Tunnel high-adhesion-strength flame-retardant waterproof composite board, preparation method and application thereof

Abstract

The application belongs to the technical field of polymer materials, and proposes a high-adhesion-strength flame-retardant waterproof composite board for tunnels and a preparation method and application thereof, which comprises: a, a waterproof board layer, raw materials of which include a flame retardant A; b, a polyurethane layer, which is sprayed on the surface of the waterproof board layer and is prepared from polyols and isocyanate at an isocyanate index R=1-1.1, wherein the polyols include a chain extender, a foaming agent, a foam stabilizer, a catalyst, a polyether polyol, water and a flame retardant B; wherein the flame retardant A is microencapsulated red phosphorus modified by vinyl triethoxysilane, and the flame retardant B is microencapsulated red phosphorus modified by γ-aminopropyl triethoxysilane. Through the above technical scheme, the problem of poor adhesion strength between the waterproof board and the polyurethane in the composite board and poor flame-retardant performance of the waterproof composite board in the prior art is solved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of polymer materials, and relates to a high-adhesion-strength flame-retardant waterproof composite board for tunnels and a preparation method and application thereof. BACKGROUND

[0002] As an important part of transportation infrastructure, tunnel engineering requires waterproof, fireproof, and structural durability to ensure long-term safe operation. Traditional tunnel waterproofing techniques mainly rely on single-layer waterproof membranes or concrete self-waterproofing structures, but these methods have limitations in practical applications. For example, single-layer waterproof membranes have insufficient adhesion strength to the base surface, leading to peeling and leakage problems; concrete self-waterproofing structures are difficult to completely prevent water penetration due to material micro-cracks and pores. In addition, the complex internal environment of tunnels often faces challenges such as high humidity, temperature changes, and mechanical stress, which require higher durability and adaptability of waterproof materials.

[0003] In recent years, sprayed polyurethane materials have gradually become an important material in tunnel waterproofing engineering due to their excellent adhesion and mechanical properties. Polyurethane can form a high-strength bond with the concrete base surface, and has good elasticity and crack resistance, effectively adapting to the deformation of the tunnel structure. However, a single polyurethane layer still has deficiencies in fire resistance and long-term durability, especially under high-temperature or fire conditions, the flame-retardant properties of polyurethane need to be further improved. To overcome the above problems, the field of tunnel engineering has gradually developed a three-layer composite structure of "waterproof board-polyurethane-waterproof board".

[0004] However, although the three-layer structure has excellent performance, its construction steps are complex, the material usage is large, the cost is high, and it is difficult to meet the actual application requirements in some scenarios with extremely high adhesion strength requirements. For example, there are problems such as poor adhesion strength between the waterproof board and the polyurethane, easy leakage, poor flame retardant performance, and insufficient durability. For example, Chinese Patent No. 2023102972435 discloses a sprayed polyurethane insulation material for cold region tunnels and its application and construction method. The sprayed polyurethane insulation material disclosed in the patent uses a combination of various polyether polyols and polyester polyols to form a combined polyether, which can provide good flowability, good mutual solubility of A material, B material, and other additives, and excellent foam size stability. The use of flame-retardant polyester ether polyol and nano-particle grafted DOPO in A material improves the flame-retardant properties of the sprayed polyurethane and also improves the thermal insulation performance of the polyurethane. In specific applications, the sprayed polyurethane insulation material for cold region tunnels is sprayed on the surface of the self-adhesive waterproof board to form a sprayed polyurethane foam layer, which has flame-retardant and waterproof functions. However, the adhesion strength between the waterproof board and the polyurethane in the method disclosed in the patent is not explored. SUMMARY

[0005] The application provides a tunnel high-adhesion-strength flame-retardant waterproof composite board and a preparation method and application thereof, and solves the problems of poor adhesion strength between a waterproof board and polyurethane and poor flame-retardant performance of the waterproof composite board in the prior art.

[0006] The technical scheme of the application is implemented as follows:

[0007] The tunnel high-adhesion-strength flame-retardant waterproof composite board comprises:

[0008] a. a waterproof board layer, raw materials of which are composed of 22-24 wt% PE / EVA composite resin particles, 10-11 wt% high-density polyethylene, 18-19 wt% linear low-density polyethylene and 46-50 wt% flame-retardant masterbatch, wherein the flame-retardant masterbatch comprises 50 wt% flame retardant A and 50 wt% high-density polyethylene;

[0009] b. a polyurethane layer, which is sprayed on the surface of the waterproof board layer, raw materials of which are prepared by polyol and isocyanate at an isocyanate index R=1-1.1, and the polyol comprises 7.5-8.5 parts of 1,6-hexanediol, 1-1.3 parts of a foaming agent, 0.9-1.1 parts of a foam stabilizer, 1.4-1.6 parts of a catalyst, 65-85 parts of a polyether polyol, 2-3 parts of water and 32-36 parts of flame retardant B according to mass fraction; the catalyst is N,N-dimethylcyclohexylamine, stannous octoate and dibutyltin diacetate at a mass ratio of 0.8-1.2:0.8-1.2:1.1-1.2; the viscosity of the polyether polyol is 5000-7700 mpa·s, and the hydroxyl value is 480-520 mgKOH / g;

[0010] wherein flame retardant A is microencapsulated red phosphorus modified by vinyltriethoxysilane, and flame retardant B is microencapsulated red phosphorus modified by γ-aminopropyltriethoxysilane.

[0011] Preferably, the preparation method of the flame retardant A comprises the following steps:

[0012] Vinyltriethoxysilane is added into an ethanol aqueous solution, the pH is adjusted to 3-4, and stirring is performed to obtain a hydrolyzed silane solution;

[0013] Microencapsulated red phosphorus is dispersed in ethanol, and then the above hydrolyzed silane solution is added, hydrochloric acid aqueous solution is added dropwise to adjust the pH to 5-6, and reflux reaction is performed at 50-60 DEG C for 3-4 h, centrifugation is performed, the precipitate is taken, washing is performed, and drying is performed to obtain the flame retardant A; wherein the mass ratio of the microencapsulated red phosphorus to the vinyltriethoxysilane is 1:0.03-0.05.

[0014] Preferably, in the preparation method of the flame retardant A, the amount of the vinyltriethoxysilane and the aqueous ethanol solution is 1 g: 10-15 mL. Further, the amount of the vinyltriethoxysilane and the aqueous ethanol solution is 1 g: 12-15 mL.

[0015] Preferably, in the preparation method of the flame retardant A, the aqueous ethanol solution is composed of ethanol and water in a volume ratio of 9:1.

[0016] Preferably, in the preparation method of the flame retardant A, the pH is adjusted to 3-4 by acetic acid.

[0017] Preferably, in the preparation method of the flame retardant A, the amount of the microencapsulated red phosphorus and the ethanol is 1 g: 30-55 mL. Further, the amount of the microencapsulated red phosphorus and the ethanol is 1 g: 50-55 mL.

[0018] Preferably, in the preparation method of the flame retardant A, the stirring step includes a stirring rate of 300-500 rpm and a stirring time of 30-35 min. Further, the stirring rate is 400-500 rpm.

[0019] Preferably, in the preparation method of the flame retardant A, the ultrasonic step includes an ultrasonic power of 200-400 W, a frequency of 20-40 kHz, and an ultrasonic time of 15-20 min.

