Anti-aging fire hose lining material and preparation method thereof

Abstract

The invention discloses an anti-aging fire hose lining material and a preparation method thereof. The anti-aging fire hose lining material comprises the following components in parts by mass: 50-60 parts of polypropylene; 25 to 35 parts of thermoplastic rubber; 0.2 to 0.5 part of an antioxidant; 12 to 18 parts of industrial white oil; 15 to 25 parts of a toughening agent; 0.05 to 0.2 part of a metal deactivator; and 0.5-1 part of an anti-hydrolysis agent. According to the present invention, the material has significant anti-aging performance, and the aging process of the material is inhibited from different mechanisms by adding a variety of anti-aging components such as the antioxidant, the metal deactivator, the anti-hydrolysis agent and the like; particularly, multiple antioxidants cooperate, amines, thioesters and organophosphorus are precisely compounded, free radicals are efficiently captured, hydroperoxide is decomposed, aging is resisted from the source, and the service life of the water hose is prolonged. Due to the special proportion of the materials, the light-weight effect is achieved.

Description

Technical Field

[0001] The invention relates to a fire hose material, in particular to an anti-aging fire hose lining material and a preparation method thereof. Background Art

[0002] Fire hoses play a vital role in firefighting operations, and the performance of their lining materials directly affects the service life and reliability of the hoses. Traditional fire hose lining materials have problems such as easy aging, insufficient toughness, and heavy weight. After long-term use or in harsh environments, they are prone to cracking and hardening, which reduces the performance and safety of fire hoses.

[0003] Existing fire hose lining materials are usually made of polypropylene, thermoplastic rubber, antioxidants, industrial white oil, and toughening agents through extrusion molding. They have good toughness, but are prone to aging due to oxidation, hydrolysis, and other reasons after long-term use. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide an anti-aging fire hose lining material and a preparation method of the anti-aging fire hose lining material.

[0005] In order to solve the above technical problems, the anti-aging fire hose lining material of the present invention comprises the following components in parts by weight:

[0006] Polypropylene: 50-60 parts;

[0007] Thermoplastic rubber: 25–35 parts;

[0008] Antioxidant: 0.2–0.5 phr;

[0009] Industrial white oil: 12–18 parts;

[0010] Toughener: 15–25 parts;

[0011] Metal passivator 0.05-0.2 parts;

[0012] Anti-hydrolysis agent 0.5-1 part.

[0013] Preferably, the antioxidant is a composite antioxidant of three kinds of antioxidants, namely, an amine antioxidant, a thioester antioxidant, and an organophosphorus antioxidant in a mass ratio of 6:(1-3):(1-3).

[0014] Preferably, the amine antioxidant is prepared by the following method: adding dichloromethane as an organic solvent to a reaction container, dissolving diphenylamine in dichloromethane at room temperature, placing the reaction container in a water bath of 0-5 degrees, slowly dropping a mixed solution of tert-butyl chloride and anhydrous aluminum chloride, controlling the liquid temperature in the reaction container not to exceed 5 degrees, stirring for 30-60 minutes, collecting the reaction precipitate and washing with water 1-3 times to obtain an antioxidant.

[0015] Preferably, the thermoplastic rubber is styrene-ethylene-butylene-styrene.

[0016] Preferably, the following components are included in parts by weight: polypropylene: 55-60 parts; thermoplastic rubber: 25-30 parts; antioxidant: 0.2 parts; industrial white oil: 16 parts.

[0017] Preferably, the antioxidant includes the following components in parts by mass: 60 parts of amine antioxidant, 20 parts of thioester antioxidant, and 20 parts of organophosphorus antioxidant. The thioester antioxidant is dilauryl thiodipropionate, and the organophosphorus antioxidant is tris(nonylphenyl)phosphite.

[0018] Preferably, the toughening agent is ethylene-vinyl acetate copolymer and polyolefin elastomer in a mass ratio of 5:4.

[0019] Preferably, the metal passivator is 2-mercaptobenzothiazole.

[0020] Preferably, the anti-hydrolysis agent is 3-aminopropyltriethoxysilane and calcium chloride in a mass ratio of 3:7.

