A hydraulic hose with good corrosion resistance and preparation method thereof

Abstract

The present invention relates to the technical field of rubber materials, and proposes a hydraulic hose with good corrosion resistance and a preparation method thereof. A hydraulic hose with good corrosion resistance comprises, from the inside to the outside, an inner rubber layer, a steel wire reinforcement layer and an outer rubber layer, and the raw materials of the inner rubber layer comprise the following components by mass: 100 parts of nitrile rubber, 15-20 parts of carbon black, 60-70 parts of filler, 1-3 parts of antioxidant, 8-13 parts of plasticizer, 3-6 parts of activator, 1-2.5 parts of vulcanizer, 1.5-3 parts of accelerator, and the filler comprises a siloxane-modified inorganic filler, and the inorganic filler is zinc oxide-coated barium sulfate. Through the above technical scheme, the problem of poor corrosion resistance of hydraulic hoses prepared from nitrile rubber in the related art is solved.

Description

Technical Field

[0001] The invention relates to the technical field of rubber materials, and in particular to a hydraulic hose with good corrosion resistance and a preparation method thereof. Background Art

[0002] The hose industry has developed rapidly in terms of technology improvement, material update and application in the past two decades, especially the hydraulic hose has developed the fastest. The structure of the hydraulic hose is composed of an inner rubber layer, a skeleton layer and an outer rubber layer. The material of the skeleton layer has developed from synthetic fiber to steel wire. The hydraulic hose currently used is a steel wire reinforced hydraulic hose. Steel wire reinforced hydraulic hose is divided into steel wire braided hydraulic hose, steel wire wound hydraulic hose and steel wire braided hydraulic hose according to different structures; the material of the inner rubber layer and the outer rubber layer has also developed from the original natural rubber to synthetic rubber, mainly styrene-butadiene rubber, chloroprene rubber, nitrile rubber, ethylene-propylene rubber, fluororubber, silicone rubber, etc. Nitrile rubber is widely used as the inner rubber layer material and outer rubber layer material of hydraulic hose because of its good oil resistance, wear resistance, heat resistance, air tightness and aging resistance. However, the acid and alkali resistance of nitrile rubber itself is poor, so the corrosion resistance of the prepared hydraulic hose is poor. Summary of the invention

[0003] The invention provides a hydraulic hose with good corrosion resistance and a preparation method thereof, which solves the problem of poor corrosion resistance of the hydraulic hose made of nitrile rubber in the related art.

[0004] The technical solution of the present invention is as follows:

[0005] A hydraulic hose with good corrosion resistance comprises, from the inside to the outside, an inner rubber layer, a steel wire reinforcement layer and an outer rubber layer. The raw materials of the inner rubber layer comprise the following components in parts by mass: 100 parts of nitrile rubber, 15-20 parts of carbon black, 60-70 parts of filler, 1-3 parts of antioxidant, 8-13 parts of plasticizer, 3-6 parts of activator, 1-2.5 parts of vulcanizer, and 1.5-3 parts of accelerator. The filler comprises a siloxane-modified inorganic filler, and the inorganic filler is zinc oxide-coated barium sulfate.

[0006] The hydraulic hose of the present invention comprises an inner rubber layer, a steel wire reinforcement layer and an outer rubber layer from the inside to the outside, wherein the inner rubber layer directly contacts the transported material and has good corrosion resistance and sealing performance, the steel wire reinforcement layer is used to withstand pressure and serves as the skeleton of the hydraulic hose, and the outer rubber layer serves as a protective layer and should have good wear resistance and aging resistance.

[0007] As a further technical solution, the raw materials of the outer rubber layer include the following components in parts by mass: 100 parts of chloroprene rubber, 40-60 parts of ethylene-vinyl alcohol copolymer, 20-30 parts of nano-alumina, 20-30 parts of carbon black, 3-5 parts of vulcanizing agent, and 2-4 parts of antioxidant.

[0008] The antioxidant in the present invention can be any one or more conventional antioxidants in the art, for example, it can be one or more of antioxidant 264, antioxidant 2246, and antioxidant BHT; by adding the antioxidant, the oxidation of the hydraulic hose is inhibited, and the heat resistance, light resistance, radiation resistance, and flex resistance are improved, thereby extending the service life of the product.

