Polar HDPE (high-density polyethylene)-based material special for pipelines for aquaculture facilities as well as preparation method and application of polar HDPE-based material

Abstract

The invention provides a polar HDPE (high-density polyethylene)-based special material for pipelines for aquaculture facilities as well as a preparation method and application of the polar HDPE-based special material. The preparation method specifically comprises the following steps: mixing oyster shell powder coated TiO2 inorganic micro-nano functional powder, a surface activation modifier, a high-polarity HDPE material and a processing aid A, and carrying out melt extrusion granulation to obtain high-polarity HDPE / oyster shell powder coated TiO2 filled master batches; and blending extrusion-grade HDPE, ultra-high molecular weight polyethylene, the high-polarity HDPE / oyster shell powder coated TiO2 filling master batch, an antioxidant and a processing aid B, and carrying out melt extrusion granulation to obtain the novel material with high strength, high toughness and aging resistance. And meanwhile, the material also has excellent weldability. The novel material prepared by adopting the formula design and the production process provided by the scheme of the invention can completely meet high requirements of pipeline products for aquatic product (seawater and fresh water) aquaculture facilities on material performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a special material for pipelines used in aquaculture facilities based on polar HDPE, a preparation method thereof, and an application thereof. Background Art

[0002] With the improvement of people's living standards, the demand for aquatic products will continue to grow. It is estimated that by 2030, China will have a gap of 20 million tons of aquatic products to make up, and increasing the output of aquatic products mainly depends on the development of aquaculture. Nowadays, aquaculture mostly focuses on onshore and offshore aquaculture, and basically does not utilize the deep-sea areas with a relatively large proportion in the nearly 3 million km 2 of the marine national territory. Therefore, developing offshore aquaculture, especially deep-sea aquaculture, to form a "blue granary" of high-quality protein and provide food safety assurance has become the focus of the future development of the aquaculture industry. Moreover, deep-sea aquaculture not only optimizes the spatial layout of aquaculture but also effectively promotes the transformation and upgrading of marine fisheries.

[0003] The development of offshore aquaculture is inseparable from the support of fishery facilities and equipment. In order to resist the influence of harsh sea conditions (including wind, waves, and currents), ensure life and property safety, and at the same time protect the aquaculture objects from marine physical, chemical, or biological disasters, plastic pipes and pipe fittings, as important components in offshore aquaculture facilities and equipment, must meet performance requirements such as good corrosion resistance, impact resistance, weather resistance, flexibility, and sealing performance. To achieve such requirements, the key lies in the characteristics of the selected materials and the structural design of the products.

[0004] High-density polyethylene (HDPE) material is a thermoplastic resin with high crystallinity, non-toxic, odorless, and semi-transparent granular shape. It has good weather resistance, corrosion resistance, chemical stability, anti-aging ability, and excellent elongation at break. It does not produce electrochemical corrosion and can adapt to the harsh high-intensity sunlight, corrosive environment, and large waves at sea. Currently, it has been used as a material for making marine cages and rafts. However, the HDPE material also has the defect of excessive flexibility and insufficient rigidity. The overly flexible performance makes the raft prone to creep and bend, thus making it difficult for the aquaculture and harvesting of aquatic products.

[0005] In summary, modifying HDPE resin through raw material and process design to prepare a special material with excellent performance suitable for marine aquaculture pipelines to ensure aquaculture safety and good comprehensive benefits is a technical problem that needs to be urgently solved by those skilled in the art. Summary of the Invention

[0006] The purpose of the present invention is to provide a preparation method for a special material for polar HDPE-based pipelines for aquaculture facilities. In the present invention, extrusion-grade HDPE, ultra-high molecular weight polyethylene, high-polarity HDPE, and oyster shell powder@TiO2 micro-nano new materials are used as raw materials. Through simple blending and extrusion, a new material that takes into account mechanical properties and aging resistance and has low cost is obtained. The overall technical solution is simple and efficient, with low energy consumption, safe and environmentally friendly process, suitable for large-scale industrial production, and has broad market prospects.

[0007] To achieve the above object, the present invention provides a preparation method for a special material for polar HDPE-based pipelines for aquaculture facilities, comprising the following steps:

[0008] (1) Preparation of high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch: Mix oyster shell powder@TiO2 inorganic micro-nano functional powder, surface activation modifier, high-polarity HDPE material, and processing aid A evenly, and melt-extrude and pelletize to obtain high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch;

[0009] (2) Preparation of special material for polar HDPE-based pipelines for aquaculture facilities: Blend extrusion-grade HDPE, ultra-high molecular weight polyethylene (UHMWPE), the high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch prepared in step (1), antioxidant, and processing aid B, and melt-extrude and pelletize to obtain a special polar HDPE-based material suitable for pipelines for aquaculture facilities.

