as PA, PET and the like. Therefore, a universal color master batch or universal color master batch with high carbon black content and high melt flow rate is designed, and can simultaneously meet the use requirements of a non-polar polymer and a polar polymer system, the application of the color master batch can be further expanded, and the requirements of the industry are met.

Disclosure of Invention

The invention aims to solve the problems and the defects in the prior art and provide a universal color master batch with high carbon black content and high Melt Flow Rate (MFR). The universal color master batch still has a high melt flow rate (MFR is more than 70g/10min and even more than 100g/10min when the load is 21.6kg and the test temperature is 190 ℃ (containing PE) or the test temperature is 230 ℃ (containing PP)) when the mass content of the carbon black in the universal color master batch is up to 50-60 percent, and is easy to disperse in polymer melts with different viscosities, especially PA and PET systems with low viscosities in the melts at high temperatures. Meanwhile, the universal carbon black master batch is suitable for non-polar or weakly polar polymer systems such as PE, PP, PS and the like, is also suitable for polar polymer systems such as PA, PVC, PET, ABS and the like, and is a real universal carbon black master batch.

The invention also provides a preparation method of the universal color master batch with high carbon black content and high melt flow rate, wherein the method comprises the steps of firstly uniformly blending the oxidized polyethylene wax, the polyolefin resin and the high-structure-degree carbon black by a double-rotor continuous mixing roll, further uniformly mixing the mixture with the chlorinated polyethylene resin, the stabilizer and other additives by a single-screw extruder with a side feeding device, and then carrying out an underwater pelletizing process to obtain a final product.

The invention is realized by the following technical scheme:

the general color master batch with high carbon black content and high melt flow rate is prepared from the following raw materials in parts by mass:

the general color master batch with high carbon black content and high melt flow rate has the further technical scheme that the oxidized polyethylene wax is one or a combination of powdery products which are obtained by high-temperature oxidation of high-density polyethylene (HDPE) and have the viscosity (Brookfield) of 4000-8000 mPa.s at 140 ℃ and the acid value of 10-40 mg KOH/g. The oxidized polyethylene wax with a certain acid value is selected and used on the basis of considering that the oxidized polyethylene wax has certain compatibility with non-polar polymers, low-polar polymers and polar polymers, so that the condition that carbon black master batches prepared by selecting polyolefin matrix resins such as polyethylene, polypropylene and the like are only suitable for the non-polar polymers or the low-polar polymers and are not suitable for the polar polymers is avoided; meanwhile, the oxidized polyethylene wax also has the function of improving the dispersibility of the carbon black in the process of preparing the carbon black master batch.

The general color master batch with high carbon black content and high melt flow rate has the further technical scheme that the polyolefin resin is a combination of one or three different polyethylene products of powdery Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE) and homo-polypropylene (PP). The further technical scheme is that the powder polyethylene is resin with melt mass flow rate of 100-200 g/10min under the conditions of load of 2160g and test temperature of 190 ℃; the powdery polypropylene is resin with melt mass flow rate of 100-200 g/10min under the conditions of 2160g of load and 230 ℃ of test temperature.

The general color master batch with high carbon black content and high melt flow rate is further prepared from the chlorinated polyethylene by using a water phase suspension method process, wherein the chlorinated polyethylene is a chlorinated polyethylene resin with a random structure, the chlorinated polyethylene resin is prepared from powdery high-density polyethylene and chlorine gas, the mass fraction of chlorine atoms is 33-38%, the Mooney viscosity is 45-55, and the residual melting enthalpy is 0-5J/g. Mooney viscosity measurement: the corresponding test values when the rubber is preheated for 1min and rotated for 4min are usually expressed by ML (1+4)120 ℃ under the condition of 2 r/min by selecting a large rotor at a certain temperature (120 ℃ in the invention). The randomly chlorinated polyethylene resin with the chlorine atom mass fraction of 33-38% is selected and used in the carbon black master batch formula, and the two main functions are as follows: the structure of the copolymer is equivalent to that of an ethylene-vinyl chloride random copolymer, and the copolymer has good compatibility with non-polar or low-polar polymers such as polyethylene, polypropylene and polystyrene and also has good compatibility with polar polymers such as polyamide, polyester, polyvinyl chloride, ABS and other resins; secondly, the chlorinated polyethylene resin with the structure is a compatilizer of a nonpolar (weak polarity) polymer-polar polymer blend, and can improve the compatibility problem when a small amount of carbon black master batches of polyethylene and polypropylene resin are used in polar polymer products. Due to the high elasticity and high adhesiveness of the chlorinated polyethylene resin, the defects that the final carbon black master batch product has irregular particle size and is easy to break in the processes of packaging, transportation and use, thereby influencing later-stage use and the like caused by the use of more oxidized polyethylene wax are overcome.

