Flexible composite waterproof board based on fiber skeleton and preparation method and application thereof

Abstract

The invention belongs to the technical field of waterproof plates, and particularly relates to a flexible composite waterproof plate based on a fiber skeleton and a preparation method and application of the flexible composite waterproof plate. The flexible composite waterproof plate based on the fiber skeleton comprises two waterproof layers and a fiber skeleton surface layer arranged between the two waterproof layers, the fiber skeleton surface layer comprises a fiber skeleton and a self-repairing composite material filled in gaps of the fiber skeleton. According to the flexible composite waterproof board based on the fiber skeleton, the fiber skeleton is integrally formed, and gaps of the fiber skeleton are filled with the self-repairing composite material, so that the waterproof board has very high tensile strength and elongation at break, and the problems that the structure is easy to disperse, the waterproof effect is obviously reduced and the like cannot occur even if the waterproof board is used for a long time.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of waterproof boards, and particularly relates to a flexible composite waterproof board based on a fiber framework and a preparation method and application thereof. BACKGROUND

[0002] In building engineering, a waterproof board generally refers to a continuous sheet or coiled waterproof material for preventing water penetration. It forms a physical barrier at the interface of a building in contact with water (such as a roof, basement, bathroom, tunnel, pool, etc.) to achieve the purpose of waterproofing. Mainly including asphalt-based waterproofing membrane, polymer waterproofing membrane, self-adhesive waterproofing membrane.

[0003] The existing waterproof board has problems such as easy dispersion of structure and obvious reduction of waterproof effect during long-term use. SUMMARY

[0004] To solve the above problems, the present application provides a flexible composite waterproof board based on a fiber framework and a preparation method and application thereof to solve at least one aspect of the above technical problems.

[0005] The present application is realized by the following technical solutions: In a first aspect, the present application provides a flexible composite waterproof board based on a fiber framework, comprising two waterproof layers and a fiber framework surface layer arranged between the two waterproof layers; The fiber framework surface layer comprises a fiber framework and a self-repairing composite material filled in the gaps of the fiber framework; The preparation raw materials of the self-repairing composite material include the following components by weight: 100 parts of cement, 1 part to 5 parts of self-repairing microcapsules; The core material of the self-repairing microcapsules comprises cement particles; The wall material of the self-repairing microcapsules comprises a mixture of 12-hydroxystearic acid, linolenic acid, modified titanium dioxide and modified molecular sieve.

[0006] In some possible implementation manners, the wall material of the self-repairing microcapsules comprises the following components by weight: 100 parts of linolenic acid, 2 parts to 4 parts of 12-hydroxystearic acid, 0.01 parts to 0.05 parts of modified titanium dioxide, 10 parts to 15 parts of modified molecular sieve.

[0007] In some possible implementation manners, the preparation raw materials of the composite cement particles comprise cement, bentonite, phase change material, dispersing agent and binder.

[0008] In some possible implementation manners, the preparation raw materials of the composite cement particles comprise the following components by weight: 100 parts of cement, 30-35 parts of bentonite, 10-12 parts of binder, 0.5-0.7 parts of dispersing agent, 0.3-0.5 parts of mesoporous silicon dioxide.

[0009] In some possible implementations, the preparation raw material of the modified titanium dioxide comprises nano-titanium dioxide and silane coupling agent.

[0010] In some possible implementations, the preparation raw material of the modified molecular sieve comprises 3A molecular sieve, silane coupling agent and water.

[0011] In some possible implementations, the thickness of the fiber skeleton surface layer is 15-25 mm.

[0012] In some possible implementations, the thickness of the two layers of the waterproof layer can be independently 0.4-0.6 mm.

[0013] In some possible implementations, the rigid reinforcing agent comprises modified nano-silicon dioxide.

[0014] In some possible implementations, the toughening agent comprises aliphatic thermoplastic polyurethane.

[0015] In some possible implementations, the antioxidant comprises at least one of antioxidant 1010 and antioxidant 168.

[0016] In some possible implementations, the preparation raw material of the fiber skeleton comprises the following components in parts by weight: 60-75 parts of polyethylene terephthalate, 15-25 parts of rigid reinforcing agent, 5-10 parts of toughening agent, 0.2-0.5 parts of antioxidant.

[0017] In some possible implementations, the material of the waterproof layer comprises at least one of polyimide resin and polyethylene.

[0018] In some possible implementations, the structure of the fiber skeleton comprises two net surfaces and a plurality of X-shaped fibers; The plurality of X-shaped fibers are arranged between the two net surfaces; The two net surfaces and the plurality of X-shaped fibers are integrally formed.

[0019] In some possible implementations, the fiber diameter of the X-shaped fiber is 10-30 μm.

[0020] In a second aspect, the present application provides a preparation method of the above-mentioned flexible composite waterproof plate based on fiber skeleton, comprising the following steps: After injecting the self-repairing composite material slurry into the three-layer structure of the fiber skeleton under a preset pressure, the slurry is cured; The three-layer structure comprises a first waterproof layer, a fiber framework and a second waterproof layer which are sequentially stacked.

[0021] In some possible implementation manners, the preparation of the fiber framework comprises the following steps: The preparation raw material of the fiber framework is made into the fiber framework by using the electrospinning method.

[0022] In some possible implementation manners, in the preparation of the fiber framework by using the electrospinning method, the preparation of the spinning solution comprises the following steps: Polyethylene terephthalate, rigid reinforcing agent, toughening agent, antioxidant and hexafluoroisopropanol are mixed; In some possible implementation manners, the solid-liquid ratio of the total mass of the preparation raw material of the fiber framework and hexafluoroisopropanol is 1: (2-5).