[0010] In a preferred embodiment, in step (1), by weight, it includes the following components: 40-60 parts of high-polarity HDPE material, 40-60 parts of oyster shell powder@TiO2 inorganic micro-nano functional powder, 1.5-3.0 parts of surface activation modifier, and 1.5-5.0 parts of processing aid A; preferably, 45-50 parts of high-polarity HDPE material, 45-50 parts of oyster shell powder@TiO2 inorganic micro-nano functional powder, 2.0-2.5 parts of surface activation modifier, and 2.5-3.0 parts of processing aid A; more preferably, the total weight of the high-polarity HDPE material, oyster shell powder@TiO2 inorganic micro-nano functional powder, surface activation modifier, and processing aid A is 100 parts in total.

[0011] In a preferred embodiment, in step (1), the oyster shell powder@TiO2 inorganic micro-nano functional powder is prepared by the following method:

[0012] S1 Use mechanical grinding method to grind rutile TiO2 to a primary particle size of 2-5 μm;

[0013] S2 mixes the ground TiO2 and oyster shell powder in a mass ratio of (10:90)-(20:80), and mechanically grinds for 1-2 h to make the interfaces of the two combine, obtaining oyster shell powder@TiO2 micro-nano functional powder materials with an ordered composite structure and stabilized microstructure.

[0014] The product indexes of the prepared oyster shell powder@TiO2 inorganic micro-nano functional powder include: (1) particle size <2 μm, content ≥90%; (2) DBP oil absorption ≤25 ml / 100 g; (3) whiteness ≥90%; (4) TiO2 content ≤20%; (5) bulk density 0.25-0.35 g / cm 3 ; (6) pH value of water suspension 6.5-8.5; (7) volatile matter at 105 °C ≤0.5%.

[0015] Oyster shells have a highly regular organic-inorganic cross-layered structure. Such layered structures can achieve multi-pole toughening at different scales due to their unique structure and composition, making the strength and toughness of oyster shells several orders of magnitude higher than those of ordinary calcite minerals, and thus greatly improving the mechanical properties of resin materials. At the same time, the natural bio-mineralization characteristics and unique structure of oyster shells endow them with strong antibacterial, bactericidal, anti-corrosion and anti-tick functions. Rutile titanium dioxide (TiO2) has good chemical stability and obvious absorption effect on ultraviolet rays, which can endow the composite material with anti-aging performance. Using the mechanical force grinding method provided by the present invention to prepare oyster shell powder@TiO2 composite particles can form a micro-nano binary structure, reduce the bulk density and increase the oil absorption value, realizing the technical principle of preparing high-performance polymer composite materials by filling inorganic powder into polymers. Experimental results show that filling the oyster shell powder@TiO2 composite particles into polyolefin polymers or copolymers by this method can significantly increase the tensile strength, flexural modulus and flexural strength of the prepared composite materials, and have certain anti-ultraviolet aging performance, and can be applied to the field of marine aquaculture.

[0016] In a preferred embodiment, in step (1), the high-polarity HDPE material is glycidyl methacrylate (GMA) monomer grafted injection molding grade HDPE, with a grafting rate of 1.5-2.0% and a melt flow rate (MFR) of 5.0-8.0 g / 10 min; preferably, the grafting rate of the high-polarity HDPE material is 1.8-2.0%; MFR is 6.0-8.0 g / 10 min; more preferably, glycidyl methacrylate (GMA) monomer is used to graft HDPE-6098, with a grafting rate of 1.85%; MFR is 6.0-6.5 g / 10 min.

[0017] HDPE is a non-polar polymer with low bonding strength and poor coloring property. Therefore, in the present invention, glycidyl methacrylate (GMA) polar monomer containing epoxy functional group is melt grafted with injection molding grade HDPE material to obtain highly polar HDPE (HDPE-g-GMA). In the present invention, adding the HDPE-g-GMA and the filler masterbatch prepared from oyster shell powder @TiO2 into the HDPE matrix material can greatly improve the dispersion degree of oyster shell powder @TiO2 in the HDPE matrix. At the same time, the GMA monomer floating on the surface of the HDPE-based pipe changes the overall polarity of the HDPE substrate, improves the bonding strength between the pipe and the fitting, and is suitable for bonding with acrylic adhesives. Since the GMA monomer is alkaline and acts synergistically with the micro-nano structured oyster shell powder @TiO2, the UV aging resistance of the HDPE-based pipe and fitting is greatly improved.

