Skin collagen-based rubber sealing material and preparation method thereof

Abstract

The invention relates to a leather collagen-based rubber sealing material, which comprises the following components by mass: 5-10% of natural biomass; 20%-30% of water; 5%-8% of ethylene glycol glycidyl ether; 2%-4% of NaOH; 30%-40% of sheep pickled skin; 5%-10% of styrene butadiene rubber; 5%-10% of acrylonitrile butadiene rubber; the preparation method comprises the following steps that firstly, biomass-based chrome-free tanning agent dispersion liquid is prepared; 2, preparing a leather-based functional material; step 3, preparing a leather collagen-based rubber sealing material; the prepared collagen-based rubber sealing material can be used for a railway vehicle sealing device and has good sealing performance; the preparation method is simple in operation, accurate in regulation and control, time-saving, efficient, green and environment-friendly, and the raw materials are cheap and easy to obtain.

Description

Technical Field

[0001] The invention belongs to the technical field of natural polymer materials, and in particular relates to a collagen-based rubber sealing material and a preparation method thereof. Background Art

[0002] Focusing on natural biomass resources, we develop environmentally friendly, resource-saving, cutting-edge high-performance rubber products, especially high-performance railway truck door sealing materials. Through a series of related materials, processes, technologies and reasonable solutions to scientific problems, we create high-performance rubber products, and realize the universal use value in the fields of automotive turbocharger pipes, intake and exhaust pipes, engine and gearbox oil seals, cylinder head cover seals, spark plug seals, air springs, etc., providing theoretical basis and technical support for the processing and manufacturing of cutting-edge materials in related fields such as my country's aerospace, high-speed rail, and subway.

[0003] Focusing on natural biomass polymer material resources, aiming at the strategic goal of sustainable and high-quality development of the chemical industry and light industry, we will focus on creating environmentally friendly, resource-saving, cutting-edge high-performance rubber materials, especially high-performance elastic positioning sleeves for rail vehicles and high-performance railway freight car door sealing materials. The innovation lies in the introduction of wear-resistant natural biomass-based functional polymer materials into the positioning device of the railway passenger car axle box and the sealing of the railway open car door, designing a set of sealing materials that can meet the requirements of good sealing on all sides of the door and convenient installation, and using an advanced manufacturing method to achieve the thermal bonding technology of polymer wear-resistant materials and rubber and the hole expansion technology of the inner sleeve. In addition, the sustainable processing and manufacturing of leather materials rich in various functional properties for functional rubber sealing materials is still a blank in the field. This technology uses leather tanning-retanning technology to purposefully introduce natural starch materials, styrene-butadiene rubber and acrylonitrile-butadiene rubber into natural leather collagen, modify its collagen fibers, and give it good moisture and heat stability, sealing performance and mechanical properties, thereby realizing the effective preparation of functional leather collagen-based rubber materials. From the perspective of the aggregated structure of the rubber sealing material before and after modification, the interactive binding mechanism between the collagen fiber flexible base material and the rubber sealing material is explained, and combined with the application functional characteristics, a responsive binding model for biomass-based high-performance rubber sealing materials is proposed. Summary of the invention

[0004] In order to overcome the deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide a collagen-based rubber sealing material and a preparation method thereof, which has the characteristics of simple operation, green environmental protection, low cost, high sealing performance and mechanical properties.

[0005] To achieve the above object, the technical solution adopted by the present invention is: a leather collagen-based rubber sealing material, comprising the following components by mass percentage:

[0006] Natural biomass 5%~10%;

[0007] Water 20%~30%;

[0008] Ethylene glycol glycidyl ether 5%~8%;

[0009] NaOH 2%~4%;

[0010] Sheep acid skin 30%~40%;

[0011] Styrene butadiene rubber 5%~10%;

[0012] Acrylonitrile butadiene rubber 5%~10%.

[0013] A method for preparing a leather collagen-based rubber sealing material, comprising the following steps by mass percentage:

[0014] Step 1, preparing a biomass-based chrome-free tanning agent dispersion;

[0015] Step 2, preparing leather-based functional materials;

[0016] Step three, preparing collagen-based rubber sealing material.

