A carbon black functional masterbatch and its preparation method and application

Abstract

The present invention discloses a carbon black functional masterbatch, which is composed of the following raw materials in parts by weight: 40-80 parts of carrier resin, 0.5-2 parts of maleic anhydride grafted polyethylene, 20-50 parts of modified carbon black pigment, 0.1-0.5 parts of fluoropolymer, and 0.1-1.0 parts of antioxidant; the modified carbon black functional pigment is prepared by the following method: dissolving carbon black in toluene, heating to 80-120°C, adding a modification system thereto under stirring, heating to 115-120°C and continuing to react for 1-2h, cooling to room temperature, drying under reduced pressure to constant weight, performing Soxhlet extraction with acetone as a solvent for 24-36h, and finally drying the sample to obtain the modified carbon black pigment. At the same time, the present invention also discloses a preparation method and application of the carbon black functional masterbatch. When the carbon black functional masterbatch is used to prepare a pressure-bearing pipeline, the carbon black has good dispersibility and will not re-agglomerate.

Description

Technical Field

[0001] The invention belongs to the technical field of carbon black functional masterbatch preparation, and specifically relates to a carbon black functional masterbatch and a preparation method and application thereof. Background Art

[0002] As economic development increases the demand for energy, unconventional natural gas pipelines are also booming. In order to ensure the supply of the domestic energy market, the construction of imported natural gas pipelines has also started one after another. HDPE pressure pipes are bound to be the best choice due to their good toughness, crack resistance and ability to resist earthquake damage. In 2016, the apparent consumption of domestic PE100 grade polyethylene pressure pipe materials was about 450,000 tons. In 2022, the demand has increased to 1.42 million tons. It is predicted that the demand will further increase to 1.92 million tons in 2025. In order to meet the rapid growth of demand for special materials for pressure pipes and the intensified changes in market competition, it is necessary to strengthen the research and development of domestic PE100 grade pressure polyethylene pipe materials.

[0003] According to the requirements, the production of PE100-grade gas pipes must use mixed materials, and the performance must meet the extremely high weather resistance and aging resistance requirements on the basis of meeting the pressure-bearing performance of the pipe products. It needs to maintain a service life of up to 50 years, so the requirements are extremely high, and masterbatch is the core key technology for the production of mixed materials.

[0004] At present, the domestic production of masterbatches has not found the right carrier resin, dispersant and suitable carbon black pigment dispersion process, resulting in the inability of domestically produced masterbatches to meet the needs of gas pipe compounding. Therefore, the domestic market has long been dominated by imported masterbatch products, making the cost of domestic compounding very high. Therefore, the independent development of carbon black functional masterbatches for gas pipes can reduce the cost burden of purchasing imported masterbatches and improve the price competitiveness of compounding.

[0005] Therefore, developing a carbon black functional masterbatch with good performance that can be applied to PE100 grade gas pressure pipes and its preparation method has become the focus of research in this field. Summary of the invention

[0006] In order to solve the problems existing in the prior art, the present invention provides a carbon black functional masterbatch and a preparation method and application thereof. The carbon black functional masterbatch has a small particle size and good dispersion stability. The masterbatch is prepared into a blend by melt blending with a PE pipe material, and then extruded through a screw extruder to prepare an EP100 grade pipe that can be used for a gas pressure pipeline.

[0007] A carbon black functional masterbatch, composed of the following raw materials in parts by weight: 40-80 parts of carrier resin, 0.5-2 parts of maleic anhydride grafted polyethylene, 20-50 parts of modified carbon black pigment, 0.1-0.5 parts of fluorine-containing polymer, and 0.1-1.0 parts of antioxidant;

[0008] The modified carbon black pigment is prepared by the following method:

[0009] The carbon black is dissolved in toluene, heated to 80-120°C, and the modification system is added thereto under stirring, and the temperature is raised to 115-120°C to continue the reaction for 1-2 hours, and then cooled to room temperature, and dried under reduced pressure to constant weight, and Soxhlet extraction is performed with acetone as a solvent for 24-36 hours, and finally the sample is dried to obtain a modified carbon black pigment; the modification system is a mixed solution of a multifunctional modifier GMA, 2-phenylimidazoline, and toluene.

[0010] Preferably, the drying is carried out at 60-70°C.