The general color master batch with high carbon black content and high melt flow rate has the further technical scheme that the high-structure-degree carbon black refers to the original-state particle size of 15-20 nm and the specific surface area of 100-120 m²(iv) carbon black having an oil absorption value of 105 to 125mL/g and a coloring strength of not less than 100.

The general color master batch with high carbon black content and high melt flow rate has the further technical scheme that the stabilizer is the combination of a metal soap heat stabilizer for stabilizing chlorinated polyethylene resin and an antioxidant for preventing polyolefin resin from being oxidized and degraded. The further technical scheme is that the mass ratio of the metal soap heat stabilizer to the antioxidant is 1:1, wherein the metal soap heat stabilizer is barium stearate or calcium stearate; the antioxidant is a combination of hindered phenol primary antioxidant (such as antioxidant 1010) and phosphite ester secondary antioxidant (such as antioxidant 168), and the lubricating effect of the metal soap heat stabilizer also has the effect of improving the dispersibility of the carbon black.

The preparation method of the universal color master batch with high carbon black content and high melt flow rate comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin and a stabilizer in the raw materials of the formula for 2min at a low speed (below 500 rpm) in a high-speed mixer, starting the high speed (above 1000 rpm) to stir the materials to 55 +/-5 ℃, discharging the materials to the mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliary agent to a diluting auxiliary agent bin when the temperature is reduced to 40 +/-5 ℃;

preparing a carbon black master batch:

blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey polyolefin resin, oxidized polyethylene wax and high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing mill for blending, wherein the rotating speed of the double-rotor continuous mixing mill is controlled to be 500-550 rpm, the temperature of the mixing mill is 190-210 ℃ when the polyolefin resin is powdery homopolymerized polypropylene, and the temperature of the mixing mill is 150-180 ℃ when the polyolefin resin is powdery polyethylene;

granulating by a single-screw extruder: and (3) mixing the materials after blending in the double-rotor continuous mixing roll, chlorinated polyethylene resin and a stabilizer by a single-screw extruder with side feeding, uniformly mixing, and finally obtaining the universal color master batch with high carbon black content and high melt flow rate by an underwater granulation process of a granulator.

The preparation method of the universal color master batch with high carbon black content and high melt flow rate has the further technical scheme that the screw rotating speed of the single screw extruder is 70-80 rpm, wherein when the polyolefin resin is powdery homo-polypropylene, the temperature of the conveying section of the single screw extruder is controlled to be 120-130 ℃, and the temperature of the plasticizing section and the temperature of a machine head are controlled to be 210-220 ℃; when the polyolefin resin is polyethylene, the temperature of the conveying section of the single-screw extruder is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head are controlled to be 160-190 ℃. The chlorinated polyethylene resin, the stabilizer and other additives are not added in the double-rotor continuous mixing roll, so that firstly, dehydrochlorination reaction of the chlorinated polyethylene resin in the double-rotor continuous mixing roll due to high-temperature strong shearing action can be avoided, and the stability of the structure and the performance of the chlorinated polyethylene is kept; and secondly, the molecular chain of the polyolefin resin is broken to generate further degradation just by utilizing the high-temperature strong shearing action in the double-rotor continuous mixing mill, namely, the mobility of the carbon black master batch is improved by reducing the molecular weight of the polyolefin, so that the dispersibility of the carbon black master batch in the later use process is improved, and if the antioxidant in the stabilizer is added in the double-rotor continuous mixing mill in advance, the molecular chain breaking of the polyolefin resin is stopped in advance. However, chlorinated polyethylene resin, metal soap heat stabilizer and main/auxiliary antioxidant are added during granulation by a single screw extruder, and the stability of the structure and performance of the chlorinated polyethylene resin is kept mainly by utilizing the interaction of the chlorinated polyethylene resin and the metal soap heat stabilizer; the main/auxiliary antioxidant is utilized to stop in the single screw extruder, and degraded polyethylene and polypropylene low-molecular free radicals are generated in the double-rotor continuous mixing roll, so that the flow rate of the prepared carbon black master batch melt is relatively stable, and the control of the product quality and the relative stability in the later use process are facilitated.

Compared with the prior art, the invention has the following beneficial effects:

the invention overcomes the following defects mainly existing in the preparation of carbon black master batches in the prior art and is creatively improved: firstly, the advantages and the existence of the universal carbon black master batch are prepared by combining micromolecular liquid such as turpentine and the like as a carrierThe inventor has used solid micromolecules such as polyethylene wax, paraffin wax and the like as carriers to prepare the universal color master batch, because low molecular solids such as polyethylene wax, paraffin wax and the like usually have lower melting points (100 ℃), and the low molecular solids melted into liquid at high temperature can be used as an adhesive to mix pigments such as carbon black and the like together, and then the liquid is cooled to room temperature for crystallization or solidification to prepare the universal color master batch, thereby overcoming the defects of odor and the like existing in turpentine as carriers. However, low molecular weight substances such as polyethylene wax and paraffin wax generally have a number average molecular weight of 1000 to 3000, low self-strength, and particularly high brittleness. If the universal color master batch particles prepared by completely adopting low molecules such as polyethylene wax, paraffin wax and the like as carriers are lower in strength and higher in brittleness, the color master batch particles are fragile or irregular in particle shape in the processes of production, storage, transportation and later use, and the use effect and performance are finally influenced. Therefore, a method of using oxidized polyethylene wax with a special structure as a carrier and combining with other resin is creatively proposed. Secondly, the prior art adopts the polymer as a carrier, so that a product with high carbon black content (the mass content of the carbon black is less than or equal to 50 percent) cannot be prepared, or the prepared product has low melt flow rate (the MFR is less than or equal to 60g/10min when the load is 21.6kg, the testing temperature is 190 ℃ (containing PE) or the testing temperature is 230 ℃ (containing PP)) although the mass content of the carbon black reaches 50 percent. The invention provides a high-carbon black general-purpose color master batch which is prepared by using oxidized polyethylene wax (the Brookfield viscosity at 140 ℃ is 4000-8000 mPa.s) with moderate molecular weight obtained by high-temperature oxidation of HDPE as a main carrier and using high-mass flow rate polyethylene resin (2160g, the MFR at 190 ℃ is 100-200 g/10min) and polypropylene resin (2160g, the MFR at 230 ℃ is 100-200 g/10min) in a certain proportion together. Although the carbon black master batch obtained by using the oxidized polyethylene wax with moderate molecular weight and the polyolefin with high melt flow rate as the carrier is used for improving the problems of frangibility or irregular particle shape and the like of the carbon black master batch in the processes of production, storage, transportation and later use due to the single use of the oxidized polyethylene wax, the defects of poor particle regularity, frangibility and the like of the carbon black master batch are not completely solved, and a small amount of chlorine atom with the mass fraction of 33-38 percent and the Mooney viscosity ML (1+4) at 120 ℃ are added45-55, and 0-5J/g residual fusion enthalpy, and effectively solves the problem by using the chlorinated polyethylene resin with a random structure as a carrier resin. Selecting the randomly chlorinated polyethylene resin with the chlorine atom mass fraction of 33-38% to have two functions: the structure of the copolymer is equivalent to that of an ethylene-vinyl chloride random copolymer, and the copolymer has good compatibility with non-polar or low-polar polymers such as polyethylene, polypropylene and polystyrene and also has good compatibility with polar polymers such as polyamide, polyester, polyvinyl chloride, ABS and other resins; secondly, the chlorinated polyethylene resin with the structure is a compatilizer of a nonpolar (weak polarity) polymer-polar polymer blend, and can improve the compatibility problem when a small amount of carbon black master batches of polyethylene and polypropylene resin are used in polar polymer products. The random chlorinated polyethylene resin with the chlorine content of 33-38% obtained by adopting Small group molar attraction constant estimation method has the solubility parameter of 18.76-19.05 (J/cm)³)^1/2A solubility parameter between 16.2 and 16.6 (J/cm) for typical non-polar polymers such as polyethylene³)^1/2And the solubility parameter of polypropylene is 15.8-16.2 (J/cm)³)^1/2The solubility parameter of the copolymer is 19.4-20.5 (J/cm) compared with that of a typical polar polymer such as polyvinyl chloride³)^1/2The solubility parameter of the polyethylene terephthalate is 21.3-21.9 (J/cm)³)^1/2Further proves the scientificity and feasibility of the selection. And selecting and using oxidized polyethylene wax with an acid value of 10-40 mg KOH/g based on considering that the carrier resin has certain compatibility with nonpolar, weakly polar and polar polymers, so that the condition that carbon black master batches prepared by singly selecting polyethylene and polypropylene matrix resin are only suitable for nonpolar or weakly polar polymer products and are not suitable for polar polymer products is avoided. In addition, the oxidized polyethylene wax containing a certain acid value is more suitable for polar polymer systems such as PA, PET, PVC, ABS and the like, so that the general color master batch carrier resin contains the oxidized polyethylene wax with a partial polarity and polyethylene (polypropylene) with a partial non-polarity, and simultaneously contains chlorinated polyethylene resin with good compatibility with polar polymers and non-polar polymers, and the carrier resin combined by the three realizes the general purpose of the carbon black master batchAnd (4) sex. The chlorinated polyethylene resin, the stabilizer and other additives are not added in the double-rotor continuous mixing mill, so that dehydrochlorination reaction of the chlorinated polyethylene resin in the double-rotor continuous mixing mill due to high-temperature strong shearing action can be avoided, and the stability of the structure and the performance of the chlorinated polyethylene is kept; and secondly, the molecular chain of the polyolefin resin is broken to generate further degradation just by utilizing the high-temperature strong shearing action in the double-rotor continuous mixing mill, namely, the mobility of the carbon black master batch is improved by reducing the molecular weight of the polyolefin, so that the dispersibility of the carbon black master batch in the later use process is improved, and the molecular chain breakage of the polyolefin resin can be stopped if an antioxidant in a stabilizer is added in the double-rotor continuous mixing mill in advance. However, chlorinated polyethylene resin, metal soap heat stabilizer and main/auxiliary antioxidant are added during granulation by a single screw extruder, and the stability of the structure and performance of the chlorinated polyethylene resin is kept mainly by utilizing the interaction of the chlorinated polyethylene resin and the metal soap heat stabilizer; the main/auxiliary antioxidant is utilized to generate degraded polyethylene and polypropylene macromolecular free radicals in the double-rotor continuous mixing roll after being stopped in the single-screw extruder, so that the flow rate of the prepared carbon black master batch melt is relatively stable, and the control of the product quality and the relative stability in the later use process are facilitated.