[0018] In a preferred embodiment, in step (1), the surface activation modifier includes one or more of stearic acid, aluminate coupling agent, titanate coupling agent and silane coupling agent; preferably, an aluminate coupling agent with an aluminum content ≥8% and stearic acid are compounded and used in a mass ratio of 3:1.

[0019] In a preferred embodiment, in step (1), the processing aid A includes one or more of ethylene bisstearamide (EBS), perfluoroethylene propylene (FEP) concentrated dispersion, PE wax, zinc stearate (ZnSt2), antioxidant 1010, liquid paraffin and dimethyl silicone oil; preferably, the processing aid A selects two or more of perfluoroethylene propylene (FEP) concentrated dispersion, PE wax, zinc stearate (ZnSt2), antioxidant 1010, and more preferably, the processing aid A selects perfluoroethylene propylene (FEP) concentrated dispersion and / or antioxidant 1010.

[0020] In a preferred embodiment, in step (1), the conditions for uniform mixing include: stirring at 500-700 rpm until the temperature is above 120°C; preferably, the mixing equipment is a high-speed mixer.

[0021] In a preferred embodiment, in step (1), the melt extrusion temperature is 160-200°C; preferably, the melt extrusion equipment uses a co-rotating twin-screw extruder with a length-diameter ratio ≥40:1 for air-cooled strand pelletizing production.

[0022] In a preferred embodiment, in step (2), by weight parts, it includes the following components: 55 - 75 parts of extrusion - grade HDPE, 5.0 - 25 wt% of ultra - high - molecular - weight polyethylene (UHMWPE) based on the total weight of HDPE, 20 - 40 parts of high - polarity HDPE / oyster shell powder@TiO₂ filled masterbatch prepared in step (1), 0.2 - 0.6 parts of antioxidant, and 0.5 - 2.0 parts of processing aid B; preferably, 60 - 70 parts of extrusion - grade HDPE, 5.0 - 25 wt% of ultra - high - molecular - weight polyethylene based on the total weight of HDPE, 20 parts of high - polarity HDPE / oyster shell powder@TiO₂ filled masterbatch, 0.3 - 0.4 parts of antioxidant, and 0.6 - 1.0 parts of processing aid B; more preferably, the total weight parts of extrusion - grade HDPE, UHMWPE, high - polarity HDPE / oyster shell powder@TiO₂ filled masterbatch, antioxidant, and processing aid B total 100 parts in total; in this step, the total weight of HDPE is the weight of all HDPE in step (1) and step (2), that is, UHMWPE is 5.0 - 25 wt% of the total weight of all HDPE in step (1) and step (2).

[0023] In a preferred embodiment, in step (2), the melt flow rate (MFR) of the extrusion - grade HDPE is 0.5 - 2.0 g / 10 min (190 °C, 5.0 kg); preferably, the MFR of the extrusion - grade HDPE is 0.5 - 0.8 g / 10 min (190 °C, 5.0 kg); more preferably, the extrusion - grade HDPE is selected from one of HDPE 6380M, HDPE B5703, and HDPE 5000s, and most preferably, HDPE 6380M produced by Yanshan Petrochemical is selected.

[0024] In a preferred embodiment, in step (2), the ultra - high - molecular - weight polyethylene (UHMWPE) is in powder form, and its relative molecular weight is 300 - 700×10 4 g / mol, and the particle size is 80 - 120 um; preferably, the relative molecular weight of UHMWPE is 350 - 600×10 4 g / mol, and the particle size is 80 - 120 μm; more preferably, the relative molecular weight of UHMWPE is 500 - 600×10 4 g / mol, and it is in powder form with a particle size of 120 μm; most preferably, UHMWPE U050 with a particle size of 120 mesh and a relative molecular weight of 500×10 4 g / mol.