[0020] Preferably, in the preparation method of the flame retardant A, the centrifugation step includes a rotation speed of 4500-5000 rpm and a time of 9-10 min.

[0021] Preferably, in the preparation method of the flame retardant A, the washing step includes washing 3-5 times with anhydrous ethanol.

[0022] Preferably, in the preparation method of the flame retardant A, the drying step includes vacuum drying at 60-70 °C for 12-15 hours.

[0023] Preferably, the preparation method of the flame retardant B includes the following steps:

[0024] The γ-aminopropyltriethoxysilane is added to the aqueous ethanol solution, the pH is adjusted to 4-5, and stirring is performed to obtain a hydrolyzed silane solution;

[0025] The microencapsulated red phosphorus is dispersed in ethanol, ultrasonicated, then the hydrolyzed silane solution is added, the pH is adjusted to 7-8 by dropwise adding a trimethylol aminomethane aqueous solution, and refluxing reaction is performed at 60-70 °C for 5-6 h, centrifugation is performed, the precipitate is taken, washed, and dried to obtain the flame retardant B; wherein the mass ratio of the microencapsulated red phosphorus and the γ-aminopropyltriethoxysilane is 1:0.03-0.05.

[0026] Preferably, in the preparation method of the flame retardant B, the amount of γ-aminopropyl triethoxysilane and the aqueous ethanol solution is 1 g: 10-15 mL. Further, the amount of γ-aminopropyl triethoxysilane and the aqueous ethanol solution is 1 g: 10-12 mL.

[0027] Preferably, in the preparation method of the flame retardant B, the amount of microencapsulated red phosphorus and ethanol is 1 g: 30-55 mL. Further, the amount of microencapsulated red phosphorus and ethanol is 1 g: 50-55 mL.

[0028] Preferably, in the preparation method of the flame retardant B, the aqueous ethanol solution is composed of ethanol and water in a volume ratio of 9:1.

[0029] Preferably, in the preparation method of the flame retardant B, the pH is adjusted to 4-5 with acetic acid.

[0030] Preferably, in the preparation method of the flame retardant B, the stirring step conditions include a stirring rate of 300-500 rpm and a stirring time of 30-35 min. Further, the stirring rate is 400-500 rpm.

[0031] Preferably, in the preparation method of the flame retardant B, the ultrasonic step conditions include an ultrasonic power of 200-400 W, a frequency of 20-40 kHz, and an ultrasonic time of 15-20 min.

[0032] Preferably, in the preparation method of the flame retardant B, the centrifugation step conditions include a rotation speed of 4500-5000 rpm and a time of 9-10 min.

[0033] Preferably, in the preparation method of the flame retardant B, the washing step conditions include washing 3-5 times with anhydrous ethanol.

[0034] Preferably, in the preparation method of the flame retardant B, the drying step conditions include vacuum drying at 60-70℃ for 12-15 hours.

[0035] Preferably, the preparation method of the microencapsulated red phosphorus includes the following steps:

[0036] 1.0 g of red phosphorus is added to 8.0-12.0 g of 1 wt% dopamine hydrochloride solution for ultrasonic dispersion to obtain a dispersion liquid; under stirring, the pH is adjusted to 8.5-9.0 by adding a tris-hydroxymethyl aminomethane aqueous solution; then, under an inert gas atmosphere, the reaction is stirred at room temperature for 10-12 h; after the reaction is completed, the pH is adjusted to 5.8-6.4 with hydrochloric acid, centrifuged, the precipitate is taken, washed, and dried to obtain microencapsulated red phosphorus.

[0037] Preferably, in the preparation method of the microencapsulated red phosphorus, the ultrasonic step conditions include: ultrasonic dispersion time of 15-20 min, ultrasonic power of 200-400 W, and frequency of 20-40 kHz.

[0038] Preferably, in the preparation method of the microencapsulated red phosphorus, when the aqueous solution of tris (hydroxymethyl) aminomethane is added under stirring, the stirring step conditions include: stirring rate of 450-550 rpm and stirring time of 30-35 min.

[0039] Preferably, in the preparation method of the microencapsulated red phosphorus, the stirring rate in the stirring reaction step is 450-550 rpm.

[0040] Preferably, in the preparation method of the microencapsulated red phosphorus, the pH is adjusted to 5.8-6.4 by dropwise adding 0.95-1.05 mol / L hydrochloric acid.

[0041] Preferably, in the preparation method of the microencapsulated red phosphorus, the centrifugation step conditions include: rotation speed of 4500-5000 rpm and centrifugation time of 9-10 min.

[0042] Preferably, in the preparation method of the microencapsulated red phosphorus, the washing step conditions include: alternating washing 3-5 times with deionized water and anhydrous ethanol.

[0043] Preferably, in the preparation method of the microencapsulated red phosphorus, the drying step conditions include: drying in a vacuum drying oven at 60-70℃ for 12-15 hours.

[0044] Preferably, in the preparation method of the microencapsulated red phosphorus, the red phosphorus is first pretreated, and the specific steps include: taking red phosphorus, ultrasonically cleaning with anhydrous ethanol, then transferring to a 0.08-0.12 mol / L hydrochloric acid solution for stirring, and then washing with deionized water until neutral, and drying.

[0045] Preferably, in the pretreatment step, the amount of red phosphorus, anhydrous ethanol, and hydrochloric acid solution is 5g: 180-250mL: 80-120mL.

[0046] Preferably, the foaming agent is selected from one or more of trans-1-chloro-3,3,3-trifluoropropene, isopentane, and pentafluoropropane.

[0047] Preferably, the foam stabilizer is AK-8809 and / or AK-8810 of Jiangsu Meiside Chemical Co., Ltd.

[0048] Preferably, the isocyanate is carbodiimide-modified MDI.

[0049] Preferably, the carbodiimide-modified MDI is WANNATE CDMDI-100H from Wanhua Chemical Group Co., Ltd.

[0050] Preferably, the PE / EVA composite resin particles have a density of 0.855-0.955 g / cm 3 , a melt flow rate of 0.8-3.0 g / 10 min, and a VA content of 11.5-15%.

[0051] Preferably, the PE / EVA composite resin particles have a melting point of 105-130℃, a density of 0.855-0.955 g / cm 3 , a melt flow rate (190℃ / 2.16 kg) of 0.8-3.0 g / 10 min, a VA content of 11.5-15%, a tensile strength of ≥16 MPa, and an elongation at break of ≥600%.

[0052] Preferably, the PE / EVA composite resin particles are FFB-109 from Hebei Tiewenxincheng New Material Technology Co., Ltd.

[0053] Preferably, the high-density polyethylene has a density of 0.910-0.990 g / cm 3 and a melt flow rate of ≤1.0 g / 10 min.

[0054] Preferably, the linear low-density polyethylene has a density of 0.910-0.990 g / cm 3 and a melt flow rate of ≤1.0 g / 10 min.

[0055] Preferably, the preparation method of the waterproof board layer comprises the following steps:

[0056] A. mixing the flame retardant A and the high-density polyethylene, feeding into a double-screw granulation extruder, and performing melt mixing, extrusion, and granulation to obtain a flame retardant master batch;

[0057] B. mixing the PE / EVA composite resin particles, the high-density polyethylene, the linear low-density polyethylene, and the flame retardant master batch to obtain a mixture, melt extruding the mixture through a double-screw sheet extruder, cooling and drawing through a three-roll calender, and winding to obtain a waterproof board.

