Basalt fiber-reinforced chlorinated polyvinyl chloride material and method for manufacturing the same

Abstract

The application provides a basalt fiber reinforced chlorinated polyvinyl chloride material and a preparation method thereof, and relates to the technical field of polymer composite materials.The application adds surface modified basalt fibers to the chlorinated polyvinyl chloride, uses cycloheptane and a titanate coupling agent to perform surface treatment on the basalt fibers, and selects the basalt fibers with an average length of 5-25 mu m and a diameter of 0.5-1.5 mu m, so as to improve the compatibility of the basalt fibers and the polyvinyl chloride, ensure uniform dispersion in the chlorinated polyvinyl chloride material, and make the chlorinated polyvinyl chloride pipe material have impact resistance, tensile yield stress, Vicat softening temperature and hydrostatic performance, and fully meet the actual application requirements.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer composite materials, and more particularly to a basalt fiber reinforced chlorinated polyvinyl chloride material and a preparation method thereof. BACKGROUND

[0002] Chlorinated polyvinyl chloride (CPVC, PVC-C) is a product of further chlorination modification of polyvinyl chloride (PVC), which is a new type of high polymer composite material with excellent performance and is widely used in the transportation of cold and hot water inside and outside buildings and in the pipeline system for the transportation of corrosive and high-temperature fluids in the industrial field. However, the chlorinated polyvinyl chloride resin has a high chlorine content, and thus the prepared pipe material has low toughness and poor impact resistance, so that the chlorinated polyvinyl chloride pipe material is prone to brittle fracture during storage, transportation, installation and use, especially in low-temperature environments. In practical applications, inorganic powder fillers, mainly calcium carbonate, are often added to the chlorinated polyvinyl chloride pipe material for blending modification. Although the addition of calcium carbonate effectively improves the toughness of the pipe material, it causes the properties such as tensile yield stress and Vicat softening temperature of the pipe material to decrease.

[0003] Therefore, it has become a research focus to replace inorganic materials such as calcium carbonate with basalt fibers to enhance the performance of chlorinated polyvinyl chloride. Basalt fiber is a continuous fiber made by high-speed drawing through a bushing after natural basalt is melted at 1450-1500 DEG C, and it is a new type of inorganic, environmentally friendly and green high-performance fiber material composed of oxides such as silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, iron oxide and titanium dioxide. The basalt continuous fiber not only has high strength, but also has excellent properties such as electrical insulation, corrosion resistance and high temperature resistance. It has a silicate similar to natural minerals and can be biodegraded in the environment, which is harmless to the environment.

[0004] However, basalt fiber and resin often have poor compatibility, and the addition of basalt fiber to resin can easily lead to a decrease in mechanical properties. In order to improve the poor compatibility and bonding force between basalt fiber and resin, various methods for modifying basalt fiber have been studied, including plasma surface treatment, acidification, silane coupling, etc. The prior art discloses using alkali-free continuous basalt fiber chopped strands treated with a titanate coupling agent on the surface to enhance the performance of polyethylene composite materials. However, the modification step of basalt fiber is complex, and the degree of enhancement of the mechanical properties of the composite material after modification is still insufficient, and the mechanical properties including impact resistance, tensile yield stress, Vicat softening temperature, static hydraulic pressure performance, etc. still need to be improved.

[0005] Therefore, in order to further explore the method for modifying basalt fiber to enhance the mechanical properties of chlorinated polyvinyl chloride, it is necessary to provide a basalt fiber reinforced chlorinated polyvinyl chloride material which has good compatibility with basalt fiber, thereby having excellent impact resistance, tensile yield stress, Vicat softening temperature and static hydraulic pressure performance, and a preparation method thereof. SUMMARY

[0006] In order to overcome the shortcomings of the prior art, the primary object of the present application is to provide a basalt fiber reinforced chlorinated polyvinyl chloride material, which realizes high compatibility with basalt fiber, thereby enhancing the impact resistance, tensile yield stress, Vicat softening temperature and static hydraulic pressure performance of the chlorinated polyvinyl chloride material.