[0025] Ultra - high - molecular - weight polyethylene (UHMWPE) is a thermoplastic engineering plastic, and its molecular structure is the same as that of polyethylene (PE), and the molecular weight can reach (100 - 2000)×104 。The higher molecular weight endows UHMWPE with excellent properties such as abrasion resistance, impact resistance, self-lubrication, corrosion resistance, low-temperature resistance, hygienic non-toxicity, non-stickiness, low water absorption, and low density. At room temperature, its impact strength is more than 10 times that of ordinary polyethylene, and it can reach more than 16 times at -30°C. Between -265°C and 80°C, UHMWPE can maintain good toughness and strength. In the present invention, by blending and compounding UHMWPE with HDPE, a HDPE composite reinforcing material with good processing performance and excellent mechanical properties is prepared. Further, through the reasonable design of raw materials and ratios, the extrusion-grade HDPE, UHMWPE, HDPE-g-GMA, and oyster shell powder@TiO2 micro-nano binary structure new materials produce a synergistic effect, and a polar HDPE-based special material suitable for aquaculture facility pipelines is prepared, which is of great significance to the development of aquaculture facility equipment in China.

[0026] In a preferred embodiment, in step (2), the antioxidant includes antioxidant 1010 and / or antioxidant 168. Preferably, the antioxidant is compounded and used by antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0027] In a preferred embodiment, in step (2), the processing aid B includes one or more of calcium stearate, zinc stearate, PE wax, PPA fluorinated processing aid, white mineral oil, and dimethyl silicone oil; preferably, the processing aid B is compounded and used by PPA fluorinated processing aid and dimethyl silicone oil in a mass ratio of 1:2.

[0028] In a preferred embodiment, in step (2), the blending conditions include: the stirring and mixing speed is 600-800 rpm, and the stirring time is 5-8 min; preferably, the mixing equipment is a high-speed mixer.

[0029] In a preferred embodiment, in step (2), the melt extrusion temperature is 160-200°C, and the screw speed is: 300-400 rpm; preferably, the melt extrusion equipment uses a co-rotating twin-screw extruder with a length-to-diameter ratio of ≥40:1, water-cooled strand pelletizing, and the MFR (190°C, 5.0 kg) of the pelletized particles ≤0.5 g / 10 min.

[0030] In a preferred embodiment, in step (2), a polar HDPE-based special material suitable for aquaculture facility pipelines is prepared, and its tensile strength ≥45 MPa; elongation at break ≥500%; flexural strength ≥40 MPa; flexural modulus ≥1400 MPa; IZOD notched impact strength ≥60 MPa; heat distortion temperature (1.86 MPa) ≥75°C; melt index (190°C, 5.0 kg) ≤0.5 g / 10 min.

[0031] Another object of the present invention is to provide a special material for pipelines used in polar HDPE-based aquaculture facilities prepared by the method described in any one of the above.

[0032] Another object of the present invention is to provide a special material for pipelines used in polar HDPE-based aquaculture facilities prepared by the method described in any one of the above, which is applied to product fields such as bionic functional HDPE-based bamboo joint pipelines, pipeline components for aquaculture cages (including seawater and freshwater), and buoyancy pipelines for raft rafts. Specifically, according to the mechanical index requirements of different pipeline products, by adjusting the composition ratio of extruded HDPE, UHMWPE, and high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch, through simple blending, a special material for pipelines used in polar HDPE-based aquaculture facilities can be obtained by using a parallel co-rotating twin-screw extruder with a length-diameter ratio ≥ 40:1. The obtained special material can be used to prepare pipelines by using a general PE pipe extrusion machine.

[0033] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0034] 1. Based on the basic principle of the molten-state chemical reaction technology, this technical solution adopts a "two-step method". First, a high-polarity HDPE material and a novel oyster shell powder@TiO2 inorganic micro-nano functional powder are blended and melt-extruded to obtain a high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch; then, extruded HDPE, UHMWPE, and high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch are blended and melt-extruded to obtain a special material for pipelines used in polar HDPE-based aquaculture facilities suitable for general PE pipe extrusion equipment.

[0035] 2. In the step of preparing the special material for pipelines used in polar HDPE-based aquaculture facilities, the present invention's solution improves the impact resistance, wear resistance, and elongation at break of the existing HDPE-based pipeline materials by adding UHMWPE; by adding a high-polarity HDPE material, the surface polarity of the HDPE-based pipeline is increased, and the bonding strength between the pipeline and the pipe fittings prepared by basically the same process as this technical solution is improved; then, the oyster shell powder@TiO2 inorganic micro-nano functional powder with a micro-nano binary structure is blended with the above raw materials, which not only greatly improves the mechanical properties of the HDPE-based pipeline, but also plays the role of TiO2 in protecting the pipeline from ultraviolet aging and the aquaculture environment.