[0023] In some possible implementation manners, the temperature of the solidification is 20-35 DEG C.

[0024] In a third aspect, the present application provides an application of the above-mentioned flexible composite waterproof board based on the fiber framework in the field of engineering technology.

[0025] Compared with the prior art, the flexible composite waterproof board based on the fiber framework provided by the present application has at least the following beneficial technical effects: (1) The flexible composite waterproof board based on the fiber framework provided by the present application, wherein the fiber framework is integrally formed, and the self-repairing composite material is filled in the gap of the fiber framework, so that the waterproof board has high tensile strength and elongation at break, and does not have problems such as easy dispersion of structure and obvious reduction of waterproof effect during long-term use.

[0026] (2) The flexible composite waterproof board based on the fiber framework provided by the present application, wherein the self-repairing composite material contains self-repairing microcapsules, and when the waterproof board has scratches / cracks, titanium dioxide catalyzes the slow release and degradation of linolenic acid to release composite cement particles under light conditions, and the composite cement particles harden after absorbing water, thereby repairing the scratches / cracks.

[0027] Compared with the prior art, the preparation method of the flexible composite waterproof board based on the fiber framework provided by the present application has at least the following beneficial technical effects: In the preparation method of the flexible composite waterproof board based on the fiber framework provided by the present application, the integrally formed fiber framework is made by using the electrospinning method, and after pressure is applied to the three-layer structure, the self-repairing composite material slurry is injected and solidified, so that the preparation method is simple and easy to implement. The prepared composite waterproof board does not have problems such as easy dispersion of structure and obvious reduction of waterproof effect during long-term use. BRIEF DESCRIPTION OF DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed in the embodiments or prior art description. Obviously, the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained from the structures shown in these drawings without creative effort.

[0029] Figure 1 A structural schematic diagram of a flexible composite waterproof board based on a fiber skeleton provided by the embodiment of the present application is shown in the figure. Figure 2 A cross-sectional structural schematic diagram of a fiber skeleton provided by the comparative example 1 of the present application is shown in the figure.

[0030] Legend: 1 - waterproof layer, 2 - fiber skeleton surface layer, 21 - fiber skeleton, 22 - self-repairing composite material, 3 - fiber filaments.

[0031] The purposes of the present application, functional features and advantages will be further described with reference to the embodiments and the accompanying drawings. DETAILED DESCRIPTION

[0032] In order to make the purposes, technical solutions and advantages of the present application more clear, the following will describe and explain the present application with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, and are not used to limit the present application. Based on the embodiments provided by the present application, all other embodiments obtained by those skilled in the art without creative effort belong to the scope of protection of the present application.

[0033] Obviously, the following description is only some examples or embodiments of the present application, and for those skilled in the art, the present application can be applied to other similar situations without creative effort. In addition, it can be understood that although the efforts made in this development process may be complex and lengthy, for those skilled in the art related to the disclosed content of the present application, some design, manufacture or production changes based on the technical content disclosed in the present application are only routine technical means, and should not be understood as insufficient disclosure of the present application.

[0034] However, there will be cases of omitting unnecessary detailed description. For example, there are cases of omitting detailed description of well-known matters, repeated description of actually identical structures. This is to avoid the following description from becoming unnecessarily lengthy, facilitating understanding by those skilled in the art. In addition, the following description is provided for those skilled in the art to fully understand the present application, and is not intended to limit the subject matter recited in the claims.

[0035] All the embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions if there is no special description, and all the technical features and optional technical features of the present application can be combined with each other to form new technical solutions.

[0036] The first aspect of the embodiment of the present application provides a flexible composite waterproof board based on a fiber framework, which comprises two waterproof layers and a fiber framework surface layer arranged between the two waterproof layers. Figure 1 As shown in the figure, the fiber framework surface layer comprises a fiber framework and a self-repairing composite material filled in the interspace of the fiber framework. The fiber framework surface layer comprises a fiber framework and a self-repairing composite material filled in the interspace of the fiber framework. The raw materials for preparing the self-repairing composite material comprise the following components by weight: 100 parts of cement, 1 part to 5 parts of self-repairing microcapsules; The core material of the self-repairing microcapsules comprises composite cement particles. The wall material of the self-repairing microcapsules comprises a mixture of 12-hydroxystearic acid, linolenic acid, modified titanium dioxide and modified molecular sieve.

[0037] Figure 1 In the figure, 1 is a waterproof layer, 2 is a fiber framework surface layer, 21 is a fiber framework, and 22 is a self-repairing composite material.

[0038] The flexible composite waterproof board based on the fiber framework provided by the embodiment of the present application has high tensile strength and elongation at break. The flexible composite waterproof board based on the fiber framework provided by the embodiment of the present application will not have problems such as easy dispersion of structure and obvious reduction of waterproof effect during long-term use.

[0039] In some embodiments, the thickness of the fiber framework surface layer is 15mm to 25mm.

[0040] In some embodiments, the structure of the fiber framework comprises two net surfaces and a plurality of X-shaped fibers. The plurality of X-shaped fibers are arranged between the two net surfaces. The two net surfaces and the plurality of X-shaped fibers are integrally formed.

[0041] In some embodiments, the fiber diameter of the X-shaped fiber is 10μm to 30μm.

[0042] In some embodiments, the raw materials for preparing the fiber framework comprise the following components by weight: 60 parts to 75 parts of polyethylene terephthalate, 15 parts to 25 parts of a rigid reinforcing agent, 5 parts to 10 parts of a toughening agent, and 0.2 parts to 0.5 parts of an antioxidant.

[0043] In some embodiments, the polyethylene terephthalate has a CAS number of 25038-59-9.