[0017] The specific steps of step 1 are as follows:

[0018] 5% to 10% natural biomass, 10% to 15% water, and 5% to 8% ethylene glycol glycidyl ether were stirred at 40°C to 50°C for 2 to 4 hours, and the pH was adjusted to 10.5 with 2% to 4% NaOH to prepare a biomass-based chrome-free tanning agent dispersion;

[0019] In the step 1, the natural biomass is starch and collagen polypeptide.

[0020] The specific steps of step 2 are as follows:

[0021] Put sheep acid hides into a drum, add 30% to 40% of sheep acid hides, and obtain a biomass-based chrome-free tanning agent dispersion. After tanning, a leather-based functional material is obtained, the shrinkage temperature of which can reach 85.2°C, the tensile strength of the leather is 21.3MPa, the tear strength is 86.9N / mm, the elongation at break is 103.8%, and the mechanical strength is significantly better than that of untanned or TWS tanned leather.

[0022] The specific steps of step three are as follows:

[0023] The leather-based functional material obtained in step 2, 10%-15% water, 5%-10% styrene-butadiene rubber, and 5%-10% acrylonitrile-butadiene rubber are placed in a drum and rotated at 30°C-40°C for 2-4 hours to obtain a leather collagen-based rubber sealing material after retanning.

[0024] The beneficial effects of the present invention are:

[0025] The present invention utilizes natural biomass (starch, collagen polypeptide) as a substrate, obtains a biomass-based chrome-free tanning agent dispersion after a simple epoxy modification treatment, and successively utilizes the epoxy groups in the tanning agent molecules to chemically cross-link with the amino groups and carboxyl groups of the collagen molecules to prepare a leather-based functional material with good wet-heat stability and mechanical properties; then the prepared leather-based functional material is fully immersed in a mixed solution containing styrene-butadiene rubber and acrylonitrile-butadiene rubber, and fully stirred, infiltrated and combined to prepare a leather-collagen-based rubber sealing material with good sealing performance, which has excellent sealing and mechanical properties; the present invention effectively utilizes natural biomass resources and high-performance rubber material synthesis technology, and the prepared leather-collagen-based rubber sealing material can be used for railway vehicle sealing devices, and has good sealing performance; the preparation operation of the present invention is simple, can be precisely controlled, is time-saving and efficient, is green and environmentally friendly, and the raw materials are cheap and easily available. The following invention objectives are achieved: 1) to improve the mechanical properties and poor wet and hot stability of leather collagen fibers; 2) to improve the physical and chemical properties of leather; 3) to provide a method and product for biomass resource utilization and green rubber material production; 4) to provide a method for preparing green biomass-based high-performance rubber materials.

[0026] Compared with traditional rubber materials, the invention has simple preparation operation, is mild and controllable, time-saving and efficient, green and environmentally friendly, has good sealing and elasticity, and has great application potential in railway freight car door sealing materials. DETAILED DESCRIPTION

[0027] The present invention is further described in detail below with reference to specific embodiments.

[0028] Example 1

[0029] A leather collagen-based rubber sealing material, comprising the following components by mass percentage:

[0030] Natural biomass 5%;

[0031] Water 30%;

[0032] Ethylene glycol glycidyl ether 5%;

[0033] NaOH 2%;

[0034] Sheep sour skin 40%;

[0035] Styrene butadiene rubber 9%;

[0036] Acrylonitrile butadiene rubber 9%.

[0037] Example 2

[0038] A leather collagen-based rubber sealing material, comprising the following components by mass percentage:

[0039] Natural biomass 10%;

[0040] Water 30%;

[0041] Ethylene glycol glycidyl ether 8%;

[0042] NaOH 2%;

[0043] Sheep sour skin 30%;

[0044] Styrene butadiene rubber 10%;

[0045] Acrylonitrile butadiene rubber 10%.

