Polybutylene oxygen-barrier master batch, pipe and preparation method of polybutylene oxygen-barrier master batch

Abstract

The invention discloses a polybutylene oxygen-barrier pipe master batch, a pipe and a preparation method of the pipe. The polybutylene oxygen-barrier pipe master batch comprises fluorosilane, nano cerium oxide, polybutylene resin and a compatibilizer. Compared with other forming methods for preparing the pipe through three-layer / five-layer co-extrusion, the preparation method of the polybutylene oxygen-resistant pipe is low in raw material cost and simple in forming process. The inorganic filler nano cerium oxide is added, the particle size of nano particles is small, molecular gaps of a polymer can be filled, the porosity of the material is reduced, and a better barrier effect is achieved. The compatibilizer used in the invention has high molecular polarity, so that the molecules are tightly combined to make gas diffusion difficult, the air permeability of the pipe is reduced, and the barrier property of the pipe is improved.

Description

Technical Field

[0001] This invention relates to the field of plastic pipe technology, and more specifically, to a polybutene oxygen barrier pipe masterbatch, pipe, and preparation method thereof. Background Technology

[0002] Polybutene (PB) possesses excellent mechanical properties, processing performance, wear resistance, and outstanding creep resistance. It also exhibits good dielectric properties and chemical corrosion resistance, maintaining excellent mechanical properties even at high temperatures. Compared to commonly used PE-RT and PPR pipes, PB pipes have lower thermal conductivity, better insulation, lower coefficient of thermal expansion, and better sound insulation. Compared to cast iron pipes, PB pipes are corrosion-resistant, wear-resistant, do not scale, and have strong drainage capacity, meeting the current global requirements for energy conservation and emission reduction. They are mainly used as hot water system pipes, plastic water pipes, sealing materials, structural components, and compression packaging films. However, PB pipes have a relatively high oxygen permeability, and this oxygen permeability defect becomes more pronounced with increasing temperature, leading to an increase in the oxygen content of the hot water inside the pipes. Furthermore, PB pipes age faster and have a shorter service life in high-oxygen environments. Therefore, improving oxygen barrier properties is crucial to prevent aging and extend the service life of PB pipes. Meanwhile, oxygen barrier properties can prevent corrosion of water distributors, valves, and bathroom radiators, and also inhibit scaling, bacterial and algal growth, and the formation of biological slime within the system. According to relevant technical data, at a water temperature of 40℃, the oxygen permeation rate is greater than 0.1g / m³. 3 During the day, severe corrosion will occur in the system's metal heaters, metal valves, pipe fittings, radiators, water pumps, etc. Therefore, the production and application of oxygen-barrier polybutene plastic pipes has become the main solution.

[0003] To address the issue of oxygen permeation, some developed countries and regions have mandated the use of oxygen-barrier plastic pipes in heating systems that utilize hot water. Currently, there are two main ways to enhance the oxygen barrier properties of existing plastic pipes: one is through a metal coating, as seen in aluminum-plastic composite pipes and aluminum-plastic composite pipes; the other is by laminating a layer of high-molecular-weight barrier material, typically EVOH, onto the plastic pipe to create an oxygen-barrier pipe. However, both methods have their drawbacks. The first method is complex and costly, making the second method more popular with industry players. EVOH resin, containing alcohol, is moisture-sensitive; after absorbing moisture, its oxygen barrier effect is lost. When used as an oxygen barrier layer, it causes a large number of oxygen molecules to permeate the pipe wall and dissolve in the water. Long-term exposure to high humidity, high temperature, high pressure, and hydraulic water hammer forces significantly reduces oxygen barrier performance, consequently lowering bonding strength and further impacting the pipe's lifespan.

