A high-ductility PVC coiled material for swimming pools and a preparation method thereof

Abstract

The application belongs to the technical field of PVC coiled material and particularly relates to a high-ductility anti-seepage PVC coiled material for swimming pools and a preparation method thereof. The high-ductility anti-seepage PVC coiled material for swimming pools comprises the following components in parts by weight: 100 parts of PVC resin, 23-27 parts of plasticizer, 15-20 parts of ethylene-vinyl acetate-carbon monoxide terpolymer, 1-3 parts of stabilizer, 1-2 parts of antioxidant, 1-2 parts of calcium stearate, 1-1.5 parts of chlorinated paraffin, 0.2-0.6 parts of epoxy soybean oil and 30-35 parts of modified light calcium carbonate. The PVC coiled material prepared by the application has high tensile properties, tear strength and waterproof performance, and the PVC coiled material has excellent low-temperature resistance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of PVC coiled material, and particularly relates to a high-ductility anti-seepage PVC coiled material for swimming pools and a preparation method thereof. BACKGROUND

[0002] The coiled material for swimming pools is a waterproof material specially designed for laying inside swimming pools. With the improvement of performance requirements of waterproof materials for swimming pool projects, polyvinyl chloride (PVC) coiled material has gradually become the mainstream choice due to its excellent anti-seepage property, chemical corrosion resistance and convenient construction.

[0003] In actual application, the traditional PVC coiled material still has significant technical bottlenecks in ductility and low-temperature bending resistance. Since the structure of a swimming pool may produce slight displacement or cracks due to factors such as foundation settlement and temperature change, these changes pose a severe test to the waterproof layer. Ordinary waterproof materials may break due to lack of sufficient ductility, resulting in waterproof failure. In addition, in cold regions or during seasonal alternation, the temperature around the swimming pool fluctuates greatly, and the traditional PVC coiled material is prone to brittleness in a low-temperature environment, and may crack or even break when bent, affecting the waterproof effect.

[0004] A Chinese patent with publication number CN 118620336A discloses a polyvinyl chloride waterproof coiled material composition, a polyvinyl chloride waterproof coiled material and a preparation method and application thereof. The polyvinyl chloride waterproof coiled material not only has strong tensile strength and elongation, but also has good waterproof function while being able to insulate and keep warm. SUMMARY

[0005] The purpose of the present application is to provide a high-ductility anti-seepage PVC coiled material for swimming pools and a preparation method thereof.

[0006] In order to achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0007] A high-ductility anti-seepage PVC coiled material for swimming pools comprises the following components in parts by weight: 100 parts of PVC resin, 23-27 parts of plasticizer, 15-20 parts of ethylene-vinyl acetate-carbon monoxide terpolymer, 1-3 parts of stabilizer, 1-2 parts of antioxidant, 1-2 parts of calcium stearate, 1-1.5 parts of chlorinated paraffin, 0.2-0.6 parts of epoxy soybean oil and 30-35 parts of modified light calcium carbonate.

[0008] Preferably, the preparation method of the modified light calcium carbonate comprises the following steps:

[0009] (1) Pre-modifying the light calcium carbonate using a silane coupling agent to obtain pre-modified light calcium carbonate;

[0010] (2) Grafting polymethyl methacrylate onto the surface of the pre-modified light calcium carbonate to obtain modified light calcium carbonate.

[0011] Preferably, the preparation method of the modified light calcium carbonate comprises the following steps:

[0012] (1) adding light calcium carbonate into an ethanol aqueous solution, adding a silane coupling agent, heating to 60-65 DEG C under nitrogen protection, reacting for 7-10 h, centrifuging, washing, and drying to obtain pre-modified light calcium carbonate;

[0013] (2) dispersing the pre-modified light calcium carbonate in ethanol, adding methyl methacrylate and azobisisobutyronitrile, heating to 65-70 DEG C under nitrogen atmosphere, and constant temperature reaction for 8-10 h; after the reaction is completed, centrifuging, washing, and drying to obtain modified light calcium carbonate.

[0014] The modification of the light calcium carbonate can improve the tear strength of the coiled material.

[0015] Preferably, the silane coupling agent is at least one selected from silane coupling agent KH550 and silane coupling agent KH570.

