Self-repairing elastomer modified asphalt waterproof coiled material and preparation method thereof

Abstract

The invention discloses a self-repairing elastomer modified asphalt waterproof coiled material and a preparation method thereof, and relates to the technical field of waterproof coiled materials. According to the invention, bis (6-hydroxyhexyl) disulfide and 5-hexeneboronic acid are utilized to form a dual self-repairing compound, then the dual self-repairing compound reacts with a hydrogenated styrene thermoplastic elastomer, is introduced between molecular chains of the elastomer and is used for the elastomer modified asphalt waterproof coiled material, and by utilizing the fracture-rearrangement characteristics of a dynamic disulfide bond and a boric acid ester bond, the asphalt waterproof coiled material can be rapidly repaired. Self-repairing of fracture damage of the waterproof coiled material is realized; besides, a dual self-repairing compound and a hydrogenated styrene thermoplastic elastomer are subjected to a cross-linking reaction, so that the heat resistance and low-temperature flexibility of the modified asphalt waterproof coiled material are improved, and on the other hand, the content of C = C double bonds in the elastomer is reduced; the problems of chain scission degradation and the like of the elastomer under the action of heat, ultraviolet rays and oxygen can be effectively avoided, so that the ageing resistance of the modified asphalt coiled material is remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of waterproofing coiled materials, and in particular to a self-repairing elastomer-modified asphalt waterproofing coiled material and a preparation method thereof. Background Art

[0002] Thermoplastic elastomer-modified asphalt waterproofing membrane has excellent high-temperature anti-flow and low-temperature anti-cracking properties, and has been widely used in building waterproofing projects. However, during service, elastomer-modified asphalt waterproofing membrane will age and become brittle due to heat, oxygen and ultraviolet rays, and thus easily crack under the action of external forces (such as deformation of the base layer), causing leakage in the building. Therefore, improving the weather resistance of elastomer-modified asphalt waterproofing membrane and giving it crack self-healing ability are extremely important for solving the problem of building leakage. In recent years, polymer self-healing technology based on dynamic repair bonds has been widely studied and applied. Existing polymer materials based on dynamic self-healing usually use compounds with -0H, -COOH or -NH2 at both ends and compounds or prepolymers with isocyanate (-NCO) or amino (-NH2) at both ends as reactive monomers. Dynamic self-healing bonds are introduced into the polymer molecular chain through condensation reaction to give the polymer self-healing function. However, elastomers usually do not contain the above-mentioned reactive groups such as -NCO and -NH2. Further exploration of the efficient resource utilization of elastomers with self-healing function in the fields of waterproof membranes is of great research and application significance. Summary of the invention

[0003] The purpose of the present invention is to provide a self-repairing elastomer-modified asphalt waterproofing membrane and a preparation method thereof, so as to solve the problems existing in the prior art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solution: a method for preparing a self-repairing elastomer-modified asphalt waterproofing membrane, comprising the following preparation steps:

[0005] (1) 5-Hexeneboric acid and bis(6-hydroxyhexyl) disulfide were mixed, and toluene was added. The mixture was stirred at 100-110°C and 40 rpm for 8 h. The lower layer solution was separated by a water separation reflux device, and the upper layer solution was then heated to 8.8 × 10 4 The self-repairing modifier was obtained by vacuum distillation at 100 Pa for 20 min.

[0006] (2) mixing a hydrogenated styrene thermoplastic elastomer and toluene, adding a self-healing modifier, heating to 60-65° C., adding benzoyl peroxide under nitrogen protection, stirring at 60-80 rpm for 5-8 hours, cooling to room temperature, adding ethanol until precipitation occurs, taking the precipitate, and drying it at 60° C. for 1 hour to obtain a modified elastomer;

[0007] (3) 50 to 60 parts by weight of asphalt are heated to 180° C., 8 to 12 parts by weight of modified elastomer are added, and the mixture is stirred at 2000 rpm for 10 min to obtain modified asphalt. The modified asphalt is then transported to a coating machine and coated in the order of a lower isolation membrane layer, a lower modified asphalt layer, a matrix layer, an upper modified asphalt layer, and an upper isolation membrane layer to obtain a self-repairing elastomer modified asphalt waterproofing membrane.

