Composition for waterproof coiled material, waterproof coiled material and preparation method of waterproof coiled material

Abstract

The invention relates to the technical field of waterproof coiled materials, and discloses a composition for a waterproof coiled material, the waterproof coiled material and a preparation method of the waterproof coiled material. The composition comprises a main agent and an auxiliary agent, wherein the main agent comprises asphalt, fluororubber cement, a hydrogenated styrene-butadiene block copolymer, maleic anhydride grafted POE (Polyolefin Elastomer), a filler and a softener; the solid content of fluororubber in the fluororubber adhesive cement is 30-40 wt%. The waterproof coiled material prepared from the composition provided by the invention has excellent high and low temperature resistance, chemical corrosion resistance and high cohesion, and meets the long-term waterproof requirement in an extreme environment.

Description

Technical Field

[0001] This invention relates to the field of waterproof membrane technology, specifically to compositions for waterproof membranes, waterproof membranes, and methods for their preparation. Background Technology

[0002] In the field of building waterproofing, traditional modified bitumen waterproof membranes mostly use conventional elastomers such as SBS (styrene-butadiene-styrene block copolymer) and APP (atactic polypropylene) as modifiers. The process usually involves directly mixing the modifier with bitumen, fillers, and additives, and then coating it onto a base material to form the membrane.

[0003] The above-mentioned solutions mainly rely on the elasticity of modifiers to improve the basic mechanical properties of asphalt, but the performance improvement in extreme environments is limited. For example, they have a narrow range of resistance to high and low temperatures, are prone to flow and softening at high temperatures (softening point is generally below 90℃), and are prone to brittleness at low temperatures (low-temperature bending temperature is mostly -15 to -25℃); they have poor resistance to chemical corrosion and are prone to aging and failure in acid, alkali, and organic solvent environments; they have insufficient cohesion and are prone to delamination and cracking after long-term use, especially under complex stress, their waterproof performance deteriorates rapidly.

[0004] CN116023905A discloses a low-temperature resistant rubber asphalt waterproof membrane and its production method. The waterproof membrane includes a modified rubber asphalt layer and a waterproof layer. The modified rubber asphalt layer comprises: asphalt and polyether. b Amide-based thermoplastic elastomers, polyolefin elastomers, polyolefin fluororubber, methyl vinyl silicone rubber, vulcanizing agents, silver complexes, quaternary ammonium salts, and attapulgite. The method includes: first, preparing attapulgite modified with a silver complex and quaternary ammonium salt compound; second, adding appropriate weight proportions of asphalt, polyolefin fluororubber, methyl vinyl silicone rubber, and polyether... b Amide-based thermoplastic elastomers, polyolefin elastomers, vulcanizing agents, and modified attapulgite clay are added to a kneader and kneaded evenly to obtain a composite material. The composite material is then placed in a mold for a first-stage vulcanization at 150℃–170℃ for 20–30 minutes to obtain a first-stage vulcanized product. Next, the first-stage vulcanized product undergoes a second-stage vulcanization in the same mold at 310–340℃ for 5–10 minutes. After cooling and demolding, a modified rubber asphalt layer raw material is obtained. Finally, the modified rubber asphalt layer raw material obtained in step three is molded using industry-standard equipment and combined with a waterproof layer to obtain a low-temperature resistant rubber asphalt waterproof membrane. However, this existing technology uses a complex vulcanization process requiring high-temperature two-stage vulcanization, which is complex and energy-intensive. Furthermore, the poor compatibility between the polyolefin-based fluororubber and asphalt results in insufficient cohesion in the waterproof membrane, leading to delamination and cracking after long-term use. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of existing waterproof membranes having a narrow range of high and low temperature resistance and poor chemical corrosion resistance.

[0006] To achieve the above objectives, a first aspect of the present invention provides a composition for waterproof membrane, the composition comprising a main agent and an auxiliary agent, wherein the main agent contains 40-60 parts by weight of bitumen, 20-35 parts by weight of fluororubber adhesive, 8-12 parts by weight of hydrogenated styrene-butadiene block copolymer, 3-6 parts by weight of maleic anhydride-grafted POE, 8-15 parts by weight of filler and 5-12 parts by weight of softener. The solid content of fluororubber in the fluororubber mortar is 30wt%-40wt%, and the melting point of fluororubber in the fluororubber mortar is 115-135℃, and the density is ≥1.78g / mL.

