Glue for fire hose with multi-layer structure and preparation method of glue

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to adhesive for a fire hose with a multi-layer structure and a preparation method of the adhesive. According to the invention, the main components thermoplastic rubber and white oil of the adhesive for the fire hose are respectively modified, and meanwhile, the polyurethane elastomer composite material is introduced, so that the adhesive for the fire hose is prepared, and a proper melt index is obtained, the softening point is increased and the peel strength is increased through the combined action of multiple components.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a multi-layered viscose for fire hoses and a preparation method thereof. Background Art

[0002] As a flexible pipe, the fire hose is used in a special environment, and it is difficult to seal the pipe wall. Flax braided fabric as the main packaging material of the outer braided layer cannot bear all the sealing burden. In order to achieve high-efficiency sealing requirements, high-performance glue is generally used as the lining on the inner wall of the flax braided fabric to strengthen the sealing of the fire hose; the bonding adhesives commonly used in the inner wall of the fire hose are mostly chemically synthesized adhesives, mainly including polymer materials such as epoxy resin, acrylic resin, polyurethane, fluororesin and rubber.

[0003] A Chinese patent (publication number CN106336539B) discloses a flame-retardant and scalding-resistant inner and outer covering rubber material for fire hoses and its preparation method. The raw materials of the invention include NBR / PVC blended rubber alloy, chloroprene rubber, butadiene rubber, activator, antioxidant, colorant, phenolic resin, white carbon black, crusting agent, cold-resistant oil, modified reinforcing agent, composite accelerator and vulcanization aid; the covering rubber material of the invention can meet the performance and processing requirements of double-sided adhesive outer tape blank fire hose, has excellent flame retardant, high temperature resistance and ductility, and is specially used for the production of combat fire hoses with various harsh performance requirements. However, the patent does not solve the problems of melt index mismatch, low softening point, and poor peel strength of viscose for fire hoses in the prior art, which seriously affects its actual use.

[0004] Therefore, how to modify the main components of viscose for fire hoses and introduce functional components to obtain a suitable melt index through synergistic effects, improve the softening point, and increase the peel strength has become a direction that needs to be focused on. Summary of the invention

[0005] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a multi-layer structure of viscose for fire hoses and a preparation method thereof, aiming to solve the problems of the existing viscose for fire hoses, such as mismatched melt index, low softening point, and poor peel strength.

[0006] The invention modifies the main components of the fire hose viscose, namely thermoplastic rubber and white oil, respectively, and introduces a polyurethane elastomer composite material to prepare the fire hose viscose. The multi-components work together to obtain a suitable melting index, improve the softening point, and increase the peel strength.

[0007] The technical solution of the present invention is as follows:

[0008] The first aspect of the present invention provides a method for preparing a multi-layer structure of viscose for fire hose, comprising the following steps:

[0009] Step S1: by weight, 60-70 parts of thermoplastic rubber, 30-40 parts of white oil and 0.3-0.5 parts of antioxidant are mixed and stirred for 60-80 minutes to obtain glue;

[0010] Step S2: Mixing 30 to 40 parts by weight of polyester elastomer, 30 to 40 parts by weight of polyurethane elastomer and 30 to 40 parts by weight of polyolefin elastomer for 10 to 20 minutes to obtain a primary modified material;

[0011] Step S3: mixing 40 to 50 parts by weight of the primary modified material and 40 to 50 parts by weight of a polyolefin elastomer for 10 to 16 minutes to obtain a secondary modified material;

[0012] Step S4: by weight, 65 to 75 parts of the secondary modified material, 5 to 7 parts of the glue, 10 to 12 parts of rosin resin, 10 to 12 parts of C5 petroleum resin, 10 to 12 parts of polyolefin elastomer, 0.4 to 0.6 parts of antioxidant and 0.3 to 0.5 parts of ultraviolet absorber are mixed for 8 to 10 minutes to obtain a multi-layer structure of viscose for fire hose.

[0013] As a preferred technical solution of the present invention, the antioxidant is selected from any one of antioxidant 1010, antioxidant 1024, and antioxidant 1076, or a combination of at least two of them.