In conclusion, the high-carbon-black-content and high-melt-flow-rate universal carbon black master batch disclosed by the invention has the advantages that the carbon black content is up to 50-60%, the melt mass flow rate is more than 70g/10min, even more than 100g/10min, the varieties of universal carbon black master batches available in the current market are enriched, and more choices are provided for users. The carbon black master batch can simultaneously meet the use requirements of a non-polar polymer system and a polar polymer system, and has a series of advantages of small use amount, high coloring strength, good dispersibility and the like. In addition, the carbon black master batch has relatively low cost and simple preparation process. The universal carbon black master batch with high carbon black content and high melt flow rate is suitable for non-polar or weakly-polar polymer systems such as PE, PP, PS and the like, and is also suitable for polar polymer systems such as PA, PVC, PET, ABS and the like.

Drawings

FIG. 1 is a schematic view of a process flow of producing general carbon black master batches with high carbon black content and high melt flow rate.

Detailed Description

Example 1

The raw material formula (mass ratio, parts): LDPE (Loading 2160g, MFR 100g/10min at 190 ℃)16.5, oxidized PE wax (viscosity 4000mPa. s at 140 ℃ C., acid value 20mg KOH/g)10, oxidized PE wax (viscosity 6000mPa. s at 140 ℃ C., acid value 30mg KOH/g)10, oxidized PE wax (viscosity 8000mPa. s at 140 ℃ C., acid value 40mg KOH/g)10, CPE (chlorine atom mass fraction 33%, Mooney viscosity ML (1+4)120 ℃ C., 45, residual melting enthalpy 0J/g)3, high-structure carbon black (particle size 15nm, specific surface area 100 m)²The oil absorption value of 105mL/g and the coloring strength of 100)50, the antioxidant 10100.1, the antioxidant 1680.15 and the calcium stearate 0.25.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of stirring materials at a speed of more than 1000rpm to 55 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 40 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey the polyolefin resin, the oxidized polyethylene wax and the high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, then automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing roll for blending, wherein the rotating speed of the double-rotor continuous mixing roll is controlled at 500rpm, and the temperature of the mixing roll is 150-180 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. The screw rotating speed of the single-screw extruder is 70rpm, the temperature of the conveying section is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 160-190 ℃.

The properties of the universal carbon black master batch are shown in table 1.

Example 2

The raw material formula (mass ratio, parts): LLDPE (Loading 2160g, MFR 150g/10min at 190 ℃)15, oxidized PE wax (viscosity 8000mPa. s at 140 ℃ and acid value 10mg KOH/g)26, CPE (mass fraction of chlorine atom: 38%, Mooney viscosity ML (1+4)120 ℃ 55, residual melting enthalpy: 5J/g)3, high-structure carbon black (particle size: 20nm, specific surface area: 120 m)²Oil absorption value of 125mL/g, coloring strength of 110)55, antioxidant 10100.25, antioxidant 1680.25 and barium stearate 0.5.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of stirring materials at a speed of more than 1000rpm to 60 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 45 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey the polyolefin resin, the oxidized polyethylene wax and the high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, then automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing roll for blending, wherein the rotating speed of the double-rotor continuous mixing roll is controlled at 550rpm, and the temperature of the mixing roll is 150-180 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. The screw rotating speed of the single-screw extruder is 75rpm, the temperature of the conveying section is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 160-190 ℃.

The properties of the universal carbon black master batch are shown in table 1.

Example 3

The raw material formula (mass ratio, parts): HDPE (load 2160g, temperature)MFR 200g/10min at 190 ℃)10, PE oxide wax (viscosity 6000mPa. s at 140 ℃ and acid number 15mg KOH/g)24, CPE (mass fraction of chlorine atom 35%, Mooney viscosity ML (1+4)120 ℃ 48, residual melting enthalpy 1J/g)5, high structure carbon black (particle size 18nm, specific surface area 110 m) 5²Oil absorption value of 120mL/g, coloring strength of 105)60, antioxidant 10100.2, antioxidant 1680.3, calcium stearate 0.2 and barium stearate 0.3.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of stirring materials at a speed of more than 1000rpm to 50 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary bin when the temperature is reduced to 35 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey the polyolefin resin, the oxidized polyethylene wax and the high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, then automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing roll for blending, wherein the rotating speed of the double-rotor continuous mixing roll is controlled at 520rpm, and the temperature of the mixing roll is 150-180 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. The screw rotating speed of the single-screw extruder is 80rpm, the temperature of the conveying section is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 160-190 ℃.