[0004] Currently, there are various methods for preparing PB oxygen barrier pipes, including three-layer / five-layer co-extrusion, melt blending, and methods involving an EVOH oxygen barrier layer inside the pipe. For example, patent CN114211845A discloses a multifunctional PB oxygen barrier pipe, its preparation method, and its application. This multifunctional PB oxygen barrier pipe comprises a five-layer co-extrusion structure, consisting of, from the outside to the inside: a first PB layer, an outer hot melt adhesive layer, an aluminum layer, an inner hot melt adhesive layer, and a second PB layer. The resulting multifunctional PB oxygen barrier pipe retains the original excellent properties of PB through its multi-layer structure, while also possessing excellent oxygen barrier function, flame retardant properties, and thermal conductivity. Its rigidity and strength are also significantly improved, making it suitable for use in underfloor heating systems. However, this method suffers from complex molding processes and increased costs. Utility model patent CN203880249U discloses a PB oxygen barrier pipe characterized by an EVOH oxygen barrier layer surrounding the inner PB tube, which is bonded to the inner PB tube via an adhesive layer containing colored masterbatch. The prepared PB oxygen barrier pipe effectively improved its oxygen barrier performance by adding an EVOH oxygen barrier layer, and the addition of a colored masterbatch adhesive layer improved the pipe's light-shielding properties. Tests showed that the added EVOH oxygen barrier layer had a uniform thickness and the pipe's oxygen barrier rate was stable. However, there is a risk that EVOH resin, being moisture-sensitive and hygroscopic, could lead to a significant decrease in oxygen barrier performance when used as a pipe oxygen barrier layer.

[0005] CN102927379A discloses a novel oxygen-barrier polybutene pipe. This pipe uses LCP instead of EVOH as the oxygen barrier layer, and is produced using a three-layer extrusion method with a layer of high oxygen-barrier material LCP coated on its surface. However, this method for preparing the pipe suffers from problems such as complex molding processes and high costs.

[0006] CN110997792A discloses an oxygen-barrier polybutene pipe containing uniformly dispersed graphene and its preparation method. This method uses a combination of "one-pot mixing" and "melt blending" techniques to prepare the oxygen-barrier polybutene pipe, comprising polybutene resin, graphene, a second oxygen-barrier filler, a graphene surface treatment agent, a graphene coating agent, a stabilizer, and an antioxidant. However, this preparation method carries risks such as dust pollution during composite material production and difficulties in material feeding during blending due to the significant density difference between the polybutene resin particles and the resin particles. Summary of the Invention

[0007] To address the problem of high oxygen permeability in polybutene pipes, which accelerates pipe aging and affects their service life, this invention provides a polybutene oxygen-barrier masterbatch, a pipe, and a method for preparing the same. To achieve the above objective, this invention provides a polybutene oxygen-barrier pipe masterbatch comprising fluorosilane, nano-cerium oxide, polybutene resin, and a compatibilizer.

[0008] The polybutene oxygen barrier pipe masterbatch of the present invention, based on the sum of the mass percentages of the polybutene oxygen barrier pipe masterbatch as 100%, comprises 21% to 30% fluorosilane, 20% to 32% cerium oxide, 3% to 8% compatibilizer, and 45% to 50% polybutene resin.

[0009] The polybutene oxygen barrier pipe masterbatch of the present invention includes at least one of ethylene-methyl acrylate copolymer (EMA), ethylene-vinyl acetate copolymer (EVA), and ethylene-propylene binary copolymer.

[0010] The present invention also provides a polybutene oxygen barrier pipe, wherein the polybutene oxygen barrier pipe comprises a polybutene oxygen barrier pipe masterbatch and a polybutene resin substrate.

[0011] The polybutene oxygen barrier pipe of the present invention is wherein the mass ratio of the polybutene oxygen barrier pipe masterbatch to the polybutene resin substrate is 1:44-50.

[0012] The polybutene oxygen barrier pipe of the present invention can also be described in detail as follows:

[0013] Polybutene oxygen barrier pipe is composed of fluorosilane, nano-cerium oxide, polybutene resin and compatibilizer. The fluorosilane, nano-cerium oxide, compatibilizer and polybutene resin are mixed in a certain proportion to form a composite filler masterbatch. The composite filler masterbatch is then melt-blended with polybutene resin substrate and extruded to form pipe.

[0014] In the composite filler masterbatch, fluorosilane accounts for 21% to 30%, cerium oxide accounts for 20% to 32%, and the compatibilizer includes at least one of EMA, EVA and ethylene-propylene copolymer, accounting for 3% to 8%. Polybutene resin accounts for 45% to 50%. The sum of the mass percentages of all components in the composite filler masterbatch is 100%, and the mass ratio of the composite filler masterbatch to the polybutene resin substrate is 1:44-50.