[0007] A second aspect of the present invention provides a method for preparing a waterproof membrane, the method comprising using the components of the composition described in the first aspect above, including: A third aspect of the present invention provides a waterproof membrane prepared by the method described in the second aspect above.

[0008] The components of the waterproof membrane composition provided by this invention work synergistically. The fluororubber sealant and asphalt improve compatibility through the "bridging effect" of maleic anhydride-grafted POE. The hydrogenated styrene-butadiene block copolymer can improve the elasticity and mechanical strength of the asphalt, and synergistically improve the crack resistance of the waterproof membrane with the fluororubber sealant, further improving the heat aging and low-temperature degradation resistance of the waterproof membrane. The filler can enhance the rigidity and dimensional stability of the membrane. The components of the composition synergistically enhance the cohesion and overall stability between materials, and improve the overall high and low temperature resistance and corrosion resistance of the waterproof membrane.

[0009] The waterproof membrane prepared using the composition for waterproof membrane provided by this invention has excellent high and low temperature resistance, mechanical properties and chemical corrosion resistance, and its performance stability far exceeds that of traditional membranes.

[0010] The method for preparing waterproof membrane provided by this invention is simple, requires no high-temperature vulcanization, and can be formed by heating and stirring in multiple steps. It is highly operable, reduces energy consumption by more than 30%, significantly reduces costs, and is easy to scale up for production. Detailed Implementation

[0011] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0012] As previously stated, a first aspect of the present invention provides a composition for waterproof membrane, the composition comprising a main agent and an auxiliary agent, wherein the main agent contains 40-60 parts by weight of bitumen, 20-35 parts by weight of fluororubber adhesive, 8-12 parts by weight of hydrogenated styrene-butadiene block copolymer, 3-6 parts by weight of maleic anhydride-grafted POE, 8-15 parts by weight of filler and 5-12 parts by weight of softener; The solid content of fluororubber in the fluororubber mortar is 30wt%-40wt%, and the melting point of fluororubber in the fluororubber mortar is 115-135℃, and the density is ≥1.78g / mL.

[0013] Preferably, the main agent contains 50-60 parts by weight of asphalt, 20-25 parts by weight of fluororubber adhesive, 9-11.5 parts by weight of hydrogenated styrene-butadiene block copolymer, 4-6 parts by weight of maleic anhydride-grafted POE, 10-12 parts by weight of filler and 8-10 parts by weight of softener.

[0014] In a preferred embodiment, the grafting rate of the maleic anhydride-grafted POE is 1-2 MA.

[0015] According to a preferred embodiment, the hydrogenated styrene-butadiene block copolymer has a weight-average molecular weight ≥190,000, preferably 200,000-280,000; and the mass content of styrene structural units in the hydrogenated styrene-butadiene block copolymer is 28-33%. The inventors of this invention have discovered that, under this preferred condition, the resulting waterproof membrane exhibits superior chemical corrosion resistance and mechanical properties.

[0016] In a preferred embodiment, the mass ratio of the fluororubber adhesive to the asphalt is 1:1.5-2.5. The inventors of this invention have discovered that, under this preferred embodiment, the resulting waterproof membrane exhibits superior resistance to high and low temperatures and chemical corrosion.

[0017] Preferably, the average diameter of the filler particles is 600-800 mesh (Chinese standard sieve).

[0018] Preferably, the penetration of the asphalt is 60-100 / 0.1 mm.

[0019] In a preferred embodiment, the solvent in the fluororubber adhesive is selected from at least one of methylpyrrolidone and dimethyl sulfoxide.

[0020] Preferably, the fluororubber in the fluororubber adhesive is a polyvinylidene fluoride-hexafluoropropylene copolymer. The polyvinylidene fluoride-hexafluoropropylene copolymer preferably has a melting point of 120~135℃ and a density ≥1.78g / mL.

[0021] Preferably, the softener is a naphthenic oil and / or an aromatic oil.

[0022] Preferably, the filler is mica powder.

[0023] In a preferred embodiment, the adjuvant comprises 0.5-5 parts by weight of an antioxidant and 1-3 parts by weight of a coupling agent.

[0024] More preferably, the adjuvant includes 1-3 parts by weight of an antioxidant.

[0025] According to another preferred embodiment, the antioxidant is selected from hindered phenolic antioxidants and phosphite antioxidants in a mass ratio of 1:0.8-1.2. The inventors of this invention have found that, under this preferred condition, the obtained waterproof membrane exhibits excellent antioxidant properties.