[0008] Furthermore, in step (1), the ratio of 5-hexeneboric acid to toluene is 1 mol:20 mL.

[0009] Furthermore, in step (1), the molar ratio of 5-hexeneboronic acid to bis(6-hydroxyhexyl) disulfide is 1:1.2-1.6.

[0010] Furthermore, the hydrogenated styrene-based thermoplastic elastomer in step (2) has a Shore hardness of ≤75A and a melt index of ≥2g / 10min at 230°C and 5kg.

[0011] Furthermore, the hydrogenated styrene-based thermoplastic elastomer in step (2) is one or both of hydrogenated styrene-butadiene block copolymer (SEBS) and hydrogenated styrene-isoprene block copolymer (SEPS).

[0012] Furthermore, in step (2), the hydrogenated styrene-based thermoplastic elastomer is 80 to 100 parts by mass, toluene is 520 parts by mass, the self-healing modifier is 8 to 10 parts by mass, and benzoyl peroxide is 0.1 to 0.3 parts by mass.

[0013] Furthermore, the softening point of the asphalt in step (3) is 46.3°C, and the needle penetration at 25°C is 89 dmm.

[0014] Furthermore, the upper and lower isolation film layers in step (3) are PET single-sided silicone oil isolation films with a thickness of 0.1 to 1 mm.

[0015] Furthermore, the matrix layer in step (3) is a polyester non-woven fabric with a thickness of 1.0 to 1.6 mm.

[0016] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0017] The invention utilizes the reaction of the hydroxyl group of bis(6-hydroxyhexyl) disulfide with the hydroxyl group of 5-hexeneboronic acid to form a double self-healing compound containing a C=C double bond at the molecular chain end, and then reacts the double self-healing compound with a hydrogenated styrene thermoplastic elastomer. Under the action of an initiator, the C=C double bond in the double self-healing compound reacts with the C=C double bond in the hydrogenated styrene thermoplastic elastomer, and a dynamic disulfide bond and a borate bond are introduced between the molecular chains of the elastomer. The double self-healing compound is used for an elastomer-modified asphalt waterproofing membrane, and the fracture-rearrangement characteristics of the dynamic disulfide bond and the borate bond are utilized. When the elastomer-modified asphalt waterproofing membrane is When subjected to external force, the dynamic disulfide bonds and borate bonds are broken first. After the external force is eliminated, the broken disulfide bonds and borate bonds are rearranged to restore the original molecular structure, thereby realizing self-repair of broken and damaged waterproof membranes. In addition, the present invention utilizes dual self-repairing compounds to undergo cross-linking reactions with hydrogenated styrene thermoplastic elastomers, which is beneficial to improving the heat resistance and low-temperature flexibility of the modified asphalt waterproof membrane. On the other hand, it reduces the C=C double bond content in the elastomer, which can effectively avoid problems such as chain breakage and degradation of the elastomer under the action of heat, ultraviolet rays and oxygen, thereby significantly improving the anti-aging properties of the modified asphalt membrane. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0019] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the asphalt waterproofing membrane prepared in the following examples are as follows:

[0020] Self-repairing performance: Bend the modified asphalt waterproofing membrane around a round rod with a diameter of 30mm at a temperature lower than the limit low temperature flexibility to produce cracks on the surface of the modified asphalt. Place the cracked low temperature flexible specimen horizontally at 26±2℃ for 12 hours, then test its limit low temperature flexibility and calculate the self-repairing rate of the self-repairing elastomer modified asphalt coating. Self-repairing rate = limit low temperature flexibility after healing / initial limit low temperature flexibility × 100%.

[0021] Material limit low temperature flexibility: Test the low temperature flexibility of waterproof membrane in accordance with "Test Methods for Building Waterproof Membrane Part 14: Low Temperature Flexibility of Asphalt Waterproof Membrane" (GB / T328.14-2007), gradually lower or raise the test temperature until only one of the five specimens shows cracks, which is called the limit low temperature flexibility.