[0044] In some embodiments, the rigid reinforcing agent includes modified nano-silica.

[0045] In some embodiments, the modified nano-silica includes amino-silane (KH-550) modified nano-silica.

[0046] In some embodiments, the toughening agent includes aliphatic thermoplastic polyurethane.

[0047] In some embodiments, the aliphatic thermoplastic polyurethane is A series of aliphatic TPU produced by Meisen Materials Co., Ltd.

[0048] In some embodiments, the antioxidant includes at least one of antioxidant 1010, antioxidant 168.

[0049] In some embodiments, the raw materials for preparing the composite cement particles include cement, bentonite, mesoporous silica, dispersant, and binder. In this case, the mesoporous silica is used to adsorb moisture so as to solidify the cement.

[0050] In some embodiments, the raw materials for preparing the composite cement particles include the following components in the following weight proportions: 100 parts of cement, 30 parts to 35 parts of bentonite, 10 parts to 12 parts of binder, 0.5 parts to 0.7 parts of dispersant, and 0.3 parts to 0.5 parts of mesoporous silica.

[0051] In some embodiments, the cement includes Portland cement.

[0052] In some specific embodiments, the grade of the Portland cement is P·O 42.5.

[0053] In some embodiments, the binder includes at least one of polyvinyl alcohol, polyethylene glycol, polyacrylic acid, and carboxymethyl cellulose.

[0054] In some embodiments, the polyvinyl alcohol has a CAS number of 98002-49-4.

[0055] In some embodiments, the polyethylene glycol has a CAS number of 25322-68-3.

[0056] In some embodiments, the polyacrylic acid has a CAS number of 9003-01-4.

[0057] In some embodiments, the carboxymethyl cellulose has a CAS number of 9000-11-7.

[0058] In some embodiments, the dispersant includes sodium hexametaphosphate.

[0059] In some embodiments, the sodium hexametaphosphate has a CAS number of 68915-31-1.

[0060] In some embodiments, the wall material of the self-repairing microcapsule comprises the following components in parts by weight: 100 parts of linolenic acid, 2 parts to 4 parts of 12-hydroxystearic acid, 0.01 parts to 0.05 parts of modified titanium dioxide, 10 parts to 15 parts of modified molecular sieve.

[0061] In some embodiments, the raw materials for preparing the modified titanium dioxide comprise nano-titanium dioxide and a silane coupling agent. In this case, the silane coupling agent modifies the nano-titanium dioxide, so that the nano-titanium dioxide can be uniformly mixed with the 12-hydroxystearic acid and the linolenic acid.

[0062] In some embodiments, the raw materials for preparing the modified molecular sieve comprise 3A molecular sieve, a silane coupling agent, and water. In this case, the 3A molecular sieve is modified by the silane coupling agent after being absorbed with water, and the obtained modified molecular sieve can be uniformly mixed with the 12-hydroxystearic acid and the linolenic acid, thereby providing necessary moisture for the composite cement particles in the subsequent self-repairing process.

[0063] In some embodiments, the silane coupling agent comprises at least one of sulfopropyltrimethoxysilane ((CH3O)3Si-(CH2)3-SO3H), N-trimethoxysilylpropyl-N, N, N-trichloroammonium ((CH3O)3Si-(CH2)3-N + (CH3)3Cl - ).

[0064] In some embodiments, the material of the waterproof layer comprises at least one of polyimide resin (HTP1) and polyethylene.

[0065] In some embodiments, the polyimide resin (HTP1) has a CAS number of 62929-02-6.

[0066] In some embodiments, the polyethylene has a CAS number of 9002-88-4.

[0067] In some embodiments, the thickness of the two waterproof layers can be independently 0.4mm to 0.6mm.

[0068] The second aspect of the embodiments of the present application provides a preparation method of a flexible composite waterproof board based on a fiber skeleton, comprising the following steps: S10. Injecting self-repairing composite material slurry into the fiber skeleton of the three-layer structure under a preset pressure and then curing; The three-layer structure comprises a first waterproof layer, a fiber skeleton, and a second waterproof layer which are sequentially stacked.

[0069] The preparation method of the flexible composite waterproof plate based on the fiber framework provided by the embodiment of the application, after pressure is applied to the three-layer structure, the self-repairing composite material slurry is injected and solidified, and the flexible composite waterproof plate based on the fiber framework is integrally formed, and the integrally formed flexible composite waterproof plate based on the fiber framework will not have problems such as easy structure scattering and obvious reduction of waterproof effect during long-term use.

[0070] In some embodiments, in the step S10, the preset pressure is 3 MPa to 5 MPa.

[0071] In some embodiments, in the step S10, the application direction of the preset pressure is towards the fiber framework.

[0072] In some embodiments, in the step S10, the preparation of the fiber framework includes the following steps: S101. The preparation raw material of the fiber framework is made into the fiber framework by using the electrospinning method.

[0073] In the preparation of the fiber framework, the fiber framework is integrally formed by using the electrospinning method, and the structure will not scatter during long-term use.

[0074] In some embodiments, in the step S101, the preparation raw material of the fiber framework is made into the fiber framework by using the electrospinning method, including the following steps: S1011. The preparation raw material of the fiber framework is made into the fiber framework by using the electrospinning method.

[0075] In some embodiments, in the step S1011, the preparation of the spinning solution includes the following steps: S10111. Polyethylene terephthalate, rigid reinforcing agent, toughening agent, antioxidant and hexafluoroisopropanol are mixed.

[0076] In some embodiments, in the step S10111, the total mass of the preparation raw material of the fiber framework and the solid-liquid ratio of hexafluoroisopropanol are 1: (2-5).