[0021] The preparation method of the anti-aging fire hose lining material of the present invention comprises the following steps: (1) firstly adding polypropylene, thermoplastic rubber, antioxidant, industrial white oil and toughening agent into a high-speed mixer in sequence, stirring at a low speed of 100 rpm for 3-5 minutes, gradually increasing the speed to 800-1200 rpm, stirring for 10-15 minutes, and controlling the material temperature not to exceed 100°C during the mixing process; only 1 / 4 of the total amount of polypropylene is taken, and all other components are taken; (2) melt extrusion granulation: melt extrusion granulation of the uniformly mixed material through an extruder; (3) uniformly mixing the obtained particles with the remaining polypropylene; (4) sending the mixed material into a single screw extruder for extrusion molding of the inner liner pipe.

[0022] Analysis of the mechanism of action: Antioxidants can effectively capture free radicals generated during processing and use. When composite antioxidants are used, amine antioxidants prepared based on diphenylamine can provide hydrogen atoms in the amine group of the molecule to quickly capture free radicals and terminate the oxidation chain reaction. After the introduction of steric groups (such as tert-butyl), the stability of the nitrogen free radicals formed is enhanced, reducing the possibility of re-initiating oxidation. On the one hand, dilauryl thiodipropionate can decompose hydroperoxide (ROOH), which is a key intermediate in the oxidation process. If not handled in time, it will decompose and produce more free radicals to accelerate aging. Its reaction mechanism is the cleavage of the thioester bond and the nucleophilic substitution with hydroperoxide, converting ROOH into harmless alcohols to prevent the growth of free radicals; on the other hand, it can also react with the stable nitrogen free radicals produced by amine antioxidants to regenerate amine antioxidants, so that the antioxidant system can continue to operate efficiently. Organophosphorus antioxidants (tris(nonylphenyl)phosphite) also focus on decomposing hydroperoxides. The nucleophilicity of phosphorus atoms is utilized to combine with ROOH to promote its decomposition into alcohols and phosphite oxidation products, and cooperate with thioester antioxidants to curb the generation of free radicals from the source and strengthen the antioxidant defense line.

[0023] The presence of metal passivators can form stable complexes with trace metal ions (such as copper, iron, etc.) that may be mixed in the material system. These metal ions act as "catalysts" during the oxidation process, accelerating the generation of free radicals and the decomposition of hydroperoxides. The metal passivators, through chelation, make them lose their catalytic activity, indirectly improving the material's anti-aging ability.

[0024] Anti-hydrolysis ensures material stability: It is aimed at the hydrolysis problem that the material may encounter in a humid environment or during long-term use. It can interact with the moisture and easily hydrolyzed groups (such as ester groups, amide groups, etc.) in the material to prevent the hydrolysis reaction from occurring, avoid the molecular chain breakage and material performance degradation caused by hydrolysis, ensure the integrity of the lining material structure, and maintain the anti-aging foundation.

[0025] The beneficial effects of the present invention are: the present invention has significant anti-aging performance. The present invention inhibits the aging process of the material from different mechanisms by adding a variety of anti-aging ingredients, such as antioxidants, metal passivators, anti-hydrolysis agents, etc. In particular, the multi-antioxidant synergy, amines, thioesters, and organic phosphorus are precisely compounded to efficiently capture free radicals and decompose hydroperoxides, resist aging from the source, and extend the life of the water hose. The special ratio of the materials makes it lightweight. DETAILED DESCRIPTION

[0026] The instruments, reagents, materials, etc. involved in the following embodiments, unless otherwise specified, are all conventional instruments, reagents, materials, etc. in the prior art and can be obtained through regular commercial channels. The experimental methods, detection methods, etc. involved in the following embodiments, unless otherwise specified, are all conventional experimental methods, detection methods, etc. in the prior art.

[0027] The raw materials of the present invention come from:

[0028] Polypropylene, purchased from CNOOC Shell, brand HP550J;

[0029] Styrene-ethylene-butylene-styrene block copolymer (SEBS) was purchased from Kraton G1657, USA.

[0030] The industrial white oil used is No. 32 industrial white oil.

