Modified basalt fiber, asphalt coating material, preparation methods of modified basalt fiber and asphalt coating material, composition for asphalt coating material, and waterproof coiled material

Abstract

The invention relates to the field of building waterproof materials, and discloses a modified basalt fiber, an asphalt coating material, a preparation method of the modified basalt fiber, a preparation method of the asphalt coating material, a composition for the asphalt coating material and a waterproof coiled material. The preparation method of the modified basalt fiber comprises the following step: in the presence of a solvent, carrying out reaction on a raw material basalt fiber and a coupling agent I at 55-65 DEG C for 2-3 hours to obtain the modified basalt fiber. The pre-paved modified asphalt waterproof coiled material provided by the invention has relatively strong cohesiveness with post-poured cement mortar, has excellent fire resistance and puncture resistance, and is beneficial to pre-paving construction.

Description

Technical Field

[0001] This invention relates to the field of building waterproofing materials, specifically to a modified basalt fiber and its preparation method, a composition for asphalt coating, an asphalt coating and its preparation method, and a pre-laid modified asphalt waterproof membrane. Background Technology

[0002] Pre-laid waterproof membranes, as the core material of the "external protection and internal bonding" technology in underground engineering, have become the mainstream choice for underground waterproofing projects due to their advantage of being fully bonded to structural concrete and preventing water seepage. They are widely used in the waterproofing of the foundation slabs and side walls of various underground buildings.

[0003] However, existing pre-laid waterproof membranes still have obvious technical defects, including: (1) poor weather resistance. Under the long-term effects of sunlight, high temperature, low temperature and other environmental factors, asphalt will age and become brittle, reducing its waterproof performance and bonding performance; (2) poor sand layer protection. After the pre-laid membrane is completed, workers need to tie and weld steel bars on the sand surface. Welding slag is easy to fall onto the membrane, and the membrane is easy to be burned through or cause a fire risk; (3) poor bonding performance. The barrier of the sand layer on the upper surface of the pre-laid membrane is prone to the asphalt adhesive layer or hot melt adhesive layer falling off the sand surface. Poor bonding performance leads to water seeping through from the middle.

[0004] CN115139625A discloses a weather-resistant, exposed modified bitumen waterproof membrane and its preparation method. The waterproof membrane comprises, from top to bottom, a polymer-bonded sprayed layer, a basalt particle layer, a polymer-modified bitumen layer, a reinforcing layer, another polymer-modified bitumen layer, and a polyethylene film anti-adhesive layer. It is manufactured in two steps: preparation of the modified bitumen mixture and preparation of the waterproof membrane. However, the waterproof membrane provided by this prior art lacks sufficient resistance to damage and adhesion, making it difficult to use as a pre-applied waterproof membrane.

[0005] Therefore, there is an urgent need to develop a pre-laid waterproof membrane that combines weather resistance, adhesion, and protection against sand layer damage. Summary of the Invention

[0006] The purpose of this invention is to provide a pre-laid waterproof membrane that combines adhesion, damage resistance, and weather resistance.

[0007] To achieve the above objectives, a first aspect of the present invention provides a method for preparing modified basalt fibers, the method comprising: In the presence of a solvent, the raw basalt fiber is reacted with coupling agent I at 55-65℃ for 2-3 hours to obtain the modified basalt fiber. The coupling agent I is a silane coupling agent; The mass ratio of the raw material basalt fiber to the coupling agent I is 1:0.02-0.06.

[0008] A second aspect of the invention provides modified basalt fibers prepared by the method described in the first aspect.

[0009] A third aspect of the present invention provides a composition for an asphalt coating, the composition comprising a main agent and an additive; said main agent comprising a base asphalt, rock fiber and a polymer composite modifier; Based on the total weight of the composition, the content of the base bitumen is 35-90 wt%, the content of the rock fiber is 0.5-2 wt%, and the content of the polymer composite modifier is 3-6 wt%. The rock fiber comprises modified basalt fiber and sepiolite fiber in a mass ratio of 1:0.02-0.05; The modified basalt fiber is the modified basalt fiber described in the second aspect of this invention.