[0026] Preferably, the hindered phenolic antioxidant is selected from at least one of antioxidant 1010 and antioxidant 1076.

[0027] Preferably, the phosphite antioxidant is selected from at least one of antioxidant 168 and antioxidant ZG103.

[0028] In a preferred embodiment, the coupling agent is a silane coupling agent, and more preferably KH-550.

[0029] As previously described, a second aspect of the present invention provides a method for preparing a waterproof membrane, the method comprising using the components of the composition described in the first aspect, including: The components in the main agent and the components in the auxiliary agent are mixed together to obtain a waterproof membrane.

[0030] According to a preferred embodiment, the step of contact mixing of the components in the main agent and the components in the auxiliary agent includes: (1) The asphalt and softener are subjected to a first heat treatment to obtain intermediate I; (2) The mixture I, fluororubber adhesive and maleic anhydride-grafted POE are subjected to a second heat treatment to obtain intermediate II; (3) The intermediate II and the hydrogenated styrene-butadiene block copolymer are subjected to a third heat treatment to obtain intermediate III; (4) The intermediate III, filler and additives are stirred and mixed in sequence, and then coated and molded to obtain the waterproof membrane.

[0031] Preferably, the coating process includes uniformly coating a pretreated polyester substrate using a dedicated coating equipment, with the coating thickness controlled at 2-4 mm, followed by compaction with rollers, cooling to 20-30°C, and rolling to obtain the waterproof membrane.

[0032] In a preferred embodiment, the pretreated polyester tire is obtained by coating and squeezing the polyester tire in a pre-impregnation tank containing 70# and 10# asphalt at a mass ratio of 1:0.9-1.1.

[0033] Preferably, the basis weight of the polyester tire is 290-330 g / m².

[0034] In a preferred embodiment, in step (1), the conditions for the first heat treatment include: a temperature of 120-140°C and a time of 30-60 min.

[0035] In a preferred embodiment, in step (2), the conditions for the second heating treatment include: a temperature of 140-150°C; a rotation speed of 3000-5000 rpm; and a time of 90-120 min.

[0036] Preferably, the contact mixing step further includes, in step (2), the material after the second heat treatment is first subjected to vacuum treatment to remove the solvent introduced during the addition of the fluororubber mortar.

[0037] The present invention does not impose any special requirements on the conditions of the vacuum treatment. Those skilled in the art can select the conditions according to known technical means in the art. The present invention will not elaborate further here, and those skilled in the art should not understand it as a limitation of the present invention.

[0038] Preferably, in step (3), the conditions for the third heating treatment include: a temperature of 170-175℃; a rotation speed of 2500-3000rpm; and a time of 60-90min.

[0039] In a preferred embodiment, the mixing conditions in step (4) include: a temperature of 170-175°C; a rotation speed of 2000-2500 rpm; and a time of 90-150 min.

[0040] As previously stated, the third aspect of the present invention provides a waterproof membrane prepared by the method described in the second aspect.

[0041] The present invention will be described in detail below through examples. Unless otherwise specified, the instruments, reagents, and materials involved in the following examples are all conventional instruments, reagents, and materials, which can be obtained through legitimate commercial channels. Unless otherwise stated, all reagents used are commercially available analytical grade products.

[0042] Fluororubber adhesive: Fluororubber adhesive I: Self-made, the solid content of fluororubber in the fluororubber adhesive is 35wt%, the solvent is methylpyrrolidone, the solute fluororubber is vinylidene fluoride-hexafluoropropylene copolymer rubber, its melting point is 125℃, the density is 1.78g / mL, the solute is purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd., CAS is 9011-17-0.

[0043] Fluororubber adhesive DI: Self-made, the solid content of fluororubber in the fluororubber adhesive is 25wt%, the solvent is methylpyrrolidone, the solute fluororubber is vinylidene fluoride-hexafluoropropylene copolymer rubber, its melting point is 125℃, the density is 1.78g / mL, the solute is purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd., CAS is 9011-17-0.

[0044] Maleic anhydride grafted with POE: grafting rate of 1-2 MA%, purchased from Dow Chemical, brand name FUSABond® N216.

[0045] POE: Purchased from ExxonMobil, grade EXACT™ 8201, density 0.882 g / cm3.

[0046] Hydrogenated styrene Butadiene block copolymer: Hydrogenated styrene-butadiene block copolymer I: weight average molecular weight of 250,000, styrene structural units in the hydrogenated styrene-butadiene block copolymer contain 31 wt% styrene, purchased from Kuraray, Japan, brand name SEPTON 8004.