[0015] This invention also discloses a method for preparing polybutene oxygen barrier pipes, the method comprising the following steps:

[0016] (1) Dissolve fluorosilane and nano-cerium oxide in cyclohexane to prepare a transparent solution, stir, and dry to obtain a mixture.

[0017] (2) The mixture, compatibilizer, and polybutene resin are added to the hopper of a twin-screw extruder, melted, and extruded and cut to obtain polybutene oxygen barrier pipe masterbatch;

[0018] (3) Mix the polybutene oxygen barrier pipe masterbatch with the polybutene resin base material evenly, and then melt-blend and extrude it in a single screw extruder to obtain the polybutene oxygen barrier pipe.

[0019] In the preparation method of polybutene oxygen barrier pipe of the present invention, in step (1), the stirring temperature is 30-50°C and the stirring time is 1-3h.

[0020] In the preparation method of the polybutene oxygen barrier pipe of the present invention, in step (1), the drying temperature is 80-90°C and the drying time is 1-3 hours.

[0021] This invention utilizes fluorosilanes containing fluorine groups as fluorinating agents to fluorinate and modify inorganic filler nano-cerium oxide, then combines it with a highly polar compatibilizer and polybutene resin to form a composite filler masterbatch. Finally, the masterbatch and polybutene resin substrate are mixed and melt-extruded to prepare oxygen-barrier pipes with high barrier properties and low oxygen permeability coefficient. This invention has at least the following beneficial effects:

[0022] (1) Compared with other three-layer / five-layer co-extrusion molding methods for preparing pipes, the polybutene oxygen barrier pipe preparation method of the present invention has low raw material cost and simple molding process.

[0023] (2) The inorganic filler nano-cerium oxide added in this invention has a small particle size, which can fill the gaps between polymer molecules, reduce the porosity of the material, and achieve a better barrier effect.

[0024] (3) Fluorosilane is used to fluorinate nano-cerium oxide and form fluorine-containing groups on the surface to form a barrier effect.

[0025] (4) The compatibilizer molecules used in this invention have high polarity, which can make the molecules tightly bond together, making gas diffusion difficult, reducing the air permeability of the pipe, and improving the barrier properties of the pipe. Detailed Implementation

[0026] The present invention is further illustrated below with reference to specific embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions in the art or as recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are all commercially available from the conventional market. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention are within the scope of protection claimed by the present invention.

[0027] Example 1

[0028] (1) Dissolve 12.5g of fluorosilane and 12.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 45°C for 2 hours. Place the resulting mixture in a drying oven and dry it for 1 hour at 80°C to obtain the mixture.

[0029] (2) The mixture of fluorosilane and nano-cerium oxide, along with 1.6g EMA and 22g polybutene resin, is added to the hopper of a twin-screw extruder, melted, and extruded and cut to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0030] (3) Take 48g of masterbatch and mix it thoroughly with 2.4kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude it into pipe in a single screw extruder. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0031] Example 2

[0032] (1) Dissolve 10.5g of fluorosilane and 10.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 30°C for 1 hour. Place the resulting mixture in a drying oven and dry it at 80°C for 1 hour to obtain the mixture.

[0033] (2) The mixture of fluorosilane and nano-cerium oxide, along with 2.1g EVA and 22g polybutene resin, is added to the hopper of a twin-screw extruder, melted, and extruded and cut to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0034] (3) Take 45g of masterbatch and mix it thoroughly with 2.03kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude it into pipe in a single screw extruder. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0035] Example 3

[0036] (1) Dissolve 11.5g of fluorosilane and 11.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 50°C for 3 hours. Place the resulting mixture in a drying oven and dry for 2 hours at 85°C to obtain the mixture.

[0037] (2) The mixture of fluorosilane and nano-cerium oxide, along with 2.3g of ethylene propylene copolymer and 22g of polybutene resin, is added to the hopper of a twin-screw extruder and melted and extruded to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0038] (3) Take 47g of masterbatch and mix it thoroughly with 2.07kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude the mixture in a single screw extruder to form a pipe. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0039] Example 4

[0040] (1) Dissolve 13.5g of fluorosilane and 9.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix evenly and stir at 45°C for 2 hours. Place the resulting mixture in a drying oven and dry for 3 hours at 90°C to obtain the mixture.