[0058] Preferably, the temperature conditions of each zone of the double-screw granulation extruder include 175±10℃, 180±10℃, 185±10℃, 185±10℃, 190±10℃, 185±10℃, 185±10℃, and 185±10℃; the die temperature condition includes 185±10℃; the vacuum degree is ≤-0.06 MPa; and the water tank temperature is ≤50℃.

[0059] Preferably, the temperature control of each zone of the double screw sheet extruder barrel is 175±10℃, 180±10℃, 185±10℃, 190±10℃, 195±10℃, 200±10℃; the die head temperature condition includes 200±10℃; and the vacuum degree is -0.06 MPa.

[0060] The application further provides a preparation method of the high-adhesion-strength flame-retardant waterproof composite board for tunnels.

[0061] The polyol and the isocyanate are preheated to 30-40℃ respectively, taken out after being kept for 50-60 min, and then mixed and stirred to obtain the polyurethane layer raw material to be sprayed;

[0062] The polyurethane layer raw material to be sprayed is filled into a polyurethane spraying machine, and sprayed onto the surface of the waterproof board layer at a spraying speed of 4-9 kg / min; after repeated spraying for multiple times, a sprayed polyurethane layer with a thickness of 70 mm is obtained, and the composite board is prepared.

[0063] Preferably, the preparation method of the polyol comprises: adding 1,6-hexanediol, a blowing agent, water, a foam stabilizer and a catalyst into polyether polyol and stirring uniformly, and then adding the flame retardant B, and stirring to uniformly mix the components, so that the polyol is prepared.

[0064] Preferably, in the preparation method of the high-adhesion-strength flame-retardant waterproof composite board for tunnels, the stirring rate is 1000-1500 rpm, and the stirring time is 10-12 min.

[0065] Preferably, the thickness of the waterproof board layer is 1.0-1.5 mm, and preferably, according to the Railway Tunnel Waterproofing Materials Part 1: Waterproof Board (QCR 562.1-2018) standard, the standard thicknesses actually used are 1.0 mm, 1.2 mm or 1.5 mm.

[0066] Preferably, the thickness of the polyurethane layer is 70 mm.

[0067] The application further provides an application of the high-adhesion-strength flame-retardant waterproof composite board for tunnels, which is used for constructing a tunnel structure.

[0068] The tunnel structure is composed of a tunnel rock wall, an initial support shotcrete layer, a geotextile layer, a composite board layer and a secondary lining concrete layer from outside to inside; and the composite board layer adopts the high-adhesion-strength flame-retardant waterproof composite board for tunnels.

[0069] The application has the following beneficial effects:

[0070] 1. The present application proposes a "high adhesive strength flame-retardant polyurethane-waterproof board" double-layer structure. The structure optimizes the formula of the polyurethane layer and the waterproof board layer, significantly optimizes the adhesion effect between the polyurethane layer and the waterproof board layer, thereby eliminating one layer of the waterproof board in the traditional three-layer structure. This double-layer structure not only simplifies the construction process, significantly reduces the material cost and construction difficulty; secondly, adding silane-modified microencapsulated red phosphorus (RP@PDA-SiB) as flame retardant B in the sprayed polyurethane improves the overall structure's flame retardant performance, further adding silane-modified microencapsulated red phosphorus (RP@PDA-SiA) as flame retardant A in the waterproof board improves the overall structure's flame retardant performance, meets the tunnel fire safety requirements, and the structure and formula together make the composite board maintain excellent waterproof, fireproof and durable performance, which has great application prospect in the tunnel engineering field with extremely high adhesion strength requirements.

[0071] 2. The silane-modified microencapsulated red phosphorus (RP@PDA-SiA) and silane-modified microencapsulated red phosphorus (RP@PDA-SiB) used in the present application improve the flame retardant performance of the sprayed polyurethane and the waterproof board compared to unmodified microencapsulated red phosphorus.

[0072] 3. The present application selects specific chain extenders 1,6-hexanediol and catalysts such as dibutyl tin diacetate, and mixes them with different components such as polyether polyol to obtain a polyol component. During the spraying process, polyether polyol and isocyanate can fully contact and wet the waterproof board surface, and interact on the surface of the waterproof board to form a polyurethane polymer. After curing, the sprayed polyurethane block can be combined to the surface of the waterproof board with a peel strength greater than 1.4 kN / mm. BRIEF DESCRIPTION OF DRAWINGS

[0073] The present application will be further described in detail below in combination with the drawings and specific embodiments.

[0074] Figure 1 The sample clamp schematic diagram for peel strength test of the tunnel high adhesive strength flame-retardant waterproof composite board of the present application.

[0075] In the figure, 1 is a clamp, 2 is a waterproof board, and 3 is a sprayed polyurethane block. DETAILED DESCRIPTION

[0076] The technical solutions in the embodiments of the present application will be described in detail below in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0077] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety for the teachings relevant to the sentence and / or paragraph in which the reference is presented. The entire contents of any patent, patent application, and / or publication referenced herein are incorporated by reference in their entirety for the teachings relevant to the sentence and / or paragraph in which the reference is presented. The summary of the application does not necessarily encompass all aspects of the application.

[0078] The following examples and comparative examples are described below:

[0079] Blowing agent HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene), HFC-245fa (pentafluoropropane) were purchased from Quanzhou Yuxi New Material Technology Co., Ltd.

[0080] Foam stabilizer AK-8809 and AK-8810 were purchased from Jiangsu Meiside Chemical Co., Ltd.

[0081] Polyether polyol INOVOL was purchased from Shandong INOVOL Polyurethane Co., Ltd. ® R404 or INOVOL ® R635A; INOVOL ® The viscosity of R404 is 6100-7700 mpa.s (25°C), and the hydroxyl value is 480-520 mgKOH / g, INOVOL ® The viscosity of R635A is 5000-7000 mpa.s (25°C), and the hydroxyl value is 480-520 mgKOH / g;

[0082] Carbodiimide modified MDI (WANNATE CDMDI-100H) was purchased from Wanhua Chemical Group Co., Ltd.

[0083] High-density polyethylene BL3 was purchased from Iran Petrochemical Company.

[0084] Linear low-density polyethylene 9047 was purchased from Daqing Petrochemical Company.

[0085] PE / EVA composite resin particles were provided by Hebei Tiefuwuxin Material Technology Co., Ltd., with a brand name of FFB-109, meeting the indicators: melting point 105-130℃, density 0.855-0.955g / cm 3 , melt flow rate (190℃ / 2.16kg) 0.8-3.0g / 10min, VA content 11.5-15%, tensile strength ≥16MPa, elongation at break ≥600%.