[0036] 3. The pipelines prepared by using the special material for pipelines used in HDPE-based aquaculture facilities prepared by this technical solution fully meet the performance requirements of aquaculture (seawater, freshwater) for equipment and facilities. In terms of the comprehensive performance of the materials, it is completely incomparable to the HDPE aquaculture facility pipes prepared by using HDPE100-class pressure pipe materials in the existing conventional technology.

[0037] 4. The preparation process of the present invention is simple, with low energy consumption, safe and environmentally friendly in the production process, short operation time, easy to control the operation steps, and good for the production environment, and is suitable for large-scale continuous production. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] These and / or other aspects and advantages of the present invention will become clearer and easier to understand from the following detailed description of the embodiments of the present invention in conjunction with the drawings, wherein:

[0039] Figure 1 It is the microscopic morphology of the oyster shell powder raw material (a), rutile TiO2 raw material (b) and the prepared oyster shell powder@TiO2 inorganic micro-nano functional powder (c) in the embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0040] In order to enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below in conjunction with the specific embodiments, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0041] The embodiment of the present invention provides a special material for pipelines for aquaculture facilities based on polar HDPE, its preparation method and application, and solves the problem of insufficient performance of the existing pipeline materials for aquaculture facilities based on HDPE.

[0042] The technical solutions of the present application will be described in detail below through specific embodiments:

[0043] Unless otherwise specified, the technical means used in the present invention are conventional means well known to those skilled in the art. All kinds of raw materials, reagents, instruments and equipment used in the present invention can be obtained through the market or can be prepared by existing methods. The reagents used in the present invention are all analytical pure unless otherwise specified. In the embodiment of the present invention, the glycidyl methacrylate (GMA) monomer is grafted onto HDPE-6098, and the grafting rate is 1.85%; the MFR is 6.0-6.5 g / 10 min. The oyster shell powder used in the present invention is derived from the washed and pre-dried oyster shell powder in Qingdao, Shandong, and its particle size is 500-800 mesh.

[0044] In the embodiment of the present invention, the oyster shell powder@TiO2 inorganic micro-nano functional powder is prepared by the following method:

[0045] S1. Adopt the mechanical grinding method to grind rutile TiO2 and zirconia grinding medium in a mass ratio of 1:3 for 60 min until the primary particle size is 2-5 μm;

[0046] S2 mixes the ground TiO2 and oyster shell powder in a mass ratio of 15:85, and mechanically grinds the mixture and zirconia grinding media in a mass ratio of 1:4 for 90 min to bond their interfaces, obtaining oyster shell powder@TiO2 micro-nano functional powder materials with an ordered composite structure and stabilized microstructure.

[0047] The morphology of the prepared functional powder is as Figure 1 shown in (c). It can be seen from the figure that nano-scale TiO2 has been uniformly coated on the surface of micro-scale oyster shell powder, and the two form a micro-nano structure. The agglomeration of TiO2 is opened, exposing more active sites, thus saving more usage compared to the rutile TiO2 raw material.

[0048] In the present invention, parts by weight can be well-known weight units in the art such as μg, mg, g, kg, etc., or multiples thereof, such as 1 / 10, 1 / 100, 10 times, 100 times, etc.

[0049] Example 1

[0050] A preparation method of a special material for polar HDPE-based aquaculture facility pipelines:

[0051] (1) Preparation of high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch: Put 50 parts of oyster shell powder@TiO2 inorganic micro-nano functional powder, 2.0 parts of aluminate coupling agent, and 0.4 part of stearic acid into a high-speed mixer. After stirring and heating to 120 °C at medium-high speed, then add 45 parts of glycidyl methacrylate (GMA)-grafted HDPE-6098, 0.1 part of antioxidant 1010, and 2.5 parts of perfluoroethylenepropylene (FEP) concentrated dispersion liquid. Stir at 600 rpm for 5 min until uniformly dispersed, and then transfer it to a co-rotating twin-screw extruder with a length-diameter ratio of 40:1. The temperature of the extruder barrel is controlled at 150-200 °C; the screw speed is 450 rpm to obtain a high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch.

