A kind of fast vulcanized amidoxime modified nitrile rubber and its preparation method and application

Abstract

The application provides a kind of fast vulcanized amidoxime modified nitrile rubber and its preparation method and application, belongs to the field of rubber materials.The amidoxime modified nitrile rubber prepared by the application is prepared from the following weight parts of raw materials: amidoxime modified nitrile rubber green rubber 100 parts, vulcanization accelerator 0.1-5 parts, filler 20-50 parts.The amidoxime modified nitrile rubber of the application can not only be quickly vulcanized, but also has excellent mechanical properties by improving the mixing process of the amidoxime modified nitrile rubber.The application simplifies the production process, improves the production efficiency, and has significant industrial application value.The amidoxime modified nitrile rubber material of the application has wide application prospect in the fields of environmental remediation, biological medicine, electronics and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of rubber materials, and particularly relates to a kind of rapid vulcanized amine oxime modified nitrile rubber and its preparation method and application. BACKGROUND

[0002] Hydrogenated nitrile rubber (HNBR) has excellent oil resistance, outstanding heat resistance and good mechanical properties due to its saturated molecular structure, and is widely used in the fields of automobiles, aerospace and others. However, with the development of modern industry towards high precision and high performance, the demand for functionalized rubber materials is increasingly diversified. Amine oxime modification is an effective means of functionalizing HNBR, which introduces amine oxime groups into the molecular chain of HNBR, endowing the rubber with unique properties such as strong chelation ability to metal ions. This makes amine oxime modified HNBR useful in the field of environmental remediation for adsorbing and recovering heavy metal ions in wastewater, in the field of biomedicine as a sensitive material for biosensors to achieve specific recognition of biological molecules, and in the field of electronics as a conductive rubber with special properties and a battery adhesive.

[0003] Although amine oxime modified HNBR has many advantages, current research mainly focuses on modification methods and basic performance characterization, and there is relatively little research on vulcanization processes during processing, especially the use of intramolecular group self-vulcanization characteristics. In the processing of rubber, traditional vulcanization process relies on external vulcanizing agent and vulcanizing agent, which not only increases the production cost, but also may affect the purity and stability of rubber products due to the residue of vulcanizing agent. The amine oxime modified HNBR contains amine oxime groups and cyano groups in its molecule, which can undergo self-vulcanization under certain conditions, providing a new idea for simplifying the vulcanization process, improving production efficiency and product quality. However, the precise control of self-vulcanization conditions of amine oxime modified HNBR and its systematic study in practical application are still relatively lacking.

[0004] Patent application file CN117659228A proposes a new type of vulcanization method of nitrile rubber material with self-crosslinking and self-reinforcement through self-crosslinking of amine oxime bond and hydrogen bonding, which is different from external vulcanizing agent. However, the tensile strength of the nitrile rubber material is only 28.3 MPa at most, which needs to be further improved, and the method has the following problems: the vulcanization time of the vulcanization temperature below 180℃ in the examples is generally long, all of which are more than 30 minutes, which is too slow for commercial production in pursuit of economic benefits.

[0005] Therefore, how to optimize the self-vulcanization conditions of amine oxime modified HNBR, improve the vulcanization efficiency, and at the same time maintain its excellent performance, is a technical problem to be solved at present. SUMMARY

[0006] The present application aims to provide a kind of quick vulcanized amidoxime modified nitrile rubber and its preparation method and application.

[0007] The present application provides a kind of amidoxime modified nitrile rubber mix, it includes the following weight parts of raw materials: amidoxime modified nitrile rubber raw rubber 100 parts, vulcanization accelerator 0.1-5 parts, filling agent 20-50 parts;The amidoxime modified nitrile rubber raw rubber is obtained by the reaction of acrylonitrile-containing nitrile rubber and hydroxylamine hydrochloride.

[0008] Further, the amidoxime modified nitrile rubber mix includes the following weight parts of raw materials: amidoxime modified nitrile rubber raw rubber 100 parts, vulcanization accelerator 0.5-4 parts, filling agent 20-50 parts, preferably: amidoxime modified nitrile rubber raw rubber 100 parts, vulcanization accelerator 2 parts, filling agent 50 parts.