[0014] As a preferred technical solution of the present invention, the thermoplastic rubber is a modified thermoplastic rubber; the preparation method of the modified thermoplastic rubber comprises: adding 80 to 100 parts of thermoplastic rubber, 6 to 10 parts of zinc oxide, 0.6 to 1.4 parts of stearic acid, 1 to 3 parts of sulfur, 0.2 to 0.6 parts of N-tert-butyl-2-benzothiazole sulfonamide and 20 to 40 parts of amino silicon dioxide into a torque rheometer for internal kneading, heating to 140 to 150° C. after internal kneading, and keeping the temperature for 6 to 8 minutes to obtain the modified thermoplastic rubber.

[0015] As a preferred technical solution of the present invention, the conditions for the banburying include: a temperature of 70 to 74° C., a rotation speed of 60 to 80 r / min, and a time of 6 to 10 min.

[0016] As a preferred technical solution of the present invention, the preparation method of the amino silicon dioxide comprises: adding 8 to 12 parts of silicon dioxide to 260 to 300 parts of deionized water by weight, ultrasonically dispersing at room temperature for 30 to 40 minutes, then adding 2 to 6 parts of 3-aminopropyltriethoxysilane, and adjusting the pH to 7.2 to 7.6 for stirring reaction (speed of 100 to 200 r / min, temperature of 66 to 70°C, time of 10 to 12 hours), centrifuging after the stirring reaction is completed, washing the solid obtained by centrifugation three times with deionized water, and vacuum drying to obtain amino silicon dioxide.

[0017] The amino silica particles introduced into the modified thermoplastic rubber can play a role similar to a "lubricant" between polymer chains, reducing the friction between molecular chains and making the polymer chains move more easily, thereby increasing the fluidity in the molten state and improving the melt index of the viscose for fire hoses.

[0018] As a preferred technical solution of the present invention, the white oil is a modified white oil; the preparation method of the modified white oil comprises: adding 100 to 110 parts of white oil by weight into a reaction kettle with a stirrer, heating to 160 to 170°C; then adding 20 to 24 parts of maleic anhydride and 10 to 16 parts of boric acid, stirring for 60 to 80 minutes under nitrogen protection, then adding 8 to 10 parts of dibenzoyl peroxide for heating reaction, and purifying after the heating reaction is completed to obtain the modified white oil.

[0019] As a preferred technical solution of the present invention, the conditions of the heating reaction include: temperature of 170-180° C. and time of 1-3 h.

[0020] The modified white oil is modified with maleic anhydride and boric acid to introduce functional groups such as carboxyl groups, thereby improving the compatibility of the white oil with other components in the viscose for fire hoses. The carboxyl groups react with other active groups to increase the crosslinking density, thereby increasing the softening point of the viscose for fire hoses.

[0021] As a preferred technical solution of the present invention, the polyurethane elastomer is a polyurethane elastomer composite material; the preparation method of the polyurethane elastomer composite material comprises: adding 6 to 10 parts by weight of hydroxylated carbon nanotubes and 10 to 14 parts of isopropyl tri(dioctylphosphoyl) titanate to 180 to 200 parts of anhydrous ethanol, ultrasonically shaking for 50 to 60 minutes, then reacting at 70 to 80°C for 8 to 10 hours, filtering after the reaction is completed, washing with anhydrous ethanol, and drying to obtain titanate-modified carbon nanotubes; dispersing 6 to 10 parts of hydroxylated carbon nanotubes in 60 to 80 parts of ethyl acetate, then adding 40 to 50 parts of polyurethane elastomer, stirring for 2 to 4 hours, and drying to obtain a polyurethane elastomer composite material.

[0022] As a preferred technical solution of the present invention, the preparation method of the hydroxylated carbon nanotubes comprises: adding 50 to 60 parts of iron sulfate pentahydrate to 200 to 260 parts of deionized water by weight to fully dissolve, then adding 8 to 10 parts of carbon nanotubes and ultrasonically shaking for 50 to 60 minutes, then adding 100 to 120 parts of hydrogen peroxide and stirring the reaction for 10 to 12 hours, after the reaction is completed, filtering to obtain a filter cake, washing the filter cake with deionized water, and drying to obtain hydroxylated carbon nanotubes.