[0077] In some embodiments, in the step S10, the preparation of the self-repairing composite material slurry includes the following steps: S102. The cement, self-repairing microcapsules and water are mixed under stirring.

[0078] In the preparation of the self-repairing composite material slurry, the preparation raw material of the self-repairing composite material is mixed with water under stirring to form a uniform slurry. It should be noted that the rotation speed and the like are conventional techniques in the art, and can be adjusted conventionally in actual production, and therefore, are not particularly limited in the embodiment of the application.

[0079] In some embodiments, in step S102 above, the amount of water added is 0.5L / kg to 0.8L / kg.

[0080] In some embodiments, in step S102 above, the preparation of the self-healing microcapsules includes the following steps: S1021. Disperse composite cement particles in the wall material mixture.

[0081] In some embodiments, the preparation of composite cement particles in step S1021 above includes the following steps: S10211. Cement, bentonite, mesoporous silica, dispersant and binder are mixed under stirring and dried to obtain composite cement particles.

[0082] In some embodiments, the mixing process in step S10211 above includes the following steps: After the S102111 bentonite and dispersant are first mixed, the binder is added for the second mixing treatment, then cement and mesoporous silica are added for the third mixing treatment, and finally the fourth mixing treatment is carried out.

[0083] In the above mixing process, the first stirring process can fully disperse the bentonite particles; then, a binder is added for the second stirring process to increase the viscosity; the third stirring process adds cement and mesoporous silica to make the slurry uniform and free of dry powder lumps or agglomerates; the fourth stirring process makes the slurry structure more stable and uniformly dispersed.

[0084] In some embodiments, in step S102111 above, the stirring speed of the first stirring process is 300 rpm to 400 rpm.

[0085] In some embodiments, in step S102111 above, the amount of water used in the first mixing process is 45% to 55% of the cement mass.

[0086] In some embodiments, in step S102111 above, the time for the first stirring treatment is 3 min to 5 min.

[0087] In some embodiments, in step S102111 above, the stirring speed of the second stirring process is 150 rpm to 350 rpm.

[0088] In some embodiments, in step S102111 above, the second stirring treatment time is 10 min to 15 min.

[0089] In some embodiments, in step S102111 above, the stirring speed of the third stirring process is 250 rpm to 350 rpm.

[0090] In some embodiments, in the step S102111, the third stirring treatment is performed for 10-15 minutes.

[0091] In some embodiments, in the step S102111, the stirring speed of the fourth stirring treatment is 100-200 rpm.

[0092] In some embodiments, in the step S102111, the fourth stirring treatment is performed for 3-5 minutes.

[0093] In some embodiments, in the step S1021, the preparation of the wall material mixture includes the following steps: S10212. Mixing the modified titanium dioxide, the modified molecular sieve, and the mixture of 12-hydroxystearic acid and linolenic acid under stirring.

[0094] In some embodiments, in the step S10212, the stirring speed is 200-300 rpm.

[0095] In some embodiments, in the step S10212, the preparation of the modified titanium dioxide includes the following steps: s1. After mixing the nano-titanium dioxide suspension and the silane coupling agent hydrolysis solution, drying the solid.

[0096] In some embodiments, in the step s1, the preparation of the nano-titanium dioxide suspension includes the following steps: s11. Dispersing the nano-titanium dioxide in anhydrous ethanol.

[0097] In some embodiments, in the step s11, the solid-liquid ratio of the nano-titanium dioxide and the anhydrous ethanol is 1: (1.05-2).

[0098] In some embodiments, in the step s1, the preparation of the silane coupling agent hydrolysis solution includes the following steps: s12. Mixing the silane coupling agent and the mixed solvent under stirring; wherein the pH value of the mixed solvent is 4-5.

[0099] In some embodiments, in the step s12, the stirring speed is 100-200 rpm.

[0100] In some embodiments, in the step s12, the mixed solvent includes a mixture of ethanol and water.

[0101] In some embodiments, in the mixed solvent, the volume ratio of ethanol and water is (4-9):1.

[0102] In some embodiments, acetic acid is used to adjust the pH value of the mixture of ethanol and water in the mixed solvent.

[0103] In some embodiments, in the step s1 above, the step of mixing the nano-titanium dioxide suspension and the silane coupling agent hydrolysis solution comprises: s13. After the silane coupling agent hydrolysis solution is dropped into the nano-titanium dioxide suspension under stirring and constant temperature, the stirring is continued for 2h~4h.

[0104] In some embodiments, in the step s13 above, the stirring speed is 50rpm~80rpm.

[0105] In some embodiments, in the step s13 above, the constant temperature is 60℃~80℃.

[0106] In some embodiments, in the step s1 above, the drying of the solid product comprises the following steps: s14. After the obtained precipitate is washed with ethanol and water alternately, it is dried at 60℃~80℃ until the weight is constant.

[0107] In the drying of the solid product above, the obtained precipitate is washed with ethanol and water alternately to completely remove the physically adsorbed and unreacted silane molecules, and then dried to remove ethanol and water, thereby obtaining the modified titanium dioxide.

[0108] In some embodiments, in the step S10212 above, the preparation of the modified titanium dioxide further comprises a grinding step: the dried block product is ground to obtain the modified titanium dioxide.

[0109] In some embodiments, in the step S10212 above, the preparation of the modified molecular sieve comprises the following steps: s2. After the water-saturated 3A molecular sieve and the silane coupling agent hydrolysis solution are mixed under stirring and constant temperature, reflux is performed.

[0110] In the preparation of the modified molecular sieve above, the hydrolyzed silane molecules mainly undergo dehydration condensation reaction with the silicon hydroxyl groups on the outer surface of the water-saturated 3A molecular sieve, forming a firm Si-O-Si covalent bond, thereby being grafted on the surface of the molecular sieve to obtain the modified molecular sieve.