[0010] A fourth aspect of the present invention provides a method for preparing an asphalt coating, the method comprising using the components of the composition described in the third aspect of the present invention, including: (1) The base asphalt, polymer composite modifier and tackifying resin are mixed for the first time to obtain mixed modified material I; (2) The mixed modified adhesive I is mixed with recycled rubber powder and rock fiber to obtain mixed modified adhesive II; (3) The modified adhesive II is mixed with the filler in a third mixing to obtain the asphalt coating material.

[0011] The fifth aspect of the present invention provides an asphalt coating material prepared by the method described in the fourth aspect.

[0012] The sixth aspect of the present invention provides a pre-laid modified bitumen waterproof membrane, the waterproof membrane comprising a sand layer or shale layer, a first modified adhesive layer, a reinforcing base layer, a second modified adhesive layer and an anti-adhesion layer arranged in sequence. The first modified adhesive layer and the second modified adhesive layer are formed from the asphalt coating material described in the fifth aspect of the present invention.

[0013] Through the above technical solution, the present invention has at least the following advantages: (1) The asphalt coating material provided by the present invention contains modified basalt fiber. Through the synergistic effect between the modified basalt fiber and the filler, the asphalt and polymer composite modifier can be effectively reduced to reduce the layering, significantly improve the adhesion and long-term storage of asphalt waterproof membrane, and improve the aging resistance and water penetration resistance of asphalt membrane.

[0014] (2) The pre-laid modified bitumen waterproof membrane provided by the present invention has excellent fire resistance and puncture resistance, and is easy to pre-lay. Detailed Implementation

[0015] 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.

[0016] As previously stated, a first aspect of the present invention provides a method for preparing modified basalt fibers, the method comprising: In the presence of a solvent, the raw basalt fiber is reacted with coupling agent I at 55-65℃ for 2-3 hours to obtain the modified basalt fiber. The coupling agent I is a silane coupling agent; The mass ratio of the raw material basalt fiber to the coupling agent I is 1:0.02-0.06.

[0017] Preferably, the coupling agent I is selected from at least one of KH-550, KH-560, and Si-69.

[0018] Preferably, the basalt fiber has a single fiber diameter of 13-17 μm, an elastic modulus > 36 MPa, and a fiber length of 3-6 mm.

[0019] In a preferred embodiment, the solvent is a mixed solvent of ethanol and water in a volume ratio of 1:0.1-0.3.

[0020] As previously stated, a second aspect of the present invention provides modified basalt fibers prepared by the method described in the first aspect.

[0021] As previously described, a third aspect of the present invention provides a composition for an asphalt coating, the composition comprising a main agent and an additive; said main agent comprising a base asphalt, rock fiber and a polymer composite modifier; Based on the total weight of the composition, the content of the base bitumen is 35-90 wt%, the content of the rock fiber is 0.5-2 wt%, and the content of the polymer composite modifier is 3-6 wt%. The rock fiber comprises modified basalt fiber and sepiolite fiber in a mass ratio of 1:0.02-0.05; The modified basalt fiber is the modified basalt fiber described in the second aspect of this invention.

[0022] Preferably, the diameter of a single sepiolite fiber is 6-13 μm.

[0023] Preferably, the base asphalt contains a first asphalt and a second asphalt, wherein the first asphalt is asphalt with a penetration of 180-200 (0.1 mm) at 25°C, and the second asphalt is asphalt with a penetration of 60-100 (0.1 mm) at 25°C.

[0024] More preferably, the first asphalt is F400 base asphalt, and the second asphalt is 70# base asphalt and / or 90# base asphalt.

[0025] In this invention, the F400 base asphalt is a high-grade base asphalt. The low-temperature flexibility of F400 base asphalt is ≤-25℃, the softening point is 46-50℃, the penetration at 25℃ is 180-200 (0.1mm), and the flash point is >210℃. The penetration of AH-70 at 25℃ is 60-80 (0.1mm); the penetration of AH-90 at 25℃ is 80-100 (0.1mm).

[0026] More preferably, based on the total weight of the composition, the content of the first asphalt is 15-40 wt%, and the content of the second asphalt is 20-50 wt%.