[0016] Preferably, the ethylene-vinyl acetate-carbon monoxide terpolymer has a melt flow index of 30-35 g / 10 min under the condition of 190 DEG C and 2.16 kg, a melting point of 60-66 DEG C, and a density of 0.95-1.0 g / cm 3 .

[0017] Preferably, the ethylene-vinyl acetate-carbon monoxide terpolymer has a melt flow index (190 DEG C / 2.16 kg) of 35 g / 10 min, a melting point of 66 DEG C, and a density of 1.0 g / cm 3 .

[0018] The ethylene-vinyl acetate-carbon monoxide terpolymer can be commercially available or prepared by a conventional method. TM The commercially available ethylene-vinyl acetate-carbon monoxide terpolymer can be ELVALOY TM 741 of the Dow Chemical Company.

[0019] The use of the ethylene-vinyl acetate-carbon monoxide terpolymer of ELVALOY TM 741 can improve the tensile strength, elongation at break, and low-temperature resistance of the coiled material. The use of the ethylene-vinyl acetate-carbon monoxide terpolymer with a melting point can make the copolymer have better thermal stability, and when the copolymer is compounded with PVC in the processing process, the PVC coiled material can have better dimensional stability and temperature resistance, thereby affecting the performance of the final product.

[0020] Preferably, the plasticizer comprises polyester plasticizer, and the plasticizer further comprises at least one of synthetic plant ester plasticizer and trioctyl trimellitate.

[0021] Preferably, the plasticizer comprises polyester plasticizer, synthetic plant ester plasticizer and trioctyl trimellitate.

[0022] Preferably, the plasticizer comprises polyester plasticizer, synthetic plant ester plasticizer and trioctyl trimellitate in a weight ratio of (1.4-1.6):(0.2-0.4):(0.6-0.9).

[0023] The polyester plasticizer, synthetic plant ester plasticizer and trioctyl trimellitate can be commercially available or prepared by conventional methods. The commercially available polyester plasticizer can be model TD-1720 (GLOBINEX of Diay Investment Co., Ltd.). The synthetic plant ester plasticizer is model: environmentally friendly plasticizer T60 (Jiangsu Sende Chemical Technology Co., Ltd., superior product). The trioctyl trimellitate is from Jiangsu Sende Chemical Technology Co., Ltd., trioctyl trimellitate TOTM (superior product).

[0024] The present application can improve the low-temperature resistance of the coiled material by adding a specific ratio of compound plasticizer. The present application selects polyester plasticizer, synthetic plant ester plasticizer and trioctyl trimellitate for compounding. When the three plasticizers are used in a certain proportion, they can produce a synergistic effect, make up for each other's shortcomings, and play a synergistic role. By adjusting the proportion of the plasticizer, the interaction between the PVC molecular chains can be optimized, sufficient molecular fluidity can be maintained at a lower temperature, the hardening phenomenon caused by the decrease of temperature can be reduced, and the bending resistance of the PVC material can be improved.

[0025] Preferably, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 1076 and antioxidant 1098.

[0026] The preparation method of the anti-seepage high-ductility PVC coiled material for swimming pools comprises the following steps: adding components into a blender for stirring and blending uniformly, extruding by a double-screw extruder, cooling and shaping in a three-roll calender, performing radiation crosslinking, finally drawing to a coiling machine for coiling to obtain the anti-seepage high-ductility PVC coiled material for swimming pools.

[0027] Compared with the prior art, the present application has the following advantages and beneficial effects:

[0028] 1. The coiled material prepared by the present application is suitable for swimming pools, artificial lakes, water conservancy projects and other scenes, effectively solves the problems of easy cracking and leakage of traditional coiled materials, significantly prolongs the service life, and provides a safer and more durable material selection for related projects.

[0029] 2、The present application can improve the low temperature resistance of the coiled material by adding a specific ratio of compound plasticizer.

[0030] 3、The present application can improve the tensile strength and elongation at break of the coiled material by using ethylene-vinyl acetate-carbon monoxide terpolymer with specific parameters.