[0111] In some embodiments, in the step s2 above, the stirring speed is 50rpm~80rpm.

[0112] In some embodiments, in the step s2 above, the constant temperature is 60℃~80℃.

[0113] In some embodiments, in the step s2 above, the reflux time is 4h~6h.

[0114] In some embodiments, in the step S10212, the preparation of the modified molecular sieve further comprises a post-treatment.

[0115] In some embodiments, the post-treatment comprises the following steps: s3. Filtrate the filtrate and wash the residue with ethanol until the washing liquid is clear, and then dry at 80-100°C under vacuum.

[0116] In some embodiments, the time for vacuum drying is 6-12h.

[0117] In some embodiments, in the step S102, the preparation of the self-repairing microcapsule further comprises the following step: spray drying the mixed slurry obtained by dispersing the composite cement particles in the wall material mixture.

[0118] In some embodiments, the temperature for spray drying is 100-110°C.

[0119] In some embodiments, in the step S10, the curing temperature is 20-35°C.

[0120] The following further illustrates with specific examples. For the convenience of illustration, in the following examples and comparative examples, the cement is an existing Portland cement, and the grade of the Portland cement is P·O 42.5.

[0121] The CAS number of polyethylene terephthalate is 25038-59-9.

[0122] The CAS number of polyvinyl alcohol is 98002-49-4.

[0123] The CAS number of sodium hexametaphosphate is 68915-31-1.

[0124] The CAS number of polyimide resin (HTP1) is 62929-02-6.

[0125] Example 1 Example 1 provides a flexible composite waterproof board based on a fiber skeleton, which is composed of a first waterproof layer, a second waterproof layer, and a fiber skeleton surface layer arranged between the first waterproof layer and the second waterproof layer.

[0126] wherein, (1) the fiber skeleton surface layer is composed of a fiber skeleton and a self-repairing composite material filled in the voids of the fiber skeleton.

[0127] The thickness of the fiber skeleton surface layer is 25mm.

[0128] The structure of the fiber skeleton is composed of two net surfaces and a plurality of X-shaped fibers; The plurality of X-shaped fibers are arranged between the two net surfaces. The two net-shaped surfaces and the X-shaped fibers are integrally formed; The fiber diameter of the X-shaped fiber is 20 μm.

[0129] The raw materials for preparing the fiber framework are composed of the following components in parts by weight: 70 parts of polyethylene terephthalate, 20 parts of amino silane modified nano-silica, 8 parts of aliphatic thermoplastic polyurethane, 0.3 parts of antioxidant 1010.

[0130] The raw materials for preparing the self-repairing composite material are composed of the following components in parts by weight: 100 parts of cement, 5 parts of self-repairing microcapsules.

[0131] The core material of the self-repairing microcapsule is composite cement particles, and the raw materials for preparing the same are composed of the following components in parts by weight: 100 parts of cement, 33 parts of bentonite, 12 parts of polyvinyl alcohol, 0.6 parts of sodium hexametaphosphate, and 0.4 parts of mesoporous silica.

[0132] The wall material of the self-repairing microcapsule is composed of the following components in parts by weight: 100 parts of linolenic acid, 3 parts of 12-hydroxystearic acid, 0.03 parts of modified titanium dioxide, and 12 parts of modified molecular sieve.

[0133] In the wall material of the self-repairing microcapsule, the raw materials for preparing the modified titanium dioxide are nano-titanium dioxide and silane coupling agent, and the raw materials for preparing the modified molecular sieve are 3A molecular sieve, silane coupling agent, and water.

[0134] (2) The material of the first waterproof layer is polyimide resin (HTP1), and the thickness is 0.5 mm.

[0135] (3) The material of the second waterproof layer is polyimide resin (HTP1), and the thickness is 0.5 mm.

[0136] The embodiment also provides a preparation method of the flexible composite waterproof board based on the fiber framework of the embodiment, and the steps are as follows: E10. Preparation of the fiber framework E101. Preparation of the spinning solution: polyethylene terephthalate, amino silane modified nano-silica, aliphatic thermoplastic polyurethane, antioxidant 1010, and hexafluoroisopropanol are mixed. The total mass of the raw materials for preparing the fiber framework and the solid-liquid ratio of hexafluoroisopropanol are 1:3.

[0137] E102. The fiber framework is prepared by using an electrospinning method.

[0138] E20. Preparation of the self-repairing microcapsule E201. Preparation of the core material-composite cement particles: (1) Under the condition of 350 rpm, bentonite and sodium hexametaphosphate were mixed and stirred for 4 min to obtain bentonite slurry; wherein, the amount of water was 45% to 55% of the mass of cement.

[0139] (2) Under the condition of 200 rpm, polyvinyl alcohol was mixed with the bentonite slurry and stirred for 15 min.

[0140] (3) Under the condition of 250 rpm to 350 rpm, cement and mesoporous silicon dioxide were added to the slurry prepared in (2) and stirred for 12 min.

[0141] (4) The slurry prepared in (3) was continuously stirred under the condition of 200 rpm for 4 min.

[0142] (5) After the slurry obtained in (4) was spray dried, composite cement particles were obtained.

[0143] E202. Preparation of wall material mixed solution (1) Preparation of modified titanium dioxide 1) Nano-titanium dioxide suspension: nano-titanium dioxide was dispersed in anhydrous ethanol with a solid-liquid ratio of 1:1.5 to prepare a nano-titanium dioxide suspension.

[0144] 2) The pH value of the mixture of ethanol and water was adjusted to 4 using acetic acid to obtain a mixed solvent; Under the condition of 200 rpm, the silane coupling agent was added to the mixed solvent to prepare a silane coupling agent hydrolysate.

