A filler masterbatch for pipe outer wall and its preparation method

Abstract

This invention discloses a filler masterbatch for pipe outer walls and its preparation method, belonging to the field of pipe manufacturing technology. It comprises the following raw materials in parts by weight: 30-50 parts high-density polyethylene, 60-100 parts modified talc, 4-8 parts toughening agent, and 2-5 parts lubricant. The preparation steps are as follows: high-density polyethylene, modified talc, toughening agent, and lubricant are added to a high-speed mixer and mixed evenly. Then, the mixture is transferred to a twin-screw extruder for extrusion granulation at an extrusion temperature of 130-180℃ to obtain the filler masterbatch for pipe outer walls. This invention uses high-density polyethylene, modified talc, toughening agent, and lubricant as raw materials, and obtains the filler masterbatch through mixing, extrusion, and granulation. Pipes prepared using the filler masterbatch provided by this invention have good mechanical properties, wear resistance, and weather resistance, reducing subsequent maintenance and repair costs and lowering overall costs.

Description

Technical Field

[0001] This invention belongs to the field of pipeline manufacturing technology, specifically relating to a filler masterbatch for the outer wall of a pipeline and its preparation method. Background Technology

[0002] The demand for double-wall pipes in sewage / drainage systems is growing rapidly, with HD-PE double-wall pipes being particularly prominent. As society progresses, people widely recognize that using high-quality and durable products saves on maintenance and repair costs. The raw material that significantly impacts the quality of HD-PE double-wall pipes is the filler masterbatch for the pipe's outer wall. The main components of the filler masterbatch are fillers (such as calcium carbonate, kaolin, talc, wollastonite, etc.), primarily used in the processing and molding of HD-PE double-wall pipes. To meet various performance requirements of plastic products, various additives and fillers are mixed and compounded with a small amount of matrix resin. For example, Chinese patent CN109181046B discloses a method for preparing a filler masterbatch specifically for PE corrugated pipes, including... The mixture of 30-50 parts carrier resin, 40-60 parts inorganic powder, 3-6 parts coupling agent, 2-5 parts lubricant, 2-5 parts dispersant, 4-8 parts toughening agent, and 1-3 parts black powder can improve the ring stiffness and impact performance of corrugated pipes. However, polyethylene resin has high environmental requirements, poor heat resistance and aging performance, and is easily oxidized and decomposed under ultraviolet light. When used as a filler masterbatch for the outer wall of pipes, it is prone to aging and damage due to prolonged exposure to sunlight. Furthermore, the masterbatch has poor wear resistance, and its use as a filler masterbatch for the outer wall of pipes is prone to friction damage due to friction from equipment and transportation, which leads to inconvenience in pipe maintenance and replacement. Therefore, it is necessary to provide a filler masterbatch for the outer wall of pipes that is resistant to friction and aging. Summary of the Invention

[0003] The purpose of this invention is to provide a filler masterbatch for pipe outer walls and its preparation method, thereby solving the problems of poor wear resistance and weather resistance of existing filler masterbatches for pipe outer walls.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] A filler masterbatch for pipe outer walls comprises the following raw materials in parts by weight:

[0006] 30-50 parts high-density polyethylene, 60-100 parts modified talc, 4-8 parts toughening agent, and 2-5 parts lubricant.

[0007] The method for preparing the filler masterbatch for the outer wall of the pipe includes the following steps:

[0008] High-density polyethylene, modified talc, toughening agent and lubricant are added to a high-speed mixer and mixed evenly. Then the mixture is transferred to a twin-screw extruder for extrusion granulation at an extrusion temperature of 130-180℃ to obtain a filler masterbatch for pipe outer walls.

[0009] Furthermore, the modified talc is obtained through the following steps:

[0010] Talc powder was placed in a drying oven and dried at 120℃ for 6 hours. Then, it was transferred to a high-speed mixer at 60-70℃, and a polysiloxane modifier was added to the high-speed mixer. The mixture was stirred for 10-20 minutes in a rotating system at 2000-2500 r / min to obtain modified talc powder. The mass ratio of talc powder to polysiloxane modifier was 100:5-10. The polysiloxane modifier was used as a modifier for talc powder. The condensation reaction between the carboxyl group of the polysiloxane modifier and the hydroxyl group on the surface of talc powder was used to dry modify the talc powder to obtain modified talc powder.