[0023] Titanates in polyurethane elastomer composites can participate in the formation of elastomer networks, and form additional cross-linking points by combining with polyurethane elastomers. The introduced cross-linking points can enhance the interfacial bonding force between polymer matrices. At the same time, hydroxylated carbon nanotubes can form stronger hydrogen bonds and other types of intermolecular forces with elastomers, and the combined effect improves the peel strength of the viscose used for fire hoses.

[0024] The second aspect of the present invention provides a multi-layered fire hose adhesive, which is prepared by the method described in the first aspect.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) The amino-silica particles introduced into the modified thermoplastic rubber of the present invention can play a role similar to that of a "lubricant" between polymer chains, reducing the friction between molecular chains, thereby increasing fluidity in a molten state; at the same time, the active amino group introduced by the amino-silica can not only combine with the carboxyl group introduced by the modified white oil through acidification treatment, but also undergo nucleophilic substitution reaction with the titanate in the polyurethane elastomer composite material, and react with the hydroxyl group of the hydroxylated carbon nanotubes, thereby constructing a network structure. The network structure resists external forces through more tightly connected molecular chains, reduces the possibility of interface separation, and improves peel strength; at the same time, it ensures that the material can still maintain good shape and performance under high temperature environment, and effectively improves the softening point.

[0027] (2) The amino-containing silica particles introduced into the modified thermoplastic rubber of the present invention can play a role similar to a "lubricant" between polymer chains, reduce the friction between molecular chains, make the polymer chains move more easily, thereby increasing the fluidity in the molten state and improving the melt index of the viscose for fire hoses.

[0028] (3) The modified white oil of the present invention is modified by using maleic anhydride and boric acid to introduce functional groups such as carboxyl groups, thereby improving the compatibility of the white oil with other components in the viscose for fire hoses. At the same time, the carboxyl groups can react with other active groups to increase the crosslinking density, thereby increasing the softening point of the viscose for fire hoses.

[0029] (4) The titanate in the polyurethane elastomer composite material of the present invention can participate in the formation of the elastomer network and form additional cross-linking points by combining with the polyurethane elastomer. The introduced cross-linking points can enhance the interfacial bonding force between the polymer matrix. At the same time, the hydroxylated carbon nanotubes can form stronger hydrogen bonds and other types of intermolecular forces with the elastomer. The combined effect of the titanate and the hydroxylated carbon nanotubes can improve the peel strength of the adhesive for fire hoses. DETAILED DESCRIPTION

[0030] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0031] The sources of some components in the embodiments and comparative examples are as follows:

[0032] Antioxidant 1010, CAS No. 6683-19-8, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.;

[0033] Antioxidant 1024, CAS No. 32687-78-8, purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0034] Antioxidant 1076, CAS No. 2082-79-3, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.;

[0035] Thermoplastic rubber, model YH-501T, purchased from Baling Petrochemical Co., Ltd.;

[0036] White oil, CAS No. 8042-47-5, purchased from Changzhou Jiaye Chemical Co., Ltd.;

[0037] Polyester elastomer, model KH-J163, purchased from Keheng Polymer (Guangdong) Co., Ltd.;

[0038] Polyurethane elastomer, model UT6-85AU10, purchased from Qingdao Zhuoli Rubber and Plastic Materials Co., Ltd.;

[0039] Polyolefin elastomer, model 3980FL, purchased from Dongguan Dongshuo Plastic Raw Materials Co., Ltd.;

[0040] Rosin resin, model S7090P, purchased from Zhejiang Xinsong Resin Co., Ltd.;

[0041] C5 petroleum resin, model D0203, purchased from Shenzhen Jitian Chemical Co., Ltd.;

[0042] Ultraviolet absorber, brand name UV-531, purchased from Tianjin Lianlong New Materials Co., Ltd.;

[0043] Zinc oxide, CAS No. 1314-13-2, was purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0044] Stearic acid, CAS No. 57-11-4, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.;

[0045] Sulfur, CAS No. 7704-34-9, was purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0046] N-tert-butyl-2-benzothiazolesulfenamide, CAS No. 95-31-8, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.;