[0145] 3) After the silane coupling agent hydrolysate was added dropwise into the nano-titanium dioxide suspension under the condition of 70 rpm and constant temperature of 70°C, the stirring was continued for 3 h.

[0146] 4) The obtained precipitate was centrifuged, and the precipitate was washed with ethanol and water alternately, and then dried at 70°C to constant weight to obtain a blocky product; the blocky product was ground to obtain modified titanium dioxide.

[0147] (2) Preparation of modified molecular sieve 1) Under the condition of 70 rpm and constant temperature of 70°C, water-saturated 3A molecular sieve and silane coupling agent hydrolysate were mixed and refluxed for 5 h.

[0148] 2) The product prepared in 1) was subjected to suction filtration to obtain filter residue, and the filter residue was washed with ethanol until the washing liquid was clear, and then vacuum dried at 90°C for 10 h to obtain a modified molecular sieve.

[0149] E203. Disperse the composite cement particles in the wall material mixed solution to obtain a mixed slurry; spray dry the mixed slurry at 100°C to obtain self-repairing microcapsules.

[0150] E30. Preparation of self-repairing composite material slurry The cement, self-repairing microcapsules and water are mixed under stirring. The amount of water added is 0.7 L / kg.

[0151] E40. Preparation of flexible composite waterproof board After sequentially laminating the first waterproof layer, the fiber framework and the second waterproof layer to form a three-layer structure, the self-repairing composite material slurry is injected into the fiber framework of the three-layer structure under a preset pressure, and then solidified to obtain the flexible composite waterproof board based on the fiber framework provided in the embodiment; wherein the preset pressure is 4 MPa, and the solidification temperature is 25℃.

[0152] Example 2 Example 2 provides a flexible composite waterproof board based on a fiber framework, which has substantially the same structure and composition as Example 1, except that: The raw materials for preparing the self-repairing composite material are composed of the following components in parts by weight: 100 parts of cement, 1 part of self-repairing microcapsules.

[0153] The embodiment also provides a preparation method of the flexible composite waterproof board based on the fiber framework of the embodiment, which has substantially the same steps as Example 1, except that the amount of self-repairing microcapsules added is 1 part.

[0154] Example 3 Example 3 provides a flexible composite waterproof board based on a fiber framework, which has substantially the same structure and composition as Example 1, except that: The raw materials for preparing the self-repairing composite material are composed of the following components in parts by weight: 100 parts of cement, 5 parts of self-repairing microcapsules.

[0155] The embodiment also provides a preparation method of the flexible composite waterproof board based on the fiber framework of the embodiment, which has substantially the same steps as Example 1, except that the amount of self-repairing microcapsules added is 3 parts.

[0156] Example 4 Example 4 provides a flexible composite waterproof board based on a fiber framework, which has substantially the same structure and composition as Example 1, except that: The wall material of the self-repairing microcapsules is composed of the following components in parts by weight: 100 parts of linolenic acid, 2 parts of 12-hydroxystearic acid, 0.05 parts of modified titanium dioxide, and 15 parts of modified molecular sieve.

[0157] The embodiment also provides a preparation method of the flexible composite waterproof board based on the fiber framework of the embodiment, which has substantially the same steps as Example 1, except that the wall material of the self-repairing microcapsules is composed of the following components in parts by weight: 100 parts of linolenic acid, 2 parts of 12-hydroxystearic acid, 0.05 parts of modified titanium dioxide, 15 parts of modified molecular sieve.

[0158] Example 5 Example 5 provides a flexible composite waterproof board based on a fiber skeleton, which has substantially the same structure and composition as those of Example 1, except that: The wall material of the self-repairing microcapsule is composed of the following components in parts by weight: 100 parts of linolenic acid, 4 parts of 12-hydroxystearic acid, 0.01 parts of modified titanium dioxide, 10 parts of modified molecular sieve.

[0159] The embodiment also provides a preparation method of the flexible composite waterproof board based on a fiber skeleton of the embodiment, which has substantially the same steps as those of Example 1, except that: The wall material of the self-repairing microcapsule is composed of the following components in parts by weight: 100 parts of linolenic acid, 4 parts of 12-hydroxystearic acid, 0.01 parts of modified titanium dioxide, 10 parts of modified molecular sieve.

[0160] Example 6 Example 6 provides a flexible composite waterproof board based on a fiber skeleton, which has substantially the same structure and composition as those of Example 1, except that: The thickness of the fiber skeleton surface layer is 20 mm.

[0161] The preparation raw material of the fiber skeleton is composed of the following components in parts by weight: 60 parts of polyethylene terephthalate, 25 parts of amino silane modified nano silicon dioxide, 10 parts of aliphatic thermoplastic polyurethane, 0.5 parts of antioxidant 168.

[0162] The embodiment also provides a preparation method of the flexible composite waterproof board based on a fiber skeleton of the embodiment, which has substantially the same steps as those of Example 1, except that: In step E101, the total mass of the preparation raw material of the fiber skeleton and the solid-liquid ratio of hexafluoroisopropanol are 1:5.

[0163] Example 7 Example 7 provides a flexible composite waterproof board based on a fiber skeleton, which has substantially the same structure and composition as those of Example 1, except that: The thickness of the fiber skeleton surface layer is 15 mm.

[0164] The preparation raw material of the fiber skeleton is composed of the following components in parts by weight: 75 parts of polyethylene terephthalate, 15 parts of amino silane modified nano silicon dioxide, 5 parts of aliphatic thermoplastic polyurethane, 0.2 parts of antioxidant 1010, 0.2 parts of antioxidant 168.