[0086] Preparation Example 1

[0087] Preparation of microencapsulated red phosphorus

[0088] ① Take 5.0g of red phosphorus powder (RP), ultrasonically clean with 200 mL of anhydrous ethanol for 20 minutes, then transfer to 100 mL of 0.1 mol / L dilute hydrochloric acid solution and stir for 10 minutes, then wash with 500 mL of deionized water for 3 times until neutral, and dry in a 60℃ vacuum drying oven for 24 hours to obtain pretreated red phosphorus;

[0089] ② Weigh 1.0 g of dopamine hydrochloride (PDA), add 99.0 g of deionized water, and stir until completely dissolved to prepare a 1wt% dopamine hydrochloride solution;

[0090] ③ Take 1.0 g of pretreated red phosphorus, add 10.0 g of 1wt% dopamine hydrochloride solution, and ultrasonically disperse for 15 minutes at an ultrasonic power of 200W and a frequency of 20kHz to obtain a dispersion liquid; then slowly add 0.1 mol / L Tris base to the dispersion liquid while stirring to adjust the pH to 8.8, and stir at 500 rpm for 30 minutes to obtain a mixed solution. Transfer the mixed solution to a three-necked flask, and stir at 500 rpm in a constant temperature water bath at 25℃ under nitrogen protection for 12 hours. After the reaction is completed, adjust the pH to 6.0 by adding 1 mol / L hydrochloric acid, centrifuge at 5000 rpm for 10 minutes, discard the supernatant, and wash the precipitate with 50 mL of deionized water and 50 mL of anhydrous ethanol alternately for 3 times. Finally, dry the product in a 60℃ vacuum drying oven for 12 hours to obtain microencapsulated red phosphorus (RP@PDA).

[0091] Preparation Example 2

[0092] Preparation of flame retardant A (RP@PDA-SiA)

[0093] Add 1 g of KH-151 (vinyl triethoxysilane) to 12 mL of an aqueous ethanol solution (ethanol to water volume ratio 9:1), adjust the pH to 3 with acetic acid, and stir at room temperature for 30 minutes to hydrolyze the silane (stirring rate 500 rpm) to obtain a hydrolyzed silane solution;

[0094] Take 33 g of dried RP@PDA prepared in Preparation Example 1 and disperse in 1650 mL of ethanol, ultrasonic for 15 minutes (ultrasonic power 200 W, frequency 20 kHz), then slowly add the above hydrolyzed silane solution, adjust pH to 5 by dropwise adding 1 mol / L hydrochloric acid aqueous solution, reflux at 60°C for 3 hours, centrifuge (5000 rpm for 10 minutes), take the precipitate, wash (with anhydrous ethanol for 3 times), vacuum dry at 60°C for 12 hours to obtain the flame retardant A (RP@PDA-SiA).

[0095] Preparation Example 3

[0096] Preparation of flame retardant A (RP@PDA-SiA)

[0097] Take 33 g of dried RP@PDA prepared in Preparation Example 1 and disperse in 1650 mL of ethanol, ultrasonic for 15 minutes (ultrasonic power 200 W, frequency 20 kHz), then slowly add the above hydrolyzed silane solution, adjust pH to 5 by dropwise adding 1 mol / L hydrochloric acid aqueous solution, reflux at 60°C for 3 hours, centrifuge (5000 rpm for 10 minutes), take the precipitate, wash (with anhydrous ethanol for 3 times), vacuum dry at 60°C for 12 hours to obtain the flame retardant A (RP@PDA-SiA).

[0098] Take 33 g of dried RP@PDA prepared in Preparation Example 1 and disperse in 1650 mL of ethanol, ultrasonic for 15 minutes (ultrasonic power 200 W, frequency 20 kHz), then slowly add the above hydrolyzed silane solution, adjust pH to 5 by dropwise adding 1 mol / L hydrochloric acid aqueous solution, reflux at 60°C for 3 hours, centrifuge (5000 rpm for 10 minutes), take the precipitate, wash (with anhydrous ethanol for 3 times), vacuum dry at 60°C for 12 hours to obtain the flame retardant A (RP@PDA-SiA).

[0099] Preparation Example 4

[0100] Preparation of flame retardant B (RP@PDA-SiB)

[0101] Take 33 g of dried RP@PDA prepared in Preparation Example 1 and disperse in 1650 mL of ethanol, ultrasonic for 15 minutes (ultrasonic power 200 W, frequency 20 kHz), then slowly add the above hydrolyzed silane solution, adjust pH to 5 by dropwise adding 1 mol / L hydrochloric acid aqueous solution, reflux at 60°C for 3 hours, centrifuge (5000 rpm for 10 minutes), take the precipitate, wash (with anhydrous ethanol for 3 times), vacuum dry at 60°C for 12 hours to obtain the flame retardant A (RP@PDA-SiA).

[0102] Take 33 g of dried RP@PDA prepared in Preparation Example 1 and disperse in 1650 mL of ethanol, ultrasonic for 15 minutes (ultrasonic power 200 W, frequency 20 kHz), then slowly add the above hydrolyzed silane solution, adjust pH to 5 by dropwise adding 1 mol / L hydrochloric acid aqueous solution, reflux at 60°C for 3 hours, centrifuge (5000 rpm for 10 minutes), take the precipitate, wash (with anhydrous ethanol for 3 times), vacuum dry at 60°C for 12 hours to obtain the flame retardant A (RP@PDA-SiA).

[0103] Preparation Example 5

[0104] Preparation of flame retardant B (RP@PDA-SiB)

[0105] 1 g of KH-550 (γ-aminopropyltriethoxysilane) was added to 15 mL of an aqueous ethanol solution (volume ratio of ethanol to water 9:1), the pH was adjusted to 5 with acetic acid, and hydrolysis was carried out at room temperature for 35 min with stirring (stirring rate 500 rpm) to obtain a hydrolyzed silane solution;

[0106] 33 g of dried RP@PDA prepared in Preparation Example 1 was taken and dispersed in 1100 mL of ethanol, and ultrasonication was carried out for 15 min (ultrasonic power 400 W, frequency 40 kHz), then the above hydrolyzed silane solution was slowly added, a 0.1 mol / L aqueous solution of trimethylol aminomethane was added dropwise to adjust the pH to 8, and reflux reaction was carried out at 70°C for 5 h, followed by centrifugation (4500 rpm for 9 min), and the precipitate was taken and washed (5 times with anhydrous ethanol) and vacuum dried at 70°C for 15 h to obtain flame retardant B (RP@PDA-SiB).

[0107] Example 1

[0108] A high-adhesion-strength flame-retardant waterproof composite board for tunnel use, comprising: a waterproof board layer and a polyurethane layer sprayed on the surface of the waterproof board layer;

[0109] The raw material of the waterproof board layer is composed of 23 wt% PE / EVA composite resin particles, 10.5 wt% high-density polyethylene (BL3), 18.5 wt% linear low-density polyethylene (9047), and 48 wt% flame-retardant masterbatch: the flame-retardant masterbatch comprises 50 wt% flame retardant A (prepared in Preparation Example 2) and 50 wt% high-density polyethylene (BL3);

[0110] The raw material of the polyurethane layer is prepared by mixing polyol and isocyanate (carbodiimide-modified MDI) at an isocyanate index R = 1.05; in terms of mass parts, the polyol comprises 8 parts of 1,6-hexanediol, 1 part of blowing agent (HFO-1233zd(E)), 1 part of foam stabilizer (mass ratio 1:1 of AK-8809 and AK-8810), 1.5 parts of catalyst, 70 parts of polyether polyol (INOVOL ® R404), 2.5 parts of water, and 34 parts of flame retardant B (prepared in Preparation Example 4); the catalyst is dimethylcyclohexylamine, stannous octoate, and dibutyl tin diacetate at a mass ratio of 1:1:1.2;