[0031] 4、The present application can improve the tear strength of the coiled material by modifying light calcium carbonate. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0033] The raw materials used in the following embodiments of the present application are all commercially available:

[0034] Epoxy soybean oil, Jiangsu Sendi Chemical Technology Co., Ltd., epoxy soybean oil (first grade).

[0035] Chlorinated paraffin, Jiangsu Sendi Chemical Technology Co., Ltd., chlorinated paraffin-52 (first grade).

[0036] Antioxidant, Tianjin Li'an Long New Material Co., Ltd., antioxidant 1010.

[0037] Stabilizer, model FZ-801B composite stabilizer, Jiujiang Tiansheng Plastic Additives Co., Ltd.

[0038] PVC resin, Hubei Yihua Chemical Co., Ltd., model SG5.

[0039] Light calcium carbonate, Shanghai Liangjiang Titanium White Chemical Products Co., Ltd., rubber and plastic grade.

[0040] Embodiment 1

[0041] The present embodiment provides a seepage-proof high-ductility PVC coiled material for swimming pools, which comprises the following components in parts by weight: 100 parts of PVC resin, 25 parts of plasticizer, 17 parts of ethylene-vinyl acetate-carbon monoxide terpolymer, 2 parts of stabilizer, 1.4 parts of antioxidant, 1.7 parts of calcium stearate, 1.2 parts of chlorinated paraffin, 0.4 parts of epoxy soybean oil, and 32 parts of modified light calcium carbonate.

[0042] The preparation method of the modified light calcium carbonate comprises the following steps:

[0043] (1) 10 parts by weight of light calcium carbonate was added into 150 parts by weight of 90wt% ethanol aqueous solution, ultrasonic dispersion for 30 min with power of 300W, 1.5 parts by weight of silane coupling agent KH550 was added, and glacial acetic acid was used to adjust the pH to 4.5, under the protection of nitrogen, the temperature was raised to 62℃, and reacted for 9h, centrifuged, washed with ethanol and water for 2 times respectively, and dried to obtain the pre-modified light calcium carbonate;

[0044] (2) 5 parts by weight of the pre-modified light calcium carbonate was dispersed in 100 parts by weight of ethanol, ultrasonic treatment for 15 min with power of 200W, 26 parts by weight of methyl methacrylate and 0.26 parts by weight of azobisisobutyronitrile were added, the temperature was raised to 70℃ under nitrogen atmosphere, and reacted for 9h, after the reaction was completed, centrifuged, washed with ethanol and water for 3 times respectively, and vacuum dried to obtain the modified light calcium carbonate.

[0045] Ethylene-vinyl acetate-carbon monoxide terpolymer, type ELVALOY TM 741, Dow Chemical Company, USA. Melt flow index (190℃ / 2.16kg) of ethylene-vinyl acetate-carbon monoxide terpolymer, 35g / 10min, melting point 66℃, density 1.0g / cm 3 .

[0046] The plasticizer includes polyester plasticizer, synthetic plant ester plasticizer and trioctyl trimellitate in a weight ratio of 1.5:0.3:0.7. The type of the polyester plasticizer is TD-1720, GLOBINEX, Diayson Investment Co., Ltd. The synthetic plant ester plasticizer is T60 (premium product) of Jiangsu Sendi Chemical Technology Co., Ltd. The trioctyl trimellitate is TOTM (premium product) of Jiangsu Sendi Chemical Technology Co., Ltd.

[0047] The preparation method of the anti-seepage high-ductility PVC coiled material for swimming pools comprises the following steps: adding components into a blender for stirring and blending uniformly, extruding by using a double-screw extruder, the processing temperature of the double-screw extruder is: 120℃ in the first zone, 145℃ in the second zone, 160℃ in the third zone, 175℃ in the fourth zone, 175℃ in the fifth zone, and 160℃ in the sixth zone; sending into a three-roller calender for cooling and shaping, the temperature of the three-roller machine is 50℃, using an electron accelerator device for radiation crosslinking: the irradiation energy is 2MeV, the beam current is 12mA, the irradiation dose is 100kGy, and drawing to a coiling machine for coiling to obtain the anti-seepage high-ductility PVC coiled material for swimming pools with a thickness of 1.5mm.