[0165] This embodiment also provides a method for preparing the flexible composite waterproof board based on a fiber skeleton, the steps of which are basically the same as those in Embodiment 1, except that: In step E101, the total mass of the raw materials for preparing the fiber skeleton and the solid-liquid ratio of hexafluoroisopropanol are 1:2.

[0166] Comparative Example 1 Comparative Example 1 provides a waterproof board with a structure and composition basically the same as that of Example 1, except that: like Figure 2 As shown, the structure of the fiber skeleton consists of two mesh surfaces and several fiber filaments 3; Several fiber threads are arranged in a staggered manner between two mesh surfaces, with one end of a single fiber thread connected to the mesh surface and the other end suspended in the air; The diameter of the fiber filaments is 20 μm.

[0167] This comparative example also provides a method for preparing the above-mentioned waterproof membrane, the steps of which are basically the same as those in Example 1.

[0168] Comparative Example 2 Comparative Example 2 provides a waterproof board with a structure and composition basically the same as that of Example 1, except that: The fiber skeleton surface layer consists of a fiber skeleton and raw material powder for preparing a self-healing composite material that fills the gaps in the fiber skeleton.

[0169] This comparative example also provides a method for preparing the above-mentioned waterproof board, the steps of which are as follows: D10. Preparation of fiber skeleton D101. Preparation of spinning solution: A mixture of polyethylene terephthalate, aminosilane-modified nano-silica, aliphatic thermoplastic polyurethane, antioxidant 1010, and hexafluoroisopropanol. The total mass ratio of the raw materials for the fiber skeleton to the solid-liquid ratio of hexafluoroisopropanol is 1:3.

[0170] D102. The fiber skeleton is made by electrospinning.

[0171] D20. Preparation of flexible composite waterproof membrane.

[0172] After sequentially stacking the first waterproof layer, the fiber skeleton, and the second waterproof layer to form a three-layer structure, the raw materials for preparing the self-healing composite material are sprayed into the fiber skeleton of the three-layer structure.

[0173] D30. Add water and cure to obtain the waterproof board provided in this comparative example.

[0174] Comparative Example 3 Comparative Example 3 provides a waterproof board, which consists of a first waterproof layer, a second waterproof layer, and a fiber skeleton surface layer disposed between the first waterproof layer and the second waterproof layer.

[0175] wherein, The fiber framework surface layer is composed of a fiber framework and cement filled in the interspace of the fiber framework.

[0176] The thickness of the fiber framework surface layer is 25mm.

[0177] The structure of the fiber framework is composed of two net surfaces and a plurality of X-shaped fibers; The plurality of X-shaped fibers are arranged between the two net surfaces; The two net surfaces and the plurality of X-shaped fibers are integrally formed; The fiber diameter of the X-shaped fiber is 20μm.

[0178] The raw material for preparing the fiber framework is composed of the following components in parts by weight: 70 parts of polyethylene terephthalate, 20 parts of amino silane modified nano silicon dioxide, 8 parts of aliphatic thermoplastic polyurethane, 0.3 parts of antioxidant 1010.

[0179] The present comparative example also provides a preparation method of the waterproof board of the present comparative example, and the steps are as follows: D10. Preparation of fiber framework D101. Preparation of spinning solution: polyethylene terephthalate, amino silane modified nano silicon dioxide, aliphatic thermoplastic polyurethane, antioxidant 1010 and hexafluoroisopropanol are mixed. Among them, the total mass of the raw material for preparing the fiber framework and the solid-liquid ratio of hexafluoroisopropanol are 1:3.

[0180] D102. The fiber framework is prepared by electrospinning method.

[0181] D20. Preparation of cement slurry The cement is mixed with water under stirring. Among them, the amount of water added is 0.7L / kg.

[0182] D30. Preparation of waterproof board After sequentially laminating the first waterproof layer, the fiber framework and the second waterproof layer to form a three-layer structure, the self-repairing composite material slurry is injected into the fiber framework of the three-layer structure under the application of a predetermined pressure, and then solidified to obtain the flexible composite waterproof board based on the fiber framework provided by the present embodiment; wherein the predetermined pressure is 4MPa, and the solidification temperature is 25℃.

[0183] In order to verify the progressiveness of the flexible composite waterproof board based on the fiber framework and the preparation method thereof provided by the present embodiment, the performance of the waterproof boards prepared by the present embodiment and the comparative example before and after solidification is detected, and the performance before solidification is shown in Table 1, and the performance after solidification is shown in Table 2.

[0184]

[0185]

[0186] From the above table and the description of the drawings, at least the following conclusions can be drawn: (1) From the data of the examples and Comparative Example 1, the longitudinal tensile strength, the longitudinal elongation at break and the burst strength of the waterproof board before curing, and the compressive strength and the bending strength after curing are all higher than those of Comparative Example 1. It can be seen that the structure of the fiber framework has a great influence on the mechanical properties of the waterproof board, and the flexible composite waterproof board based on the fiber framework provided by the examples of the present application can significantly improve the mechanical properties of the waterproof board before and after curing.

[0187] (2) From the data of the examples and Comparative Example 2, in Comparative Example 2, even if the preparation raw materials of the powdered self-repairing composite material are directly filled into the fiber framework, and even if water is added for curing, the compressive strength and the bending strength of the waterproof board obtained are still lower than those of the examples. It can be seen that the preparation method of the flexible composite waterproof board based on the fiber framework provided by the examples of the present application can significantly improve the mechanical properties of the waterproof board by first preparing the self-repairing composite material into a slurry and then pressing it into the fiber framework.