[0027] Preferably, the polymer composite modifier comprises SEPS, synthetic rubber and SBS in a mass ratio of 1:1-2.5:0.4-1.7.

[0028] In this invention, SEPS refers to hydrogenated styrene-isoprene-styrene block copolymer, and SBS refers to styrene-butadiene-styrene block copolymer.

[0029] Preferably, the weight-average molecular weight of the SEPS is 130,000-180,000, and the content of structural units provided by styrene is 20-35 wt%.

[0030] Preferably, the synthetic rubber is styrene-butadiene rubber and / or nitrile rubber.

[0031] More preferably, the synthetic rubber is selected from at least one of solution-polymerized styrene-butadiene rubber, emulsion-polymerized styrene-butadiene rubber, and hydrogenated nitrile rubber.

[0032] Preferably, the weight-average molecular weight of the SBS is 100,000-120,000, and the content of structural units provided by styrene is 25-35 wt%.

[0033] Preferably, the additive contains tackifying resin, recycled rubber powder, and filler.

[0034] In a preferred embodiment, the tackifying resin is selected from at least one of dicyclopentadiene resin, terpene resin, and hydrogenated DCPD.

[0035] In a preferred embodiment, the filler contains calcium hydroxide and nano-calcium carbonate in a mass ratio of 0.08-0.12:1.

[0036] More preferably, based on the total weight of the composition, the content of the tackifying resin is 2-6 wt%, the content of the reclaimed rubber powder is 5-8 wt%, and the content of the filler is 25-35 wt%.

[0037] As previously described, a fourth aspect of the present invention provides a method for preparing an asphalt coating, the method comprising using the components of the composition described in the third aspect of the present invention, including: (1) The base asphalt, polymer composite modifier and tackifying resin are mixed for the first time to obtain mixed modified material I; (2) The mixed modified adhesive I is mixed with recycled rubber powder and rock fiber to obtain mixed modified adhesive II; (3) The modified adhesive II is mixed with the filler in a third mixing to obtain the asphalt coating material.

[0038] Preferably, step (1) further includes: first adding the base asphalt into the reactor, heating it to 130-180°C, stirring for 15-20 minutes, and then adding the polymer composite modifier and the tackifying resin for the first mixing.

[0039] Preferably, in step (1), the conditions for the first mixing include: a temperature of 170-180°C and a time of 1-2 hours.

[0040] Preferably, in step (2), the conditions for the second mixing include: a temperature of 170-180°C and a time of 2-2.5h.

[0041] Preferably, in step (3), the conditions for the third mixing include: a temperature of 170-180°C and a time of 0.5-1h.

[0042] As previously described, the fifth aspect of the present invention provides an asphalt coating prepared by the method described in the fourth aspect.

[0043] As mentioned above, the sixth aspect of the present invention provides a pre-laid modified bitumen waterproof membrane, which comprises a sand layer or shale layer, a first modified adhesive layer, a reinforcing base layer, a second modified adhesive layer and an anti-adhesion layer arranged in sequence. The first modified adhesive layer and the second modified adhesive layer are formed from the asphalt coating material described in the fifth aspect of the present invention.

[0044] Preferably, the thickness ratio of the sand or shale layer, the first modified adhesive layer, the reinforced base layer, the second modified adhesive layer, and the anti-sticking layer is 1:0.5-0.6:0.7-1.0:1.0-1.1:0.02-0.04.

[0045] Preferably, the sand layer contains modified basalt particles, which are prepared by placing the raw basalt particles in a high-speed stirring device at a temperature of 75-85°C and a stirring speed of 700-800 rpm, spraying a diluted solution of coupling agent II, and stirring for 20-60 minutes to obtain the modified basalt particles.

[0046] More preferably, the average particle size of the raw basalt particles is 380-830 μm.

[0047] More preferably, the coupling agent II is selected from at least one of KH550, KH560, A-171, and A-172.