[0022] Example 1

[0023] (1) 5-Hexeneboronic acid and bis(6-hydroxyhexyl) disulfide were mixed in a molar ratio of 1:1.2, and toluene was added in a ratio of 5-hexeneboronic acid to toluene of 1 mol:20 mL. The mixture was stirred at 100°C and 40 rpm for 8 h. The lower layer solution was separated by a water separation reflux device, and the upper layer solution was then heated to 8.8 × 10 4 The self-repairing modifier was obtained by vacuum distillation at 100 Pa for 20 min.

[0024] (2) 80 parts by weight of hydrogenated styrene-butadiene block copolymer and 520 parts by weight of toluene were mixed, and then 8 parts by weight of a self-healing modifier was added, and the mixture was heated to 60° C. Under nitrogen protection, 0.1 parts by weight of benzoyl peroxide was added, and the mixture was stirred at 60 rpm for 5 h. After cooling to room temperature, ethanol was added until a precipitate was precipitated, and the precipitate was taken and dried at 60° C. for 1 h to obtain a modified elastomer;

[0025] (3) 50 parts by mass of asphalt are heated to 180° C., 8 parts by mass of modified elastomer are added, and the mixture is stirred at 2000 rpm for 10 min to obtain modified asphalt. The modified asphalt is then transported to a coating machine and coated in the order of a lower isolation film layer, a lower modified asphalt layer, a matrix layer, an upper modified asphalt layer, and an upper isolation film layer to obtain a self-repairing elastomer modified asphalt waterproofing membrane; the matrix layer is a polyester non-woven fabric with a thickness of 1.3 mm; the upper and lower isolation film layers are PET single-sided silicone oil isolation films with a thickness of 0.5 mm.

[0026] Example 2

[0027] (1) 5-Hexeneboronic acid and bis(6-hydroxyhexyl) disulfide were mixed in a molar ratio of 1:1.6, and toluene was added in a ratio of 5-hexeneboronic acid to toluene of 1 mol:20 mL. The mixture was stirred at 110°C and 40 rpm for 8 h. The lower layer solution was separated by a water separation reflux device, and the upper layer solution was then heated to 8.8×10 4 The self-repairing modifier was obtained by vacuum distillation at 100 Pa for 20 min.

[0028] (2) 100 parts by mass of hydrogenated styrene-isoprene block copolymer and 520 parts by mass of toluene were mixed, and then 10 parts by mass of a self-healing modifier was added, and the mixture was heated to 65° C. Under nitrogen protection, 0.3 parts by mass of benzoyl peroxide was added, and the mixture was stirred at 80 rpm for 8 hours. After cooling to room temperature, ethanol was added until a precipitate was precipitated, and the precipitate was taken and dried at 60° C. for 1 hour to obtain a modified elastomer;

[0029] (3) 60 parts by mass of asphalt are heated to 180° C., 12 parts by mass of modified elastomer are added, and the mixture is stirred at 2000 rpm for 10 min to obtain modified asphalt. The modified asphalt is then transported to a coating machine and coated in the order of a lower isolation film layer, a lower modified asphalt layer, a matrix layer, an upper modified asphalt layer, and an upper isolation film layer to obtain a self-repairing elastomer modified asphalt waterproofing membrane; the matrix layer is a polyester non-woven fabric with a thickness of 1.3 mm; the upper and lower isolation film layers are PET single-sided silicone oil isolation films with a thickness of 0.5 mm.

[0030] Example 3

[0031] (1) 5-Hexeneboronic acid and bis(6-hydroxyhexyl) disulfide were mixed in a molar ratio of 1:1.4, and toluene was added in a ratio of 5-hexeneboronic acid to toluene of 1 mol:20 mL. The mixture was stirred at 105°C and 40 rpm for 8 h. The lower layer solution was separated by a water separation reflux device, and the upper layer solution was then heated to 8.8 × 10 4 The self-repairing modifier was obtained by vacuum distillation at 100 Pa for 20 min.