[0047] Hydrogenated styrene-butadiene block copolymer II: with a weight-average molecular weight of 70,000 and a styrene structural unit content of 33 wt% in the hydrogenated styrene-butadiene block copolymer, purchased from Sinopec, grade YH-503.

[0048] Asphalt: Road petroleum asphalt, with a penetration of 70 / 0.1mm, purchased from Sinopec, grade 70# road asphalt.

[0049] Filler: Mica powder, purchased from Hebei Huanhe Mineral Products Co., Ltd., grade 800 mesh.

[0050] Softener: naphthenic oil, purchased from Shandong Taichang Petrochemical Technology Co., Ltd.

[0051] Antioxidants: Antioxidant 1010 and Antioxidant 168 in a mass ratio of 1:1.

[0052] Coupling agent: γ-aminopropyltriethoxysilane (KH-550), purchased from Nanjing Nengde Chemical Co., Ltd.

[0053] Pre-treated polyester tires: Polyester tires (purchased from Tiandingfeng Holdings Co., Ltd., 310g / m²) were treated.2 The pretreated polyester tire is pre-prepared by brushing and squeezing dry in a pre-impregnation tank containing 70# and 10# asphalt at a mass ratio of 1:1, and then pre-fabricated.

[0054] Unless otherwise specified, each part by weight in the following examples is equal to 100g.

[0055] Example 1 This embodiment illustrates the preparation of waterproof membrane according to the following steps, referring to the formula and process in Table 1: (1) The asphalt and softener are subjected to a first heat treatment to obtain intermediate I; (2) The mixture I, fluororubber mortar and maleic anhydride-grafted POE are subjected to a second heat treatment, and then the material after the second heat treatment is subjected to vacuum treatment to obtain intermediate II; (3) The intermediate II and the hydrogenated styrene-butadiene block copolymer are subjected to a third heat treatment to obtain intermediate III; (4) The intermediate III, filler and additives (antioxidant, coupling agent) are stirred and mixed, and then the mixed material is evenly coated on the pretreated polyester substrate by special coating equipment. The coating thickness is controlled at 3mm. After being compacted by rollers, cooled to 25°C and rolled up, the waterproof membrane is obtained. The mixing conditions were: temperature 170℃, speed 2500 rpm, and time 120 min.

[0056] Example 2 This embodiment uses a similar method to Example 1, except that the formula and process are as shown in Table 1, and a waterproof membrane is prepared. All parts not listed are the same as in Example 1.

[0057] Table 1

[0058] Example 3 This embodiment uses a method similar to that of Example 1, except that an equal mass of hydrogenated styrene-butadiene block copolymer II is used to replace hydrogenated styrene-butadiene block copolymer I in Example 1 to prepare a waterproof membrane. All parts not listed are the same as in Example 1.

[0059] Example 4 This embodiment uses a method similar to that of Embodiment 1, except that, while keeping the total mass of the fluororubber sealant and the asphalt constant, the mass ratio of the fluororubber sealant and the asphalt is adjusted to 1:3 to prepare a waterproof membrane. All parts not listed are the same as in Example 1.

[0060] Comparative Example 1 This comparative example was conducted using a method similar to that of Example 1, except that the maleic anhydride-grafted POE in Example 1 was replaced with an equal mass of POE to prepare a waterproof membrane. All parts not listed are the same as in Example 1.

[0061] Comparative Example 2 This comparative example was conducted using a method similar to that of Example 1, except that the fluororubber adhesive I in Example 1 was replaced with an equal mass of fluororubber adhesive DI to prepare a waterproof membrane. All parts not listed are the same as in Example 1.

[0062] Comparative Example 3 This comparative example was conducted using a method similar to that of Example 1, except that the formulation is shown in Table 1, and a waterproof membrane was prepared. All parts not listed are the same as in Example 1.