[0011] Preferably, the amount of the modification system is 0.05-0.1 times the amount of carbon black, and the ratio of GMA, 2-phenylimidazoline and toluene in the modification system is 10 g: (0.5-1) g: (20-30) mL.

[0012] Preferably, the carbon black has an average primary particle size of 10-25 nm, an oil absorption value in the range of 50 mL / 100 g to 100 mL / 100 g, and a volatile component of less than 3.5 wt%.

[0013] Preferably, the carrier resin is a trimodal high-density polyethylene resin having a melt flow rate of 0.2-0.5 g / 10 min.

[0014] Preferably, the grafting rate of the maleic anhydride grafted polyethylene is 0.85%, and the melt flow rate is 1-3 g / 10 min.

[0015] Preferably, the fluorine-containing polymer is a copolymer formed by vinylidene fluoride and tetrafluoroethylene in a molar ratio of 1:(0.1-0.45).

[0016] Preferably, the antioxidant is a hindered phenol antioxidant, a phosphite antioxidant, or a mixture of the two in any proportion.

[0017] A method for preparing a carbon black functional masterbatch comprises the following steps:

[0018] (1) Add the carrier resin component into the internal mixer, close the internal mixer charging cover, turn on the heating to make the temperature reach 150°C, start the internal mixer, and stop the internal mixer after the resin is fully plasticized;

[0019] (2) Open the internal mixer, add modified carbon black pigment, maleic anhydride grafted polyethylene, fluorine-containing polymer and antioxidant, then start the internal mixer and continue to mix. When there is no dispersed carbon black pigment around the mixing chamber and all the materials have become a melt mass with a smooth surface, the mixing is completed;

[0020] (3) The kneaded mixture is added into the hopper of a single screw extruder, and then extruded, pulled, cooled, and pelletized by the single screw extruder to form a black masterbatch.

[0021] Preferably, the top bolt pressure of the internal mixer in step (1) is 0.39-0.59 MPa.

[0022] Preferably, the temperature of the single screw extruder in step (3) is set as follows: double cone feeding section 120-130°C, compression section 155-170°C, homogenization section 175°C, and die head temperature 145°C.

[0023] The present invention also provides application of the carbon black functional masterbatch in preparing a pressure pipe.

[0024] Advantages of the present invention:

[0025] (1) The addition of maleic anhydride grafted polyethylene compatibilizer improves the dispersion stability and compatibility of carbon black in polyethylene carrier resin to a certain extent. Since the maleic anhydride functional group can chemically react with the carboxyl, hydroxyl and other functional groups on the surface of carbon black pigment and additives, it can be firmly combined with the pigment and additives by chemical bond force, thus enhancing the binding force between the two.

[0026] (2) By adding a modification system containing a multifunctional modifier GMA to modify the carbon black surface, the combination of carbon black and polyethylene macromolecular chains can be increased, which is beneficial for the transmission and dispersion of stress, helps to solve the contradiction between high content and high dispersion of small particle size pigments, and improves the dispersion morphology and dispersion stability of carbon black in the carrier resin matrix;

[0027] (3) When the carbon black functional masterbatch provided by the present invention is used to prepare a pressure-bearing pipe, the carbon black has good dispersibility and will not re-agglomerate. Implementation

[0028] 1. A carbon black functional masterbatch, composed of the following raw materials in parts by weight: 40 parts of carrier resin, 1.5 parts of maleic anhydride grafted polyethylene, 50 parts of modified carbon black pigment, 0.2 parts of fluorine-containing polymer, and 0.2 parts of antioxidant;

[0029] Wherein, the modified carbon black pigment is prepared by the following method:

[0030] 50 parts of carbon black are added to a three-necked flask, added to 500 parts of toluene solvent, heated to 80°C, and under stirring, a modification system of 0.05 times the amount of carbon black is added thereto, the temperature is raised to 115°C and the reaction is continued for 1 hour, cooled to room temperature, discharged, dried under reduced pressure to constant weight, and Soxhlet extraction is performed with acetone as a solvent for 24 hours, and finally the sample is dried at 60°C to obtain a modified carbon black pigment; the modification system is a liquid obtained by mixing a multifunctional modifier GMA, 2-phenylimidazoline, and toluene according to 10g:0.5g:20mL;

[0031] The carbon black has an average primary particle size of 10 nm, an oil absorption value range of 100 mL / 100 g, and a volatile component of less than 3.5 wt %;

[0032] The carrier resin is a trimodal high-density polyethylene resin with a melt flow rate of 0.35 g / 10 min;

[0033] The grafting rate of the maleic anhydride grafted polyethylene is 0.85%, and the melt flow rate is 2.0 g / 10 min;

[0034] The fluorine-containing polymer is a copolymer of vinylidene fluoride and tetrafluoroethylene in a molar ratio of 1:0.1;

[0035] The antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 2:1.