[0032] (2) 90 parts by weight of hydrogenated styrene-butadiene block copolymer and 520 parts by weight of toluene were mixed, and then 9 parts by weight of a self-healing modifier was added, and the mixture was heated to 65° C. Under nitrogen protection, 0.2 parts by weight of benzoyl peroxide was added, and the mixture was stirred at 70 rpm for 8 h. After cooling to room temperature, ethanol was added until a precipitate was precipitated, and the precipitate was taken and dried at 60° C. for 1 h to obtain a modified elastomer;

[0033] (3) 55 parts by mass of asphalt are heated to 180° C., 10 parts by mass of modified elastomer are added, and the mixture is stirred at 2000 rpm for 10 min to obtain modified asphalt. The modified asphalt is then transported to a coating machine and coated in the order of a lower isolation film layer, a lower modified asphalt layer, a matrix layer, an upper modified asphalt layer, and an upper isolation film layer to obtain a self-repairing elastomer modified asphalt waterproofing membrane; the matrix layer is a polyester non-woven fabric with a thickness of 1.3 mm; the upper and lower isolation film layers are PET single-sided silicone oil isolation films with a thickness of 0.5 mm.

[0034] Comparative Example 1

[0035] The difference between Comparative Example 1 and Example 2 is that step (1) is omitted, and step (2) is changed to: 100 parts by mass of hydrogenated styrene-isoprene block copolymer and 520 parts by mass of toluene are mixed, and then 10 parts by mass of 5-hexeneboric acid are added, and the mixture is heated to 65° C., and under nitrogen protection, 0.3 parts by mass of benzoyl peroxide is added, and the mixture is stirred at 80 rpm for 8 hours. After cooling to room temperature, ethanol is added until a precipitate is precipitated, and the precipitate is taken and dried at 60° C. for 1 hour to obtain a modified elastomer; the remaining steps are the same as those in Example 2.

[0036] Comparative Example 2

[0037] The difference between Comparative Example 2 and Example 2 is that there is no step (2), and step (3) is changed to: 60 parts by mass of asphalt are heated to 180°C, 12 parts by mass of hydrogenated styrene-isoprene block copolymer and 0.1 parts by mass of self-healing modifier are added, and the mixture is stirred at 2000rpm for 10 minutes to obtain modified asphalt, and the modified asphalt is then transported to a coating machine, and coated in the order of a lower isolation film layer, a lower modified asphalt layer, a matrix layer, an upper modified asphalt layer, and an upper isolation film layer to obtain a self-healing elastomer modified asphalt waterproof membrane; the matrix layer is a polyester non-woven fabric with a thickness of 1.3 mm; the upper and lower isolation film layers are PET single-sided silicone oil isolation films with a thickness of 0.5 mm.

[0038] Comparative Example

[0039] Effect example

[0040] Table 1 below shows the performance analysis results of the asphalt waterproof membranes of Examples 1 to 3 of the present invention and Comparative Examples 1 to 2.

[0041] Table 1

[0042]

[0043] The invention utilizes the reaction of the hydroxyl group of bis(6-hydroxyhexyl) disulfide with the hydroxyl group of 5-hexeneboronic acid to form a double self-healing compound containing a C=C double bond at the molecular chain end, and then reacts the double self-healing compound with a hydrogenated styrene thermoplastic elastomer. Under the action of an initiator, the C=C double bond in the double self-healing compound reacts with the C=C double bond in the hydrogenated styrene thermoplastic elastomer, and a dynamic disulfide bond and a borate bond are introduced between the molecular chains of the elastomer. The double self-healing compound is used for an elastomer-modified asphalt waterproofing membrane, and the fracture-rearrangement characteristics of the dynamic disulfide bond and the borate bond are utilized. When the elastomer-modified asphalt waterproofing membrane is When subjected to external force, the dynamic disulfide bonds and borate bonds are broken first. After the external force is eliminated, the broken disulfide bonds and borate bonds are rearranged to restore the original molecular structure, thereby realizing self-repair of broken and damaged waterproof membranes. In addition, the present invention utilizes dual self-repairing compounds to undergo cross-linking reactions with hydrogenated styrene thermoplastic elastomers, which is beneficial to improving the heat resistance and low-temperature flexibility of the modified asphalt waterproof membrane. On the other hand, it reduces the C=C double bond content in the elastomer, which can effectively avoid problems such as chain breakage and degradation of the elastomer under the action of heat, ultraviolet rays and oxygen, thereby significantly improving the anti-aging properties of the modified asphalt membrane.