[0048] Example 2

[0049] The embodiment provides a high-ductility PVC coiled material for a swimming pool, which comprises the following components in parts by weight: 100 parts of PVC resin, 23 parts of plasticizer, 20 parts of ethylene-vinyl acetate-carbon monoxide terpolymer, 1 part of stabilizer, 2 parts of antioxidant, 1 part of calcium stearate, 1.5 parts of chlorinated paraffin, 0.2 parts of epoxy soybean oil, and 35 parts of modified light calcium carbonate.

[0050] The preparation method of the modified light calcium carbonate comprises the following steps:

[0051] (1) 10 parts by weight of light calcium carbonate are added into 150 parts by weight of 90wt% ethanol aqueous solution, ultrasonic dispersion is carried out at a power of 300W for 30 min, 1.5 parts by weight of silane coupling agent KH550 is added, and glacial acetic acid is used to adjust the pH to 5, under the protection of nitrogen, the temperature is increased to 65 DEG C, reaction is carried out for 10 h, centrifugation is carried out, and then the pre-modified light calcium carbonate is obtained by washing with ethanol and water for 2 times and drying;

[0052] (2) 5 parts by weight of the pre-modified light calcium carbonate are dispersed in 100 parts by weight of ethanol, ultrasonic treatment is carried out at a power of 200W for 15 min, 25 parts by weight of methyl methacrylate and 0.28 parts by weight of azobisisobutyronitrile are added, the temperature is increased to 65 DEG C under the protection of nitrogen, constant temperature reaction is carried out for 10 h, after the reaction is completed, centrifugation is carried out, and then the modified light calcium carbonate is obtained by washing with ethanol and water for 3 times and vacuum drying.

[0053] The ethylene-vinyl acetate-carbon monoxide terpolymer is ELVALOY 741 of Dow Chemical Company, USA. TM The melt flow index (190 DEG C / 2.16 kg) of the ethylene-vinyl acetate-carbon monoxide terpolymer is 35 g / 10 min, the melting point is 66 DEG C, and the density is 1.0 g / cm 3 .

[0054] The plasticizer comprises polyester plasticizer, synthetic plant ester plasticizer and trioctyl trimellitate in a weight ratio of 1.4:0.2:0.9. The polyester plasticizer is TD-1720 of GLOBINEX of Diayson Investment Co., Ltd. The synthetic plant ester plasticizer is T60 (superior product) of Jiangsu Sendi Chemical Technology Co., Ltd. The trioctyl trimellitate is TOTM (superior product) of Jiangsu Sendi Chemical Technology Co., Ltd.

[0055] The preparation method of the anti-seepage high-ductility PVC coiled material for swimming pools comprises the following steps: adding components into a stirrer to stir and blend uniformly, extruding by a double-screw extruder, the processing temperature of the double-screw extruder is: 120 DEG C for the first zone, 145 DEG C for the second zone, 160 DEG C for the third zone, 175 DEG C for the fourth zone, 175 DEG C for the fifth zone, and 160 DEG C for the sixth zone; sending into a three-roller calender to cool and shape, the temperature of the three-roller calender is 50 DEG C, using an electron accelerator device to radiate crosslinking: the irradiation energy is 2 MeV, the beam current is 12 mA, the irradiation dose is 100 kGy, and drawing to a coiling machine to coil, so that the anti-seepage high-ductility PVC coiled material for swimming pools with a thickness of 1.5 mm is obtained.

[0056] Example 3

[0057] The difference between the present example and Example 1 is that the plasticizer comprises polyester plasticizer and trioctyl trimellitate at a weight ratio of 1.5:0.7. The model of the polyester plasticizer is TD-1720, GLOBINEX, Diayson Investment Co., Ltd. The trioctyl trimellitate is from Jiangsu Sende Chemical Technology Co., Ltd., and the trioctyl trimellitate TOTM (superior grade) is used.

[0058] Example 4

[0059] The difference between the present example and Example 1 is that the plasticizer comprises polyester plasticizer and synthetic plant ester plasticizer at a weight ratio of 1.5:0.3. The model of the polyester plasticizer is TD-1720, GLOBINEX, Diayson Investment Co., Ltd. The synthetic plant ester plasticizer is from Jiangsu Sende Chemical Technology Co., Ltd., and the model is environmental protection plasticizer T60 (superior grade).