[0011] Furthermore, the polysiloxane modifier is obtained through the following steps:

[0012] S1. Add hydrogen-containing silicone oil, allyl isothiocyanate, isopropanol chloroplatinate solution and isopropanol to a flask, and react at 80°C for 6-12 hours. After the reaction is complete, remove the isopropanol by rotary evaporation to obtain the intermediate product.

[0013] S2. Add the cysteine-based benzophenone graft and DMF to a flask, stir for 3-5 min, then add dibutyltin dilaurate dropwise. After the addition is complete, add the DMF solution of the intermediate product dropwise while stirring. After the addition is complete, heat to 50℃ and stir for 4-6 h, then cool to room temperature and continue the reaction for 48 h. Finally, remove DMF by vacuum distillation to obtain the polysiloxane modifier.

[0014] First, a hydrosilylation reaction is carried out using allyl isothiocyanate and hydrogen-containing silicone oil to introduce -N=C=S groups onto the long silicon chain. Then, the amino group in the cysteine-based benzophenone graft reacts with the -N=C=S group to form a polysiloxane modifier containing a thiourea structure, a hydroxybenzophenone structure, and an active carboxyl group.

[0015] Furthermore, the ratio of hydrogen-containing silicone oil, allyl isothiocyanate, isopropanol chloroplatinate solution, and isopropanol in S1 is 5g:2.4-3.0g:0.3-0.5g:100-200mL, the active hydrogen content in the hydrogen-containing silicone oil is 0.5%, and the mass fraction of chloroplatinic acid in the isopropanol chloroplatinate solution is 1-3wt%.

[0016] Furthermore, the mass ratio of cysteine-based benzophenone graft, dibutyltin dilaurate, and intermediate in S2 is 8.5-9.0:0.05-0.06:7.8-8.2.

[0017] Furthermore, the cysteine-based benzophenone graft compound was obtained through the following steps:

[0018] 2-Hydroxy-4-acryloyloxybenzophenone, benzoin dimethyl ether, L-cysteine, and anhydrous ethanol were mixed and stirred until homogeneous. The mixture was then placed under a UV lamp with a wavelength of 100-400 nm for 30-60 min. After the reaction was completed, the anhydrous ethanol was removed by rotary evaporation to obtain the cysteine-based benzophenone graft. The molar ratio of 2-hydroxy-4-acryloyloxybenzophenone, benzoin dimethyl ether, L-cysteine, and anhydrous ethanol was 0.1 mol: 0.26-0.38 g: 0.1-0.11 mol: 300-500 mL. Using 2-hydroxy-4-acryloyloxybenzophenone and L-cysteine ​​as raw materials and benzoin dimethyl ether as a photoinitiator, the cysteine-based benzophenone graft was obtained through a mercapto-olefin click reaction. The graft contained a hydroxybenzophenone structure, amino and carboxyl active groups.

[0019] Furthermore, the toughening agent is polyolefin elastomer POE.

[0020] Furthermore, the lubricant is one or more of polyethylene wax, EVA wax, or oxidized polyethylene wax.

[0021] The beneficial effects of this invention are:

[0022] 1. This invention provides a filler masterbatch for pipe outer walls, which is obtained by mixing, extruding and granulating high-density polyethylene, modified talc, toughening agent and lubricant. It has good wear resistance and weather resistance. Pipes prepared using the filler masterbatch provided by this invention have good mechanical properties, wear resistance and weather resistance, reducing the investment in later maintenance and repair and lowering costs.

[0023] 2. This invention adds self-made modified talc powder to the filler masterbatch used on the outer wall of the pipe. The talc powder is chemically modified with a polysiloxane modifier, reducing the hydroxyl content on the talc powder surface while introducing hydrophobic siloxane long chains. This improves the compatibility between talc powder and high-density polyethylene (HDPE), ensuring uniform dispersion of the flake-like talc powder within the HDPE. Under external force, stress concentration is generated, introducing surrounding groups to create microcracks that absorb deformation energy, thus improving impact resistance. Furthermore, the introduction of a polysiloxane structure into the masterbatch matrix, with its high Si-O-Si bond energy, excellent heat resistance, and good chain flexibility, further enhances the material's impact resistance. In addition, the polysiloxane modifier molecular chain also contains hydroxybenzophenone and thiourea structures. The hydroxybenzophenone structure absorbs ultraviolet light, while the thiourea structure effectively decomposes hydrogen peroxide and terminates reactive oxygen free radicals. Combined with the ultraviolet reflection and blocking effects of talc powder, these three elements synergistically enhance the material's excellent weather resistance.