[0036] 2. A method for preparing a carbon black functional masterbatch, comprising the following steps:

[0037] (1) Add the carrier resin component into the internal mixer, set the top bolt pressure of the internal mixer to 0.5 MPa, close the internal mixer charging cover, turn on the heating to make the temperature reach 150°C, start the internal mixer, and mix the resin until it is completely plasticized, then stop mixing;

[0038] (2) Open the internal mixer, add modified carbon black pigment, maleic anhydride grafted polyethylene, fluorine-containing polymer and antioxidant, then start the internal mixer and continue to mix. When there is no dispersed carbon black pigment around the mixing chamber and all the materials have become a melt mass with a smooth surface, the mixing is completed;

[0039] (3) The kneaded mixture is added into the hopper of a single screw extruder. The temperature of the single screw extruder is set as follows: double cone feeding section 125°C, compression section 170°C, homogenization section 175°C, and die head temperature 145°C. After extrusion, strip pulling, cooling, and pelletizing by the single screw extruder, a black masterbatch is finally formed.

[0040] 1. A carbon black functional masterbatch, composed of the following raw materials in parts by weight: 50 parts of carrier resin, 2.0 parts of maleic anhydride grafted polyethylene, 50 parts of modified carbon black pigment, 0.4 parts of fluorine-containing polymer, and 0.5 parts of antioxidant;

[0041] Wherein, the modified carbon black pigment is prepared by the following method:

[0042] 50 parts of carbon black were added to a three-necked flask, and solvent toluene was added, and the mixture was heated to 120°C. Under stirring, a modification system with an amount of 0.1 times that of carbon black was added thereto, and the mixture was heated to 120°C and continued to react for 1 hour, and then cooled to room temperature, discharged, and dried under reduced pressure to constant weight. Soxhlet extraction was performed with acetone as a solvent for 36 hours, and finally the sample was dried at 60°C to obtain a modified carbon black pigment; the modification system was a liquid obtained by mixing a multifunctional modifier GMA, 2-phenylimidazoline, and toluene in a ratio of 10 g: 0.5 g: 20 mL;

[0043] The carbon black has an average primary particle size of 15 nm, an oil absorption value range of 90 mL / 100 g, and a volatile component of less than 3.5 wt %;

[0044] The carrier resin is a trimodal high-density polyethylene resin with a melt flow rate of 0.35 g / 10 min;

[0045] The grafting rate of the maleic anhydride grafted polyethylene is 0.85%, and the melt flow rate is 2.0 g / 10 min;

[0046] The fluorine-containing polymer is a copolymer of vinylidene fluoride and tetrafluoroethylene in a molar ratio of 1:0.15;

[0047] The antioxidant is antioxidant 1010.

[0048] 2. A method for preparing a carbon black functional masterbatch, comprising the following steps:

[0049] (1) Add the carrier resin component into the internal mixer, set the top bolt pressure of the internal mixer to 0.5 MPa, close the internal mixer charging cover, turn on the heating to make the temperature reach 150°C, start the internal mixer, and mix the resin until it is completely plasticized, then stop mixing;

[0050] (2) Open the internal mixer, add modified carbon black pigment, maleic anhydride grafted polyethylene, fluorine-containing polymer and antioxidant, then start the internal mixer and continue to mix. When there is no dispersed carbon black pigment around the mixing chamber and all the materials have become a melt mass with a smooth surface, the mixing is completed;

[0051] (3) The kneaded mixture is added into the hopper of a single screw extruder. The temperature of the single screw extruder is set as follows: double cone feeding section 125°C, compression section 170°C, homogenization section 175°C, and die head temperature 145°C. After extrusion, strip pulling, cooling, and pelletizing by the single screw extruder, a black masterbatch is finally formed.