[0047] Silica, product number S104597, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0048] 3-Aminopropyltriethoxysilane, CAS No. 919-30-2, purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0049] Maleic anhydride, CAS No. 108-31-6, was purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0050] Boric acid, CAS No. 10043-35-3, was purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0051] Dibenzoyl peroxide, CAS No. 94-36-0, was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.;

[0052] Iron sulfate pentahydrate, CAS No. 142906-29-4, was purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0053] Carbon nanotubes, CAS No. 16291-96-6, were purchased from Shanghai MacLean Biochemical Technology Co., Ltd.;

[0054] Hydrogen peroxide, CAS No. 7722-84-1, was purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0055] Isopropyl tri(dioctylphosphoyl) titanate, CAS No. 65345-34-8, purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0056] Ethyl acetate, CAS No. 141-78-6, was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0057] Preparation of modified thermoplastic rubber: (1) By weight, 12 parts of silica were added to 300 parts of deionized water, and ultrasonically dispersed at room temperature for 40 minutes, then 6 parts of 3-aminopropyltriethoxysilane were added, and the pH was adjusted to 7.6 for stirring reaction (speed of 200 r / min, temperature of 70°C, time of 10 hours), and after the stirring reaction was completed, centrifugation was performed, and the solid obtained by centrifugation was washed three times with deionized water and vacuum dried to obtain amino silica. (2) By weight, 100 parts of thermoplastic rubber, 10 parts of zinc oxide, 1.4 parts of stearic acid, 3 parts of sulfur, 0.6 parts of N-tert-butyl-2-benzothiazole sulfonamide and 40 parts of amino silica were added to a torque rheometer for internal kneading (temperature of 74°C, speed of 80 r / min, time of 6 minutes), and after the internal kneading was completed, the temperature was raised to 150°C and kept warm for 6 minutes to obtain modified thermoplastic rubber.

[0058] Preparation of modified white oil: 110 parts of white oil, by weight, are added to a reactor with a stirrer and heated to 160°C; then 24 parts of maleic anhydride and 16 parts of boric acid are added, stirred for 60 minutes under nitrogen protection, and then 10 parts of dibenzoyl peroxide are added for heating reaction (temperature is 170°C, time is 3h), and after the heating reaction is completed, it is purified to obtain modified white oil.

[0059] Preparation of polyurethane elastomer composite material: (1) By weight, add 60 parts of iron sulfate pentahydrate to 260 parts of deionized water and fully dissolve, then add 10 parts of carbon nanotubes and ultrasonically shake for 60 minutes, then add 120 parts of hydrogen peroxide and stir to react for 12 hours, after the reaction is completed, filter to obtain a filter cake, wash the filter cake with deionized water, and dry to obtain hydroxylated carbon nanotubes. (2) By weight, add 10 parts of hydroxylated carbon nanotubes and 14 parts of isopropyl tri(dioctylphosphoyl) titanate to 200 anhydrous ethanol and ultrasonically shake for 60 minutes, then react at 80°C for 8 hours, after the reaction is completed, filter, wash with anhydrous ethanol, and dry to obtain titanate-modified carbon nanotubes; disperse 10 parts of hydroxylated carbon nanotubes in 80 parts of ethyl acetate, then add 50 parts of polyurethane elastomer and stir for 2 hours, and dry to obtain a polyurethane elastomer composite material.

[0060] Example 1

[0061] This embodiment provides a method for preparing a multi-layer structure of viscose for fire hose, comprising the following steps:

[0062] Step S1: by weight, 70 parts of modified thermoplastic rubber, 40 parts of modified white oil and 0.5 parts of antioxidant 1010 were mixed and stirred for 80 minutes to obtain glue;

[0063] Step S2: mixing 40 parts of polyester elastomer, 40 parts of polyurethane elastomer composite material and 40 parts of polyolefin elastomer by weight for 20 minutes to obtain a primary modified material;

[0064] Step S3: mixing 50 parts by weight of the primary modified material and 50 parts by weight of a polyolefin elastomer for 16 minutes to obtain a secondary modified material;

[0065] Step S4: by weight, 75 parts of the secondary modified material, 7 parts of the glue, 12 parts of rosin resin, 12 parts of C5 petroleum resin, 12 parts of polyolefin elastomer, 0.6 parts of antioxidant 1010 and 0.5 parts of ultraviolet absorber are mixed for 10 minutes to obtain a multi-layered fire hose adhesive.