[0024] 3. The present invention adds self-made modified talc powder to the filler masterbatch used on the outer wall of the pipe. The introduction of modified talc powder increases the surface hardness of the material, making it difficult to scratch. The polysiloxane modifier on the surface of the modified talc powder has migration properties, and the molecular chains can migrate to the surface of the material to form a lubricating protective film, and drive the uniform dispersion of talc powder, ultimately resulting in a material with excellent wear resistance. Detailed Implementation

[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] Example 1

[0027] A polysiloxane modifier is obtained through the following steps:

[0028] S1. Add 5g of hydrogen-containing silicone oil, 2.4g of allyl isothiocyanate, 0.3g of isopropanol chloroplatinate solution and 100mL of isopropanol to a flask and react at 80℃ for 6h. After the reaction is complete, remove the isopropanol by rotary evaporation to obtain the intermediate product. The active hydrogen content in the hydrogen-containing silicone oil is 0.5%, which was purchased from Nanjing Shengtek New Materials Co., Ltd. The mass fraction of chloroplatinic acid in the isopropanol chloroplatinate solution is 1wt%.

[0029] S2. Add 8.5g of cysteine-based benzophenone graft and 100mL of DMF to a flask, stir for 3min, and then add 0.05g of dibutyltin dilaurate dropwise. After the addition is complete, add a solution consisting of 7.8g of intermediate product and 100mL of DMF dropwise while stirring. After the addition is complete, heat to 50℃ and stir for 4h. Then cool to room temperature and continue the reaction for 48h. Finally, remove DMF by vacuum distillation to obtain the polysiloxane modifier.

[0030] Cysteine-based benzophenone grafts were obtained through the following steps:

[0031] 0.1 mol of 2-hydroxy-4-acryloyloxybenzophenone, 0.26 g of benzoin dimethyl ether, 0.1 mol of L-cysteine ​​and 300 mL of anhydrous ethanol were mixed and stirred evenly. The mixture was then placed under a UV lamp with a wavelength of 100-400 nm for 30 min. After the reaction was completed, the anhydrous ethanol was removed by rotary evaporation to obtain the cysteine-based benzophenone graft.

[0032] Example 2

[0033] A polysiloxane modifier is obtained through the following steps:

[0034] S1. Add 5g of hydrogen-containing silicone oil, 3.0g of allyl isothiocyanate, 0.5g of isopropanol chloroplatinate solution and 200mL of isopropanol to a flask and react at 80℃ for 12h. After the reaction is complete, remove the isopropanol by rotary evaporation to obtain the intermediate product. The active hydrogen content in the hydrogen-containing silicone oil is 0.5%, which was purchased from Nanjing Shengtek New Materials Co., Ltd. The mass fraction of chloroplatinic acid in the isopropanol chloroplatinate solution is 3wt%.

[0035] S2. Add 9.0 g of cysteine-based benzophenone graft and 100 mL of DMF to a flask, stir for 5 min, and then add 0.06 g of dibutyltin dilaurate dropwise. After the addition is complete, add a solution consisting of 8.2 g of intermediate product and 100 mL of DMF dropwise while stirring. After the addition is complete, heat to 50 °C and stir for 6 h. Then cool to room temperature and continue the reaction for 48 h. Finally, remove DMF by vacuum distillation to obtain the polysiloxane modifier.

[0036] Cysteine-based benzophenone grafts were obtained through the following steps:

[0037] 0.1 mol of 2-hydroxy-4-acryloyloxybenzophenone, 0.38 g of benzoin dimethyl ether, 0.11 mol of L-cysteine ​​and 500 mL of anhydrous ethanol were mixed and stirred evenly. The mixture was then placed under a UV lamp with a wavelength of 100-400 nm for 60 min. After the reaction was completed, the anhydrous ethanol was removed by rotary evaporation to obtain the cysteine-based benzophenone graft.

[0038] Comparative Example 1

[0039] A polysiloxane modifier is obtained through the following steps:

[0040] S1. Add 5g of hydrogen-containing silicone oil, 3.0g of acrylic acid, 0.5g of isopropanol chloroplatinic acid solution and 200mL of isopropanol to a flask and react at 80℃ for 12h. After the reaction is complete, remove the isopropanol by rotary evaporation to obtain the intermediate product. The active hydrogen content in the hydrogen-containing silicone oil is 0.5%, which was purchased from Nanjing Shengtek New Materials Co., Ltd. The mass fraction of chloroplatinic acid in the isopropanol chloroplatinic acid solution is 1wt%.