[0052] 1. A carbon black functional masterbatch, composed of the following raw materials in parts by weight: 60 parts of carrier resin, 1.0 parts of maleic anhydride grafted polyethylene, 40 parts of modified carbon black pigment, 0.5 parts of fluorine-containing polymer, and 0.7 parts of antioxidant;

[0053] Wherein, the modified carbon black pigment is prepared by the following method:

[0054] 40 parts of carbon black were added to a three-necked flask, and solvent toluene was added, and the mixture was heated to 100°C. Under stirring, a modification system of 0.05 times the amount of carbon black was added thereto, and the mixture was heated to 120°C and continued to react for 1 hour, and then cooled to room temperature, discharged, and dried under reduced pressure to constant weight. Soxhlet extraction was performed with acetone as a solvent for 24 hours, and finally the sample was dried at 60°C to obtain a modified carbon black pigment; the modification system was a liquid obtained by mixing a multifunctional modifier GMA, 2-phenylimidazoline, and toluene in a ratio of 10 g: 0.5 g: 20 mL;

[0055] The carbon black has an average primary particle size of 18 nm, an oil absorption value range of 80 mL / 100 g, and a volatile component of less than 3.5 wt %;

[0056] The carrier resin is a trimodal high-density polyethylene resin with a melt flow rate of 0.35 g / 10 min;

[0057] The grafting rate of the maleic anhydride grafted polyethylene is 0.85%, and the melt flow rate is 2.0 g / 10 min;

[0058] The fluorine-containing polymer is a copolymer of vinylidene fluoride and tetrafluoroethylene at a molar ratio of 1:0.25.

[0059] The antioxidant is antioxidant 168.

[0060] 2. A method for preparing a carbon black functional masterbatch, comprising the following steps:

[0061] (1) Add the carrier resin component into the internal mixer, set the top bolt pressure of the internal mixer to 0.5 MPa, close the internal mixer charging cover, turn on the heating to make the temperature reach 150°C, start the internal mixer, and mix the resin until it is completely plasticized, then stop mixing;

[0062] (2) Open the internal mixer, add modified carbon black pigment, maleic anhydride grafted polyethylene, fluorine-containing polymer and antioxidant, then start the internal mixer and continue to mix. When there is no dispersed carbon black pigment around the mixing chamber and all the materials have become a melt mass with a smooth surface, the mixing is completed;

[0063] (3) The kneaded mixture is added into the hopper of a single screw extruder. The temperature of the single screw extruder is set as follows: double cone feeding section 125°C, compression section 170°C, homogenization section 175°C, and die head temperature 145°C. After extrusion, strip pulling, cooling, and pelletizing by the single screw extruder, a black masterbatch is finally formed.

[0064] 1. A carbon black functional masterbatch, composed of the following raw materials in parts by weight: 70 parts of carrier resin, 0.5 parts of maleic anhydride grafted polyethylene, 30 parts of modified carbon black pigment, 0.5 parts of fluorine-containing polymer, and 1.0 parts of antioxidant;

[0065] Wherein, the modified carbon black pigment is prepared by the following method:

[0066] 40 parts of carbon black were added to a three-necked flask, and solvent toluene was added, and the mixture was heated to 100°C. Under stirring, a modification system of 0.05 times the amount of carbon black was added thereto, and the mixture was heated to 120°C and continued to react for 1 hour, and then cooled to room temperature, discharged, and dried under reduced pressure to constant weight, and then subjected to Solite extraction, and then subjected to Soxhlet extraction with acetone as solvent for 24 hours, and finally the sample was dried at 60°C to obtain a modified carbon black pigment; the modification system was a liquid obtained by mixing a multifunctional modifier GMA, 2-phenylimidazoline, and toluene in a ratio of 10 g: 0.5 g: 20 mL;

[0067] The carbon black has an average primary particle size of 20 nm, an oil absorption value range of 70 mL / 100 g, and a volatile component of less than 3.5 wt %;

[0068] The carrier resin is a trimodal high-density polyethylene resin with a melt flow rate of 0.35 g / 10 min;

[0069] The grafting rate of the maleic anhydride grafted polyethylene is 0.85%, and the melt flow rate is 2.0 g / 10 min;

[0070] The fluorine-containing polymer is a copolymer of vinylidene fluoride and tetrafluoroethylene in a molar ratio of 1:0.3;

[0071] The antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 2:1.