[0111] The preparation method of the composite board comprises the following steps:

[0112] S1, preparing a waterproof board layer, comprising the following steps:

[0113] A, mixing the flame retardant A and the high-density polyethylene (BL3), feeding into a twin-screw granulation extruder, carrying out melt mixing, extrusion, and granulation to obtain a flame retardant masterbatch; the temperature conditions of each zone of the twin-screw granulation extruder include 175°C, 180°C, 185°C, 185°C, 190°C, 185°C, 185°C, and 185°C; the temperature condition of the die head includes 185°C; the vacuum degree is -0.06 MPa; and the water tank temperature is 50°C;

[0114] B, mixing the PE / EVA composite resin particles, the high-density polyethylene, the linear low-density polyethylene, and the flame retardant masterbatch to obtain a mixture, melt extruding the mixture through a twin-screw sheet extruder, extruding through a T-shaped die head, and extruding to a three-roller calender for cooling and traction, and winding up to obtain a waterproof board; the temperature control of each zone of the barrel of the twin-screw sheet extruder is 175°C, 180°C, 185°C, 190°C, 195°C, and 200°C; the temperature condition of the die head includes 200°C; and the vacuum degree is -0.06 MPa.

[0115] S2, preparing a polyurethane layer raw material to be sprayed, including the following steps:

[0116] The 1,6-hexanediol, the blowing agent (HFO-1233zd (E)), the water, the foam stabilizer, and the catalyst are added to the polyether polyol and stirred uniformly, and then the flame retardant B is added, and after the components are uniformly mixed by stirring, a polyol raw material is prepared; the polyol raw material and the isocyanate are preheated to 35°C, and after being kept for 55 min, they are taken out, and then mixed and stirred to obtain a polyurethane layer raw material to be sprayed.

[0117] S3, injecting the polyurethane layer raw material to be sprayed prepared in step S2 into a polyurethane spraying machine, spraying onto the surface of a waterproof board layer (the waterproof board prepared in step S1, the waterproof board having a thickness of 1.2 mm), and spraying repeatedly at a spraying speed of 6 kg / min, to obtain a sprayed polyurethane layer having a thickness of 70 mm, so as to prepare a composite board.

[0118] Example 2

[0119] A kind of high adhesive strength flame-retardant waterproof composite board for tunnel, comprising: waterproof board layer and the polyurethane layer sprayed on the surface of the waterproof board layer;

[0120] The raw material of the waterproof board layer is composed of 24wt% PE / EVA composite resin particles FFB-109, 11wt% high-density polyethylene (BL3), 19wt% linear low-density polyethylene (9047), and 46wt% flame retardant masterbatch, and the flame retardant masterbatch includes 50wt% flame retardant A (prepared in preparation example 3) and 50wt% high-density polyethylene (BL3).

[0121] The polyurethane layer raw material is prepared by mixing polyol and isocyanate (carbodiimide modified MDI) at an isocyanate index R = 1; the polyol includes 7.5 parts of 1,6-hexanediol, 1.1 parts of blowing agent (HFC-245fa), 0.9 parts of foam stabilizer (mass ratio 1:1 of AK-8809 and AK-8810), 1.6 parts of catalyst, 65 parts of polyether polyol (INOVOL ® R404), 3 parts of water, and 36 parts of flame retardant B (prepared in Preparation Example 5); the catalyst is dimethylcyclohexylamine, stannous octoate, and dibutyl tin diacetate at a mass ratio of 0.8:1.2:1.1;

[0122] The preparation method of the composite board comprises the following steps:

[0123] S1, preparing a waterproof board layer, comprising the following steps:

[0124] A, mixing the flame retardant A and the high-density polyethylene (BL3), and feeding into a double-screw granulation extruder to perform melt mixing, extrusion, and granulation to obtain a flame retardant master batch; the temperature conditions of each zone of the double-screw granulation extruder include 185°C, 190°C, 195°C, 195°C, 200°C, 195°C, 195°C, and 195°C; the die head temperature condition includes 195°C; the vacuum degree is -0.06 MPa; and the water tank temperature is 40°C.

[0125] B, mixing the PE / EVA composite resin particles, the high-density polyethylene, the linear low-density polyethylene, and the flame retardant master batch to obtain a mixture, melt extruding the mixture through a double-screw sheet extruder, extruding through a T-shaped die head, cooling and pulling through a three-roll calender, and winding to obtain a waterproof board; the temperature control of each zone of the barrel of the double-screw sheet extruder is 185°C, 190°C, 195°C, 200°C, 205°C, and 210°C; the die head temperature condition includes 210°C; and the vacuum degree is -0.06 MPa.

[0126] S2, preparing a polyurethane layer raw material to be sprayed, comprising the following steps:

[0127] The 1,6-hexanediol, the blowing agent (HFO-1233zd (E)), the water, the foam stabilizer, and the catalyst are added to the polyether polyol and stirred uniformly, and then the flame retardant B is added, and after stirring to uniformly mix the components, the polyol raw material is prepared; the polyol raw material and the isocyanate are preheated to 40°C, taken out after maintaining for 50 min, and then mixed and stirred to obtain the polyurethane layer raw material to be sprayed.

[0128] S3, the polyurethane layer raw material prepared in step S2 is added to a polyurethane spraying machine, and sprayed onto the surface of the waterproof board layer (waterproof board prepared in step S1, waterproof board thickness 1.2 mm), the spraying speed is 4 kg / min, after repeated spraying for multiple times, the sprayed polyurethane layer thickness is 70 mm, and the composite board is prepared.

[0129] Example 3

[0130] The tunnel high-bonding-strength flame-retardant waterproof composite board comprises a waterproof board layer and a polyurethane layer sprayed on the surface of the waterproof board layer.

[0131] The raw material of the waterproof board layer is composed of 22 wt% PE / EVA composite resin particles FFB-109, 10 wt% high-density polyethylene (BL3), 18 wt% linear low-density polyethylene (9047) and 50 wt% flame-retardant masterbatch, and the flame-retardant masterbatch comprises 50 wt% flame-retardant agent A (prepared in the preparation example 2) and 50 wt% high-density polyethylene (BL3).

[0132] The polyurethane layer raw material is prepared by mixing polyol and isocyanate (carbodiimide modified MDI) at an isocyanate index R = 1.1; the polyol comprises 8.5 parts of 1,6-hexanediol, 0.9 parts of foaming agent (isopentane), 1.1 parts of foam stabilizer (mass ratio 1:1 of AK-8809 and AK-8810), 1.4 parts of catalyst, 85 parts of polyether polyol (INOVOL ® R404), 2 parts of water and 32 parts of flame-retardant agent B (prepared in the preparation example 4); the catalyst is dimethylcyclohexylamine, stannous octoate and dibutyl tin diacetate at a mass ratio of 1.2:0.8:1.2;

[0133] The preparation method of the composite board comprises the following steps:

[0134] S1, preparing a waterproof board layer, comprising the following steps:

[0135] A, mixing the flame-retardant agent A and the high-density polyethylene (BL3), feeding into a double-screw granulation extruder, and carrying out melt mixing, extrusion and granulation to obtain a flame-retardant masterbatch; the temperature conditions of each zone of the double-screw granulation extruder include 165℃, 170℃, 175℃, 175℃, 180℃, 175℃, 175℃ and 175℃; the die head temperature condition includes 175℃; the vacuum degree is -0.06 MPa; and the water tank temperature is 40℃.

