Waterproof lining material for swimming pool and preparation method thereof

Abstract

The invention relates to the field of swimming pool materials, in particular to a waterproof lining material for a swimming pool and a preparation method of the waterproof lining material. Comprising 38 to 64 parts of nitrile rubber, 15 to 30 parts of butyl rubber, 10 to 20 parts of polyvinyl chloride, 12 to 24 parts of modified allophane, 6 to 12 parts of a styrene-butadiene-styrene block copolymer, 1 to 3 parts of a lubricant, 1 to 2 parts of a vulcanizing agent, 1.6 to 2.4 parts of a vulcanization accelerator and 0.5 to 1 part of an anti-aging agent. The waterproof lining material capable of being used for the swimming pool is prepared, a composite material is formed in a mode of combining rubber, plastic and SBS, and the performance better than that of a single material can be obtained. Meanwhile, modified allophane is used as the filler, so that the strength of the material is improved, and the corrosion resistance and the aging resistance are improved.

Description

Technical Field

[0001] The invention relates to the field of swimming pool materials, and in particular to a waterproof lining material for a swimming pool and a preparation method thereof. Background Art

[0002] In order to highlight the theme and create a personalized taste, many large swimming pools have begun to pay attention to the application of waterproof decorative materials. However, due to the particularity of the water-related environment, the time-consuming and costly construction and paving have brought considerable difficulties to the selection of waterproof decorative materials. Looking at the current situation of the supply market, various materials emerge in an endless stream, making the market flourishing, but also dazzling and difficult to distinguish between good and bad. For long-term water-related use environments, swimming pool lining materials need to have three major elements: high strength; good internal waterproofing; strong corrosion resistance.

[0003] The water in the swimming pool contains certain fungicides and chemicals due to its special nature. The chlorine in the water is highly corrosive. The material of the swimming pool waterproof lining must not only be able to withstand long-term immersion in mixed water without deformation or discoloration, but also be able to withstand chlorine corrosion. However, the existing swimming pool waterproof lining is difficult to achieve this level. After a period of frequent use, it will age and corrode severely, thus affecting the waterproof effect. Summary of the invention

[0004] In view of the problems existing in the prior art, the object of the present invention is to provide a waterproof lining material for a swimming pool and a preparation method thereof.

[0005] The purpose of the present invention is achieved by the following technical solutions:

[0006] In a first aspect, the present invention provides a waterproof lining material for a swimming pool, which comprises, calculated by weight:

[0007] 38-64 parts of nitrile rubber, 15-30 parts of butyl rubber, 10-20 parts of polyvinyl chloride, 12-24 parts of modified allophane, 6-12 parts of styrene-butadiene-styrene block copolymer, 1-3 parts of lubricant, 1-2 parts of vulcanizing agent, 1.6-2.4 parts of vulcanization accelerator and 0.5-1 part of antioxidant.

[0008] Preferably, the type of the nitrile rubber is one of NBR-2707, NBR-2870 and NBR-3345.

[0009] Preferably, the type of butyl rubber is one of IIR-1751, IIR-301 and IIR-1953.

[0010] Preferably, the melt index of polyvinyl chloride is 13-18 g / 10 min (190°C / 2.16 kg) and the density is 1.36-1.39 g / cm 3 .

[0011] Preferably, in the styrene-butadiene-styrene block copolymer, the weight content of styrene is 38%-42%, and the melt index is 1-3 g / 10 min (200° C. / 5 kg).

[0012] Preferably, the lubricant is any one of magnesium stearate, zinc stearate and sodium stearate.

[0013] Preferably, the vulcanizing agent is sulfur.

[0014] Preferably, the vulcanization accelerator is any one of vulcanization accelerator TMTD, vulcanization accelerator M, vulcanization accelerator ZDMC, and vulcanization accelerator H.

[0015] Preferably, the antioxidant is any one of 4,4'-dioctyldiphenylamine, N-phenyl-2-naphthylamine and 2-mercaptobenzimidazole.