[0072] 2. A method for preparing a carbon black functional masterbatch, comprising the following steps:

[0073] (1) Add the carrier resin component into the internal mixer, set the top bolt pressure of the internal mixer to 0.5 MPa, close the internal mixer charging cover, turn on the heating to make the temperature reach 150°C, start the internal mixer, and mix the resin until it is completely plasticized, then stop mixing;

[0074] (2) Open the internal mixer, add modified carbon black pigment, maleic anhydride grafted polyethylene, fluorine-containing polymer and antioxidant, then start the internal mixer and continue to mix. When there is no dispersed carbon black pigment around the mixing chamber and all the materials have become a melt mass with a smooth surface, the mixing is completed;

[0075] (3) The kneaded mixture is added into the hopper of a single screw extruder. The temperature of the single screw extruder is set as follows: double cone feeding section 125°C, compression section 170°C, homogenization section 175°C, and die head temperature 145°C. After extrusion, strip pulling, cooling, and pelletizing by the single screw extruder, a black masterbatch is finally formed.

[0076] 1. A carbon black functional masterbatch, composed of the following raw materials in parts by weight: 80 parts of carrier resin, 0.5 parts of maleic anhydride grafted polyethylene, 20 parts of modified carbon black pigment, 0.1 parts of fluorine-containing polymer, and 0.5 parts of antioxidant;

[0077] Wherein, the modified carbon black pigment is prepared by the following method:

[0078] 20 parts of carbon black were added to a three-necked flask, and solvent toluene was added, and the mixture was heated to 100°C. Under stirring, a modification system of 0.05 times the amount of carbon black was added thereto, and the mixture was heated to 120°C and continued to react for 1 hour, and then cooled to room temperature, discharged, and dried under reduced pressure to constant weight. Soxhlet extraction was performed with acetone as a solvent for 24 hours, and finally the sample was dried at 60°C to obtain a modified carbon black pigment; the modification system was a liquid obtained by mixing a multifunctional modifier GMA, 2-phenylimidazoline, and toluene in a ratio of 10 g: 0.5 g: 20 mL;

[0079] The carbon black has an average primary particle size of 22 nm, an oil absorption value range of 60 mL / 100 g, and a volatile component of less than 3.5 wt %;

[0080] The carrier resin is a trimodal high-density polyethylene resin with a melt flow rate of 0.2 g / 10 min;

[0081] The grafting rate of the maleic anhydride grafted polyethylene is 0.85%, and the melt flow rate is 1.0 g / 10 min;

[0082] The fluorine-containing polymer is a copolymer of vinylidene fluoride and tetrafluoroethylene in a molar ratio of 1:0.35;

[0083] The antioxidant is antioxidant 1010.

[0084] 2. A method for preparing a carbon black functional masterbatch, comprising the following steps:

[0085] (1) Add the carrier resin component into the internal mixer, set the top bolt pressure of the internal mixer to 0.5 MPa, close the internal mixer charging cover, turn on the heating to make the temperature reach 150°C, start the internal mixer, and mix the resin until it is completely plasticized, then stop mixing;

[0086] (2) Open the internal mixer, add modified carbon black pigment, maleic anhydride grafted polyethylene, fluorine-containing polymer and antioxidant, then start the internal mixer and continue to mix. When there is no dispersed carbon black pigment around the mixing chamber and all the materials have become a melt mass with a smooth surface, the mixing is completed;

[0087] (3) The kneaded mixture is added into the hopper of a single screw extruder. The temperature of the single screw extruder is set as follows: 130°C for the double cone feeding section, 170°C for the compression section, 175°C for the homogenization section, and 145°C for the die head. The mixture is extruded, pulled by the material strip, cooled, and pelletized by the single screw extruder to form a black masterbatch.