[0046] Example 3

[0047] A leather collagen-based rubber sealing material, comprising the following components by mass percentage:

[0048] Natural biomass 10%;

[0049] Water 30%;

[0050] Ethylene glycol glycidyl ether 6%;

[0051] NaOH 4%;

[0052] Sheep sour skin 40%;

[0053] Styrene butadiene rubber 5%;

[0054] Acrylonitrile butadiene rubber 5%.

[0055] Example 4

[0056] A leather collagen-based rubber sealing material, comprising the following components by mass percentage:

[0057] Natural biomass 10%;

[0058] Water 30%;

[0059] Ethylene glycol glycidyl ether 6%;

[0060] NaOH 3%;

[0061] Sheep sour skin 35%;

[0062] Styrene butadiene rubber 8%;

[0063] Acrylonitrile butadiene rubber 8%.

[0064] Example 5

[0065] A leather collagen-based rubber sealing material, comprising the following components by mass percentage:

[0066] Natural biomass 8%;

[0067] Water 25%;

[0068] Ethylene glycol glycidyl ether 8%;

[0069] NaOH 4%;

[0070] Sheep sour skin 40%;

[0071] Styrene butadiene rubber 10%;

[0072] Acrylonitrile butadiene rubber 5%.

[0073] Example 6

[0074] A leather collagen-based rubber sealing material, comprising the following components by mass percentage:

[0075] Natural biomass 10%;

[0076] Water 20%;

[0077] Ethylene glycol glycidyl ether 8%;

[0078] NaOH 4%;

[0079] Sheep sour skin 40%;

[0080] Styrene butadiene rubber 8%;

[0081] Acrylonitrile butadiene rubber 10%.

[0082] Example 7

[0083] A method for preparing a leather collagen-based rubber sealing material, comprising the following steps by mass percentage:

[0084] A method for preparing a leather collagen-based rubber sealing material, comprising the following steps by mass percentage:

[0085] Step 1, preparing a biomass-based chrome-free tanning agent dispersion;

[0086] 10% natural biomass (starch, collagen polypeptide), 15% water, 8% ethylene glycol glycidyl ether were stirred at 40°C for 2h, and the pH was adjusted to 10.5 with 2% (1mol / L) NaOH to prepare a biomass-based chrome-free tanning agent dispersion;

[0087] The natural biomass is starch and collagen polypeptide;

[0088] Step 2, preparing leather-based functional materials;

[0089] Put sheep acid hides into a drum, add 30% of sheep acid hides to obtain a biomass-based chrome-free tanning agent dispersion, and the leather-based functional material obtained after tanning has a shrinkage temperature of up to 85.2°C, a tensile strength of 21.3MPa, a tear strength of 86.9N / mm, and an elongation at break of 103.8%, and its mechanical strength is significantly better than that of untanned or TWS-tanned leather;

[0090] Step 3, preparing a collagen-based rubber sealing material;

[0091] The leather-based functional material obtained in step 2, 15% water, 10% styrene butadiene rubber and 10% acrylonitrile butadiene rubber are placed in a drum and rotated at 30° C. for 4 hours to obtain a leather collagen-based rubber sealing material after retanning.

[0092] Example 8

[0093] A method for preparing a leather collagen-based rubber sealing material, comprising the following steps by mass percentage:

[0094] Step 1, preparing a biomass-based chrome-free tanning agent dispersion;

[0095] 8% natural biomass (starch, collagen polypeptide), 12.5% ​​water, 8% ethylene glycol glycidyl ether were stirred at 45°C for 3h, and the pH was adjusted to 10.5 with 4% (1mol / L) NaOH to prepare a biomass-based chrome-free tanning agent dispersion;

[0096] The natural biomass is starch and collagen polypeptide;

[0097] Step 2, preparing leather-based functional materials;

[0098] Put sheep acid hides into a drum, add the biomass-based chrome-free tanning agent dispersion obtained in step 1 accounting for 40% of the sheep acid hides, and the leather-based functional material obtained after tanning has a shrinkage temperature of up to 85.2°C, a tensile strength of 21.3MPa, a tear strength of 86.9N / mm, and an elongation at break of 103.8%, and its mechanical strength is significantly better than that of untanned or TWS-tanned leather;