[0016] Preferably, the preparation method of modified allophane comprises:

[0017] S1, γ-aminopropyltriethoxysilane and ethanol solution are mixed, heated and refluxed for 2-4 hours, then allophane powder is added, refluxed for 6-10 hours, filtered, washed and dried to obtain amino allophane;

[0018] S2, dissolving allyl alcohol glycidyl ether in anhydrous ethanol, heating and refluxing for 0.3-0.8h, then adding amination of allophane, continuing to reflux and stir for 2-6h, filtering, washing and drying to obtain allyl allophane;

[0019] S3. Allyl phenyl ether, allyl allophane and toluene are mixed and dispersed uniformly, stirred for 8-12 hours in the presence of an initiator at 55-75° C., the solvent is removed by rotary evaporation, and the mixture is washed and dried to obtain modified allophane.

[0020] Preferably, in S1, the mass fraction of the ethanol solution is 70%-90%; the particle size of the allophane powder is 7.2-8.6 μm, and the specific surface area is 55-65 m 2 / g, the SiO2 content in the composition is greater than 32%, and the Al2O3 content is greater than 50%.

[0021] Preferably, in S1, the mass volume ratio of γ-aminopropyltriethoxysilane, allophane powder and ethanol solution is (0.15-0.3) g: (1-2) g: (20-30) mL.

[0022] Preferably, in S2, the mass volume ratio of allyl alcohol glycidyl ether, aminosilane-modified allophane and anhydrous ethanol is (0.47-0.94) g: 1 g: (40-60) mL.

[0023] Preferably, in S3, the initiator is azobisisobutyronitrile or azobisisoheptanenitrile, and the added amount is 3%-8% of the mass of allyl phenyl ether.

[0024] Preferably, in S3, the mass volume ratio of allyl allophane, allyl phenyl ether and toluene is 1 g:(0.13-0.26) g:(20-30) mL.

[0025] In a second aspect, the present invention provides a method for preparing a waterproof lining material for a swimming pool, comprising the following steps:

[0026] (1) First, nitrile rubber, butyl rubber, polyvinyl chloride and styrene-butadiene-styrene block copolymer are mixed in an internal mixer and kneaded at 125-145° C. for 8-16 minutes;

[0027] (2) adding modified allophane, lubricant and antioxidant to the internal mixer in step (1) in sequence, and mixing for 2-4 minutes for each raw material added;

[0028] (3) Mix the product obtained in step (2), a vulcanizing agent and a vulcanization accelerator, vulcanize in a mold at 135-165° C. and 6-10 MPa for 0.5-1 h, cool and demold after molding, and obtain a waterproof lining material for a swimming pool.

[0029] The beneficial effects of the present invention are:

[0030] 1. The present invention prepares a waterproof lining material that can be used for swimming pools. The composite material is formed by combining rubber, plastic and SBS, which can obtain better performance than a single material. At the same time, the filler of the present invention uses modified allophane, which not only increases the strength of the material, but also improves the corrosion resistance and aging resistance.

[0031] 2. The modified allophane is obtained by modifying allophane with a large specific surface area. Specifically, the allophane is first activated with aminosilane to obtain amino allophane; then, it is combined with allyl alcohol glycidyl ether by amino-epoxy groups to obtain allylated allophane; then, it is polymerized with allyl phenyl ether containing anisole to finally obtain a polymer-coated allophane structure, i.e., modified allophane.

[0032] 3. The modified allophane prepared by the present invention not only has the advantage of high strength of allophane, but also utilizes its porous adsorption to chemically modify it, thereby enhancing its compatibility with rubber. At the same time, the modified allophane contains a large number of chemical groups, which greatly enhances the corrosion resistance and aging resistance of waterproof materials. DETAILED DESCRIPTION

[0033] The technical solution of the present invention is described below through specific examples. It should be understood that one or more method steps mentioned in the present invention do not exclude the presence of other method steps before and after the combination step or the insertion of other method steps between these explicitly mentioned steps; it should also be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or to limit the scope of the present invention. The change or adjustment of the relative relationship thereof shall also be regarded as the scope of the present invention without substantially changing the technical content.