[0060] Example 5

[0061] The difference between the present example and Example 1 is that the plasticizer comprises polyester plasticizer, synthetic plant ester plasticizer and trioctyl trimellitate at a weight ratio of 1.2:0.9:0.4.

[0062] Comparative Example 1

[0063] The difference between the present comparative example and Example 1 is that the plasticizer is polyester plasticizer, and the model of the polyester plasticizer is TD-1720 (GLOBINEX, Diayson Investment Co., Ltd.).

[0064] Comparative Example 2

[0065] The difference between the present comparative example and Example 1 is that the ethylene-vinyl acetate-carbon monoxide terpolymer is ELVALOYTM 742, The Dow Chemical Company, and the melt flow index (190 DEG C / 2.16 kg) of the ethylene-vinyl acetate-carbon monoxide terpolymer is 35 g / 10 min, the melting point is 45 DEG C, and the density is 1.02 g / cm 3 .

[0066] Comparative Example 3

[0067] The difference between this comparative example and Example 1 is that the modified light calcium carbonate is replaced by light calcium carbonate, Shanghai Liangjiang Titanium White Chemical Products Co., Ltd., rubber and plastic grade.

[0068] Comparative Example 4

[0069] The difference between this comparative example and Example 1 is that the one kind of anti-seepage high ductility PVC coiled material for swimming pool comprises the following components in parts by weight: PVC resin 100 parts, plasticizer 36 parts, ethylene-vinyl acetate-carbon monoxide terpolymer 10 parts, stabilizer 2 parts, antioxidant 1.4 parts, calcium stearate 1.7 parts, chlorinated paraffin 1.2 parts, epoxy soybean oil 0.4 parts, and modified light calcium carbonate 28 parts.

[0070] Comparative Example 5

[0071] This comparative example discloses a composition for polyvinyl chloride waterproof coiled material, polyvinyl chloride waterproof coiled material, and its preparation method and application in Chinese Patent Publication No. CN 118620336 B. The waterproof coiled material with a thickness of 1.5 mm is prepared by the method of Example 1 in the publication.

[0072] Performance test

[0073] The anti-seepage high ductility PVC coiled materials for swimming pool prepared in Examples 1-5 and Comparative Examples 1-5 are subjected to performance tests.

[0074] Tensile properties, right-angle tear strength, and low-temperature bending resistance: tested according to GB 12592-2011 “Polyvinyl chloride waterproof coiled material”. The results are shown in Table 1.

[0075] Table 1 Performance test results

[0076]

[0077] As shown in Table 1, the tensile properties and tear strength of the PVC coiled materials prepared in Examples 1-5 are superior to those of the PVC coiled material of the prior art in Comparative Example 5. It is determined that the waterproof performance of the coiled materials prepared in Examples 1-5 is excellent. The low-temperature resistance of the PVC coiled materials of Examples 1-2 is excellent.

[0078] In Comparative Example 1, only polyester plasticizer is used as the plasticizer, and the low-temperature resistance of the coiled material decreases.

[0079] In Comparative Example 2, the ethylene-vinyl acetate-carbon monoxide terpolymer is replaced by ELVALOY TM 742, the tensile properties of the coiled material decrease, and the low-temperature bending resistance decreases.

[0080] In Comparative Example 3, the light calcium carbonate is not modified, and the tear strength of the coiled material decreases.

[0081] The ratio of the plasticizer, ethylene-vinyl acetate-carbon monoxide terpolymer and modified light calcium carbonate in Comparative Example 4 is changed, and the mechanical properties of the coiled material decrease, and the low temperature resistance decreases, indicating that the three have a synergistic effect.

[0082] In summary, the anti-seepage high-ductility PVC coiled material for swimming pools prepared by the present application has excellent tensile strength and elongation at break, ensuring that the material is not easily damaged when subjected to external stress, enhancing the overall stability and durability of the waterproof layer. At the same time, the high elongation at break means that the material has good flexibility, can adapt to the slight movement or cracks of the foundation structure without breaking, effectively preventing water penetration. This feature makes the PVC coiled material not only suitable for waterproofing projects of newly built swimming pools, but also provides an ideal solution for the renovation of old swimming pools, extending the service life of the facilities.