[0048] Preferably, the reinforcing base layer is a basalt fiber reinforced polyester base, wherein the density of the reinforcing mesh of the basalt fiber reinforced polyester base is 4 mesh × 4 mesh, and the basis weight is 100 ± 10 g / mm². 2 The diameter of a single filament in the reinforced body is 1-1.5 mm.

[0049] In this invention, the 4-mesh × 4-mesh means that the reinforced mesh is a square mesh structure with 4 mesh openings per 1 inch in both the longitudinal and transverse directions.

[0050] The present invention will be described in detail below through examples. In the following examples, the reagents and raw materials involved are all commercially available products, and the reagents are all analytical grade products.

[0051] Base asphalt: First Asphalt, F400 base asphalt, with a penetration of 180-200 (0.1mm) at 25℃, was purchased from Foshan Gaofu PetroChina Fuel Asphalt Co., Ltd. The second asphalt, 70# base asphalt, with a penetration of 60-80 (0.1mm) at 25℃, was purchased from Maoming Branch of China Petroleum & Chemical Corporation. Raw material basalt fiber I: single fiber diameter is 15μm, elastic modulus is 37MPa, fiber length is 3mm, purchased from Shandong Tonghui Glass Fiber Co., Ltd. Raw material basalt fiber II: single fiber diameter is 18μm, elastic modulus is 39MPa, fiber length is 9mm, purchased from Taian Hongtong New Material Co., Ltd. Coupling agent I: KH550, purchased from Nanjing Baiju Technology Co., Ltd.; Sepiolite fiber: The diameter of a single fiber is 10μm; Polymer composite modifier: SEPS, with a weight-average molecular weight of 150,000, and 27 wt% of structural units provided by styrene, brand name YH-4010, was purchased from Baling Petrochemical Company. Synthetic rubber, solution-polymerized styrene-butadiene rubber, grade 1901, purchased from Baling Petrochemical; SBS: Weight average molecular weight of 100,000-120,000, with 31 wt% of structural units provided by styrene, grade LG411S, purchased from Ningbo Yanpu International Trade Co., Ltd. Tackifying resin: Dicyclopentadiene resin, purchased from Shandong Luhua Co., Ltd.; Reclaimed rubber powder: purchased from Hebei Hexingyuan Rubber Technology Co., Ltd.; Filler: Calcium hydroxide was purchased from Hefei Zhongke Flame Retardant New Materials Co., Ltd. Nano-calcium carbonate, purchased from Lingshou County Derui Mining Co., Ltd.; Raw material basalt particles: average particle size 380-830μm, purchased from Lingshou County Huixin Mining Processing Plant Co., Ltd.; Coupling agent II: KH560, purchased from Nanjing Baiju Technology Co., Ltd.

[0052] Preparation Example 1 Modified basalt fibers are prepared through the following steps: First, 50g of raw material basalt fiber I was dispersed in a solvent (the solvent was obtained by mixing ethanol and water in a volume ratio of 1:0.2), and then 2g of coupling agent I was added. After reacting at 60℃ for 2h, the modified basalt fiber was obtained by drying.

[0053] The modified basalt fiber obtained was named M-01.

[0054] Preparation Example 2 The same process as in Preparation Example 1 was used, except that in this preparation example, the amount of raw material basalt fiber I was 50g and the amount of coupling agent I was 1g.

[0055] The modified basalt fiber obtained was named M-02.

[0056] Preparation Example 3 The same process as in Preparation Example 1 was used, except that in this preparation example, the raw material basalt fiber I was replaced with raw material basalt fiber II.

[0057] The modified basalt fiber obtained was named M-03.

[0058] Comparative Preparation Example 1 The same process as in Preparation Example 1 was used, except that in this comparative preparation example, the amount of basalt fiber used was 50g and the amount of coupling agent I used was 0.8g.

[0059] The modified basalt fiber obtained was named DM-01.

[0060] Example 1 Asphalt coating is prepared through the following steps: (1) First, add the base asphalt into the reactor, heat it to 180°C, stir for 15 minutes, then add the polymer composite modifier and tackifying resin for the first mixing. The first mixing time is 2 hours to obtain the mixed modified material I.