[0066] Example 2

[0067] This embodiment provides a method for preparing a multi-layer structure of viscose for fire hose, comprising the following steps:

[0068] Step S1: by weight, 60 parts of modified thermoplastic rubber, 30 parts of modified white oil and 0.3 parts of antioxidant 1024 were mixed and stirred for 60 minutes to obtain glue;

[0069] Step S2: mixing 30 parts of polyester elastomer, 30 parts of polyurethane elastomer composite material and 30 parts of polyolefin elastomer by weight for 10 minutes to obtain a primary modified material;

[0070] Step S3: mixing 40 parts by weight of the primary modified material and 40 parts by weight of a polyolefin elastomer for 10 minutes to obtain a secondary modified material;

[0071] Step S4: by weight, 65 parts of the secondary modified material, 5 parts of the glue, 10 parts of rosin resin, 10 parts of C5 petroleum resin, 10 parts of polyolefin elastomer, 0.4 parts of antioxidant 1024 and 0.3 parts of ultraviolet absorber are mixed for 8 minutes to obtain a multi-layer structure of fire hose adhesive.

[0072] Example 3

[0073] This embodiment provides a method for preparing a multi-layer structure of viscose for fire hose, comprising the following steps:

[0074] Step S1: by weight, 65 parts of modified thermoplastic rubber, 35 parts of modified white oil and 0.4 parts of antioxidant 1076 were mixed and stirred for 70 minutes to obtain glue;

[0075] Step S2: mixing 35 parts of polyester elastomer, 35 parts of polyurethane elastomer composite material and 35 parts of polyolefin elastomer by weight for 15 minutes to obtain a primary modified material;

[0076] Step S3: mixing 45 parts of the primary modified material and 45 parts of the polyolefin elastomer by weight for 12 minutes to obtain a secondary modified material;

[0077] Step S4: by weight, 70 parts of the secondary modified material, 6 parts of the glue, 11 parts of rosin resin, 11 parts of C5 petroleum resin, 11 parts of polyolefin elastomer, 0.5 parts of antioxidant 1076 and 0.4 parts of ultraviolet absorber are mixed for 9 minutes to obtain a multi-layer structure of fire hose adhesive.

[0078] Comparative Example 1

[0079] This comparative example provides a method for preparing viscose for fire hoses, which differs from Example 1 in that commercially available thermoplastic rubber is used instead of modified thermoplastic rubber, commercially available white oil is used instead of modified white oil, and commercially available polyurethane elastomer is used instead of polyurethane elastomer composite material.

[0080] Comparative Example 2

[0081] This comparative example provides a method for preparing viscose for fire hoses, which differs from comparative example 1 in that modified thermoplastic rubber is used instead of commercially available thermoplastic rubber.

[0082] Comparative Example 3

[0083] This comparative example provides a method for preparing viscose for fire hoses, which differs from comparative example 1 in that modified white oil is used instead of commercially available white oil.

[0084] Comparative Example 4

[0085] This comparative example provides a method for preparing viscose for fire hoses. The difference from comparative example 1 is that a polyurethane elastomer composite material is used instead of a commercially available polyurethane elastomer.

[0086] Comparative Example 5

[0087] This comparative example provides a method for preparing viscose for fire hoses, which differs from Example 1 in that commercially available thermoplastic rubber is used instead of modified thermoplastic rubber.

[0088] Comparative Example 6

[0089] This comparative example provides a method for preparing viscose for fire hoses, which differs from Example 1 in that commercially available white oil is used instead of modified white oil.

[0090] Comparative Example 7

[0091] This comparative example provides a method for preparing viscose for fire hoses, which differs from Example 1 in that a commercially available polyurethane elastomer is used instead of the polyurethane elastomer composite material.

[0092] The performance of the fire hose adhesive provided in the above embodiments and comparative examples was tested, and the specific testing method is as follows:

[0093] (1) Melt index test

[0094] The melt index is tested according to the requirements of "GB / T 3682.2-2018 Plastics Thermoplastics Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) Determination".

[0095] (2) Softening point test

[0096] The softening point is tested with reference to the requirements of GB / T 15332-1994 Hot Melt Adhesive - Determination of Softening Point - Ring and Ball Method.