[0007] Another object of the present application is to provide a preparation method of the above-mentioned basalt fiber reinforced chlorinated polyvinyl chloride material.

[0008] Another object of the present application is to provide an application of the above-mentioned basalt fiber reinforced chlorinated polyvinyl chloride material in the preparation of chlorinated polyvinyl chloride pipes.

[0009] Still another object of the present application is to provide a chlorinated polyvinyl chloride pipe prepared from the above-mentioned basalt fiber reinforced chlorinated polyvinyl chloride material.

[0010] To achieve the above-mentioned objects, the present application adopts the following technical solutions:

[0011] The present application protects a basalt fiber reinforced chlorinated polyvinyl chloride material, which comprises the following components by weight: chlorinated polyvinyl chloride 100 parts, surface modified basalt fiber 5-20 parts, heat stabilizer 4-6 parts, titanium white 2-5 parts, and impact modifier 5-10 parts.

[0012] The surface modified basalt fiber is a basalt fiber treated by cycloheptane and titanate coupling agent, and the average length of the basalt fiber is 5-25 microns and the diameter is 0.5-1.5 microns.

[0013] The cycloheptane serves to make the titanate coupling agent more uniformly coat the basalt fiber, so that the interface adhesion of the basalt fiber and the chlorinated polyvinyl chloride is better, the compatibility is improved, and the mechanical properties are further improved.

[0014] The basalt fibers have an average length of 5–25 μm and a diameter of 0.5–1.5 μm. Basalt fibers within this size range exhibit uniform dispersion, excellent processability, and good performance in CPVC materials. This is primarily due to the larger interfacial bonding area between the basalt fibers and CPVC molecules, resulting in stronger interfacial interactions and the ability to withstand higher energy under external forces, thus contributing to the higher overall performance of the CPVC composite material. Conversely, basalt fibers smaller than this size have an excessively large specific surface area, leading to extremely large interfacial bonding areas and bond strength with CPVC molecules. This results in poorer processability, higher processing and dispersion resistance, and a tendency for uneven dispersion of basalt fibers within the CPVC material, causing inconsistent material properties and hindering the ability to withstand higher energy levels. Basalt fibers larger than this size have a small specific surface area in CPVC materials, resulting in a small bonding area and low bonding strength at the molecular interface of CPVC materials. Furthermore, microscopic voids can occur, becoming stress concentration points. When subjected to external energy impacts, they absorb less energy and have poor mechanical properties. Therefore, the overall performance of CPVC composite materials is not high.

[0015] Preferably, in the surface-modified basalt fiber, the mass ratio of cycloheptane to titanate coupling agent is 0.5 to 1.5:1.

[0016] Preferably, the amount of cycloheptane used in the surface-modified basalt fiber is 0.5% to 2.5% of the mass of the basalt fiber.

[0017] Preferably, the preparation method of the surface-modified basalt fiber includes the following steps:

[0018] Cycloheptane and titanate coupling agent are mixed evenly in a certain proportion, sprayed into basalt fiber, and mixed by high-speed heating to obtain the surface-modified basalt fiber.

[0019] Specifically, the titanate coupling agent is selected from at least one of monoalkoxy type, monoalkoxy pyrophosphate type, or chelate type.

[0020] More specifically, the titanate coupling agent is selected from at least one of triisostearoyl titanate, tri(dioctylpyrophosphoryloxy)titanate isopropyl tri(dioctylphenol polyoxyethylene ether) phosphate.

[0021] Specifically, the temperature of the heating and mixing is 115–125°C.

[0022] Preferably, the chlorinated polyvinyl chloride has a chlorine content of 66.5% to 67.5%, and the determination method is GB / T 7139-2023.