[0041] Example 3

[0042] A modified talc powder is obtained through the following steps:

[0043] 100g of talc powder was placed in a drying oven and dried at 120℃ for 6 hours. Then it was transferred to a high-speed mixer at 60℃. 5g of the polysiloxane modifier from Example 1 was added to the high-speed mixer and mixed for 10 minutes in a rotating system at 2000r / min to obtain modified talc powder.

[0044] Example 4

[0045] A modified talc powder is obtained through the following steps:

[0046] 100g of talc powder was placed in a drying oven and dried at 120°C for 6 hours. Then it was transferred to a high-speed mixer at 70°C. 10g of the polysiloxane modifier from Example 2 was added to the high-speed mixer and mixed for 20 minutes in a rotating system at 2500r / min to obtain modified talc powder.

[0047] Comparative Example 2

[0048] A modified talc powder, compared with Example 3, replaces the polysiloxane modifier in Example 3 with the substance in Comparative Example 1, and the other raw materials and preparation process are the same as in Example 3.

[0049] Comparative Example 3

[0050] A modified talc powder, compared with Example 3, replaces the polysiloxane modifier in Example 3 with stearic acid, and the remaining raw materials and preparation process are the same as in Example 3.

[0051] Example 5

[0052] A filler masterbatch for pipe outer walls comprises the following raw materials in parts by weight:

[0053] 30 parts of high-density polyethylene, 60 parts of modified talc powder (Example 3), 4 parts of toughening agent, and 2 parts of lubricant.

[0054] The method for preparing the filler masterbatch for the outer wall of the pipe includes the following steps:

[0055] High-density polyethylene, modified talc, toughening agent and lubricant are added to a high-speed mixer and mixed evenly. Then the mixture is transferred to a twin-screw extruder for extrusion granulation at an extrusion temperature of 130-180℃ to obtain a filler masterbatch for pipe outer walls.

[0056] The toughening agent is polyolefin elastomer POE (DuPont POE8200), and the lubricant is polyethylene wax.

[0057] Example 6

[0058] A filler masterbatch for pipe outer walls comprises the following raw materials in parts by weight:

[0059] 40 parts of high-density polyethylene, 80 parts of modified talc powder (Example 4), 6 parts of toughening agent, and 4 parts of lubricant.

[0060] The method for preparing the filler masterbatch for the outer wall of the pipe includes the following steps:

[0061] High-density polyethylene, modified talc, toughening agent and lubricant are added to a high-speed mixer and mixed evenly. Then the mixture is transferred to a twin-screw extruder for extrusion granulation at an extrusion temperature of 130-180℃ to obtain a filler masterbatch for pipe outer walls.

[0062] The toughening agent is polyolefin elastomer POE (DuPont POE8200), and the lubricant is EVA wax.

[0063] Example 7

[0064] A filler masterbatch for pipe outer walls comprises the following raw materials in parts by weight:

[0065] 50 parts of high-density polyethylene, 100 parts of modified talc powder (Example 4), 8 parts of toughening agent, and 5 parts of lubricant.

[0066] The method for preparing the filler masterbatch for the outer wall of the pipe includes the following steps:

[0067] High-density polyethylene, modified talc, toughening agent and lubricant are added to a high-speed mixer and mixed evenly. Then the mixture is transferred to a twin-screw extruder for extrusion granulation at an extrusion temperature of 130-180℃ to obtain a filler masterbatch for pipe outer walls.

[0068] The toughening agent is polyolefin elastomer POE (DuPont POE8200), and the lubricant is polyethylene wax.

[0069] Comparative Example 4

[0070] A filler masterbatch for the outer wall of a pipe, compared with Example 5, replaces the modified talc powder in Example 5 with the substance in Comparative Example 2, while the other raw materials and preparation process remain unchanged.

[0071] Comparative Example 5

[0072] A filler masterbatch for the outer wall of a pipe, compared with Example 5, replaces the modified talc powder in Example 5 with the substance in Comparative Example 3, while the other raw materials and preparation process remain unchanged.

[0073] The filler masterbatches obtained in Examples 5-7 and Comparative Examples 4-5 were blended with high-density polyethylene at a mass ratio of 80:20 and then compressed to prepare samples. The preparation method of the compression molded samples was in accordance with GB / T9352-2008. The performance of the obtained samples was then tested.