[0034] In order to better understand the above technical scheme, the exemplary embodiments of the present invention are described in more detail below. Although exemplary embodiments of the present invention are shown, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present invention and to enable the scope of the present invention to be fully communicated to those skilled in the art.

[0035] The present invention will be further described below in conjunction with the following examples.

[0036] Example 1

[0037] A waterproof lining material for a swimming pool, calculated by weight, comprising:

[0038] 52 parts of nitrile rubber NBR-2707, 21 parts of butyl rubber IIR-1751, 15 parts of polyvinyl chloride, 18 parts of modified allophane, 9 parts of styrene-butadiene-styrene block copolymer, 2 parts of lubricant magnesium stearate, 1.5 parts of vulcanizing agent sulfur, 2 parts of vulcanization accelerator TMTD and 0.6 parts of antioxidant 4,4'-dioctyldiphenylamine.

[0039] Among them, the melt index of polyvinyl chloride is 15g / 10min (190℃ / 2.16kg) and the density is 1.37g / cm 3 ; In the styrene-butadiene-styrene block copolymer, the weight content of styrene is 40% and the melt index is 2g / 10min (200℃ / 5kg).

[0040] Wherein, the preparation method of modified allophane comprises:

[0041] S1. Mix γ-aminopropyltriethoxysilane and 80% ethanol solution, heat and reflux for 2-4 hours, then add allophane powder (the particle size of allophane powder is 7.2-8.6 μm, and the specific surface area is 55-65 m 2 / g, the SiO2 content in the composition is greater than 32%, and the Al2O3 content is greater than 50%), the mass volume ratio of γ-aminopropyltriethoxysilane, allophane powder and ethanol solution is 0.22g:1.5g:25mL, and the reflux is continued for 8h, and the filter residue is filtered and washed three times with water, and then dried under vacuum to obtain amination allophane;

[0042] S2, dissolving allyl alcohol glycidyl ether in anhydrous ethanol, heating and reflux for 0.5h, then adding amino allophane, the mass volume ratio of allyl alcohol glycidyl ether, aminosilane-modified allophane and anhydrous ethanol is 0.71g:1g:50mL, continuing to reflux and stir for 4h, filtering to obtain a filter residue, washing it three times with alcohol, and then drying it under vacuum to obtain allyl allophane;

[0043] S3. Mix allyl phenyl ether and toluene, and after fully dissolving, add allyl allophane, the mass volume ratio of allyl allophane, allyl phenyl ether and toluene is 1g:0.2g:25mL, disperse until uniform, add initiator azobisisobutyronitrile under the protection of nitrogen, the addition amount is 5% of the mass of allyl phenyl ether, stir and treat at 65°C for 10h, then remove the solvent by rotary evaporation, wash three times with alcohol, and vacuum dry to obtain modified allophane.

[0044] The method for preparing the above-mentioned waterproof lining material for swimming pool comprises the following steps:

[0045] (1) First, nitrile rubber, butyl rubber, polyvinyl chloride and styrene-butadiene-styrene block copolymer were mixed in an internal mixer and kneaded at 135° C. for 12 min;

[0046] (2) adding modified allophane, lubricant and antioxidant to the internal mixer in step (1) in sequence, and mixing for 3 minutes for each raw material added;

[0047] (3) The product obtained in step (2), a vulcanizing agent and a vulcanization accelerator are mixed, and vulcanized in a mold at 155° C. and 7 MPa for 0.8 h. After molding, the mold is cooled and demolded to obtain a waterproof lining material for a swimming pool.

[0048] Example 2

[0049] A waterproof lining material for a swimming pool, calculated by weight, comprising:

[0050] 38 parts of nitrile rubber NBR-2870, 15 parts of butyl rubber IIR-301, 10 parts of polyvinyl chloride, 12 parts of modified allophane, 6 parts of styrene-butadiene-styrene block copolymer, 1 part of lubricant zinc stearate, 1 part of vulcanizing agent sulfur, 1.6 parts of vulcanization accelerator M and 0.5 parts of antioxidant N-phenyl-2-naphthylamine.