[0099] Step 3, preparing a collagen-based rubber sealing material;

[0100] The leather-based functional material obtained in step 2, 12.5% ​​water, 10% styrene-butadiene rubber, and 5% acrylonitrile-butadiene rubber are placed in a drum, rotated at 35° C. for 3 hours, and a leather collagen-based rubber sealing material is obtained after retanning;

[0101] Example 9

[0102] A method for preparing a leather collagen-based rubber sealing material, comprising the following steps by mass percentage:

[0103] Step 1, preparing a biomass-based chrome-free tanning agent dispersion;

[0104] 10% natural biomass (starch, collagen polypeptide), 10% water, 8% ethylene glycol glycidyl ether were stirred at 50°C for 4 hours, and the pH was adjusted to 10.5 with 4% (1 mol / L) NaOH to prepare a biomass-based chrome-free tanning agent dispersion;

[0105] The natural biomass is starch and collagen polypeptide;

[0106] Step 2, preparing leather-based functional materials;

[0107] Put sheep acid hides into a drum, add 40% of the sheep acid hides to obtain a biomass-based chrome-free tanning agent dispersion, and the leather-based functional material obtained after tanning can reach a shrinkage temperature of 85.2°C, the leather tensile strength is 21.3MPa, the tear strength is 86.9N / mm, and the elongation at break is 103.8%. The mechanical strength is significantly better than that of untanned or TWS-tanned leather;

[0108] Step 3, preparing a collagen-based rubber sealing material;

[0109] The leather-based functional material obtained in step 2, 10% water, 8% styrene-butadiene rubber and 10% acrylonitrile-butadiene rubber are placed in a drum and rotated at 40° C. for 4 hours to obtain a leather collagen-based rubber sealing material after retanning.

Claims

1. A leather collagen-based rubber sealing material, characterized by: Includes the following components: Natural biomass 5%~10%; Water 20%~30%; Ethylene glycol glycidyl ether 5%~8%; NaOH 2%~4%; Sheep acid skin 30%~40%; Styrene butadiene rubber 5%~10%; Acrylonitrile butadiene rubber 5%~10%.

2. A method for preparing a collagen-based rubber sealing material, characterized in that: The following steps are involved: Step 1, preparing a biomass-based chrome-free tanning agent dispersion; Step 2, preparing leather-based functional materials; Step three, preparing collagen-based rubber sealing material.

3. The method for preparing a collagen-based rubber sealing material according to claim 2, characterized in that, by mass percentage, The specific steps of step 1 are as follows: 5% to 10% natural biomass, 10% to 15% water, and 5% to 8% ethylene glycol glycidyl ether were stirred at 40°C to 50°C for 2 to 4 hours, and the pH was adjusted to 10.5 with 2% to 4% NaOH to prepare a biomass-based chrome-free tanning agent dispersion; In the step 1, the natural biomass is starch and collagen polypeptide.

4. The method for preparing a collagen-based rubber sealing material according to claim 2, characterized in that: The specific steps of step 2 are as follows: Put sheep acid hides into a drum, add 30% to 40% of sheep acid hides, and obtain a biomass-based chrome-free tanning agent dispersion. After tanning, a leather-based functional material is obtained, the shrinkage temperature of which can reach 85.2°C, the tensile strength of the leather is 21.3MPa, the tear strength is 86.9N / mm, the elongation at break is 103.8%, and the mechanical strength is significantly better than that of untanned or TWS tanned leather.

5. The method for preparing a collagen-based rubber sealing material according to claim 2, characterized in that: The specific steps of step three are as follows: The leather-based functional material obtained in step 2, 10%-15% water, 5%-10% styrene-butadiene rubber, and 5%-10% acrylonitrile-butadiene rubber are placed in a drum and rotated at 30°C-40°C for 2-4 hours to obtain a leather collagen-based rubber sealing material after retanning.