[0136] B, mixing the PE / EVA composite resin particles, high-density polyethylene, linear low-density polyethylene and flame-retardant masterbatch to obtain a mixture, melting and extruding the mixture through a double-screw sheet extruder, extruding through a T-shaped die, cooling and drawing through a three-roller calender, winding to obtain a waterproof board; the temperature of each zone of the barrel of the double-screw sheet extruder is controlled at 165°C, 170°C, 175°C, 180°C, 185°C and 190°C; the temperature of the head of the double-screw sheet extruder is 190°C; the vacuum degree is -0.06 MPa.

[0137] S2, preparing a polyurethane layer raw material to be sprayed, including the following steps:

[0138] 1,6-hexanediol, a blowing agent (HFO-1233zd (E)), water, a foam stabilizer and a catalyst are added to the polyether polyol and stirred uniformly, then after the flame retardant B is added, the components are uniformly mixed after stirring, and then the polyurethane layer raw material to be sprayed is prepared; the polyurethane layer raw material to be sprayed is prepared by preheating the polyol raw material and isocyanate to 30°C, keeping for 60 min, then mixing and stirring.

[0139] S3, injecting the polyurethane layer raw material to be sprayed prepared in step S2 into a polyurethane spraying machine, spraying onto the surface of the waterproof board layer (the waterproof board prepared in step S1, the waterproof board thickness is 1.2 mm), the spraying speed is 9 kg / min, after repeating the spraying for multiple times, the sprayed polyurethane layer thickness is 70 mm, and then a composite board is prepared.

[0140] Example 4

[0141] The tunnel high-bonding-strength flame-retardant waterproof composite board comprises a waterproof board layer and a polyurethane layer sprayed on the surface of the waterproof board layer.

[0142] The raw material of the waterproof board layer is composed of 23 wt% PE / EVA composite resin particles, 10.5 wt% high-density polyethylene (BL3), 18.5 wt% linear low-density polyethylene (9047) and 48 wt% flame-retardant masterbatch; the flame-retardant masterbatch comprises 50 wt% flame retardant A (prepared in preparation example 2) and 50 wt% high-density polyethylene (BL3);

[0143] The polyurethane layer raw material is prepared by mixing the polyol and isocyanate (carbodiimide modified MDI) at an isocyanate index R = 1.05; the polyol comprises 8 parts of 1,6-hexanediol, 1 part of a blowing agent (HFO-1233zd (E)), 1 part of a foam stabilizer (AK-8809 and AK-8810 at a mass ratio of 1:1), 1.5 parts of a catalyst, 80 parts of a polyether polyol (INOVOL ®R404), 2.5 parts of water and 34 parts of the flame retardant B (prepared in Preparation Example 5); the catalyst is dimethylcyclohexylamine, stannous octoate and dibutyl tin diacetate in a mass ratio of 1:1:1.1;

[0144] The preparation method of the composite board comprises the following steps:

[0145] S1, preparing a waterproof board layer, comprising the following steps:

[0146] A, mixing the flame retardant A and the high-density polyethylene (BL3) and feeding into a double-screw granulation extruder to perform melt mixing, extrusion and granulation to obtain a flame retardant master batch; the temperature conditions of each zone of the double-screw granulation extruder include 175℃, 180℃, 185℃, 185℃, 190℃, 185℃, 185℃ and 185℃; the die head temperature condition includes 185℃; the vacuum degree is -0.06 MPa; and the water tank temperature is 50℃.

[0147] B, mixing the PE / EVA composite resin particles, the high-density polyethylene, the linear low-density polyethylene and the flame retardant master batch to obtain a mixture, melt extruding the mixture through a double-screw sheet extruder, extruding through a T-shaped die head, cooling and drawing through a three-roller calender, winding up to obtain a waterproof board; the temperature control of each zone of the double-screw sheet extruder barrel includes 175℃, 180℃, 185℃, 190℃, 195℃ and 200℃; the die head temperature condition includes 200℃; and the vacuum degree is -0.06 MPa.

[0148] S2, preparing a polyurethane layer raw material to be sprayed, comprising the following steps:

[0149] 1,6-hexanediol, a blowing agent (HFO-1233zd(E)), water, a foam stabilizer and a catalyst are added into the polyether polyol and stirred uniformly, then the flame retardant B is added, and after the components are uniformly mixed through stirring, the polyol raw material is prepared; the polyol raw material and the isocyanate are preheated to 35℃, taken out after being kept for 55 min, and then mixed and stirred to obtain the polyurethane layer raw material to be sprayed.

[0150] S3, the polyurethane layer raw material to be sprayed prepared in step S2 is injected into a polyurethane spraying machine, sprayed onto the surface of the waterproof board layer (the waterproof board prepared in step S1, the waterproof board thickness is 1.2 mm), the spraying speed is 6 kg / min, and after repeated spraying for multiple times, the sprayed polyurethane layer thickness is 70 mm, so that the composite board is prepared.

[0151] Example 5

[0152] The tunnel high-adhesion-strength flame-retardant waterproof composite board comprises a waterproof board layer and a polyurethane layer sprayed on the surface of the waterproof board layer.

[0153] The raw material of the waterproof board layer is composed of 23wt% PE / EVA composite resin particles, 10.5wt% high-density polyethylene (BL3), 18.5wt% linear low-density polyethylene (9047), and 48wt% flame-retardant masterbatch: the flame-retardant masterbatch includes 50wt% flame retardant A (prepared in Preparation Example 3) and 50wt% high-density polyethylene (BL3);

[0154] The raw material of the polyurethane layer is prepared by polyol and isocyanate (carbodiimide modified MDI) at an isocyanate index R = 1; in terms of mass fraction, the polyol includes 8 parts of 1,6-hexanediol, 1 part of foaming agent (HFO-1233zd (E)), 1 part of foam stabilizer (AK-8809 and AK-8810 at a mass ratio of 1:1), 1.5 parts of catalyst, 75 parts of polyether polyol (INOVOL ® R404), 2.5 parts of water, and 34 parts of flame retardant B (prepared in Preparation Example 4); the catalyst is dimethylcyclohexylamine, stannous octoate, and dibutyl tin diacetate at a mass ratio of 1.2:1:1.2;

[0155] The preparation method of the composite board includes the following steps:

[0156] S1, preparing a waterproof board layer, including the following steps:

[0157] A, mixing the flame retardant A and the high-density polyethylene (BL3), and feeding into a double-screw granulation extruder to perform melt mixing, extrusion, and granulation to obtain a flame-retardant masterbatch; the temperature conditions of each zone of the double-screw granulation extruder include 175℃, 180℃, 185℃, 185℃, 190℃, 185℃, 185℃, and 185℃; the die head temperature condition includes 185℃; the vacuum degree is -0.06MPa; and the water tank temperature is 50℃;

[0158] B, mixing the PE / EVA composite resin particles, the high-density polyethylene, the linear low-density polyethylene, and the flame-retardant masterbatch to obtain a mixture, melt-extruding the mixture through a double-screw sheet extruder, extruding through a T-shaped die head, cooling and pulling through a three-roll calender, winding, and obtaining a waterproof board; the temperature control of each zone of the barrel of the double-screw sheet extruder is 175℃, 180℃, 185℃, 190℃, 195℃, and 200℃; the die head temperature condition includes 200℃; and the vacuum degree is -0.06MPa.