[0074] Tensile strength: The tensile properties of the material samples were tested according to GB / T1040-2018 "Determination of tensile properties of plastics". The tensile speed was 50 mm / min, and the measurement was performed 5 times. The final result was the average value.

[0075] Notched impact strength: Tested on a UJ-40 impact testing machine according to GB / T1843, 5 times, and the final result is the average value;

[0076] Coefficient of friction: The surface friction coefficient of the material was determined using a friction / peel tester and in accordance with ISO 8295-1995 "Determination of coefficient of friction of plastic films and sheets". The measurement was performed three times and the final result was the average value.

[0077] Weather resistance: The xenon lamp accelerated aging test was conducted according to GB / T16422.2-1999. The test temperature was 65℃±3℃ and the relative humidity was (65℃±3)%. The tensile strength was observed after 1000h of xenon lamp aging. The smaller the change in tensile strength, the higher the weather resistance.

[0078] The results are shown in Table 1:

[0079] Table 1

[0080]

[0081] As can be seen from Table 1, compared with Comparative Examples 4 and 5, the filler masterbatches obtained in Examples 5, 6 and 7 not only have better mechanical properties, but also excellent friction resistance and aging resistance.

[0082] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0083] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A filler masterbatch for the outer wall of a pipe, characterized in that, Including the following parts by weight of raw materials: 30-50 parts high-density polyethylene, 60-100 parts modified talc, 4-8 parts toughening agent, and 2-5 parts lubricant; The modified talc powder is obtained through the following steps: Talc powder was placed in a drying oven and dried at 120℃ for 6 hours. Then it was transferred to a high-speed mixer at 60-70℃. Polysiloxane modifier was added to the high-speed mixer and mixed for 10-20 minutes in a rotating system at 2000-2500 r / min to obtain modified talc powder. The mass ratio of talc powder to polysiloxane modifier was 100:5-10. The polysiloxane modifier is obtained through the following steps: S1. Add hydrogen-containing silicone oil, allyl isothiocyanate, isopropanol chloroplatinate solution and isopropanol to a flask, and react at 80°C for 6-12 hours. After the reaction is complete, remove the isopropanol by rotary evaporation to obtain the intermediate product. S2. Add cysteine-based benzophenone graft and DMF to a flask, stir for 3-5 min, then add dibutyltin dilaurate dropwise. After the addition is complete, add the DMF solution of the intermediate product dropwise while stirring. After the addition is complete, heat to 50℃ and stir for 4-6 h, then cool to room temperature and continue the reaction for 48 h. Finally, remove DMF by vacuum distillation to obtain the polysiloxane modifier. The ratio of hydrogen-containing silicone oil, allyl isothiocyanate, isopropanol chloroplatinate solution, and isopropanol in S1 is 5g:2.4-3.0g:0.3-0.5g:100-200mL. The active hydrogen content in the hydrogen-containing silicone oil is 0.5%, and the mass fraction of chloroplatinic acid in the isopropanol chloroplatinate solution is 1-3wt%. The mass ratio of cysteine-based benzophenone graft, dibutyltin dilaurate, and intermediate in S2 is 8.5-9.0:0.05-0.06:7.8-8.

2. Cysteine-based benzophenone grafts were obtained through the following steps: 2-hydroxy-4-acryloyloxybenzophenone, benzoin dimethyl ether, L-cysteine ​​and anhydrous ethanol were mixed and stirred evenly. The mixture was then placed under a UV lamp with a wavelength of 100-400 nm for 30-60 min. After the reaction was completed, the anhydrous ethanol was removed by rotary evaporation to obtain the cysteine-based benzophenone graft. The ratio of 2-hydroxy-4-acryloyloxybenzophenone, benzoin dimethyl ether, L-cysteine ​​and anhydrous ethanol is 0.1 mol: 0.26-0.38 g: 0.1-0.11 mol: 300-500 mL.

2. The method for preparing a filler masterbatch for the outer wall of a pipe according to claim 1, characterized in that, Includes the following steps: High-density polyethylene, modified talc, toughening agent and lubricant are added to a high-speed mixer and mixed evenly. Then the mixture is transferred to a twin-screw extruder for extrusion granulation at an extrusion temperature of 130-180℃ to obtain a filler masterbatch for pipe outer walls.

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