[0088] 1. A carbon black functional masterbatch, composed of the following raw materials in parts by weight: 70 parts of carrier resin, 1.5 parts of maleic anhydride grafted polyethylene, 30 parts of modified carbon black pigment, 0.4 parts of fluorine-containing polymer, and 0.7 parts of antioxidant;

[0089] Wherein, the modified carbon black pigment is prepared by the following method:

[0090] 40 parts of carbon black were added to a three-necked flask, and solvent toluene was added, and the mixture was heated to 90°C. Under stirring, a modification system with an amount of 0.05 times that of carbon black was added thereto, and the mixture was heated to 120°C and continued to react for 1 hour, and then cooled to room temperature, discharged, and dried under reduced pressure to constant weight. Soxhlet extraction was performed with acetone as a solvent for 24 hours, and finally the sample was dried at 60°C to obtain a modified carbon black pigment; the modification system was a liquid obtained by mixing a multifunctional modifier GMA, 2-phenylimidazoline, and toluene in a ratio of 10 g: 1 g: 30 mL;

[0091] The carbon black has an average primary particle size of 25 nm, an oil absorption value range of 50 mL / 100 g, and a volatile component of less than 3.5 wt %;

[0092] The carrier resin is a trimodal high-density polyethylene resin with a melt flow rate of 0.5 g / 10 min;

[0093] The grafting rate of the maleic anhydride grafted polyethylene is 0.85%, and the melt flow rate is 3.0 g / 10 min;

[0094] The fluorine-containing polymer is a copolymer of vinylidene fluoride and tetrafluoroethylene in a molar ratio of 1:0.45;

[0095] The antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 2:1.

[0096] 2. A method for preparing a carbon black functional masterbatch, comprising the following steps:

[0097] (1) Add the carrier resin component into the internal mixer, set the top bolt pressure of the internal mixer to 0.5 MPa, close the internal mixer charging cover, turn on the heating to make the temperature reach 150°C, start the internal mixer, and mix the resin until it is completely plasticized, then stop mixing;

[0098] (2) Open the internal mixer, add modified carbon black pigment, maleic anhydride grafted polyethylene, fluorine-containing polymer and antioxidant, then start the internal mixer and continue to mix. When there is no dispersed carbon black pigment around the mixing chamber and all the materials have become a melt mass with a smooth surface, the mixing is completed;

[0099] (3) The kneaded mixture is added into the hopper of a single screw extruder. The temperature of the single screw extruder is set as follows: double cone feeding section 120°C, compression section 155°C, homogenization section 175°C, and die head temperature 145°C. After extrusion, strip pulling, cooling, and pelletizing by the single screw extruder, a black masterbatch is finally formed.

[0100] A carbon black functional masterbatch is composed of the following raw materials in parts by weight: 60 parts of carrier resin, 40 parts of carbon black pigment, 1.0 part of maleic anhydride grafted polyethylene, 0.5 part of fluorine-containing polymer, and 0.7 part of antioxidant; the rest is the same as in Example 3.

[0101] A carbon black functional masterbatch is composed of the following raw materials in parts by weight: 60 parts of carrier resin, 40 parts of modified carbon black pigment, 0.5 parts of fluorine-containing polymer, and 0.7 parts of antioxidant; the rest is the same as in Example 3.

[0102] A carbon black functional masterbatch is composed of the following raw materials in parts by weight: 60 parts of carrier resin, 40 parts of carbon black, 0.4 parts of fluorine-containing polymer, and 0.7 parts of antioxidant; the rest is the same as in Example 3.

[0103] 1. Performance Testing

[0104] The performance of the above carbon black functional masterbatch was tested, and the results are shown in Table 1.

[0105] Table 1 Carbon black functional masterbatch test results

[0106]

[0107] According to Table 1 above, the carbon black functional masterbatch prepared by the present invention has a smaller carbon black particle size and relatively better dispersibility than the carbon black functional masterbatch using ordinary carbon black and without adding maleic anhydride grafted polyethylene.

[0108] 2. Pipe preparation

[0109] In order to verify the application performance of the prepared masterbatch, the polyethylene pipe base material and the prepared carbon black functional masterbatch were mixed in a certain weight ratio. After blending in a high-speed mixer, a twin-screw extruder (TSE40-48 twin-screw extruder produced by Nanjing Ruiya Company) was used to melt blend and extrude granulate to obtain the mixed material. The temperatures of each section of the extruder were 160℃, 180℃, 190℃, 190℃, 200℃, 200℃, 200℃, 200℃, 200℃, 200℃, 200℃, 205℃, respectively. The obtained mixed materials were extruded into DN32SDR11 pipes through a single screw pipe extruder (JWS65-33, produced by Shanghai Jinwei Machinery Manufacturing Co., Ltd.), and the temperatures of each section of the extruder were 170℃, 190℃, 190℃, 190℃, 195℃ (die temperature), respectively. The screw speed was adjusted, the unit time capacity was recorded, and the time interval for cleaning the die accumulation was counted. The obtained pipes were tested for carbon black dispersion, carbon black content, oxidation induction period and other properties according to national standards. The test results are shown in Table 2. Among them, the proportion of modified carbon black pigment in the mixture of polyethylene pipe base material and carbon black functional masterbatch is 2.0-2.5wt%.