[0052] (2) Preparation of Special Pipe Material Based on Polar HDPE for Aquaculture Facilities: 69.8 parts of HDPE-6380M, 9.0 parts of UHMWPE U050, 20 parts of high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch, 0.4 parts of antioxidant (a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1), and 0.8 parts of processing aid B (a mixture of PPA fluorinated processing aid and dimethyl silicone oil in a mass ratio of 1:2) were jointly put into a high-speed mixer and stirred at 600 rpm for 2 min until evenly dispersed, then transferred to a co-rotating twin-screw extruder with a length-diameter ratio of 48:1 for water-cooled strand pelletizing. The temperature control range of the extruder barrel was 150 °C to 200 °C, and the screw speed was 350 rpm to obtain the special pipe material based on polar HDPE for aquaculture facilities.

[0053] Example 2

[0054] A preparation method of a special pipe material based on polar HDPE for aquaculture facilities:

[0055] (1) Preparation of high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch: The same as in Example 1.

[0056] (2) Preparation of Special Pipe Material Based on Polar HDPE for Aquaculture Facilities: 65 parts of HDPE-6380M, 13.8 parts of UHMWPE U050, 20 parts of high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch, 0.4 parts of antioxidant (a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1), and 0.8 parts of processing aid B (a mixture of PPA fluorinated processing aid and dimethyl silicone oil in a mass ratio of 1:2) were jointly put into a high-speed mixer and stirred at 600 rpm for 2 min until evenly dispersed, then transferred to a co-rotating twin-screw extruder with a length-diameter ratio of 48:1 for water-cooled strand pelletizing. The temperature control range of the extruder barrel was 150 °C to 200 °C, and the screw speed was 350 rpm to obtain the special pipe material based on polar HDPE for aquaculture facilities.

[0057] Example 3

[0058] A preparation method of a special pipe material based on polar HDPE for aquaculture facilities:

[0059] (1) Preparation of high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch: The same as in Example 1.

[0060] (2) Preparation of special pipeline material based on polar HDPE for aquaculture facilities: 61 parts of HDPE-6380M, 17.8 parts of UHMWPE U050, 20 parts of high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch, 0.4 part of antioxidant (a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1), and 0.8 part of processing aid B (a mixture of PPA fluorine-containing processing aid and dimethyl silicone oil in a mass ratio of 1:2) were jointly put into a high-speed mixer and stirred at 600 rpm for 2 min until evenly dispersed, and then transferred to a co-rotating twin-screw extruder with a length-diameter ratio of 48:1 for water-cooled strand pelletization. The temperature control range of the extruder barrel was 150°C to 200°C, and the screw speed was 350 rpm, thus obtaining the special pipeline material based on polar HDPE for aquaculture facilities.

[0061] Comparative Example 1

[0062] Preparation method of special pipeline material based on polar HDPE for aquaculture facilities:

[0063] (1) Preparation of special pipeline material based on polar HDPE for aquaculture facilities: 78.8 parts of HDPE-6380M, 20 parts of high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch, 0.4 part of antioxidant (a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1), and 0.8 part of white mineral oil were jointly put into a high-speed mixer and stirred at 600 rpm for 2 min until evenly dispersed, and then transferred to a co-rotating twin-screw extruder with a length-diameter ratio of 48:1 for water-cooled strand pelletization. The temperature control range of the extruder barrel was 150°C to 200°C, and the screw speed was 350 rpm, thus obtaining the special pipeline material based on polar HDPE for aquaculture facilities.

[0064] Comparative Example 2: The HDPE 7600M resin produced by Beijing Yanshan Petrochemical is a PE100 grade bimodal distribution HDPE pipe special resin with low MFR, suitable for extrusion molding, and has properties such as high toughness, high rigidity, excellent stress cracking resistance, heat resistance, cold resistance, wear resistance, dielectric property, and chemical corrosion resistance. Typical application fields include pressure pipes such as water supply pipes and industrial pipes.

[0065] Application Example 1

[0066] The ultraviolet aging resistance performance tests were respectively carried out on the oyster shell powder@TiO2 inorganic micro-nano functional powder, oyster shell powder raw material, and TiO2 raw material prepared by the present invention, and the results are shown in Table 1.