[0041] (2) The mixture of fluorosilane, nano-cerium oxide, 2.5g of EMA and EVA, and 22g of polybutene resin were added to the hopper of a twin-screw extruder and melted and extruded to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0042] (3) Take 47g of masterbatch and mix it thoroughly with 2.2kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude it into pipe in a single screw extruder. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0043] Example 5

[0044] (1) Dissolve 12.5g of fluorosilane and 10.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 30°C for 1 hour. Place the resulting mixture in a drying oven and dry for 2 hours at 85°C to obtain the mixture.

[0045] (2) The mixture of fluorosilane, nano-cerium oxide, 1.9g of EMA and ethylene-propylene copolymer, and 22g of polybutene resin were added to the hopper of a twin-screw extruder and melted and extruded to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0046] (3) Take 46g of masterbatch and mix it thoroughly with 2.21kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude the mixture in a single screw extruder to form a pipe. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0047] Example 6

[0048] (1) Dissolve 11.5g of fluorosilane and 12.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 40°C for 2 hours. Place the resulting mixture in a drying oven and dry for 2 hours at 85°C to obtain the mixture.

[0049] (2) The mixture of fluorosilane, nano-cerium oxide, 1.7g of EVA and ethylene-propylene copolymer, and 22g of polybutene resin were added to the hopper of a twin-screw extruder and melted and extruded to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0050] (3) Take 47g of masterbatch and mix it thoroughly with 2.26kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude it into pipe in a single screw extruder. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0051] Example 7

[0052] (1) Dissolve 10.5g of fluorosilane and 13.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 50°C for 3 hours. Place the resulting mixture in a drying oven and dry for 2 hours at 85°C to obtain the mixture.

[0053] (2) The mixture of fluorosilane and nano-cerium oxide, along with 1.6g EMA and 22g polybutene resin, is added to the hopper of a twin-screw extruder, melted, and extruded and cut to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0054] (3) Take 47g of masterbatch and mix it thoroughly with 2.3kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude the mixture in a single screw extruder to form a pipe. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0055] Example 8

[0056] (1) Dissolve 10.5g of fluorosilane and 14.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 30°C for 1 hour. Place the resulting mixture in a drying oven and dry it at 80°C for 1 hour to obtain the mixture.

[0057] (2) The mixture of fluorosilane and nano-cerium oxide, along with 1.6g EVA and 22g polybutene resin, is added to the hopper of a twin-screw extruder, melted, and extruded and cut to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0058] (3) Take 48g of masterbatch and mix it thoroughly with 2.4kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude it into pipe in a single screw extruder. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0059] Example 9

[0060] (1) Dissolve 10.5g of fluorosilane and 15.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 30°C for 2 hours. Place the resulting mixture in a drying oven and dry it for 1 hour at 80°C to obtain the mixture.

[0061] (2) The mixture of fluorosilane and nano-cerium oxide, along with 1.8g of ethylene propylene copolymer and 22g of polybutene resin, is added to the hopper of a twin-screw extruder and melted and extruded to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0062] (3) Take 49g of masterbatch and mix it thoroughly with 2.45kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude the mixture in a single screw extruder to form a pipe. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0063] Example 10

[0064] (1) Dissolve 12.5g of fluorosilane and 12.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 30°C for 3 hours. Place the resulting mixture in a drying oven and dry it for 1 hour at 80°C to obtain the mixture.

[0065] (2) The mixture of fluorosilane and nano-cerium oxide, along with 2.4g EMA and 22g polybutene resin, is added to the hopper of a twin-screw extruder, melted, and extruded and cut to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0066] (3) Take 49g of masterbatch and mix it thoroughly with 2.2kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude the mixture in a single screw extruder to form a pipe. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0067] Example 11

[0068] (1) Dissolve 12.5g of fluorosilane and 11.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 45°C for 2 hours. Place the resulting mixture in a drying oven and dry it for 1 hour at 80°C to obtain the mixture.

[0069] (2) The mixture of fluorosilane and nano-cerium oxide, along with 2.6g of EVA and 22g of polybutene resin, is added to the hopper of a twin-screw extruder, melted, and extruded and cut to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0070] (3) Take 48g of masterbatch and mix it thoroughly with 2.4kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude it into pipe in a single screw extruder. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0071] Example 12

[0072] (1) Dissolve 11.5g of fluorosilane and 12.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 45°C for 2 hours. Place the resulting mixture in a drying oven and dry for 2 hours at 80°C to obtain the mixture.