[0009] The plasticizer in the present invention can be any one or more conventional plasticizers in the art, for example, it can be one or more of dibutyl phthalate, dioctyl sebacate, and dioctyl adipate; by adding the plasticizer, the mobility of the polymer chain is increased, the plasticity and fluidity during processing and molding are improved, the flexibility of the product is increased, and the hardness, rigidity and brittleness of the product are reduced.

[0010] The activator in the present invention can be any one or more conventional activators in the art, for example, it can be one or more of zinc oxide, magnesium oxide, stearic acid, and zinc stearate; by adding the activator, the activity of the accelerator is increased, the amount of the accelerator is reduced, and the vulcanization time is shortened.

[0011] The vulcanizing agent in the present invention can be any one or more conventional vulcanizing agents in the art, for example, it can be one or both of sulfur and peroxide, and the peroxide can be one or both of dicumyl peroxide and benzoyl peroxide; by adding the vulcanizing agent, the rubber molecules are cross-linked to form a network structure, so that the nitrile rubber is transformed from a plastic material to an elastic material.

[0012] The accelerator in the present invention can be any one or more conventional accelerators in the art, for example, it can be one or more of accelerator M, accelerator TMTD, accelerator TETD, accelerator CA, accelerator CZ, and accelerator DM; by adding the accelerator, the reaction between the nitrile rubber and the vulcanizing agent is promoted, the vulcanization speed is increased, the vulcanization temperature is reduced, the vulcanization time is shortened, the amount of the vulcanizing agent is reduced, and the mechanical properties of the product are improved.

[0013] As a further technical solution, the raw materials of the siloxane-modified inorganic filler include siloxane, zinc oxide and barium sulfate in a mass ratio of 5:0.1 to 2:50.

[0014] The siloxane in the present invention can be any one or more siloxanes, for example, one or more of aminosiloxane, mercaptosiloxane, and vinylsiloxane, preferably aminosiloxane. After zinc oxide-coated barium sulfate is modified by aminosiloxane, the surface has amino groups, which can form hydrogen bonds with the nitrile groups in nitrile rubber, thereby improving the affinity between inorganic fillers and nitrile rubber, thereby further improving the corrosion resistance and mechanical strength of the hydraulic hose.

[0015] As a further technical solution, the raw materials of the siloxane-modified inorganic filler include siloxane, zinc oxide and barium sulfate in a mass ratio of 5:0.5 to 1.5:50.

[0016] In the present invention, the mass ratio of siloxane, zinc oxide and barium sulfate is limited to 5:0.5-1.5:50, thereby further improving the corrosion resistance and mechanical strength of the hydraulic hose.

[0017] As a further technical solution, the preparation method of the siloxane-modified inorganic filler comprises the following steps:

[0018] S1, mixing zinc oxide and barium sulfate, and grinding them to obtain zinc oxide-coated barium sulfate;

[0019] S2. Dispersing the zinc oxide-coated barium sulfate in water, adding siloxane for modification, filtering, and drying to obtain a siloxane-modified inorganic filler.

[0020] As a further technical solution, the filler further includes dibasic acid-modified talc powder, and the mass ratio of the dibasic acid-modified talc powder to the siloxane-modified inorganic filler is 1:6 to 4:3.

[0021] In the present invention, the siloxane-modified inorganic filler and the dibasic acid-modified talcum powder are compounded and used as fillers, thereby further improving the corrosion resistance and mechanical strength of the hydraulic hose. Since the talcum powder is used as an acid-alkali resistant filler, the surface of the talcum powder is organic after being modified by the dibasic acid, and it also carries a strong polar group carboxyl, which has better affinity with the strong polar group nitrile group in the nitrile rubber. At the same time, the carboxyl group and the nitrile group can form a hydrogen bond. The dibasic acid-modified talcum powder and the siloxane-modified inorganic filler are compounded and used, thereby further improving the corrosion resistance and mechanical strength of the hydraulic hose.