[0023] Preferably, the impact modifier is a core-shell type impact modifier based on organosilicon-acrylic acid. Specifically, the core of the core-shell type impact modifier includes methyl methacrylate, acrylate, and organosilicon, and the shell includes grafted polymethyl methacrylate.

[0024] Preferably, the heat stabilizer is a calcium-zinc stabilizer.

[0025] Preferably, the basalt fiber reinforced chlorinated polyvinyl chloride material further includes at least one of a processing modifier, a lubricant, or a release agent.

[0026] More preferably, the processing modifier is selected from at least one of methyl methacrylate / acrylate copolymer, methyl methacrylate / styrene copolymer, methyl methacrylate / vinyl acetate copolymer, or acrylonitrile / styrene copolymer.

[0027] The lubricant is polyethylene wax; the release agent is selected from at least one of oxidized polyethylene wax, silicone release agent, or acrylate release agent.

[0028] This invention also protects a method for preparing basalt fiber reinforced chlorinated polyvinyl chloride material, comprising the following steps:

[0029] Weigh each component according to the ratio, and mix them at high speed at 110-130℃ to obtain the basalt fiber reinforced chlorinated polyvinyl chloride material.

[0030] The application of the above-mentioned basalt fiber reinforced chlorinated polyvinyl chloride material in the preparation of chlorinated polyvinyl chloride pipes is also within the scope of protection of this invention.

[0031] This invention also protects a chlorinated polyvinyl chloride pipe made from the above-mentioned basalt fiber reinforced chlorinated polyvinyl chloride material.

[0032] Preferably, the chlorinated polyvinyl chloride pipe has an outer diameter of 75 mm and a wall thickness of 5.6 mm.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] 1. This invention provides a basalt fiber reinforced chlorinated polyvinyl chloride material that combines excellent impact resistance, tensile yield stress, Vicat softening temperature, and hydrostatic properties, meeting practical application requirements and can be widely used in the preparation of chlorinated polyvinyl chloride pipes.

[0035] 2. This invention uses cycloheptane to enhance the coating of basalt fibers with titanate coupling agents, thereby improving the compatibility between basalt fibers and chlorinated polyvinyl chloride materials, and providing a new technical solution for the modification of basalt fibers.

[0036] 3. This invention selects basalt fibers with an average length of 5-25 μm and a diameter of 0.5-1.5 μm to modify the mechanical properties of chlorinated polyvinyl chloride. Basalt fibers in this size range are uniformly dispersed in CPVC materials, have excellent processability, and good performance.

[0037] 4. The preparation method described in the technical solution of the present invention is simple, easy to operate, and suitable for large-scale industrial production. Attached Figure Description

[0038] Figure 1 This is a cross-sectional SEM image of the CPVC material modified with basalt fiber.

[0039] Figure 2 Surface SEM of CPVC material modified with basalt fiber. Detailed Implementation

[0040] 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.

[0041] The reagents used in the various embodiments and comparative examples of this invention are described below:

[0042] The basalt fibers used were treated with cycloheptane and titanate coupling agent. The amount of cycloheptane and titanate used, and the treatment method are described in step S0 below.

[0043] Surface-modified basalt fiber 1#: treated with cycloheptane and titanate coupling agent, the basalt fiber has an average length of 15μm and a diameter of 1μm, the amount of cycloheptane is 1.5% of the mass of basalt fiber, and the mass ratio of titanate coupling agent to cycloheptane is 1:1.

[0044] Surface-modified basalt fiber #2: treated with cycloheptane and titanate coupling agent, the basalt fiber has an average length of 5μm and a diameter of 0.5μm, and the amount of cycloheptane used is the same as that of #1.

[0045] Surface-modified basalt fiber #3: treated with cycloheptane and titanate coupling agent, the basalt fiber has an average length of 25μm and a diameter of 1.5μm, and the amount of cycloheptane used is the same as that of #1.

[0046] Surface-modified basalt fiber 4: treated with cycloheptane and titanate coupling agent, the average length and diameter of the basalt fiber are the same as 1#, and the amount of cycloheptane used is 0.5% of the mass of the basalt fiber.