[0159] S2, preparing a raw material of the polyurethane layer to be sprayed, including the following steps:

[0160] The 1,6-hexanediol, blowing agent (HFO-1233zd (E)), water, foam stabilizer and catalyst are added into the polyether polyol and stirred until uniform, then the flame retardant B is added, after the components are uniformly mixed by stirring, the polyol raw material is prepared; the polyol raw material and isocyanate are preheated to 35℃, and taken out after 55 min, then mixed and stirred to obtain the polyurethane layer raw material to be sprayed.

[0161] S3, the polyurethane layer raw material to be sprayed prepared in step S2 is added to the polyurethane spraying machine, and sprayed onto the surface of the waterproof plate layer (the waterproof plate prepared in step S1, the waterproof plate thickness is 1.2 mm), the spraying speed is 6 kg / min, after repeated spraying for several times, the sprayed polyurethane layer with a thickness of 70 mm is obtained, and the composite board is prepared.

[0162] Comparative Example 1

[0163] The raw material of the waterproof plate layer, the polyurethane layer raw material and the preparation method of the composite board are the same as Example 1, and compared with Example 1, the difference is only that the flame retardant B in the polyurethane layer raw material is unmodified microencapsulated red phosphorus.

[0164] Comparative Example 2

[0165] The raw material of the waterproof plate layer, the polyurethane layer raw material and the preparation method of the composite board are the same as Example 1, and compared with Example 1, the difference is only that the microencapsulated red phosphorus in the flame retardant A and the flame retardant B is not pretreated in the preparation method of the microencapsulated red phosphorus.

[0166] Specifically, the preparation of the microencapsulated red phosphorus includes the following steps:

[0167] ① 1.0 g of dopamine hydrochloride (PDA) is weighed, added to 99.0 g of deionized water, and stirred until completely dissolved to prepare a 1 wt% dopamine hydrochloride solution;

[0168] ② 1.0 g of unpretreated red phosphorus is taken, added to 10.0 g of 1 wt% dopamine hydrochloride solution, ultrasonically dispersed for 15 minutes, ultrasonic power 200 W, frequency 20 kHz, to obtain a dispersion liquid; then while stirring, 0.1 mol / L tris base is slowly added to the dispersion liquid to adjust the pH to 8.8, and stirred at 500 rpm for 30 min to obtain a mixed liquid, the mixed liquid is transferred to a three-necked flask, constant temperature water bath 25 ℃, magnetic stirring 500 rpm, nitrogen protection, reaction for 12 hours; after the reaction is completed, 1 mol / L hydrochloric acid is added dropwise to adjust the pH to 6.0, centrifuged at 5000 rpm for 10 minutes, the supernatant is discarded, and the precipitate is washed with 50 mL of deionized water and 50 mL of anhydrous ethanol alternately for 3 times, finally the product is placed in a 60℃ vacuum drying oven for drying for 12 hours, to obtain the microencapsulated red phosphorus (RP@PDA).

[0169] Comparative Example 3

[0170] The raw material of the waterproof board layer, the raw material of the polyurethane layer, and the preparation method of the composite board are the same as Example 1. Compared with Example 1, the only difference is that in the preparation process of the flame retardant A, the microencapsulated red phosphorus is dispersed in ethanol, and then the hydrolyzed silane solution is added, and the pH is adjusted to 7 by adding 0.1 mol / L trimethylol aminomethane aqueous solution. Specifically, it includes:

[0171] 1 g KH-151 (vinyl triethoxysilane) is added to 12 mL of an ethanol aqueous solution (volume ratio of ethanol to water 9:1), the pH is adjusted to 3 with acetic acid, and it is hydrolyzed at room temperature for 30 min (stirring rate 500 rpm) to obtain a hydrolyzed silane solution;

[0172] 33 g of dried RP@PDA prepared in Preparation Example 1 is dispersed in 1650 mL of ethanol, and ultrasonic treatment is performed for 15 min (ultrasonic power 200 W, frequency 20 kHz), then the above hydrolyzed silane solution is slowly added, the pH is adjusted to 7 by adding 0.1 mol / L trimethylol aminomethane aqueous solution, and reflux reaction is performed at 60°C for 3 hours. Centrifugation (5000 rpm for 10 min), take the precipitate, wash (with anhydrous ethanol for 3 times), and vacuum drying at 60°C for 12 hours to obtain the flame retardant A.

[0173] Comparative Example 4

[0174] The raw material of the waterproof board layer, the raw material of the polyurethane layer, and the preparation method of the composite board are the same as Example 1. Compared with Example 1, the only difference is that in the preparation process of the flame retardant B, the microencapsulated red phosphorus is dispersed in ethanol, and then the above hydrolyzed silane solution is added, and the pH is adjusted to 6 by adding 1 mol / L hydrochloric acid aqueous solution.

[0175] Specifically, 1 g of KH-550 (γ-aminopropyl triethoxysilane) is added to 12 mL of an ethanol aqueous solution (volume ratio of ethanol to water 9:1), the pH is adjusted to 4 with acetic acid, and it is hydrolyzed at room temperature for 30 min (stirring rate 400 rpm) to obtain a hydrolyzed silane solution;

[0176] 33 g of dried RP@PDA prepared in Preparation Example 1 is dispersed in 1650 mL of ethanol, and ultrasonic treatment is performed for 20 min (ultrasonic power 200 W, frequency 20 kHz), then the above hydrolyzed silane solution is slowly added, the pH is adjusted to 6 by adding 1 mol / L hydrochloric acid aqueous solution, and reflux reaction is performed at 60°C for 6 hours. Centrifugation (5000 rpm for 10 min), take the precipitate, wash (with anhydrous ethanol for 3 times), and vacuum drying at 60°C for 12 hours to obtain the flame retardant B.

[0177] Comparative Example 5

[0178] The raw material of the waterproof board layer, the raw material of the polyurethane layer and the preparation method of the composite board are the same as Example 1, and the only difference compared with Example 1 is that the flame retardant A in the raw material of the waterproof board layer is replaced by the flame retardant B.

[0179] Comparative Example 6

[0180] The raw material of the waterproof board layer, the raw material of the polyurethane layer and the preparation method of the composite board are the same as Example 1, and the only difference compared with Example 1 is that the flame retardant A in the raw material of the waterproof board layer is replaced by the flame retardant B.

[0181] Comparative Example 7

[0182] The raw material of the waterproof board layer, the raw material of the polyurethane layer and the preparation method of the composite board are the same as Example 1, and the only difference compared with Example 1 is that the flame retardant B in the raw material of the polyurethane layer is replaced by the flame retardant A.

[0183] Application Example 1

[0184] The application of the high-adhesion-strength flame-retardant waterproof composite board for tunnel is used to build a tunnel structure; the tunnel structure is composed of a tunnel rock wall, a primary support sprayed concrete layer, a geotextile layer, a composite board layer and a secondary lining concrete layer from outside to inside; the composite board layer adopts the high-adhesion-strength flame-retardant waterproof composite board for tunnel described in any one of Examples 1-5.

[0185] Test Example

[0186] The composite boards prepared in the examples and comparative examples are tested for performance, and the results are shown in Table 1 below.