[0061] (2) At 180°C, the mixed modified adhesive I obtained in step (1) is mixed with recycled rubber powder and rock fiber (specifically, a combination of M-01 and sepiolite fiber) for a second time. The second mixing time is 2 hours to obtain mixed modified adhesive II. (3) At 180°C, the mixed modified adhesive II obtained in step (2) is mixed with the filler for a third time for 1 hour to obtain asphalt coating material.

[0062] (4) Place the raw basalt particles in a high-speed stirring device at a temperature of 85°C and a stirring speed of 800 rpm, spray with a diluted solution of coupling agent II, stir for 40 min, and dry to obtain modified basalt particles.

[0063] (5) Preparation of pre-laid modified bitumen waterproof membrane: The pre-laid modified bitumen waterproof membrane is prepared by sequentially layering a sand layer, a first modified adhesive layer, a reinforcing base layer, a second modified adhesive layer, and an anti-sticking layer with a thickness ratio of 1:0.6:0.9:1.0:0.02; wherein the sand layer is the modified basalt particles obtained in step (4); the first and second modified adhesive layers are formed by the bitumen coating material obtained in step (3); the reinforcing base layer is a basalt fiber reinforced polyester base, the reinforcing mesh density of which is 4 mesh × 4 mesh and the basis weight is 100±10g / mm 2 The diameter of a single filament of the reinforcing body is 1.5mm; the anti-adhesive layer is a PE film.

[0064] The remaining specific process parameters of this embodiment are shown in Table 1.

[0065] Examples 2-4 Examples 2-4 all adopted the same process as Example 1, and the differences are listed in Table 1.

[0066] Example 5 Example 5 uses the same process as Example 1, except that the rock fiber is modified basalt fiber M-01 and no sepiolite fiber is added.

[0067] Example 6 Example 6 uses the same process as Example 1, except that the rock fiber (specifically a combination of M-01 and sepiolite fiber) is replaced with rock fiber (specifically a combination of M-03 and sepiolite fiber).

[0068] Comparative Examples 1-3 Comparative Examples 1-3 all used the same process as Example 1, with the differences listed in Table 1.

[0069] In Table 1, composition a refers to the mass ratio of modified basalt fiber to sepiolite fiber in the rock fiber; composition b refers to the mass ratio of SEPS, synthetic rubber and SBS in the polymer composite modifier; and composition c refers to the mass ratio of calcium hydroxide to nano calcium carbonate in the filler.

[0070] Table 1

[0071] Test case The performance test data of the pre-laid modified bitumen waterproof membranes prepared in the examples and comparative examples are shown in Table 2.

[0072] The standard requirements in Table 2 are those of GB / T23457-2017 "Pre-laid Waterproof Membranes".

[0073] The peel strength of the waterproof membrane was tested according to GB / T328.20 "Test Methods for Waterproofing Membranes - Part 20: Peel Performance of Bitumen Waterproofing Membranes". The test temperature was 23±2℃. The specific test method was as follows: the main material side of one membrane was bonded to the self-adhesive side of the overlap edge of another membrane, with the bonding surface being (50×70)mm. A 2kg roller with a width of 50mm-60mm was used to repeatedly roll the membrane three times. After bonding, the membrane was left to stand for 24 hours. The initial and final quarter regions of the stress-strain diagram were removed. The average peel force or peak area force of the middle half of the region was divided by the specimen width to obtain the peel strength of the specimen, expressed in N / mm. The test result was the arithmetic mean of the results from five specimens.

[0074] The low-temperature flexibility of waterproof membranes was tested according to GB / T328.14 "Test Methods for Waterproofing Membranes - Part 14: Low-Temperature Flexibility of Bituminous Waterproofing Membranes". The specific test method was as follows: The bending shaft diameter was 50mm. Ten specimens were taken longitudinally, five on the upper surface and five on the lower surface. For each surface, at least four out of five specimens were visually inspected for no cracks to indicate that the surface passed. If both the upper and lower surfaces passed, the surface was considered to meet the low-temperature flexibility requirements.

[0075] The procedure for thermal aging is as follows: remove the isolation material from the surface of the specimen, place the specimen horizontally in an oven at (70±2)℃ for (168±2)h, remove it and place it in a room at (23±2)℃ for 24h before testing.