The properties of the universal carbon black master batch are shown in table 1.

Example 4

The raw material formula (mass ratio, parts): LDPE (load of 2160g, MFR 150g/10min at 190 ℃), LLDPE (load of 2160g, MFR 100g/10min at 190 ℃)10, oxidized PE wax (viscosity of 5000mPa. s at 140 ℃ and acid value of 30mg KOH/g)29, CPE (chlorine atom mass fraction of 3)6%, Mooney viscosity ML (1+4) at 120 ℃ of 50, residual enthalpy of fusion of 4J/g)5, and high-structure carbon black (particle diameter 20nm, specific surface area 115 m)²/g, oil absorption value of 115mL/g, coloring strength of 115)50, an antioxidant 10100.3, an antioxidant 0.2, calcium stearate 0.3 and barium stearate 0.2.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of stirring materials at a speed of more than 1000rpm to 55 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 30 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey the polyolefin resin, the oxidized polyethylene wax and the high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, then automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing roll for blending, wherein the rotating speed of the double-rotor continuous mixing roll is controlled at 550rpm, and the temperature of the mixing roll is 150-180 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. The screw rotating speed of the single-screw extruder is 75rpm, the temperature of the conveying section is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 160-190 ℃. .

The properties of the universal carbon black master batch are shown in table 1.

Example 5

The raw material formula (mass ratio, parts): LDPE (load of 2160 g; MFR of 200g/10min at 190 ℃), HDPE (load of 2160 g; MFR of 100g/10min at 190 ℃)5, oxidized PE wax (viscosity of 6500mPa.s at 140 ℃ C., acid value of 35mg KOH/g)26, CPE (chlorine atom mass fraction of 35%, Mooney viscosity ML (1+4) of 120 ℃ C., 45; residual enthalpy of fusion of 4J/g)3, high-structure carbon black (particle size of 15nm, specific surface area of 100 m) 10, and method for producing the same²Oil absorption value of 125mL/g, coloring strength of 120)55, antioxidant 10100.2, antioxidant 1680.3, calcium stearate 0.3 and barium stearate 0.2.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of stirring materials at a speed of more than 1000rpm to 58 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 36 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey the polyolefin resin, the oxidized polyethylene wax and the high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing roll for blending, wherein the rotating speed of the double-rotor continuous mixing roll is controlled at 525rpm, and the temperature of the mixing roll is 150-180 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. The screw rotating speed of the single-screw extruder is 75rpm, the temperature of the conveying section is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 160-190 ℃.

The properties of the universal carbon black master batch are shown in table 1.

Example 6

The raw material formula (mass ratio, parts): LLDPE (Loading 2160 g; MFR 200g/10min at 190 ℃), HDPE (Loading 2160 g; MFR 150g/10min at 190 ℃), oxidized PE wax (viscosity 4500mPa. s at 140 ℃; acid value 40mg KOH/g)26, CPE (chlorine atom mass fraction 37%, Mooney viscosity ML (1+4)120 ℃ 55; residual melting enthalpy 3J/g)4, high-structure carbon black (particle size 20 nm; specific surface area 112 m/g) 10, and method for producing the same²Per g, oil absorption value of 120mL/g, coloring strength of 100)60, an antioxidant 10100.3, an antioxidant 1680.2, calcium stearate 0.2 and barium stearate 0.3.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of stirring materials at a speed of more than 1000rpm to 60 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 40 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey the polyolefin resin, the oxidized polyethylene wax and the high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, then automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing roll for blending, wherein the rotating speed of the double-rotor continuous mixing roll is controlled at 550rpm, and the temperature of the mixing roll is 150-180 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. The screw rotating speed of the single-screw extruder is 80rpm, the temperature of the conveying section is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 160-190 ℃.

The properties of the universal carbon black master batch are shown in table 1.

Example 7

The raw material formula (mass ratio, parts): LDPE (load 2160g, MFR at 190 ℃ 145g/10min)5, LLDPE (load 2160g, MFR at 190 ℃ 170g/10min)2.5, HDPE (load 2160g, MFR at 190 ℃ 150g/10min)2.5, oxidized PE wax (viscosity 4000mPa.s at 140 ℃ and acid value 25mg KOH/g)15, oxidized PE wax (viscosity 6000mPa.s at 140 ℃ and acid value 35mg KOH/g)15, CPE (chlorine atom mass fraction 33%, Mooney viscosity ML (1+4)120 ℃ 45, residual melting enthalpy 0J/g)3, high structure carbon black (particle size 20nm, specific surface area 105 m) 3²Oil absorption value of 125mL/g, coloring strength of 110)56.5, antioxidant 10100.2, antioxidant 1680.3 and calcium stearate 0.5.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of stirring materials at a speed of more than 1000rpm to 55 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 40 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey the polyolefin resin, the oxidized polyethylene wax and the high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, then automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing roll for blending, wherein the rotating speed of the double-rotor continuous mixing roll is controlled at 500rpm, and the temperature of the mixing roll is 150-180 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. The screw rotating speed of the single-screw extruder is 70rpm, the temperature of the conveying section is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 160-190 ℃.