[0047] Surface-modified basalt fiber #5: treated with cycloheptane and titanate coupling agent, the average length and diameter of the basalt fiber are the same as #1, and the amount of cycloheptane used is 2.5% of the mass of the basalt fiber.

[0048] Surface-modified basalt fiber 6#: treated with cycloheptane and titanate coupling agent, the basalt fiber has an average length of 15μm and a diameter of 0.1μm, and the amount of cycloheptane used is the same as that of 1#.

[0049] Surface-modified basalt fiber 7#: treated with cycloheptane and titanate coupling agent, the basalt fiber has an average length of 15μm and a diameter of 3μm, and the amount of cycloheptane used is the same as that of 1#.

[0050] Surface-modified basalt fiber #8: treated with cycloheptane and titanate coupling agent, the average length of the basalt fiber is 30μm and the diameter is 1μm. The amount of cycloheptane used is the same as that of #1.

[0051] Surface-modified basalt fiber #9: treated with ethanol and titanate coupling agent, the basalt fiber has an average length of 15μm and a diameter of 1μm, and the amount of ethanol used is 1.5% of the mass of the basalt fiber.

[0052] Surface-modified basalt fiber 10#: treated with white oil and titanate coupling agent, the basalt fiber has an average length of 15μm and a diameter of 1μm, and the amount of white oil used is 1.5% of the mass of the basalt fiber.

[0053] Surface-modified basalt fiber 11#: treated with cycloheptane, the average length of the basalt fiber is 15μm and the diameter is 1μm, and the amount of cycloheptane used is 1.5% of the mass of the basalt fiber.

[0054] Surface-modified basalt fiber 12#: treated with titanate, the basalt fiber has an average length of 15μm and a diameter of 1μm, and the amount of titanate used is 1.5% of the mass of the basalt fiber.

[0055] Chlorinated polyvinyl chloride: R327, Shandong Gaoxin Chemical Co., Ltd.

[0056] Heat stabilizer: Calcium-zinc stabilizer, MC6156R / C, Bairroch New Material Technology Co., Ltd.

[0057] Titanium dioxide: SR-2400, Shandong Dongjia Group Co., Ltd.

[0058] Processing modifier: HPA-40, Shandong Rike Chemical Co., Ltd.

[0059] Impact modifier: S-2001, MITSUBISHI RAYON CO.,LTD.

[0060] Lubricant: Polyethylene wax AC-6A, Honeywell.

[0061] Release agent: Oxidized polyethylene wax: AC-629A, Honeywell.

[0062] Titanate coupling agent: Di(octylphenol polyoxyethylene ether) phosphite, LD-70, Yangzhou Lida Resin Co., Ltd.

[0063] The chlorinated polyvinyl chloride materials and chlorinated polyvinyl chloride pipes of the various embodiments and comparative examples of the present invention are prepared through the following process:

[0064] S0. Preparation of surface-modified basalt fibers

[0065] 1. Co-treatment with cycloheptane, ethanol or white oil and titanate coupling agent: Mix cycloheptane, ethanol or white oil and titanate coupling agent evenly according to the mass ratio;

[0066] Basalt fiber is added to the hot mixing cylinder of a high-speed mixer at a mixing temperature of 120°C. After starting at low speed for 30 seconds, the uniformly mixed cycloheptanine, ethanol or white oil and titanate coupling agent are added to the hot mixing cylinder of the high-speed mixer by spraying. Then, the high-speed mode is started and the machine is run for 5 minutes before switching to low speed mode to obtain surface-modified basalt fiber.

[0067] 2. Cycloheptanine treatment: Add basalt fiber into the hot mixing cylinder of a high-speed mixer. After starting at low speed for 30 seconds, add cycloheptanine into the hot mixing cylinder of the high-speed mixer by spraying. Then start the high-speed mode and run for 5 minutes before switching to low speed mode to obtain surface-modified basalt fiber.