[0188] (3) From the data of the examples and Comparative Example 3, in Comparative Example 3, no self-repairing microcapsules are contained, although the longitudinal tensile strength, the longitudinal elongation at break and the burst strength before curing, and the compressive strength and the bending strength after curing are all relatively high, they are still lower than those of the examples. It can be seen that the flexible composite waterproof board based on the fiber framework provided by the examples of the present application contains self-repairing microcapsules, which can improve the mechanical properties of the waterproof board to a certain extent. However, since Comparative Example 3 does not contain self-repairing microcapsules, the waterproof board no longer has the function of self-repairing.

[0189] (4) From the data of Example 1 to Example 7, the content of the self-repairing microcapsules and the fiber framework surface layer can significantly affect the mechanical properties of the waterproof board.

[0190] It should be noted that the present application is not limited to the above-described embodiments. The above-described embodiments are only examples, and embodiments having substantially the same structure and playing the same role and effect as the technical idea within the scope of the technical solutions of the present application are all included in the technical scope of the present application. In addition, within the scope of the main idea of the present application, various modifications that can be thought of by those skilled in the art, and other ways constructed by combining part of the constituent elements of the embodiments are also included in the scope of the present application.

Claims

1. A flexible composite waterproofing sheet based on a fibrous skeleton, characterized in that, The waterproof layer comprises two layers of waterproof layers and a fiber skeleton surface layer arranged between the two layers of waterproof layers; The fiber skeleton surface layer comprises a fiber skeleton and a self-repairing composite material filled in the interspace of the fiber skeleton; The raw material of the self-repairing composite material comprises the following components in parts by weight: 100 parts of cement, 1 part to 5 parts of self-repairing microcapsules; The core material of the self-repairing microcapsules comprises composite cement particles; The wall material of the self-repairing microcapsules comprises a mixture of 12-hydroxystearic acid, linolenic acid, modified titanium dioxide and modified molecular sieve.

2. The flexible composite underlayment based on a fiber skeleton according to claim 1, characterized in that, At least one of the following (1) to (12) characteristics is satisfied: (1) The wall material of the self-repairing microcapsules comprises the following components in parts by weight: 100 parts of linolenic acid, 2 parts to 4 parts of 12-hydroxystearic acid, 0.01 parts to 0.05 parts of modified titanium dioxide, 10 parts to 15 parts of modified molecular sieve; (2) The raw material of the composite cement particles comprises cement, bentonite, mesoporous silica, dispersant and binder; (3) The raw material of the composite cement particles comprises the following components in parts by weight: 100 parts of cement, 30 parts to 35 parts of bentonite, 10 parts to 12 parts of binder, 0.5 parts to 0.7 parts of dispersant, 0.3 parts to 0.5 parts of mesoporous silica; (4) The raw material of the modified titanium dioxide comprises nano-titanium dioxide and silane coupling agent; (5) The raw material of the modified molecular sieve comprises 3A molecular sieve, silane coupling agent and water; (6) The thickness of the fiber skeleton surface layer is 15 mm to 25 mm; (7) The thickness of the two layers of waterproof layers can be independently 0.4 mm to 0.6 mm; (8) The rigid reinforcing agent comprises modified nano-titanium dioxide; (9) The toughening agent comprises aliphatic thermoplastic polyurethane; (10) The antioxidant comprises at least one of antioxidant 1010 and antioxidant 168; (11) The raw material of the fiber skeleton comprises the following components in parts by weight: 60 parts to 75 parts of polyethylene terephthalate, 15 parts to 25 parts of rigid reinforcing agent, 5 parts to 10 parts of toughening agent, 0.2 parts to 0.5 parts of antioxidant; (12) The material of the waterproof layer comprises at least one of polyimide resin and polyethylene.

3. The flexible composite sheet based on a fibrous skeleton according to claim 1 or 2, characterized in that, The structure of the fiber skeleton comprises two net surfaces and a plurality of X-shaped fibers; The plurality of X-shaped fibers are arranged between the two net surfaces; The two net surfaces and the plurality of X-shaped fibers are integrally formed.

4. The fiber skeleton based flexible composite underlayment panel of claim 3, wherein, The fiber diameter of the X-shaped fiber is 10 μm to 30 μm.

5. A method of manufacturing a flexible composite waterproof sheet based on a fiber skeleton according to any one of claims 1 to 4, characterized by, The method comprises the following steps: Under a predetermined pressure, the self-repairing composite material slurry is injected into the fiber skeleton of the three-layer structure and then solidified; The three-layer structure comprises a first waterproof layer, a fiber skeleton and a second waterproof layer which are sequentially stacked.

6. The method for preparing the flexible composite waterproof board based on a fiber skeleton according to claim 5, characterized in that, The preparation of the fiber skeleton comprises the following steps: The raw material of the fiber skeleton is made into a fiber skeleton by using an electrospinning method.

7. The method for preparing a flexible composite waterproof board based on a fiber skeleton according to claim 6, characterized in that, In the step of making the raw material of the fiber skeleton into a fiber skeleton by using an electrospinning method, the preparation of the spinning solution comprises the following steps: Polyethylene terephthalate, rigid reinforcing agent, toughening agent, antioxidant and hexafluoroisopropanol are mixed.

8. The method for preparing the flexible composite waterproof board based on a fiber skeleton according to claim 7, characterized in that, The solid-liquid ratio of the total mass of the raw material of the fiber skeleton to hexafluoroisopropanol is 1:2 to 5.

9. The method of manufacturing a flexible composite waterproof sheet based on a fiber skeleton according to any one of claims 5 to 7, characterized in that, The temperature of the solidification is 20-35°C.

10. Use of a flexible composite sheet based on a fibrous skeleton according to any one of claims 1 to 4 in the field of engineering technology.

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