[0051] Among them, the melt index of polyvinyl chloride is 15g / 10min (190℃ / 2.16kg) and the density is 1.37g / cm 3 ; In the styrene-butadiene-styrene block copolymer, the weight content of styrene is 40% and the melt index is 2g / 10min (200℃ / 5kg).

[0052] Wherein, the preparation method of modified allophane comprises:

[0053] S1. Mix γ-aminopropyltriethoxysilane and 70% ethanol solution, heat and reflux for 2 hours, then add allophane powder (the particle size of allophane powder is 7.2-8.6 μm, and the specific surface area is 55-65 m 2 / g, the SiO2 content in the composition is greater than 32%, and the Al2O3 content is greater than 50%), the mass volume ratio of γ-aminopropyltriethoxysilane, allophane powder and ethanol solution is 0.15g:1g:20mL, and the reflux is continued for 6h, and the amination of allophane is obtained by suction filtration, washing and drying.

[0054] S2, dissolving allyl alcohol glycidyl ether in anhydrous ethanol, heating and reflux for 0.3h, then adding amino allophane, the mass volume ratio of allyl alcohol glycidyl ether, aminosilane-modified allophane and anhydrous ethanol is 0.47g:1g:40mL, continuing to reflux and stir for 2h, filtering, washing and drying to obtain allyl allophane;

[0055] S3. Mix allyl phenyl ether and toluene, and after fully dissolving, add allyl allophane, the mass volume ratio of allyl allophane, allyl phenyl ether and toluene is 1g:0.13g:20mL, disperse until uniform, add initiator azobisisoheptanenitrile under the protection of nitrogen, the addition amount is 3% of the mass of allyl phenyl ether, stir and treat at 55°C for 8h, then remove the solvent by rotary evaporation, wash three times with alcohol, and vacuum dry to obtain modified allophane.

[0056] The method for preparing the above-mentioned waterproof lining material for swimming pool comprises the following steps:

[0057] (1) First, nitrile rubber, butyl rubber, polyvinyl chloride and styrene-butadiene-styrene block copolymer were mixed in an internal mixer and kneaded at 125° C. for 8 min;

[0058] (2) adding modified allophane, lubricant and antioxidant to the internal mixer in step (1) in sequence, and mixing for 2 minutes for each raw material added;

[0059] (3) The product obtained in step (2), a vulcanizing agent and a vulcanization accelerator are mixed, and vulcanized in a mold at 135° C. and 6 MPa for 0.5 h. After molding, the mold is cooled and demolded to obtain a waterproof lining material for a swimming pool.

[0060] Example 3

[0061] A waterproof lining material for a swimming pool, calculated by weight, comprising:

[0062] 64 parts of nitrile rubber NBR-3345, 30 parts of butyl rubber IIR-301, 20 parts of polyvinyl chloride, 24 parts of modified allophane, 12 parts of styrene-butadiene-styrene block copolymer, 3 parts of lubricant sodium stearate, 2 parts of vulcanizing agent sulfur, 2.4 parts of vulcanization accelerator ZDMC and 1 part of antioxidant 2-mercaptobenzimidazole.

[0063] Among them, the melt index of polyvinyl chloride is 15g / 10min (190℃ / 2.16kg) and the density is 1.37g / cm 3 ; In the styrene-butadiene-styrene block copolymer, the weight content of styrene is 40% and the melt index is 2g / 10min (200℃ / 5kg).

[0064] Wherein, the preparation method of modified allophane comprises:

[0065] S1. Mix γ-aminopropyltriethoxysilane and 90% ethanol solution, heat and reflux for 4 hours, then add allophane powder (the particle size of allophane powder is 7.2-8.6 μm, and the specific surface area is 55-65 m 2 / g, the SiO2 content in the composition is greater than 32%, and the Al2O3 content is greater than 50%), the mass volume ratio of γ-aminopropyltriethoxysilane, allophane powder and ethanol solution is 0.3g:2g:30mL, and the reflux is continued for 10h, and the amination of allophane is obtained by suction filtration, washing and drying.