[0068] 3. Titanate treatment: Add basalt fiber into the hot mixing cylinder of a high-speed mixer. After starting at low speed for 30 seconds, add the titanate coupling agent into the hot mixing cylinder of the high-speed mixer by spraying. Then start the high-speed mode and run for 5 minutes before switching to low speed mode to obtain surface-modified basalt fiber.

[0069] S1. Preparation of basalt fiber reinforced chlorinated polyvinyl chloride material.

[0070] Accurately weigh the following components according to the specified proportions: chlorinated polyvinyl chloride, surface-modified basalt fiber, heat stabilizer, titanium dioxide, processing modifier, impact modifier, lubricant, and release agent.

[0071] Weigh out chlorinated polyvinyl chloride, surface-modified basalt fiber, heat stabilizer, titanium dioxide, processing modifier, impact modifier, lubricant, and release agent and add them to the hot mixing cylinder of the high-speed mixer. Start the high-speed mode and stir. When the material temperature rises to 120°C, open the discharge valve and discharge the evenly mixed material (dry mix) into the cold mixing cylinder of the high-speed mixer. When the dry mix cools down to 50°C, open the valve of the cold mixing cylinder of the high-speed mixer and discharge the dry mix to obtain basalt fiber reinforced chlorinated polyvinyl chloride material.

[0072] S2. Prepare the corresponding chlorinated polyvinyl chloride pipes.

[0073] The basalt fiber reinforced chlorinated polyvinyl chloride material prepared above was added to a parallel twin-screw extruder, with the barrel temperature set to 160℃~180℃ and the die temperature set to 165℃~200℃; it was then molded and cut to obtain the chlorinated rigid polyvinyl chloride pipe.

[0074] The outer diameter of the chlorinated polyvinyl chloride pipe is 75mm and the wall thickness is 5.6mm, which conforms to the national standard GB / T 18993.2—2020.

[0075] The performance testing methods and standards for basalt fiber reinforced chlorinated polyvinyl chloride materials in various embodiments and comparative examples of the present invention are as follows:

[0076] The chlorinated polyvinyl chloride pipes prepared according to the method in S2 were tested in accordance with GB / T 18993.2—2020 "Chronicized polyvinyl chloride (PVC-C) piping systems for hot and cold water".

[0077] Drop hammer impact test (TIR / %): GB / T14152;

[0078] Hydrostatic strength (43MPa / 1h): GB / T6111-2018;

[0079] Tensile yield stress / MPa: GB / T8804.2;

[0080] Vicat softening temperature / °C: GB / T8802.

[0081] Examples 1-6

[0082] This embodiment provides a series of basalt fiber reinforced chlorinated polyvinyl chloride materials, and the weight parts of each component in the formulation are shown in Table 1.

[0083] Table 1. Formulations (per serving) for Examples 1-6

[0084]

[0085]

[0086] Comparative Examples 1-9

[0087] This comparative example provides a series of basalt fiber reinforced chlorinated polyvinyl chloride materials, the weight parts of each component in the formulation are shown in Table 2.

[0088] Table 2 Comparative Examples 1-9 Formulas (per serving)

[0089]

[0090] The performance test results of the basalt fiber reinforced chlorinated polyvinyl chloride materials in each embodiment and comparative example according to the methods mentioned above are shown in Table 3.

[0091] The chlorinated polyvinyl chloride pipes prepared from basalt fiber reinforced chlorinated polyvinyl chloride materials in Examples 1-6 and Comparative Examples 1-9 were tested according to the methods mentioned above. The test results are shown in Table 3.

[0092] Table 3 Performance test results of each embodiment and comparative example

[0093]

[0094]

[0095] As can be seen from Table 3, the pipes made from the basalt fiber reinforced chlorinated polyvinyl chloride materials prepared in Examples 1 to 7 of the present invention all have excellent impact resistance, tensile yield stress, Vicat softening temperature and hydrostatic strength, among which Example 1 has the best overall performance.