[0031] Ethylene-vinyl acetate copolymer was purchased from DuPont, brand EVA 265;

[0032] Polyolefin elastomer (POE), purchased from Mitsui Chemicals, brand DF8299;

[0033] Dilauryl thiodipropionate was purchased from Zhengzhou Weifeng Biotechnology Co., Ltd., product number ku65;

[0034] Tris(nonylphenyl)phosphite, purchased from Shanghai Gaoming Chemical Co., Ltd., model 859696;

[0035] Embodiment 1, anti-aging fire hose lining material, comprising the following components in parts by weight:

[0036] Polypropylene: 55 parts; Thermoplastic rubber: 30 parts; Antioxidant: 0.2 parts; Industrial white oil: 16 parts;

[0037] Toughening agent: 20 parts; metal deactivator: 0.1 parts; anti-hydrolysis agent: 0.8 parts. The thermoplastic rubber adopts styrene-ethylene-butylene-styrene block copolymer (SEBS).

[0038] The antioxidant includes the following components by weight: 60 parts of amine antioxidant, 20 parts of thioester antioxidant, and 20 parts of organic phosphorus antioxidant. The thioester antioxidant is dilauryl thiodipropionate, and the organic phosphorus antioxidant is tris(nonylphenyl)phosphite.

[0039] The amine antioxidant is prepared by the following method: 250 ml of dichloromethane is added as an organic solvent in a reaction container, 60 g of diphenylamine is dissolved in the dichloromethane at room temperature, the reaction container is placed in a water bath at 0-5 degrees, a mixed solution of 40 g of tert-butyl chloride and 12 g of anhydrous aluminum chloride is slowly added dropwise, the liquid temperature in the reaction container is controlled not to exceed 5 degrees, stirring is performed for 30-60 minutes, and the reaction precipitate is collected and washed with water twice at room temperature to obtain an antioxidant.

[0040] The toughening agent is ethylene-vinyl acetate copolymer (EVA) and polyolefin elastomer (POE) with a mass ratio of 5:4.

[0041] The metal passivator is 2-mercaptobenzothiazole (MBT), and the molecular formula is C7H5NS2.

[0042] The anti-hydrolysis agent is 3-aminopropyltriethoxysilane (APTES) and calcium chloride in a mass ratio of 3:7.

[0043] The preparation method of this embodiment comprises the following steps: (1) firstly adding polypropylene, thermoplastic rubber, antioxidant, industrial white oil and toughening agent into a high-speed mixer in sequence, stirring at a low speed of 100 rpm for 3-5 minutes, gradually increasing the speed to 800-1200 rpm, stirring for 10-15 minutes, and controlling the material temperature not to exceed 100°C during the mixing process; only 1 / 4 of the total amount of polypropylene is taken, and all other components are taken; (2) melt extrusion granulation: the uniformly mixed material is melt extruded and granulated through an extruder; (3) the obtained granules are uniformly mixed with the remaining polypropylene; (4) the mixed material is sent into a single screw extruder for extrusion molding of the liner pipe.

[0044] Example 2: The difference between this example and example 1 is that the antioxidant is used in an amount of 0.3 parts.

[0045] Example 3: The difference between this example and example 1 is that the antioxidant is used in an amount of 0.3 parts, and the antioxidant is diphenylamine.

[0046] Example 4: The difference between this example and Example 1 is that the antioxidant is 0.3 parts, and the antioxidant is dilauryl thiodipropionate.

[0047] Example 5: The difference between this example and Example 1 is that the antioxidant is 0.3 parts, and the antioxidant is tris(nonylphenyl)phosphite.

[0048] Example 6: The difference between this example and Example 1 is that the antioxidant is used in an amount of 0.3 parts, and the antioxidant is tris(nonylphenyl)phosphite, and the anti-hydrolysis agent is calcium chloride.

[0049] Example 7: This example differs from Example 1 in that all the polypropylene is added in step (1).

[0050] Embodiment 8: This embodiment differs from Embodiment 1 in that: polypropylene: 60 parts; thermoplastic rubber: 25 parts.