[0066] S2, dissolving allyl alcohol glycidyl ether in anhydrous ethanol, heating and reflux for 0.8h, then adding amino allophane, the mass volume ratio of allyl alcohol glycidyl ether, aminosilane-modified allophane and anhydrous ethanol is 0.94g:1g:60mL, continuing to reflux and stir for 6h, filtering, washing and drying to obtain allyl allophane;

[0067] S3. Mix allyl phenyl ether and toluene, and after fully dissolving, add allyl allophane, the mass volume ratio of allyl allophane, allyl phenyl ether and toluene is 1g:0.26g:30mL, disperse until uniform, add initiator azobisisobutyronitrile under the protection of nitrogen, the addition amount is 8% of the mass of allyl phenyl ether, stir and treat at 75°C for 12h, then remove the solvent by rotary evaporation, wash three times with alcohol, and vacuum dry to obtain modified allophane.

[0068] The method for preparing the above-mentioned waterproof lining material for swimming pool comprises the following steps:

[0069] (1) First, nitrile rubber, butyl rubber, polyvinyl chloride and styrene-butadiene-styrene block copolymer were mixed in an internal mixer and kneaded at 145° C. for 16 min;

[0070] (2) adding modified allophane, lubricant and antioxidant to the internal mixer in step (1) in sequence, and mixing for 4 minutes for each raw material added;

[0071] (3) The product obtained in step (2), a vulcanizing agent and a vulcanization accelerator are mixed, and vulcanized in a mold at 165° C. and 10 MPa for 1 h. After molding, the mold is cooled and demolded to obtain a waterproof lining material for a swimming pool.

[0072] Comparative Example 1

[0073] A waterproof lining material for a swimming pool, which differs from Example 1 in that the modified allophane in the composition is replaced by allophane powder, and the other components and the preparation method remain unchanged.

[0074] Comparative Example 2

[0075] A waterproof lining material for a swimming pool, which differs from Example 1 in that the modified allophane in the composition is replaced by amino allophane (prepared in the same manner as in Example 1), and the other components and preparation method remain unchanged.

[0076] Comparative Example 3

[0077] A waterproof lining material for a swimming pool, which differs from Example 1 in that the modified allophane in the ingredients is replaced by a mixture of allophane powder and allyl phenyl ether, the mass ratio of the allophane powder to the allyl phenyl ether is 1:0.2, and the other ingredients and the preparation method remain unchanged.

[0078] Experimental testing

[0079] The performance of the waterproof lining materials prepared in Example 1 and Comparative Examples 1-3 was tested. The tensile strength and elongation at break were based on GB / T 528-2009, the oxygen index was based on ASTM D2863, and the aging resistance test was:2 The steel sheet was irradiated under a xenon lamp for 300 hours to observe whether its surface was cracked. The corrosion resistance test was: soaked in a 10wt% NaCl solution at 60°C for 168 hours, then its tensile strength was tested and the change rate was calculated.

[0080] The data detection results are shown in Table 1:

[0081] Table 1 Performance results of different waterproof lining materials

[0082]

[0083]

[0084] From the results in Table 1, it can be seen that the waterproof lining material prepared in Example 1 of the present invention has high strength, good toughness and good wear resistance; no cracking occurs after aging treatment for 300 hours, indicating that it has strong aging resistance; after being soaked in NaCl solution for 168 hours, the tensile strength only decreases by 5.8%, which is much lower than other comparative examples, indicating that it has better chlorine corrosion resistance. In summary, it can be shown that the material prepared in Example 1 of the present invention is more suitable for use as a waterproof lining material in a swimming pool.

[0085] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms should not be understood as necessarily being directed to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine different embodiments or examples described in this specification.