[0063] Test case The performance of the waterproof membranes prepared in the above examples was tested, specifically: (1) Chemical corrosion resistance: Refer to the tensile property test method in GB 18242-2008; the waterproof membranes prepared in the above examples were soaked in 10wt% H2SO4 for 7 days and in 10wt% NaOH for 7 days respectively, and the tensile strength retention rate was measured. Tensile strength retention rate after acid immersion % = (Tensile strength after 7 days of acid immersion / Tensile strength before acid immersion) × 100%; Tensile strength retention rate after alkali immersion % = (Tensile strength after 7 days of alkali immersion / Tensile strength before alkali immersion) × 100%; (2) Low temperature flexibility: Refer to the method in GB / T 328.14-2007 to determine the minimum low temperature at which the waterproof membranes prepared in the above examples can be crack-free; (3) Tensile strength: The tensile strength of the waterproof membranes prepared in the above examples before aging and after aging were determined according to the method in GB / T 328.8-2007. The aging conditions were: 80℃, 10d. Tensile strength retention rate after aging % = (Tensile strength after aging / Tensile strength before aging) × 100%; (4) Heat resistance: The extreme temperature (no slippage, no flow) shall be tested according to the method in GB / T 328.11-2007. (5) Thermo-oxidative aging: Refer to the method in GB 23441-2009, and test the low-temperature flexibility after treatment at 70℃ for 7 days.

[0064] The test results are shown in Table 2: Table 2

[0065] Continued from Table 2

[0066] The results above show that the waterproof membrane prepared using the composition for waterproof membrane provided by the present invention has excellent chemical corrosion resistance, high and low temperature resistance, and mechanical properties.

[0067] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composition for waterproof membrane, characterized in that, The composition includes a main agent and an auxiliary agent, wherein the main agent contains 40-60 parts by weight of asphalt, 20-35 parts by weight of fluororubber adhesive, 8-12 parts by weight of hydrogenated styrene-butadiene block copolymer, 3-6 parts by weight of maleic anhydride-grafted POE, 8-15 parts by weight of filler and 5-12 parts by weight of softener. The solid content of fluororubber in the fluororubber mortar is 30wt%-40wt%, and the melting point of fluororubber in the fluororubber mortar is 115-135℃, and the density is ≥1.78g / mL.

2. The composition according to claim 1, characterized in that, The hydrogenated styrene-butadiene block copolymer has a weight-average molecular weight ≥ 190,000, and the mass content of styrene structural units in the hydrogenated styrene-butadiene block copolymer is 28-33%.

3. The composition according to claim 1 or 2, characterized in that, The mass ratio of the fluororubber mortar to the asphalt is 1:1.5-2.

5.

4. The composition according to claim 1 or 2, characterized in that, The penetration of the asphalt is 60-100 / 0.1 mm; And / or, the solvent in the fluororubber adhesive is selected from at least one of methylpyrrolidone and dimethyl sulfoxide; And / or, the fluororubber in the fluororubber adhesive is a polyvinylidene fluoride-hexafluoropropylene copolymer; And / or, the softener is a naphthenic oil and / or an aromatic oil; And / or, the filler is mica powder.

5. The composition according to claim 1 or 2, characterized in that, The adjuvants include 0.5-5 parts by weight of antioxidant and 1-3 parts by weight of coupling agent.

6. The composition according to claim 5, characterized in that, The antioxidant is selected from hindered phenolic antioxidants and phosphite antioxidants in a mass ratio of 1:0.8-1.2; And / or, the coupling agent is a silane coupling agent.

7. A method for preparing a waterproof membrane, characterized in that, This method is performed using any of the components in the composition according to any one of claims 1-6, comprising: The components in the main agent and the components in the auxiliary agent are mixed together to obtain a waterproof membrane.

8. The method according to claim 7, characterized in that, The steps of contact mixing of the components in the main agent and the components in the auxiliary agent include: (1) The asphalt and softener are subjected to a first heat treatment to obtain intermediate I; (2) The mixture I, fluororubber adhesive and maleic anhydride-grafted POE are subjected to a second heat treatment to obtain intermediate II; (3) The intermediate II and the hydrogenated styrene-butadiene block copolymer are subjected to a third heat treatment to obtain intermediate III; (4) The intermediate III, filler and additives are stirred and mixed in sequence, and then coated and molded to obtain the waterproof membrane.

9. The method according to claim 8, characterized in that, In step (1), the conditions for the first heat treatment include: a temperature of 120-140℃ and a time of 30-60 min; And / or, in step (2), the conditions for the second heat treatment include: a temperature of 140-150°C; a rotation speed of 3000-5000 rpm; and a time of 90-120 min. And / or, in step (3), the conditions for the third heating treatment include: a temperature of 170-175°C; a rotation speed of 2500-3000 rpm; and a time of 60-90 min. And / or, in step (4), the mixing conditions include: a temperature of 170-175°C; a rotation speed of 2000-2500 rpm; and a time of 90-150 min.

10. A waterproof membrane prepared by the method according to any one of claims 7-9.

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