[0073] (2) The mixture of fluorosilane and nano-cerium oxide, along with 2.8g of ethylene propylene copolymer and 22g of polybutene resin, is added to the hopper of a twin-screw extruder and melted and extruded to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0074] (3) Take 48g of masterbatch and mix it thoroughly with 2.16kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude it into pipe in a single screw extruder. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0075] Example 13

[0076] (1) Dissolve 11.5g of fluorosilane and 11.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 45°C for 2 hours. Place the resulting mixture in a drying oven and dry for 3 hours at 80°C to obtain the mixture.

[0077] (2) The mixture of fluorosilane, nano-cerium oxide, 3.0g of EMA and EVA, and 22g of polybutene resin were added to the hopper of a twin-screw extruder and melted and extruded to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0078] (3) Take 48g of masterbatch and mix it thoroughly with 2.2kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude the mixture in a single screw extruder to form a pipe. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0079] Example 14

[0080] (1) Dissolve 10.5g of fluorosilane and 10.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix evenly and stir at 50°C for 3 hours. Place the resulting mixture in a drying oven and dry for 3 hours at 90°C to obtain the mixture.

[0081] (2) The mixture of fluorosilane, nano-cerium oxide, 3.2g of EMA and ethylene-propylene copolymer, and 22g of polybutene resin were added to the hopper of a twin-screw extruder and melted and extruded to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0082] (3) Take 46g of masterbatch and mix it thoroughly with 2.25kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude it into pipe in a single screw extruder. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0083] Example 15

[0084] (1) Dissolve 11.5g of fluorosilane and 10.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 40°C for 2 hours. Place the resulting mixture in a drying oven and dry for 2 hours at 80°C to obtain the mixture.

[0085] (2) The mixture of fluorosilane, nano-cerium oxide, 3.4g of EVA and ethylene-propylene copolymer, and 22g of polybutene resin were added to the hopper of a twin-screw extruder and melted and extruded to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0086] (3) Take 47g of masterbatch and mix it thoroughly with 2.35kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude it into pipe in a single screw extruder. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0087] Comparative Example 1

[0088] (1) Without adding nano-cerium oxide, 12.5g of fluorosilane was dissolved in cyclohexane to prepare a transparent solution. The solution was stirred at 45°C for 2 hours. The resulting mixture was then placed in a drying oven and dried at 80°C for 1 hour.

[0089] (2) The dried fluorosilane material, 1.6g EMA and 22g polybutene resin were added to the hopper of a twin-screw extruder to melt and extrude and cut to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0090] (3) Take 36g of masterbatch and mix it thoroughly with 1.8kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude it into pipe in a single screw extruder. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0091] Comparative Example 2

[0092] (1) Dissolve 12.5g of fluorosilane and 12.5g of nano-cerium oxide in cyclohexane to prepare a transparent solution. Mix them evenly and stir at 45°C for 2 hours. Place the resulting mixture in a drying oven and dry it for 1 hour at 80°C to obtain the mixture.

[0093] (2) Without adding compatibilizer, the mixture of fluorosilane and nano-cerium oxide and 22g of polybutene resin are added to the hopper of a twin-screw extruder to melt and extrude and cut, so as to obtain polybutene oxygen barrier pipe masterbatch with suitable particle size and uniform coarseness.

[0094] (3) Take 45g of masterbatch and mix it thoroughly with 2.25kg of polybutene resin substrate in a rotary dryer. Then, melt-blend and extrude it into pipe in a single screw extruder. Finally, use a plastic pipe oxygen permeability tester to test the oxygen permeability coefficient of the prepared pipe.