[0022] As a further technical solution, the raw materials of the dibasic acid-modified talc powder include dibasic acid and talc powder in a mass ratio of 1 to 5:50.

[0023] The dibasic acid in the present invention may be any one or more compounds containing two carboxyl groups, for example, it may be one or more of 5-methylisophthalic acid, benzylmalonic acid, suberic acid, preferably 5-methylisophthalic acid.

[0024] As a further technical solution, the preparation method of the dibasic acid modified talc comprises the following steps: mixing the dibasic acid with a solvent, adding talc to modify it, and drying to obtain the dibasic acid modified talc.

[0025] The solvent in the present invention may be any one or more solvents that can dissolve the dibasic acid, preferably methanol.

[0026] As a further technical solution, the mass ratio of the dibasic acid-modified talc to the siloxane-modified inorganic filler is 2:5 to 3:4.

[0027] The present invention limits the mass ratio of the dibasic acid modified talc powder to the siloxane modified inorganic filler to 2:5-3:4, thereby further improving the corrosion resistance and mechanical strength of the hydraulic hose.

[0028] The present invention also proposes a preparation method for the hydraulic hose, comprising the following steps: mixing the components other than the vulcanizer in the raw materials of the inner rubber layer, adding the vulcanizer and continuing to mix, extruding, and coating to obtain the inner rubber layer, weaving a steel wire reinforcement layer on the outer surface of the inner rubber layer, coating the outer surface of the steel wire reinforcement layer with an outer rubber layer, and vulcanizing to obtain the hydraulic hose.

[0029] As a further technical solution, the vulcanization temperature is 160-170° C., the pressure is 5-15 MPa, and the time is 20-40 min.

[0030] The working principle and beneficial effects of the present invention are:

[0031] The present invention adopts siloxane-modified inorganic filler, wherein the inorganic filler is zinc oxide-coated barium sulfate as filler, which provides good corrosion resistance for the hydraulic hose. Barium sulfate is used as a corrosion-resistant inorganic filler, and the barium sulfate is first coated with zinc oxide and then modified with siloxane, which can improve the modification effect of siloxane on barium sulfate, thereby improving the corrosion resistance of the hydraulic hose and also improving the mechanical strength. DETAILED DESCRIPTION

[0032] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] In the following examples and comparative examples: the raw materials of the outer rubber layer include the following components in parts by mass: 100 parts of chloroprene rubber, 50 parts of ethylene-vinyl alcohol copolymer, 30 parts of nano-alumina, 30 parts of carbon black, 4 parts of sulfur, and 3 parts of antioxidant;

[0034] The parameters of the raw materials in the following examples and comparative examples are as follows:

[0035] The nitrile rubber is nitrile rubber NBR1052;

[0036] The average particle size of zinc oxide is 50nm;

[0037] The barium sulfate is 1250 mesh barium sulfate;

[0038] The talcum powder is 1250 mesh talcum powder.

[0039] Example 1

[0040] A hydraulic hose with good corrosion resistance, comprising an inner rubber layer, a steel wire reinforcement layer and an outer rubber layer from the inside to the outside, wherein the raw materials of the inner rubber layer comprise the following components in parts by mass: 100 parts of nitrile rubber, 15 parts of carbon black, 70 parts of barium sulfate coated with zinc oxide modified by siloxane, 1 part of antioxidant 264, 8 parts of dioctyl sebacate, 3 parts of zinc oxide, 3 parts of stearic acid, 2.5 parts of sulfur, and 3 parts of accelerator M;

[0041] The preparation method is as follows:

[0042] S1, mixing 0.2 parts of zinc oxide and 100 parts of barium sulfate, and grinding to obtain zinc oxide-coated barium sulfate;

[0043] S2, dispersing the zinc oxide-coated barium sulfate in 1000 parts of water, adding 10 parts of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane for modification, filtering, and drying to obtain siloxane-modified zinc oxide-coated barium sulfate;

[0044] S3. Mix the components of the raw materials of the inner rubber layer except sulfur at 145°C for 5 minutes, add sulfur and continue mixing at 50°C for 5 minutes, extrude and coat the rubber to obtain the inner rubber layer, weave a steel wire reinforcement layer on the outer surface of the inner rubber layer, cover the outer surface of the steel wire reinforcement layer with an outer rubber layer, and vulcanize at 170°C and 15MPa for 20 minutes to obtain a hydraulic hose.