[0076] The procedure for burning is as follows: Use a portable flame gun, place it on a clean glazed tile with the granules facing up, keep the flame at a 45° angle to the roll material, and let the outer flame contact the roll material surface for 10 seconds. Remove the flame gun and check whether the roll material has been ignited or melted.

[0077] The puncture resistance of waterproof membranes was tested according to the method in Appendix B of CJ / T234-2006.

[0078] Table 2

[0079] The results above show that the pre-laid modified bitumen waterproof membrane provided by the present invention has strong adhesion to itself and to the post-poured cement mortar, and also has excellent fire resistance and puncture resistance, which is beneficial for pre-laying construction.

[0080] 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 method for preparing modified basalt fibers, characterized in that, The method includes: In the presence of a solvent, the raw basalt fiber is reacted with coupling agent I at 55-65℃ for 2-3 hours to obtain the modified basalt fiber. The coupling agent I is a silane coupling agent; The mass ratio of the raw material basalt fiber to the coupling agent I is 1:0.02-0.

06.

2. The method according to claim 1, characterized in that, The raw material basalt fiber has a single fiber diameter of 13-17μm, an elastic modulus >36MPa, and a fiber length of 3-6mm.

3. Modified basalt fibers prepared by the method according to claim 1 or 2.

4. A composition for use in asphalt coatings, characterized in that, The composition contains a main agent and an auxiliary agent; the main agent contains a matrix asphalt, rock fiber and a polymer composite modifier; Based on the total weight of the composition, the content of the base bitumen is 35-90 wt%, the content of the rock fiber is 0.5-2 wt%, and the content of the polymer composite modifier is 3-6 wt%. The rock fiber comprises modified basalt fiber and sepiolite fiber in a mass ratio of 1:0.02-0.05; The modified basalt fiber is the modified basalt fiber as described in claim 3.

5. The composition according to claim 4, characterized in that, The base asphalt contains a first asphalt and a second asphalt, wherein the first asphalt is asphalt with a penetration of 180-200 (0.1 mm) at 25°C, and the second asphalt is asphalt with a penetration of 60-100 (0.1 mm) at 25°C. And / or, based on the total weight of the composition, the content of the first asphalt is 15-40 wt%, and the content of the second asphalt is 20-50 wt%; And / or, the polymer composite modifier comprises SEPS, synthetic rubber and SBS in a mass ratio of 1:1-2.5:0.4-1.

7.

6. The composition according to claim 4 or 5, characterized in that, The additives contain tackifying resin, recycled rubber powder, and fillers; And / or, based on the total weight of the composition, the content of the tackifying resin is 2-6 wt%, the content of the reclaimed rubber powder is 5-8 wt%, and the content of the filler is 25-35 wt%.

7. A method for preparing asphalt coating material, characterized in that, This method is performed using any of the components in the composition according to any one of claims 4-6, comprising: (1) The base asphalt, polymer composite modifier and tackifying resin are mixed for the first time to obtain mixed modified material I; (2) The mixed modified adhesive I is mixed with recycled rubber powder and rock fiber to obtain mixed modified adhesive II; (3) The modified adhesive II is mixed with the filler in a third mixing to obtain the asphalt coating material.

8. The method according to claim 7, characterized in that, In step (1), the conditions for the first mixing include: a temperature of 170-180°C and a time of 1-2 hours; And / or, in step (2), the conditions for the second mixing include: a temperature of 170-180°C and a time of 2-2.5 h; And / or, in step (3), the conditions for the third mixing include: a temperature of 170-180°C and a time of 0.5-1h.

9. The asphalt coating prepared by the method of claim 7 or 8.

10. A pre-laid modified bitumen waterproof membrane, characterized in that, The waterproof membrane contains a sand or shale layer, a first modified adhesive layer, a reinforcing base layer, a second modified adhesive layer, and an anti-sticking layer, which are stacked in sequence. The first modified adhesive layer and the second modified adhesive layer are formed from the asphalt coating material of claim 9.

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