The properties of the universal carbon black master batch are shown in table 1.

Example 8

The raw material formula (mass ratio, parts): PP (load of 2160g, MFR 100g/10min at 230 ℃)15, oxidized PE wax (viscosity 5500mPa.s at 140 ℃ and acid value 30mg KOH/g)26, CPE (mass fraction of chlorine atom 35%, Mooney viscosity ML (1+4)120 ℃ 55, residual melting enthalpy 2J/g)3, high-structure carbon black (particle size 15nm, specific surface area 100 m)²The oil absorption value of 105-125 mL/g, the coloring strength of 105)55, an antioxidant 10100.2, an antioxidant 1680.3 and barium stearate 0.5.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of stirring materials at a speed of more than 1000rpm to 55 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 40 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey polyolefin resin, oxidized polyethylene wax and high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing mill for blending, wherein the rotating speed of the double-rotor continuous mixing mill is controlled at 500rpm, and the temperature of the mixing mill is 200-210 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. Wherein the screw rotating speed of the single screw extruder is 70rpm, the temperature of the conveying section is controlled to be 120-130 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 210-220 ℃.

The properties of the universal carbon black master batch are shown in table 1.

Example 9

The raw material formula (mass ratio, parts): PP (load of 2160g, MFR 150g/10min at 230 ℃), oxidized PE wax (viscosity of 4000mPa. s at 140 ℃ C., acid value of 20mg KOH/g)13, oxidized PE wax (viscosity of 8000mPa. s at 140 ℃ C., acid value of 30mg KOH/g)13, CPE (chlorine atom mass fraction of 36%, Mooney viscosity ML (1+4) of 120 ℃ C., 45, residual melting enthalpy of 1J/g)5, high-structure carbon black (particle size of 20nm, specific surface area of 110 m/g) 5²Oil absorption value of 105mL/g, coloring strength of 115)50, antioxidant 10100.2, antioxidant 1680.3, calcium stearate 0.2 and barium stearate 0.3.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of stirring materials at a speed of more than 1000rpm to 60 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 45 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey polyolefin resin, oxidized polyethylene wax and high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing mill for blending, wherein the rotating speed of the double-rotor continuous mixing mill is controlled at 550rpm, and the temperature of the mixing mill is 200-210 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. Wherein the screw rotating speed of the single screw extruder is 70rpm, the temperature of the conveying section is controlled to be 120-130 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 210-220 ℃.

The properties of the universal carbon black master batch are shown in table 1.

Example 10

The raw material formula (mass ratio, parts): PP (load of 2160g, MFR 200g/10min at 230 ℃)15, oxidized PE wax (viscosity 4000mPa. s at 140 ℃ and acid value 40mg KOH/g)10, oxidized PE wax (viscosity 7000mPa. s at 140 ℃ and acid value 30mg KOH/g)8, CPE (chlorine atom mass fraction 38%, Mooney viscosity ML (1+4)120 ℃ 50, residual melting enthalpy 1J/g)3.5, high structure carbon black (particle size 15nm, specific surface area 120 m) 15, molecular weight of the carbon black, and melt viscosity of the carbon black²The oil absorption value of 110mL/g, the coloring strength of 100)) 53, the antioxidant 10100.1, the antioxidant 1680.15 and the calcium stearate 0.25.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of stirring materials at a speed of more than 1000rpm to 55 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 35 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey the polyolefin resin, the oxidized polyethylene wax and the high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, then automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing roll for blending, wherein the rotating speed of the double-rotor continuous mixing roll is controlled at 500rpm, and the temperature of the mixing roll is 200-210 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. Wherein the screw rotating speed of the single screw extruder is 75rpm, the temperature of the conveying section is controlled to be 120-130 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 210-220 ℃.

The properties of the universal carbon black master batch are shown in table 1.

Comparative example 1

The raw material formula (mass ratio, parts): LDPE (2160g load, MFR 100g/10min at 190 ℃)49 and high-structure carbon black (15 nm particle diameter, 100m specific surface area)²The oil absorption value of 105mL/g and the coloring strength of 100)50, the antioxidant 10100.2, the antioxidant 1680.3 and the calcium stearate 0.5.