[0067] The oyster shell powder@TiO2, oyster shell powder raw material and TiO2 raw material were made into a simple coating film (the formula was 5 g of the sample, 5 g of water-based acrylic acid and 0.01 g of methyl cellulose), and irradiated by a Q8-UV1 type ultraviolet accelerated aging test machine (equipped with a xenon lamp tube of the UVB-340 type, adjusting the ultraviolet radiation intensity to 1000 mV / m 2 , the distance from the light source to the test piece was 254 mm) for a total of 500 h. The chromaticity values of the coating film before and after light irradiation (L0*, a0* and b0* and L*, a* and b* respectively) were detected by an SP-60 color difference meter (Xrite Company, USA), and tested once every 100 h. Then, the color difference value (△E*) and the yellowing difference value (△b*) were calculated according to the following formula to characterize its ultraviolet aging resistance performance.

[0068]

[0069] Table 1 Test results of ultraviolet aging resistance performance of oyster shell powder@TiO2 inorganic micro-nano functional powder, oyster shell powder raw material and TiO2 raw material simple coating film

[0070]

[0071] In the table, L*, a* and b* represent the lightness value, red-green value and yellow-blue value respectively. The smaller the positive increase of △E* and △b* indicates that the color difference value and the yellowing degree of the coating film after ultraviolet light irradiation are smaller, that is, the ultraviolet aging resistance performance is stronger. It can be seen from Table 1 that the ultraviolet aging resistance performance of the oyster shell powder@TiO2 inorganic micro-nano functional powder prepared by the present invention has been significantly improved compared with the oyster shell powder raw material, and is close to the performance of the TiO2 raw material.

[0072] The oyster shell powder@TiO2 powder prepared by the present invention only contains 15% TiO2, indicating that the present invention can greatly reduce the dosage of TiO2 by uniformly coating TiO2 on the surface of oyster shell powder and firmly combining the two, achieving the same ultraviolet aging resistance performance as TiO2, and effectively saving the production cost while ensuring the performance. The prepared oyster shell powder@TiO2 of the present invention is filled into a special polar HDPE-based pipeline material, which can significantly improve its ultraviolet aging resistance performance.

[0073] Application Example 2

[0074] The materials obtained in Examples 1-3 and Comparative Examples 1-2 were subjected to performance tests, and the results are shown in Table 2.

[0075] Among them, the tensile properties, flexural strength, flexural modulus and IZOD notched impact strength are tested in accordance with GB / T1040.1-2006, GB / T9341-2000 and GB / T1843-1996 respectively; the heat distortion temperature is tested in accordance with ASTM-D648, the load condition is 1.86 MPa, and the heating rate is 50 °C / min; the MFR is tested in accordance with GB / T3682-2000, the set temperature is 190 °C, and the weight of the weight is 5.0 kg.

[0076] Table 2 Performance test results of the materials obtained in Examples 1-3 and Comparative Examples 1-2

[0077]

[0078] As can be seen from Table 2, in Examples 1-3, when the dosage of the high-polarity HDPE / oyster shell powder@TiO2 filled masterbatch is 20 parts by weight, by adjusting the concentration ratio of the extrusion-grade HDPE and UHMWPE, the comprehensive properties of the prepared polar HDPE-based pipeline special material are all excellent, far exceeding the comprehensive properties of the material without adding UHMWPE (Comparative Example 1) and the HDPE 7600M material produced by Yanshan Petrochemical (Comparative Example 2).

[0079] From the above two performance tests, it can be seen that the special material prepared by using the formulation design and production process provided by the solution of the present invention has outstanding mechanical properties while maintaining the flexibility of the material, and at the same time has excellent ultraviolet aging resistance, and can fully meet the requirements of the pipeline products for aquaculture (seawater, fresh water) facilities for material properties.

[0080] The foregoing description of the specific exemplary embodiments of the present invention is for purposes of illustration and exemplification. These descriptions are not intended to limit the invention to the precise forms disclosed, and it is apparent that many modifications and variations are possible in light of the above teaching. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical applications, so that those skilled in the art can implement and utilize the various different exemplary embodiments of the present invention as well as various different selections and modifications. The scope of the present invention is intended to be defined by the claims and their equivalents.

Claims

1. A preparation method of a special material for pipelines used in polar HDPE-based aquaculture facilities, characterized in that, It includes the following steps: (1) Prepare a highly polar HDPE / oyster shell powder@TiO2 filled masterbatch: Mix the oyster shell powder@TiO2 inorganic micro-nano functional powder, surface activation modifier, highly polar HDPE material, and processing aid A evenly, and melt-extrude and pelletize to obtain the highly polar HDPE / oyster shell powder@TiO2 filled masterbatch; (2) Prepare a special material for polar HDPE-based aquaculture facility pipes: Blend extrusion-grade HDPE, ultra-high molecular weight polyethylene, the highly polar HDPE / oyster shell powder@TiO2 filled masterbatch prepared in step (1), antioxidant, and processing aid B, and melt-extrude and pelletize to obtain a special polar HDPE-based material suitable for pipes in aquaculture facilities.