[0083] In cold climate conditions, the temperature around the swimming pool fluctuates greatly, which puts higher requirements on waterproof materials. The PVC coiled material for swimming pools prepared by the present application has superior low temperature resistance, maintaining good flexibility and bending resistance even at extremely low temperatures, avoiding brittle fracture caused by low temperature. Significantly improves the reliability of the waterproof layer in harsh weather conditions, ensuring its long-term effective waterproof effect. At the same time, good low temperature resistance also broadens the application range of the PVC coiled material, making it not only suitable for warm areas, but also able to provide long-lasting protection in cold environments, meeting the needs of different geographical regions.

[0084] The anti-seepage high-ductility PVC coiled material for swimming pools of the present application has excellent tear resistance strength. Whether it is accidental scratches during construction or physical damage during daily use, the high tear resistance strength can effectively resist damage caused by external forces, reducing the risk of water leakage caused by material damage. The improvement of tear resistance strength not only improves the safety and stability of the waterproof system, but also reduces maintenance costs, as it reduces the need for frequent repairs or replacements. The high-performance PVC coiled material of the present application provides a more reliable, economical and easy-to-maintain waterproofing solution for consumers, greatly improving the operating efficiency and service life of the swimming pool facilities.

[0085] The above is the preferred embodiment of the present application. It should be noted that for those skilled in the art, without departing from the principles of the present application, several improvements and refinements can be made, which should also be considered within the scope of protection of the present application.

Claims

1. A high-elongation, waterproof PVC roll for swimming pools, characterized in that, The product comprises the following components in parts by weight: 100 parts PVC resin, 23-27 parts plasticizer, 15-20 parts ethylene-vinyl acetate-carbon monoxide terpolymer, 1-3 parts stabilizer, 1-2 parts antioxidant, 1-2 parts calcium stearate, 1-1.5 parts chlorinated paraffin, 0.2-0.6 parts epoxidized soybean oil, and 30-35 parts modified light calcium carbonate. The preparation method of modified light calcium carbonate includes the following steps: (1) Light calcium carbonate is pre-modified using a silane coupling agent to obtain pre-modified light calcium carbonate; (2) Graft polymethyl methacrylate onto the surface of pre-modified light calcium carbonate to obtain modified light calcium carbonate; The ethylene-vinyl acetate-carbon monoxide terpolymer exhibits a melt flow index of 30-35 g / 10 min, a melting point of 60-66 °C, and a density of 0.95-1.0 g / cm³ under conditions of 190 °C and 2.16 kg. 3 ; Plasticizers include polyester plasticizers, synthetic plant ester plasticizers, and trioctyl trimellitate in a weight ratio of (1.4-1.6):(0.2-0.4):(0.6-0.9).

2. The high-elongation, waterproof PVC roll for swimming pools according to claim 1, characterized in that, The preparation method of the modified light calcium carbonate includes the following steps: (1) Add light calcium carbonate to an ethanol aqueous solution, add silane coupling agent, heat the reaction under nitrogen protection, centrifuge, wash and dry to obtain pre-modified light calcium carbonate; (2) Disperse the pre-modified light calcium carbonate in ethanol, add methyl methacrylate and azobisisobutyronitrile, heat to 65-70℃ under nitrogen atmosphere, and react at a constant temperature for 8-10h. After the reaction is completed, centrifuge, wash and dry to obtain modified light calcium carbonate.

3. The high-elongation, waterproof PVC roll for swimming pools according to claim 2, characterized in that, The silane coupling agent is selected from at least one of silane coupling agent KH550 and silane coupling agent KH570.

4. The high-elongation, waterproof PVC roll for swimming pools according to claim 1, characterized in that, The antioxidant is selected from at least one of antioxidant 1010, antioxidant 1076, and antioxidant 1098.

5. A method for preparing a high-elongation, waterproof PVC roll for swimming pools according to any one of claims 1-4, characterized in that, The process includes the following steps: adding the components to a mixer and mixing until uniform, extruding with a twin-screw extruder, feeding into a three-roll calender for cooling and shaping, performing radiation crosslinking, and finally drawing it to a coiler for coiling to obtain a high-elongation, waterproof PVC roll for swimming pools.

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