[0045] Example 2

[0046] A hydraulic hose with good corrosion resistance, comprising an inner rubber layer, a steel wire reinforcement layer and an outer rubber layer from the inside to the outside, wherein the raw materials of the inner rubber layer comprise the following components in parts by mass: 100 parts of nitrile rubber, 20 parts of carbon black, 60 parts of barium sulfate coated with zinc oxide modified by siloxane, 3 parts of antioxidant 2246, 13 parts of dibutyl phthalate, 3 parts of magnesium oxide, 1 part of diisopropylbenzene peroxide, and 1.5 parts of accelerator CZ;

[0047] The preparation method is as follows:

[0048] S1, mixing 0.2 parts of zinc oxide and 100 parts of barium sulfate, and grinding to obtain zinc oxide-coated barium sulfate;

[0049] S2, dispersing the zinc oxide-coated barium sulfate in 1000 parts of water, adding 10 parts of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane for modification, filtering, and drying to obtain siloxane-modified zinc oxide-coated barium sulfate;

[0050] S3. Mix the components of the raw materials of the inner rubber layer except dicumyl peroxide at 145°C for 5 minutes, add dicumyl peroxide and continue mixing at 50°C for 5 minutes, extrude and coat the rubber to obtain the inner rubber layer, weave a steel wire reinforcement layer on the outer surface of the inner rubber layer, cover the outer surface of the steel wire reinforcement layer with an outer rubber layer, and vulcanize at 160°C and 5MPa for 40 minutes to obtain a hydraulic hose.

[0051] Example 3

[0052] The difference from Example 1 is only that: 1 part of zinc oxide.

[0053] Example 4

[0054] The difference from Example 1 is only that: 3 parts of zinc oxide.

[0055] Example 5

[0056] The difference from Example 1 is only that: 4 parts of zinc oxide.

[0057] Example 6

[0058] A hydraulic hose with good corrosion resistance, comprising an inner rubber layer, a steel wire reinforcement layer and an outer rubber layer from the inside to the outside, wherein the raw materials of the inner rubber layer comprise the following components in parts by mass: 100 parts of nitrile rubber, 15 parts of carbon black, 60 parts of barium sulfate coated with zinc oxide modified by siloxane, 10 parts of dibasic acid modified talc, 1 part of antioxidant 264, 8 parts of dioctyl sebacate, 3 parts of zinc oxide, 3 parts of stearic acid, 2.5 parts of sulfur, and 3 parts of accelerator M;

[0059] The preparation method is as follows:

[0060] S1, mixing 3 parts of zinc oxide and 100 parts of barium sulfate, and grinding to obtain zinc oxide-coated barium sulfate;

[0061] S2, dispersing the zinc oxide-coated barium sulfate in 1000 parts of water, adding 10 parts of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane for modification, filtering, and drying to obtain siloxane-modified zinc oxide-coated barium sulfate;

[0062] S3, after mixing 5 parts of 5-methylisophthalic acid with 150 parts of methanol, adding 100 parts of talc for modification, and drying to obtain dibasic acid modified talc;

[0063] S4. Mix the components of the raw materials of the inner rubber layer except sulfur at 145°C for 5 minutes, add sulfur and continue mixing at 50°C for 5 minutes, extrude and coat the rubber to obtain the inner rubber layer, weave a steel wire reinforcement layer on the outer surface of the inner rubber layer, cover the outer surface of the steel wire reinforcement layer with an outer rubber layer, and vulcanize at 170°C and 15MPa for 20 minutes to obtain a hydraulic hose.

[0064] Example 7

[0065] The only difference from Example 6 is that: 50 parts of barium sulfate coated with siloxane-modified zinc oxide and 20 parts of dibasic acid-modified talc.

[0066] Example 8

[0067] The only difference from Example 6 is that: 40 parts of barium sulfate coated with siloxane-modified zinc oxide and 30 parts of dibasic acid-modified talc.