[0086] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A waterproof lining material for a swimming pool, characterized in that: Calculated by weight, including: 38-64 parts of nitrile rubber, 15-30 parts of butyl rubber, 10-20 parts of polyvinyl chloride, 12-24 parts of modified allophane, 6-12 parts of styrene-butadiene-styrene block copolymer, 1-3 parts of lubricant, 1-2 parts of vulcanizing agent, 1.6-2.4 parts of vulcanization accelerator and 0.5-1 part of antioxidant.

2. A waterproof lining material for a swimming pool according to claim 1, characterized in that: The model of nitrile rubber is one of NBR-2707, NBR-2870, and NBR-3345; the model of butyl rubber is one of IIR-1751, IIR-301, and IIR-1953.

3. A waterproof lining material for a swimming pool according to claim 1, characterized in that: The melt index of polyvinyl chloride is 13-18g / 10min (190℃ / 2.16kg) and the density is 1.36-1.39g / cm 3 ; In the styrene-butadiene-styrene block copolymer, the weight content of styrene is 38%-42%, and the melt index is 1-3g / 10min (200℃ / 5kg).

4. A waterproof lining material for a swimming pool according to claim 1, characterized in that: The lubricant is any one of magnesium stearate, zinc stearate and sodium stearate; the antioxidant is any one of 4,4'-dioctyldiphenylamine, N-phenyl-2-naphthylamine and 2-mercaptobenzimidazole.

5. A waterproof lining material for a swimming pool according to claim 1, characterized in that: The vulcanizing agent is sulfur; and the vulcanization accelerator is any one of the vulcanization accelerator TMTD, the vulcanization accelerator M, the vulcanization accelerator ZDMC, and the vulcanization accelerator H.

6. A waterproof lining material for a swimming pool according to claim 1, characterized in that: The preparation method of modified allophane comprises: S1, γ-aminopropyltriethoxysilane and ethanol solution are mixed, heated and refluxed for 2-4 hours, then allophane powder is added, refluxed for 6-10 hours, filtered, washed and dried to obtain amino allophane; S2, dissolving allyl alcohol glycidyl ether in anhydrous ethanol, heating and refluxing for 0.3-0.8h, then adding amination of allophane, continuing to reflux and stir for 2-6h, filtering, washing and drying to obtain allyl allophane; S3. Allyl phenyl ether, allyl allophane and toluene are mixed and dispersed uniformly, stirred for 8-12 hours in the presence of an initiator at 55-75° C., the solvent is removed by rotary evaporation, and the mixture is washed and dried to obtain modified allophane.

7. A waterproof lining material for a swimming pool according to claim 6, characterized in that: In S1, the mass volume ratio of γ-aminopropyltriethoxysilane, allophane powder and ethanol solution is (0.15-0.3) g: (1-2) g: (20-30) mL.

8. A waterproof lining material for a swimming pool according to claim 6, characterized in that: In S2, the mass volume ratio of allyl alcohol glycidyl ether, aminosilane-modified hydrophobic stone and anhydrous ethanol is (0.47-0.94) g:1 g:(40-60) mL.

9. A waterproof lining material for a swimming pool according to claim 6, characterized in that: In S3, the mass volume ratio of allyl allophane, allyl phenyl ether and toluene is 1 g:(0.13-0.26) g:(20-30) mL.

10. A method for preparing the waterproof lining material for a swimming pool according to claim 1, characterized in that: The following steps are involved: (1) First, nitrile rubber, butyl rubber, polyvinyl chloride and styrene-butadiene-styrene block copolymer are mixed in an internal mixer and kneaded at 125-145° C. for 8-16 minutes; (2) adding modified allophane, lubricant and antioxidant to the internal mixer in step (1) in sequence, and mixing for 2-4 minutes for each raw material added; (3) Mix the product obtained in step (2), a vulcanizing agent and a vulcanization accelerator, vulcanize in a mold at 135-165° C. and 6-10 MPa for 0.5-1 h, cool and demold after molding, and obtain a waterproof lining material for a swimming pool.

Images