[0095] Examples 1-15 show the preparation of polybutene oxygen-barrier pipes by adjusting the amount and type of nano-inorganic fillers and compatibilizers and mixing them with polybutene resin. The oxygen permeability coefficient data of the pipes are shown in the table below:

[0096] Table 1. Changes in oxygen permeability coefficient of pipes in Examples 1-15

[0097]

[0098]

[0099] As can be seen from the above examples and comparative examples, the oxygen permeability coefficient of the prepared polybutene oxygen barrier pipe is as low as 0.01 g / m. 3 The oxygen permeability coefficient of polybutene oxygen barrier pipes was investigated by adjusting the amount of inorganic filler nano-cerium oxide, the amount of compatibilizer, and the type of compatibilizer. With increasing amounts of nano-cerium oxide and compatibilizer, the oxygen permeability coefficient of the pipe gradually decreased. In Comparative Example 1, the oxygen permeability coefficient of the polybutene pipe prepared without the addition of inorganic filler nano-cerium oxide increased to 4.29 g / m². 3 The oxygen barrier performance of the pipe decreased on day 1, indicating that the addition of nano-cerium oxide has a significant effect on improving the oxygen barrier performance of the pipe. In Comparative Example 2, the oxygen permeability coefficient of the pipe prepared without the addition of a compatibilizer increased significantly, indicating that the addition of a compatibilizer can effectively improve the oxygen barrier performance of the pipe.

[0100] This invention provides a polybutene oxygen barrier pipe masterbatch, pipe, and its preparation method. It utilizes fluorosilanes containing fluorine groups as fluorinating agents to fluorinate and modify inorganic filler nano-cerium oxide. This is then combined with a highly polar compatibilizer and polybutene resin to form a composite filler masterbatch. Finally, the masterbatch and polybutene resin substrate are mixed and melt-extruded to prepare a polybutene oxygen barrier pipe with high barrier properties and a low oxygen permeability coefficient. Compared with other three-layer / five-layer co-extrusion methods for preparing pipes, this method has lower raw material costs and a simpler molding process. The fluorination and modification of nano-cerium oxide with fluorosilanes creates fluorine-containing groups on the surface, forming a barrier effect. The small particle size of the inorganic filler nano-cerium oxide allows it to form a nano-barrier wall with the highly polar compatibilizer, filling the molecular gaps in the polymer, reducing material porosity, and effectively improving the oxygen barrier performance of the pipe. This solves the problem of insufficient oxygen barrier effect and high oxygen permeability leading to accelerated pipe aging and reduced service life, showing great application prospects in the field of plastic pipes.

[0101] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A polybutene oxygen-barrier pipe masterbatch, characterized in that, The polybutene oxygen barrier pipe masterbatch includes fluorosilane, nano-cerium oxide, polybutene resin, and compatibilizer.

2. The polybutene oxygen barrier pipe masterbatch according to claim 1, characterized in that, Based on the total mass percentage of the polybutene oxygen barrier pipe masterbatch being 100%, the fluorosilane accounts for 21% to 30%, the cerium oxide accounts for 20% to 32%, the compatibilizer accounts for 3% to 8%, and the polybutene resin accounts for 45% to 50%.

3. The polybutene oxygen-barrier pipe masterbatch according to claim 1, characterized in that, The compatibilizer includes at least one of ethylene-methyl acrylate copolymer (EMA), ethylene-vinyl acetate copolymer (EVA), and ethylene-propylene binary copolymer.

4. A polybutene oxygen-barrier pipe, characterized in that, The polybutene oxygen barrier pipe includes the polybutene oxygen barrier pipe masterbatch and polybutene resin substrate as described in any one of claims 1-3.

5. The polybutene oxygen barrier pipe according to claim 4, characterized in that, The mass ratio of the polybutene oxygen barrier pipe masterbatch to the polybutene resin substrate is 1:44-50.

6. A method for preparing the polybutene oxygen-barrier pipe according to any one of claims 4-5, characterized in that, Includes the following steps: (1) Dissolve fluorosilane and nano-cerium oxide in cyclohexane to prepare a transparent solution, stir, and dry to obtain a mixture. (2) The mixture, compatibilizer, and polybutene resin are added to the hopper of a twin-screw extruder, melted, and extruded and cut to obtain polybutene oxygen barrier pipe masterbatch; (3) Mix the polybutene oxygen barrier pipe masterbatch with the polybutene resin base material evenly, and then melt-blend and extrude it in a single screw extruder to obtain the polybutene oxygen barrier pipe.

7. The preparation method according to claim 6, characterized in that, In step (1), the stirring temperature is 30-50°C and the stirring time is 1-3 hours.

8. The preparation method according to claim 6 or 7, characterized in that, In step (1), the drying temperature is 80-90°C and the drying time is 1-3 hours.

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