[0051] Comparative Example 1: The difference between this comparative example and Example 1 is that the antioxidant is used in an amount of 0.3 parts, and the antioxidant is tris(nonylphenyl)phosphite, and no anti-hydrolysis agent is used.

[0052] Control Example 2: The difference between this control example and Example 1 is that the antioxidant is used: 0.3 parts, and the antioxidant is tris(nonylphenyl)phosphite, the anti-hydrolysis agent is calcium chloride, and the thermoplastic rubber is replaced by polyvinyl chloride.

[0053] According to the test method of fire hose standard GB 6246-2011, the inner liner with specification 40 was tested and the test results were shown in Table 1. After aging in hot air at 100℃ for 72 hours, the retention rate of tensile strength (%) and the retention rate of tensile elongation (%) refer to the ratio between the aging period and the pre-aging period. The water seepage of wet hose is measured under a water pressure of 0.5Mpa.

[0054] Table 1

[0055]

[0056] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An anti-aging fire hose lining material, characterized by: The composition comprises the following components in parts by weight: polypropylene: 50-60 parts; Thermoplastic rubber: 25–35 parts; Antioxidant: 0.2–0.5 phr; Industrial white oil: 12–18 parts; Toughener: 15–25 parts; Metal passivator 0.05-0.2 parts; Anti-hydrolysis agent 0.5-1 part.

2. The anti-aging fire hose lining material according to claim 1 is characterized in that: The antioxidants are three composite antioxidants of amine antioxidants, thioester antioxidants and organic phosphorus antioxidants in a mass ratio of 6:(1-3):(1-3).

3. The anti-aging fire hose lining material according to claim 1 is characterized in that: The amine antioxidant is prepared by the following method: adding dichloromethane as an organic solvent into a reaction container, dissolving diphenylamine in the dichloromethane at room temperature, placing the reaction container in a water bath at 0-5 degrees, slowly dropping a mixed solution of tert-butyl chloride and anhydrous aluminum chloride, controlling the liquid temperature in the reaction container not to exceed 5 degrees, stirring for 30-60 minutes, collecting the reaction precipitate and washing it with water 1-3 times to obtain the antioxidant.

4. The anti-aging fire hose lining material according to claim 3 is characterized in that: The thermoplastic rubber is styrene-ethylene-butylene-styrene.

5. The anti-aging fire hose lining material according to claim 4 is characterized in that: The invention comprises the following components in parts by weight: polypropylene: 55-60 parts; thermoplastic rubber: 25-30 parts; antioxidant: 0.2 parts; industrial white oil: 16 parts.

6. The anti-aging fire hose lining material according to claim 5, characterized in that: The antioxidant includes the following components in parts by mass: 60 parts of amine antioxidant, 20 parts of thioester antioxidant, and 20 parts of organophosphorus antioxidant. The thioester antioxidant is dilauryl thiodipropionate, and the organophosphorus antioxidant is tris(nonylphenyl)phosphite.

7. The anti-aging fire hose lining material according to claim 1, characterized in that: The toughening agent is ethylene-vinyl acetate copolymer and polyolefin elastomer in a mass ratio of 5:

4.

8. The anti-aging fire hose lining material according to claim 1, characterized in that: The metal passivator is 2-mercaptobenzothiazole.

9. The anti-aging fire hose lining material according to claim 1, characterized in that: The anti-hydrolysis agent is 3-aminopropyltriethoxysilane and calcium chloride in a mass ratio of 3:

7.

10. A method for preparing an anti-aging fire hose lining material, characterized in that: The method comprises the following steps: (1) firstly adding polypropylene, thermoplastic rubber, antioxidant, industrial white oil and toughening agent into a high-speed mixer in sequence, stirring at a low speed of 100 rpm for 3-5 minutes, gradually increasing the speed to 800-1200 rpm, stirring for 10-15 minutes, and controlling the material temperature not to exceed 100°C during the mixing process; only 1 / 4 of the total amount of polypropylene is taken, and all other components are taken; (2) melt extrusion granulation: the uniformly mixed material is melt extruded and granulated through an extruder; (3) the obtained granules are uniformly mixed with the remaining polypropylene; (4) the mixed material is sent into a single-screw extruder for extrusion molding of an inner liner pipe.

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