[0068] Example 9

[0069] The only difference from Example 6 is that: 30 parts of barium sulfate coated with siloxane-modified zinc oxide and 40 parts of dibasic acid-modified talc.

[0070] Comparative Example 1

[0071] A hydraulic hose with good corrosion resistance, comprising an inner rubber layer, a steel wire reinforcement layer and an outer rubber layer from the inside to the outside, wherein the raw materials of the inner rubber layer comprise the following components in parts by mass: 100 parts of nitrile rubber, 15 parts of carbon black, 70 parts of siloxane-modified barium sulfate, 1 part of antioxidant 264, 8 parts of dioctyl sebacate, 3 parts of zinc oxide, 3 parts of stearic acid, 2.5 parts of sulfur, and 3 parts of accelerator M;

[0072] The preparation method is as follows:

[0073] S1, dispersing 100 parts of barium sulfate in 1000 parts of water, adding 10 parts of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane for modification, filtering, and drying to obtain siloxane-modified barium sulfate;

[0074] S2. Mix the components of the raw materials of the inner rubber layer except sulfur at 145°C for 5 minutes, add sulfur and continue mixing at 50°C for 5 minutes, extrude and coat the rubber to obtain the inner rubber layer, weave a steel wire reinforcement layer on the outer surface of the inner rubber layer, cover the outer surface of the steel wire reinforcement layer with an outer rubber layer, and vulcanize at 170°C and 15MPa for 20 minutes to obtain a hydraulic hose.

[0075] The inner rubber layer of the hydraulic hose obtained in Examples 1 to 9 and Comparative Example 1 was peeled off, and the initial tensile strength was measured according to the method in GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber", wherein the sample was a 1A dumbbell-shaped sample with a thickness of 4 mm; the sample was immersed in a sulfuric acid solution with a mass concentration of 20% and a sodium hydroxide solution with a mass concentration of 20% for 96 hours, respectively, and then the acid-treated tensile strength and the alkali-treated tensile strength were tested, and the change rate of the acid-treated tensile strength and the change rate of the alkali-treated tensile strength were calculated according to the following formula:

[0076] Change rate of tensile strength after acid treatment = (initial tensile strength - acid treatment tensile strength) ÷ initial tensile strength × 100%;

[0077] Alkali treatment tensile strength change rate = (initial tensile strength - alkali treatment tensile strength) ÷ initial tensile strength × 100%;

[0078] The results are recorded in Table 1.

[0079] Table 1 Corrosion resistance test results of the inner rubber layer of hydraulic hose

[0080]

[0081] It can be seen from Table 1 that after the inner rubber layer of the hydraulic hose provided by the present invention is immersed in a sulfuric acid solution with a mass concentration of 20% for 96 hours, the change rate of the tensile strength after acid treatment is less than 5.45%, and after being immersed in a sodium hydroxide solution with a mass concentration of 20% for 96 hours, the change rate of the tensile strength after alkali treatment is less than 3.64%. It has good corrosion resistance, and provides a hydraulic hose with good corrosion resistance.

[0082] Compared with Comparative Example 1, Examples 1 and Examples 3 to 5 use siloxane-modified zinc oxide-coated barium sulfate, and the tensile strength of the inner rubber layer of the obtained hydraulic hose is higher than that of Comparative Example 1, and the change rate of the tensile strength after acid treatment and the change rate of the tensile strength after alkali treatment are lower than those of Comparative Example 1, indicating that the siloxane-modified inorganic filler, wherein the inorganic filler is zinc oxide-coated barium sulfate as a filler, can improve the mechanical strength and corrosion resistance of the inner rubber layer of the hydraulic hose, thereby improving the mechanical strength and corrosion resistance of the hydraulic hose.

[0083] The tensile strength of the inner rubber layer of the hydraulic hose obtained in Examples 3 to 4 is higher than that in Example 1 and Example 5, and the change rate of the tensile strength after acid treatment and the change rate of the tensile strength after alkali treatment are lower than those in Example 1 and Example 5, indicating that the mass ratio of siloxane, zinc oxide and barium sulfate is 5:0.5 to 1.5:50, which can further improve the mechanical strength and corrosion resistance of the inner rubber layer of the hydraulic hose, thereby further improving the mechanical strength and corrosion resistance of the hydraulic hose.