[0187] Table 1

[0188]

[0189] The method of the above test data is as follows:

[0190] The detection standard of the spray polyurethane closed cell rate refers to GB / T 10799.

[0191] The detection standard of the limiting oxygen index refers to GB / T 2406.2-2009.

[0192] The vertical burning detection refers to GB / T 2408-2008.

[0193] The determination of the combustion performance grade is carried out according to the provisions of 5.1.1 in GB 8624-2012.

[0194] The determination of the smoke production characteristic grade is carried out according to the provisions of Appendix B in GB 8624-2012.

[0195] The peeling strength test method refers to GB / T 7760, and is as follows:

[0196] Sample size: the standard sample is composed of a waterproof plate with a total length of 75±1 mm and a width of 25.0±0.1 mm and a sprayed polyurethane block with a length of 50.0±0.1 mm, a width of 25.0±0.1 mm and a thickness of 70 mm, that is, the length and width of the combined part of the sprayed polyurethane block and the waterproof plate are 50.0±1 mm and 25.0±0.1 mm respectively, and the combined part of the two is as far as possible in the central range of the waterproof plate during sample preparation;

[0197] wherein the area of the waterproof plate is greater than the bottom area of the sprayed polyurethane block, the part of the waterproof plate greater than the sprayed polyurethane block is clamped in the clamp of the tensile tester, the sprayed polyurethane block is fixed below, the peeling strength test is carried out, and the peeling strength of the sample is obtained. The schematic diagram of the peeling strength test clamp is shown in the following figure Figure 1 as shown, wherein the clamp is the clamp mentioned in GB / T 7760.

[0198] The above is only a preferred embodiment of the present application and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A high adhesive strength flame-retardant waterproof composite board for tunnel, characterized by, Comprise: a, waterproof board layer, raw material is composed of 22-24wt% PE / EVA composite resin particles, 10-11wt% high density polyethylene, 18-19wt% linear low density polyethylene, 46-50wt% flame retardant masterbatch, the flame retardant masterbatch includes 50wt% flame retardant A and 50wt% high density polyethylene; b, polyurethane layer, sprayed on the surface of the waterproof board layer, raw material is prepared by polyol and isocyanate with isocyanate index R=1-1.1 ratio, by mass fraction, the polyol includes 7.5-8.5 parts 1,6-hexanediol, 1-1.3 parts blowing agent, 0.9-1.1 parts foam stabilizer, 1.4-1.6 parts catalyst, 65-85 parts polyether polyol, 2-3 parts water and 32-36 parts flame retardant B;The catalyst is N,N-dimethylcyclohexylamine, stannous octoate and dibutyltin diacetate with a mass ratio of 0.8-1.2:0.8-1.2:1.1-1.2;The viscosity of the polyether polyol is 5000-7700mpa·s, and the hydroxyl value is 480-520mgKOH / g; Wherein, the flame retardant A is microencapsulated red phosphorus modified by vinyltriethoxysilane, and the flame retardant B is microencapsulated red phosphorus modified by γ-aminopropyltriethoxysilane; The preparation method of the microencapsulated red phosphorus comprises the following steps: The red phosphorus is first pretreated, and the specific steps include: taking red phosphorus, ultrasonic cleaning with anhydrous ethanol, then transferring to 0.08-0.12 mol / L hydrochloric acid solution and stirring, then washing with deionized water until neutral, and drying;Then 1.0g red phosphorus is added to 8.0-12.0g 1wt% dopamine hydrochloride solution for ultrasonic dispersion, to obtain a dispersion liquid;Under stirring, the pH is adjusted to 8.5-9.0 by adding a trimethylolamine aqueous solution;Then under inert gas atmosphere, stirring at room temperature for 10-12h, after the reaction is completed, the pH is adjusted to 5.8-6.4 by using hydrochloric acid, centrifuged, the precipitate is taken, washed and dried to obtain microencapsulated red phosphorus.

2. The high adhesive strength flame-retardant waterproof composite board for tunnel according to claim 1, characterized in that, The preparation method of the flame retardant A comprises the following steps: Vinyltriethoxysilane is added to an ethanol aqueous solution, the pH is adjusted to 3-4, and stirring is carried out to obtain a hydrolyzed silane solution; The microencapsulated red phosphorus is dispersed in ethanol, ultrasonic is carried out, then the above hydrolyzed silane solution is added, the pH is adjusted to 5-6 by adding hydrochloric acid solution dropwise, and reflux reaction is carried out at 50-60℃ for 3-4h, centrifuged, the precipitate is taken, washed and dried to obtain the flame retardant A;Wherein, the mass ratio of the microencapsulated red phosphorus to vinyltriethoxysilane is 1:0.03-0.

05.

3. The high adhesive strength flame-retardant waterproof composite board for tunneling according to claim 1 or 2, characterized in that, The preparation method of the flame retardant B comprises the following steps: γ-Aminopropyltriethoxysilane is added to an ethanol aqueous solution, the pH is adjusted to 4-5, and stirring is carried out to obtain a hydrolyzed silane solution; The microencapsulated red phosphorus is dispersed in ethanol, ultrasonic treatment is performed, then the above hydrolyzed silane solution is added, the pH is adjusted to 7-8 by dropwise adding a trimethylol aminomethyl alcohol aqueous solution, and reflux reaction is performed at 60-70 DEG C for 5-6 h, centrifugation is performed, the precipitate is taken, washing is performed, and drying is performed to obtain the flame retardant B; wherein the mass ratio of the microencapsulated red phosphorus to the gamma-aminopropyl triethoxysilane is 1:0.03-0.

05.

4. The high adhesive strength flame-retardant waterproof composite board for tunneling according to claim 1, characterized in that, The blowing agent is selected from one or several of trans-1-chloro-3,3,3-trifluoropropene, isopentane and pentafluoropropane.

5. The high adhesive strength flame-retardant waterproof composite board for tunneling according to claim 1, characterized in that, The isocyanate is a carbodiimide modified MDI.

6. The high adhesive strength flame-retardant waterproof composite board for tunneling according to claim 1, characterized in that, The density of the PE / EVA composite resin particles is 0.855-0.955 g / cm 3 , the melt flow rate is 0.8-3.0 g / 10 min, and the VA content is 11.5-15%.

7. The method of producing a high adhesive strength flame-retardant waterproof composite board for a tunnel according to any one of claims 1 to 6, characterized by, The method comprises the following steps: The polyol and the isocyanate are preheated to 30-40 DEG C respectively, taken out after maintaining for 50-60 min, then mixed and stirred to obtain the polyurethane layer raw material to be sprayed; The polyurethane layer raw material to be sprayed is filled into a polyurethane spraying machine, sprayed to the surface of the waterproof board layer, the spraying speed is 4-9 kg / min, and after repeated spraying for multiple times, the obtained sprayed polyurethane layer has a thickness of 70 mm, and the composite board is prepared.

8. The use of high adhesive strength flame-retardant waterproof composite board for tunnel according to any one of claims 1-6, characterized in that, For constructing a tunnel structure; The tunnel structure is composed of a tunnel rock wall, an initial support shotcrete layer, a geotextile layer, a composite board layer and a secondary lining concrete layer from outside to inside; the composite board layer adopts the high adhesive strength flame-retardant waterproof composite board for tunnels according to any one of claims 1-6.

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