[0110] Table 2 Raw material ratio and pipe performance test results

[0111]

[0112] According to the experimental data of the embodiments and comparative examples in Table 2 above, it can be seen that the carbon black dispersion of the pipe prepared by extruding the mixed material prepared by using the polyethylene carbon black functional masterbatch of the present invention is good, the oxidation resistance, elongation at break and anti-static hydraulic strength of the pipe are significantly improved, and the production capacity per unit time and the time interval for cleaning the die material accumulation are significantly improved and extended compared with the comparative example, so the material has good processability.

Claims

1. A carbon black functional masterbatch, characterized in that: The method is composed of the following raw materials in parts by weight: 40-80 parts of carrier resin, 0.5-2 parts of maleic anhydride grafted polyethylene, 20-50 parts of modified carbon black pigment, 0.1-0.5 parts of fluorine-containing polymer, and 0.1-1.0 parts of antioxidant; The modified carbon black pigment is prepared by the following method: Dissolve carbon black in toluene, heat to 80-120°C, add the modification system thereto under stirring, heat to 115-120°C and continue the reaction for 1-2h, cool to room temperature, dry under reduced pressure to constant weight, perform Soxhlet extraction with acetone as solvent for 24-36h, and finally dry the sample to obtain a modified carbon black pigment; the modification system is a mixed solution of a multifunctional modifier GMA, 2-phenylimidazoline and toluene; The amount of the modified system is 0.05-0.1 times the amount of carbon black, and the ratio of GMA, 2-phenylimidazoline and toluene in the modified system is 10g: (0.5-1) g: (20-30) mL.

2. The carbon black functional masterbatch according to claim 1, characterized in that: The carbon black has an average primary particle size of 10-25 nm, an oil absorption value in the range of 50 mL / 100 g to 100 mL / 100 g, and a volatile component of less than 3.5 wt %.

3. The carbon black functional masterbatch according to claim 2, characterized in that: The carrier resin is a trimodal high-density polyethylene resin with a melt flow rate of 0.2-0.5 g / 10 min.

4. The carbon black functional masterbatch according to claim 3, characterized in that: The grafting rate of the maleic anhydride grafted polyethylene is 0.85%, and the melt flow rate is 1-3 g / 10 min.

5. The carbon black functional masterbatch according to claim 4, characterized in that: The fluorine-containing polymer is a copolymer formed by vinylidene fluoride and tetrafluoroethylene in a molar ratio of 1:(0.1-0.45).

6. The carbon black functional masterbatch according to claim 5, characterized in that: The antioxidant is one of a hindered phenol antioxidant and a phosphite antioxidant or a mixture of the two in any proportion.

7. A method for preparing the carbon black functional masterbatch according to claim 1, characterized in that: The following steps are involved: (1) Add the carrier resin component into the internal mixer, close the internal mixer charging cover, turn on the heating to make the temperature reach 150°C, start the internal mixer, and stop the internal mixer after the resin is fully plasticized; (2) Open the internal mixer, add modified carbon black pigment, maleic anhydride grafted polyethylene, fluorine-containing polymer and antioxidant, then start the internal mixer and continue to mix. When there is no dispersed carbon black pigment around the mixing chamber and all the materials have become a melt mass with a smooth surface, the mixing is completed; (3) The kneaded mixture is added into the hopper of a single screw extruder, and is extruded, pulled by the material strip, cooled, and pelletized by the single screw extruder to form a black masterbatch.

8. The method for preparing a carbon black functional masterbatch according to claim 7, characterized in that: The upper bolt pressure of the internal mixer in step (1) is 0.39-0.59 MPa; the temperature of the single screw extruder in step (3) is set to: double cone feeding section 120-130°C, compression section 155-170°C, homogenization section 175°C, and head temperature 145°C.

9. Use of the carbon black functional masterbatch according to claim 1 in the preparation of pressure pipes.

Images