[0096] Comparative Example 1 used basalt fibers with a diameter smaller than the specified range, resulting in a decrease in both impact resistance and Vicat softening temperature. Comparative Example 2 used basalt fibers with a diameter larger than the specified range, leading to a decrease in the toughness and heat resistance of the resulting pipe. Comparative Example 3 used basalt fibers with an average length larger than the specified range, resulting in a slight improvement in the toughness, tensile strength, and heat resistance of the pipe compared to Comparative Example 2, but still inferior to the example. Comparative Examples 4 and 5 used ethanol and white oil, respectively, instead of cycloheptane in Example 1, resulting in poor performance, highlighting the importance of cycloheptane. Comparative Example 6 demonstrated the significant impact of titanate coupling agents on the invention. Comparative Example 7 showed that titanate alone was insufficient to improve pipe performance, requiring the addition of cycloheptane. Comparative Examples 8 and 9 demonstrated that the amount of basalt fiber added needed to achieve the technical effects of the invention within a certain range; otherwise, the overall performance of the pipe would significantly decrease.

[0097] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A basalt fiber reinforced chlorinated polyvinyl chloride material, characterized in that, The components include the following parts by weight: 100 parts of chlorinated polyvinyl chloride, 5-20 parts of surface-modified basalt fiber, 4-6 parts of heat stabilizer, 2-5 parts of titanium dioxide, and 5-10 parts of impact modifier. The surface-modified basalt fiber is a basalt fiber that has been surface-treated with cycloheptane and titanate coupling agent, and the average length of the basalt fiber is 5~25μm and the diameter is 0.5~1.5μm. The preparation method of the surface-modified basalt fiber includes the following steps: Cycloheptane and titanate coupling agent are mixed evenly in a certain proportion, sprayed into basalt fiber, and mixed by high-speed heating to obtain the surface-modified basalt fiber. The titanate coupling agent is selected from at least one of triisostearoyl titanate, tri(dioctylpyrophosphoryloxy)titanate isopropyl ester or di(octylphenol polyoxyethylene ether) phosphate. In the surface-modified basalt fiber, the mass ratio of cycloheptane to titanate coupling agent is 0.5~1.5:

1.

2. The basalt fiber reinforced chlorinated polyvinyl chloride material according to claim 1, characterized in that, The amount of cycloheptane used in the surface-modified basalt fiber is 0.5 to 2.5% of the mass of the basalt fiber.

3. The basalt fiber reinforced chlorinated polyvinyl chloride material according to claim 1, characterized in that, The chlorinated polyvinyl chloride has a chlorine content of 66.5% to 67.5%.

4. The basalt fiber reinforced chlorinated polyvinyl chloride material according to claim 1, characterized in that, The basalt fiber reinforced chlorinated polyvinyl chloride material also includes at least one of a processing modifier, a lubricant, or a release agent.

5. The basalt fiber reinforced chlorinated polyvinyl chloride material according to claim 1, characterized in that, The heat stabilizer is a calcium-zinc stabilizer.

6. A method for preparing the basalt fiber reinforced chlorinated polyvinyl chloride material according to any one of claims 1 to 5, characterized in that, Includes the following steps: Weigh each component according to the ratio, and mix them at high speed at 110~130℃ to obtain the basalt fiber reinforced chlorinated polyvinyl chloride material.

7. The application of the basalt fiber reinforced chlorinated polyvinyl chloride material according to any one of claims 1 to 5 in the preparation of chlorinated polyvinyl chloride pipes.

8. A chlorinated polyvinyl chloride pipe, characterized in that, It is prepared from the basalt fiber reinforced chlorinated polyvinyl chloride material described in any one of claims 1 to 5.

9. The chlorinated polyvinyl chloride pipe according to claim 8, characterized in that, The chlorinated polyvinyl chloride pipe has an outer diameter of 75 mm and a wall thickness of 5.6 mm.

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