2. The preparation method of the special pipeline material for polar HDPE-based aquaculture facilities according to claim 1, characterized in that, In step (1), by weight, it includes the following components: 40-60 parts of highly polar HDPE material, 40-60 parts of oyster shell powder@TiO2 inorganic micro-nano functional powder, 1.5-3.0 parts of surface activation modifier, and 1.5-5.0 parts of processing aid A.

3. The preparation method of the special pipeline material for polar HDPE-based aquaculture facilities as described in claim 1, wherein, In step (1), the oyster shell powder@TiO2 inorganic micro-nano functional powder is prepared by the following method: S1 Use the mechanical grinding method to grind rutile TiO2 to a primary particle size of 2-5 μm; S2 Mix the ground TiO2 with oyster shell powder in a mass ratio of (10:90)-(20:80), and mechanically grind for 1-2 h to obtain the oyster shell powder@TiO2 micro-nano functional powder material.

4. The preparation method of the special pipeline material for polar HDPE-based aquaculture facilities according to claim 3, characterized in that, The main indicators of the oyster shell powder@TiO2 inorganic micro-nano functional powder are as follows: (1) particle size < 2 μm, content ≥ 90%; (2) DBP oil absorption ≤ 25 ml / 100 g; (3) whiteness ≥ 90%; (4) TiO2 content ≤ 20%; (5) bulk density 0.25 - 0.35 g / cm 3 ; (6) pH value of water suspension 6.5 - 8.5; (7) volatile matter at 105°C ≤ 0.5%.

5. The preparation method of the special pipeline material for polar HDPE-based aquaculture facilities according to claim 1, wherein, In step (1), the highly polar HDPE material is glycidyl methacrylate monomer-grafted injection molding grade HDPE, with a grafting rate of 1.5-2.0% and a melt flow rate of 5.0-8.0 g / 10 min; The surface activation modifier includes one or more of stearic acid, aluminate coupling agent, titanate coupling agent, and silane coupling agent; The processing aid A includes one or more of ethylene bisstearamide, polyperfluoroethylene propylene concentrated dispersion, PE wax, zinc stearate, antioxidant 1010, liquid paraffin, and dimethyl silicone oil.

6. The preparation method of the special pipeline material for polar HDPE-based aquaculture facilities according to claim 1, wherein, In step (2), by weight, it includes the following components: 55-75 parts of extrusion-grade HDPE, 5.0-25 wt% of ultra-high molecular weight polyethylene based on the total weight of HDPE, 20-40 parts of the highly polar HDPE / oyster shell powder@TiO2 filled masterbatch prepared in step (1), 0.2-0.6 parts of antioxidant, and 0.5-2.0 parts of processing aid B.

7. The preparation method of the special pipeline material for polar HDPE-based aquaculture facilities as described in claim 1, wherein, In step (2), the melt flow rate of the extrusion-grade HDPE is 0.5-2.0 g / 10 min; The ultra-high molecular weight polyethylene is in powder form, with a relative molecular weight of 300 to 700×10 4 g / mol and a particle size of 80 to 120 μm; The antioxidant includes antioxidant 1010 and / or antioxidant 168; The processing aid B includes one or more of calcium stearate, zinc stearate, PE wax, PPA fluorine-containing processing aid, white mineral oil, and dimethyl silicone oil.

8. The preparation method of the special pipeline material for polar HDPE-based aquaculture facilities according to claim 1, characterized in that, In step (2), a polar HDPE-based special material applicable to pipes for aquaculture facilities is prepared, with a tensile strength ≥ 45 MPa; an elongation at break ≥ 500%; a flexural strength ≥ 40 MPa; a flexural modulus ≥ 1400 MPa; an IZOD notched impact strength ≥ 60 MPa; and a heat distortion temperature ≥ 75 °C.

9. A special material for pipes for aquaculture facilities based on polar HDPE prepared by the method according to any one of claims 1-8.

10. Application of the special material for pipes for aquaculture facilities based on polar HDPE prepared by the method according to any one of claims 1-8 in the fields of bionic functional HDPE-based bamboo joint pipes, pipe components for aquaculture cages, and buoyancy pipes for raft rafts.

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