[0044] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A method for preparing a self-repairing elastomer-modified asphalt waterproofing membrane, characterized in that: The method comprises the following preparation steps: (1) 5-Hexeneboric acid and bis(6-hydroxyhexyl) disulfide were mixed, and toluene was added. The mixture was stirred at 100-110°C and 40 rpm for 8 h. The lower layer solution was separated by a water separation reflux device, and the upper layer solution was then heated to 8.8 × 10 4 The self-repairing modifier was obtained by vacuum distillation at 400 Pa for 20 min. (2) mixing a hydrogenated styrene thermoplastic elastomer and toluene, adding a self-healing modifier, heating to 60-65° C., adding benzoyl peroxide under nitrogen protection, stirring at 60-80 rpm for 5-8 hours, cooling to room temperature, adding ethanol until precipitation occurs, taking the precipitate, and drying it at 60° C. for 1 hour to obtain a modified elastomer; (3) 50 to 60 parts by weight of asphalt are heated to 180° C., 8 to 12 parts by weight of modified elastomer are added, and the mixture is stirred at 2000 rpm for 10 min to obtain modified asphalt. The modified asphalt is then transported to a coating machine and coated in the order of a lower isolation membrane layer, a lower modified asphalt layer, a matrix layer, an upper modified asphalt layer, and an upper isolation membrane layer to obtain a self-repairing elastomer modified asphalt waterproofing membrane.

2. The method for preparing a self-repairing elastomer-modified asphalt waterproofing membrane according to claim 1, characterized in that: The ratio of 5-hexeneboric acid to toluene in step (1) is 1 mol:20 mL.

3. The method for preparing a self-repairing elastomer-modified asphalt waterproofing membrane according to claim 1, characterized in that: The molar ratio of 5-hexeneboronic acid to bis(6-hydroxyhexyl) disulfide in step (1) is 1:1.2-1.

6.

4. The method for preparing a self-repairing elastomer-modified asphalt waterproofing membrane according to claim 1, characterized in that: The hydrogenated styrene thermoplastic elastomer in step (2) has a Shore hardness of ≤75A and a melt index of ≥2g / 10min at 230°C and 5kg.

5. The method for preparing a self-repairing elastomer-modified asphalt waterproofing membrane according to claim 1, characterized in that: The hydrogenated styrene-based thermoplastic elastomer in step (2) is one or both of hydrogenated styrene-butadiene block copolymer (SEBS) and hydrogenated styrene-isoprene block copolymer (SEPS).

6. The method for preparing a self-repairing elastomer-modified asphalt waterproofing membrane according to claim 1, characterized in that: In step (2), the hydrogenated styrene thermoplastic elastomer is 80 to 100 parts by mass, toluene is 520 parts by mass, the self-healing modifier is 8 to 10 parts by mass, and benzoyl peroxide is 0.1 to 0.3 parts by mass.

7. The method for preparing a self-repairing elastomer-modified asphalt waterproofing membrane according to claim 1, characterized in that: The softening point of the asphalt in step (3) is 46.3°C, and the needle penetration at 25°C is 89 dmm.

8. The method for preparing a self-repairing elastomer-modified asphalt waterproofing membrane according to claim 1, characterized in that: The upper and lower isolation film layers in step (3) are PET single-sided silicone oil isolation films with a thickness of 0.1 to 1 mm.

9. The method for preparing a self-repairing elastomer-modified asphalt waterproofing membrane according to claim 1, characterized in that: The matrix layer in step (3) is a polyester non-woven fabric with a thickness of 1.0 to 1.6 mm.

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