The preparation process comprises the following steps:

high-speed mixing and diluting of an auxiliary agent: stirring part of powdery polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of more than 1000rpm to stir the materials to 55 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 40 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: and starting an integrated feeding system to respectively convey the residual polyethylene resin, the diluted auxiliary agent mixture and the high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing roll for blending, wherein the temperature of the mixing roll is 150-180 ℃. Granulating by a single screw extruder: and finally, carrying out underwater granulation process on the uniform material after blending in the double-rotor continuous mixing roll by using a granulator to obtain the polymer carbon black master batch. Wherein the screw rotating speed of the single screw extruder is 70rpm, the temperature of the conveying section is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 160-190 ℃.

The properties of the carbon black masterbatch are determined in Table 2.

Comparative example 2

The raw material formula (mass ratio, parts): HDPE (Loading 2160g, MFR 100g/10min at 190 ℃)26.5, oxidized PE wax (viscosity 6000mPa. s at 140 ℃ and acid value 0mg KOH/g)20, CPE (mass fraction of chlorine atom 35%, Mooney viscosity ML (1+4)120 ℃ 50, residual melting enthalpy 3J/g)3, high-structure carbon Black (particle size 15nm, specific surface area 110 m)²The oil absorption value of 110mL/g and the coloring strength of 110)50, the antioxidant 10100.2, the antioxidant 1680.3 and the calcium stearate 0.5.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin, metal soap heat stabilizer, antioxidant and other additives in the raw materials of the formula for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of 1000rpm to stir the materials to 60 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted additives to a diluting additive bin when the temperature is reduced to 40 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey the polyolefin resin, the oxidized polyethylene wax and the high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, then automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing roll for blending, wherein the rotating speed of the double-rotor continuous mixing roll is controlled at 500rpm, and the temperature of the mixing roll is 150-180 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. Wherein the screw rotating speed of the single screw extruder is 70rpm, the temperature of the conveying section is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 160-190 ℃.

The properties of the carbon black masterbatch are determined in Table 2.

Comparative example 3

The raw material formula (mass ratio, parts): LLDPE (Loading 2160g, MFR 200g/10min at 190 ℃)18.5, oxidized PE wax (viscosity 4000mPa. s at 140 ℃ and acid number 40mg KOH/g)30, high-structure carbon black (particle size 20nm, specific surface area 120 m)²/g, oil absorption value of 115mL/g, tinting strength of 105)50, an antioxidant 10100.2, an antioxidant 1680.3 and calcium stearate 0.5.

The preparation process comprises the following steps:

high-speed mixing and diluting of an auxiliary agent: stirring part of powdery polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of more than 1000rpm to stir the materials to 55 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 40 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: and starting an integrated feeding system to respectively convey the residual polyolefin resin, the diluted auxiliary agent mixture, oxidized polyethylene wax and high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, automatically metering by a weightlessness scale in the weighing bin, and continuously and directly putting into a double-rotor continuous mixing mill for blending, wherein the rotating speed of the double-rotor continuous mixing mill is controlled at 500rpm, and the temperature of the mixing mill is 150-180 ℃. Granulating by a single screw extruder: and finally, carrying out underwater granulation process on the materials mixed in the double-rotor continuous mixing roll by using a granulator to obtain the polymer master batch. Wherein the screw rotating speed of the single screw extruder is 80rpm, the temperature of the conveying section is controlled to be 80-100 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 160-190 ℃.

The properties of the carbon black masterbatch are determined in Table 2.

Comparative example 4

The raw material formula (mass ratio, parts): PP (load)2160g, MFR 150g/10min at 230 ℃ 49, and high-structure carbon black (particle diameter 15nm, specific surface area 110 m)²/g, oil absorption value of 115mL/g, tinting strength of 105)50, an antioxidant 10100.2, an antioxidant 1680.3 and calcium stearate 0.5.

The preparation process comprises the following steps:

high-speed mixing and diluting of an auxiliary agent: stirring part of powdery polypropylene resin in the raw materials of the formula, metal soap heat stabilizer, antioxidant and other additives in a high-speed mixer for 2min at a low speed of 500rpm, starting the high speed of over 1000rpm to stir the materials to 55 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted additives to a diluting additive bin when the temperature is reduced to 40 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: and starting the integrated feeding system to respectively convey the residual polypropylene resin, the diluted auxiliary agent mixture and the high-structure-degree carbon black to an intermediate bin of the dynamic weighing system, automatically metering by a weightlessness scale in the weighing bin, and continuously and directly putting into a double-rotor continuous mixing mill for blending, wherein the rotating speed of the double-rotor continuous mixing mill is controlled at 500rpm, and the temperature of the mixing mill is 200-210 ℃. Granulating by a single screw extruder: and finally, carrying out underwater granulation process on the materials mixed in the double-rotor continuous mixing roll by using a granulator to obtain the polymer master batch. Wherein the screw rotating speed of the single screw extruder is 70rpm, the temperature of the conveying section is controlled to be 120-130 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 210-220 ℃.