[0097] (3) Peel strength test

[0098] The peel strength is tested according to the requirements of GB / T 532-2008 Determination of the bond strength between vulcanized rubber or thermoplastic rubber and fabric.

[0099] The above performance test data is shown in Table 1.

[0100] Table 1 Performance test results

[0101] Melt index (g / 10min) Softening point(℃) Peel strength (N / mm) Example 1 5.7 122 15.4 Example 2 5.3 119 14.7 Example 3 5.5 121 14.9 Comparative Example 1 3.4 100 9.5 Comparative Example 2 4.1 102 9.9 Comparative Example 3 3.6 108 9.7 Comparative Example 4 3.4 101 11.3 Comparative Example 5 4.5 112 12.8 Comparative Example 6 4.8 115 13.4 Comparative Example 7 4.6 114 13.2

[0102] From the above content, it can be seen that the present invention modifies the main components of the viscose for fire hose, thermoplastic rubber and white oil, respectively, and introduces a polyurethane elastomer composite material to prepare a viscose for fire hose (Example 1 to Example 3), which has a melt index of 5.3 to 5.7 g / 10 min, a softening point of 119 to 122° C., and a peel strength of 14.7 to 15.4 N / mm.

[0103] Compared with Example 1, the use of commercially available thermoplastic rubber instead of modified thermoplastic rubber, the use of commercially available white oil instead of modified white oil, and the use of commercially available polyurethane elastomer instead of polyurethane elastomer composite material, the melt index becomes worse, the softening point decreases, and the peel strength decreases (Comparative Example 1); Compared with Comparative Example 1, the use of modified thermoplastic rubber instead of commercial thermoplastic rubber improves the melt index (Comparative Example 2); Compared with Comparative Example 1, the use of modified white oil instead of commercial white oil increases the softening point (Comparative Example 3); Compared with Comparative Example 1, the use of polyurethane elastomer composite material When the commercially available polyurethane elastomer is replaced, the peel strength increases (Comparative Example 4); compared with Example 1, when the commercially available thermoplastic rubber is used to replace the modified thermoplastic rubber, the melt index deteriorates, the softening point decreases, and the peel strength decreases (Comparative Example 5); compared with Example 1, when the commercially available white oil is used to replace the modified white oil, the melt index deteriorates, the softening point decreases, and the peel strength decreases (Comparative Example 6); compared with Example 1, when the commercially available polyurethane elastomer is used to replace the polyurethane elastomer composite material, the melt index deteriorates, the softening point decreases, and the peel strength decreases (Comparative Example 7).

[0104] In summary, the present invention modifies the main components of the viscose for fire hose, namely thermoplastic rubber and white oil, respectively, and introduces a polyurethane elastomer composite material to prepare the viscose for fire hose. The suitable melt index is obtained through the joint action of multiple components, the softening point is improved, and the peel strength is increased.

Claims

1. A method for preparing a multi-layered fire hose adhesive, characterized in that: The following steps are involved: Step S1: by weight, 60-70 parts of thermoplastic rubber, 30-40 parts of white oil and 0.3-0.5 parts of antioxidant are mixed and stirred for 60-80 minutes to obtain glue; Step S2: Mixing 30 to 40 parts by weight of polyester elastomer, 30 to 40 parts by weight of polyurethane elastomer and 30 to 40 parts by weight of polyolefin elastomer for 10 to 20 minutes to obtain a primary modified material; Step S3: mixing 40 to 50 parts by weight of the primary modified material and 40 to 50 parts by weight of a polyolefin elastomer for 10 to 16 minutes to obtain a secondary modified material; Step S4: by weight, 65 to 75 parts of the secondary modified material, 5 to 7 parts of the glue, 10 to 12 parts of rosin resin, 10 to 12 parts of C5 petroleum resin, 10 to 12 parts of polyolefin elastomer, 0.4 to 0.6 parts of antioxidant and 0.3 to 0.5 parts of ultraviolet absorber are mixed for 8 to 10 minutes to obtain a multi-layer structure of viscose for fire hose.