[0084] The tensile strength of the inner rubber layer of the hydraulic hose obtained in Examples 6 to 9 is higher than that in Example 4, and the change rate of the tensile strength after acid treatment and the change rate of the tensile strength after alkali treatment are lower than those in Example 4, indicating that the compound use of siloxane-modified inorganic filler and dibasic acid-modified talc as filler can further improve the mechanical strength and corrosion resistance of the inner rubber layer of the hydraulic hose, thereby further improving the mechanical strength and corrosion resistance of the hydraulic hose.

[0085] The tensile strength of the inner rubber layer of the hydraulic hose obtained in Examples 7 to 8 is higher than that in Example 6 and Example 9, and the change rate of the tensile strength after acid treatment and the change rate of the tensile strength after alkali treatment are lower than those in Example 6 and Example 9, indicating that the mass ratio of dibasic acid-modified talc to siloxane-modified inorganic filler is 2:5 to 3:4, which can further improve the mechanical strength and corrosion resistance of the inner rubber layer of the hydraulic hose, thereby further improving the mechanical strength and corrosion resistance of the hydraulic hose.

[0086] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A hydraulic hose with good corrosion resistance, comprising an inner rubber layer, a steel wire reinforcement layer and an outer rubber layer from the inside to the outside, characterized in that: The raw materials of the inner rubber layer include the following components in parts by mass: 100 parts of nitrile rubber, 15-20 parts of carbon black, 60-70 parts of filler, 1-3 parts of antioxidant, 8-13 parts of plasticizer, 3-6 parts of activator, 1-2.5 parts of vulcanizer, and 1.5-3 parts of accelerator. The filler includes a siloxane-modified inorganic filler, and the inorganic filler is zinc oxide-coated barium sulfate. The raw materials of the siloxane-modified inorganic filler include siloxane, zinc oxide and barium sulfate in a mass ratio of 5:0.5 to 1.5:50; The average particle size of the zinc oxide is 50 nm; the barium sulfate is 1250 mesh barium sulfate; The preparation method of the siloxane-modified inorganic filler comprises the following steps: S1, mixing zinc oxide and barium sulfate, and grinding them to obtain zinc oxide-coated barium sulfate; S2. Dispersing the zinc oxide-coated barium sulfate in water, adding siloxane for modification, filtering, and drying to obtain a siloxane-modified inorganic filler.

2. A hydraulic hose with good corrosion resistance according to claim 1, characterized in that: The filler also includes dibasic acid modified talc.

3. A hydraulic hose with good corrosion resistance according to claim 2, characterized in that: The raw materials of the dibasic acid-modified talc powder include dibasic acid and talc powder in a mass ratio of 1 to 5:

50.

4. A hydraulic hose with good corrosion resistance according to claim 2 or 3, characterized in that: The preparation method of the dibasic acid modified talc comprises the following steps: mixing the dibasic acid with a solvent, adding talc to modify the mixture, and drying the mixture to obtain the dibasic acid modified talc.

5. The hydraulic hose with good corrosion resistance according to claim 2, characterized in that: The mass ratio of the dibasic acid-modified talc to the siloxane-modified inorganic filler is 2:5 to 3:

4.

6. The method for preparing a hydraulic hose with good corrosion resistance according to any one of claims 1 to 5, characterized in that: The following steps are involved: After kneading the components except the vulcanizing agent in the raw materials of the inner rubber layer, the vulcanizing agent is added and continued to be kneaded, extruded, and coated to obtain the inner rubber layer, a steel wire reinforcement layer is woven on the outer surface of the inner rubber layer, an outer rubber layer is coated on the outer surface of the steel wire reinforcement layer, and vulcanized to obtain the hydraulic hose.

7. The method for preparing a hydraulic hose with good corrosion resistance according to claim 6, characterized in that: The vulcanization temperature is 160-170° C., the pressure is 5-15 MPa, and the time is 20-40 min.

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