The properties of the carbon black masterbatch are determined in Table 2.

Comparative example 5

The raw material formula (mass ratio, parts): 26.5 PP (load of 2160g, MFR 200g/10min at 230 ℃), 20 PE oxide wax (viscosity of 6500mPa. s at 140 ℃ and acid value of 0mg KOH/g), 3 CPE (mass fraction of chlorine atom 35%, Mooney viscosity ML (1+4) of 50 ℃ and residual melting enthalpy 3J/g), and 3 high-structure carbon black (particle size of 20nm, specific surface area of 105 m)²The oil absorption value of 110mL/g and the coloring strength of 110)50, the antioxidant 10100.2, the antioxidant 1680.3 and the calcium stearate 0.5.

The preparation process comprises the following steps:

mixing chlorinated polyethylene resin with a stabilizer at a high speed: stirring powdery chlorinated polyethylene resin in the raw materials of the formula and auxiliaries such as a metal soap heat stabilizer, an antioxidant and the like for 2min at a low speed of 500rpm in a high-speed mixer, starting the high speed of over 1000rpm to stir the materials to 40 +/-5 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted auxiliaries to a diluting auxiliary storage bin when the temperature is reduced to 40 +/-5 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey the polypropylene resin, the oxidized polyethylene wax and the high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, then automatically metering by a weightlessness scale in a weighing bin, and continuously and directly putting into a double-rotor continuous mixing roll for blending, wherein the rotating speed of the double-rotor continuous mixing roll is controlled at 500rpm, and the temperature of the mixing roll is 200-210 ℃. Granulating by a single screw extruder: and (3) further uniformly mixing the materials mixed in the double-rotor continuous mixing mill with auxiliary agents such as chlorinated polyethylene resin and a stabilizer through a single-screw extruder with side feeding, and finally obtaining the polymer master batch through an underwater granulation process of a granulator. Wherein the screw rotating speed of the single screw extruder is 70rpm, the temperature of the conveying section is controlled to be 120-130 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 210-220 ℃.

The properties of the carbon black masterbatch are determined in Table 2.

Comparative example 6

The raw material formula (mass ratio, parts): PP (load of 2160g, MFR 100g/10min at 230 ℃), oxidized PE wax (viscosity 7000mPa. s at 140 ℃ and acid value 40mg KOH/g)30, and highly structured carbon black (particle diameter of 15nm, specific surface area of 110 m)²/g, oil absorption value of 115mL/g, tinting strength of 110)50, an antioxidant 10100.2, an antioxidant 1680.3 and calcium stearate 0.5.

The preparation process comprises the following steps:

high-speed mixing and diluting of an auxiliary agent: stirring part of powdery polypropylene resin in the raw materials of the formula, metal soap heat stabilizer, antioxidant and other additives in a high-speed mixer for 2min at a low speed of 500rpm, starting the high speed of 1000rpm above to stir the materials to 60 ℃, discharging the materials to a mixer with jacket water cooling for continuous mixing, and discharging the diluted additives to a diluting additive bin when the temperature is reduced to 40 ℃.

Preparing a carbon black master batch: blending by a double-rotor continuous mixing mill: starting an integrated feeding system to respectively convey the polypropylene resin, the diluted mixing aid, oxidized polyethylene wax and high-structure-degree carbon black to an intermediate bin of a dynamic weighing system, automatically metering by a weightlessness scale in the weighing bin, and continuously and directly putting into a double-rotor continuous mixing mill for blending, wherein the rotating speed of the double-rotor continuous mixing mill is controlled at 500rpm, the temperature of the mixing mill is 200-210 ℃, and the temperature of the mixing mill is 150-180 ℃ when the polyolefin resin is powdery polyethylene. Granulating by a single screw extruder: and finally, carrying out underwater granulation process on the materials mixed in the double-rotor continuous mixing roll by using a granulator to obtain the polymer master batch. Wherein the screw rotating speed of the single screw extruder is 80rpm, the temperature of the conveying section is controlled to be 120-130 ℃, and the temperature of the plasticizing section and the machine head is controlled to be 210-220 ℃.

The properties of the carbon black masterbatch are determined in Table 2.

Table 1 performance summary of examples 1 to 10

Carbon black mass content was tested according to international standard ISO 6964; carbon black masterbatch melt mass flow rate was tested according to international standard ISO 1133, PE: load 21600g, temperature 190 ℃, PP: the load is 21600g and the temperature is 230 ℃; the carbon black particle dispersion size rating and the dispersion appearance rating were measured according to international standard ISO 18553.

TABLE 2 summary of the properties of comparative examples 1 to 6

Carbon black mass content was tested according to international standard ISO 6964; carbon black masterbatch melt mass flow rate was tested according to international standard ISO 1133, PE: load 21600g, temperature 190 ℃, PP: the load is 21600g and the temperature is 230 ℃; the carbon black particle dispersion size rating and the dispersion appearance rating were measured according to international standard ISO 18553.