2. The method for preparing a multi-layered fire hose adhesive according to claim 1, characterized in that: The antioxidant is selected from any one of antioxidant 1010, antioxidant 1024, and antioxidant 1076, or a combination of at least two thereof.

3. The method for preparing a multi-layered fire hose adhesive according to claim 1, characterized in that: The thermoplastic rubber is a modified thermoplastic rubber; The preparation method of the modified thermoplastic rubber comprises: adding 80 to 100 parts of thermoplastic rubber, 6 to 10 parts of zinc oxide, 0.6 to 1.4 parts of stearic acid, 1 to 3 parts of sulfur, 0.2 to 0.6 parts of N-tert-butyl-2-benzothiazole sulfonamide and 20 to 40 parts of amino silicon dioxide into a torque rheometer for internal kneading, heating to 140 to 150° C. after internal kneading, and keeping the temperature for 6 to 8 minutes to obtain the modified thermoplastic rubber.

4. The method for preparing a multi-layered fire hose adhesive according to claim 3, characterized in that: The conditions of the banburying include: a temperature of 70 to 74° C., a rotation speed of 60 to 80 r / min, and a time of 6 to 10 min.

5. The method for preparing a multi-layered fire hose adhesive according to claim 3, characterized in that: The preparation method of the amino silicon dioxide comprises: adding 8 to 12 parts of silicon dioxide to 260 to 300 parts of deionized water by weight, ultrasonically dispersing at room temperature for 30 to 40 minutes, then adding 2 to 6 parts of 3-aminopropyltriethoxysilane, adjusting the pH to 7.2 to 7.6, and stirring the reaction (speed of 100 to 200 r / min, temperature of 66 to 70° C., and time of 10 to 12 hours), centrifuging after the stirring reaction is completed, washing the solid obtained by centrifugation with deionized water three times, and vacuum drying to obtain the amino silicon dioxide.

6. The method for preparing a multi-layered fire hose adhesive according to claim 1, characterized in that: The white oil is modified white oil; The preparation method of the modified white oil comprises: adding 100 to 110 parts of white oil by weight into a reaction kettle with a stirrer, heating to 160 to 170° C.; then adding 20 to 24 parts of maleic anhydride and 10 to 16 parts of boric acid, stirring for 60 to 80 minutes under nitrogen protection, and then adding 8 to 10 parts of dibenzoyl peroxide for heating reaction, and purifying after the heating reaction is completed to obtain the modified white oil.

7. The method for preparing a multi-layered fire hose adhesive according to claim 6, characterized in that: The conditions of the heating reaction include: temperature of 170-180° C. and time of 1-3 hours.

8. The method for preparing a multi-layered fire hose adhesive according to claim 1, characterized in that: The polyurethane elastomer is a polyurethane elastomer composite material; The preparation method of the polyurethane elastomer composite material comprises: adding 6 to 10 parts by weight of hydroxylated carbon nanotubes and 10 to 14 parts of isopropyl tri(dioctylphosphoyl) titanate to 180 to 200 parts of anhydrous ethanol, ultrasonically shaking for 50 to 60 minutes, then reacting at 70 to 80° C. for 8 to 10 hours, filtering after the reaction is completed, washing with anhydrous ethanol, and drying to obtain titanate-modified carbon nanotubes; dispersing 6 to 10 parts of hydroxylated carbon nanotubes in 60 to 80 parts of ethyl acetate, then adding 40 to 50 parts of polyurethane elastomer, stirring for 2 to 4 hours, and drying to obtain the polyurethane elastomer composite material.

9. The method for preparing a multi-layered fire hose adhesive according to claim 8, characterized in that: The preparation method of the hydroxylated carbon nanotubes comprises: adding 50 to 60 parts of iron sulfate pentahydrate to 200 to 260 parts of deionized water by weight to fully dissolve, then adding 8 to 10 parts of carbon nanotubes for ultrasonic vibration for 50 to 60 minutes, then adding 100 to 120 parts of hydrogen peroxide for stirring and reacting for 10 to 12 hours, after the reaction is completed, filtering to obtain a filter cake, washing the filter cake with deionized water, and drying to obtain the hydroxylated carbon nanotubes.

10. A multi-layered adhesive for fire hose, characterized in that: Prepared according to the method according to any one of claims 1 to 9.