[0009] In the formula of the present application, "parts" means weight parts, 1 part is 1g.

[0010] Further, the vulcanization accelerator is fatty acid or aromatic acid, preferably stearic acid;

[0011] The filling agent is any one or mixture of any several of barium sulfate, calcium silicate, carbon black, diatomite, silicon powder and white carbon black, preferably carbon black.

[0012] Further, the amidoxime modified nitrile rubber mix also includes any one or mixture of any several of vulcanizing agent, vulcanization aid, acid absorbent, pigment, plasticizer, release agent, metal oxide.

[0013] Further, the vulcanizing agent is selected from 2,4-di-tert-butyl peroxide isopropyl benzene, benzoyl peroxide or bis-dipent;

[0014] The vulcanization aid is selected from N,N'-m-phenylene bismaleimide, multifunctional maleimide, 1,3,5-triallyl cyanurate or triallyl isocyanurate.

[0015] Further, the preparation method of the amidoxime modified nitrile rubber raw rubber includes the following steps: acrylonitrile-containing nitrile rubber solution, hydroxylamine hydrochloride and alkali solution are reacted, and then obtained.

[0016] Further, the content of acrylonitrile in the nitrile rubber is 1-60wt%;The nitrile rubber is ordinary nitrile rubber, carboxyl nitrile rubber or hydrogenated nitrile rubber, preferably hydrogenated nitrile rubber;

[0017] The mass fraction of the acrylonitrile-containing nitrile rubber solution is 5-15%, preferably 10%;

[0018] The mass fraction of the alkali solution is 5-20%, preferably 17-18%.

[0019] Further, the molar ratio of acrylonitrile units, hydroxylamine hydrochloride and alkali in the acrylonitrile-containing nitrile rubber is 1:1:1-1.5; the solvent in the acrylonitrile-containing nitrile rubber solution is tetrahydrofuran, toluene, xylene, dichloromethane, dichloroethane, trichloromethane or acetonitrile; the alkali is sodium hydroxide, potassium hydroxide, lithium hydroxide or anhydrous sodium carbonate; the solvent in the alkali solution is methanol, ethanol or isopropanol; and the reaction conditions are as follows: under an inert gas atmosphere, at 30-90℃ for 1-25h.

[0020] Further, the molar ratio of acrylonitrile units, hydroxylamine hydrochloride and alkali in the acrylonitrile-containing nitrile rubber is 1:1:1.1; and the reaction conditions are as follows: under an inert gas atmosphere, at 40-80℃ for 2-24h.

[0021] Further, the solvent used in the reaction is preferably used in an amount that can completely dissolve the monomer and maintain good fluidity of the reaction system, and the solvent used in the reaction is preferably used in an amount of 5-10 times the mass of the rubber.

[0022] Further, after the reaction, the following purification step is further included: after the reaction, water is added for precipitation, washing and drying, and the product is obtained.

[0023] The application further provides a method for preparing the above-mentioned amidoxime-modified nitrile rubber compound, and the method comprises the following steps: plasticizing the amidoxime-modified nitrile rubber raw rubber, then adding the remaining raw materials and mixing uniformly, and vulcanizing, and the product is obtained.

[0024] Further, the plasticizing conditions are as follows: plasticizing at 10-40℃ for 1-5min; and the vulcanizing conditions are as follows: vulcanizing at a pressure of 5-25MPa and at 160-200℃ for 1-60min.

[0025] Further, the plasticizing conditions are as follows: plasticizing at a speed of 40r·min -1 -1 at 23±1℃ for 2-3min; and the vulcanizing conditions are as follows: vulcanizing at a pressure of 10MPa and at 180℃ for 1.2 times TC90+3min.

[0026] Further, TC90 represents the process curing time (min), which refers to the time required from the start of heating of the rubber compound to the time when the torque reaches 90% of the maximum torque.

[0027] Further, when the amidoxime-modified nitrile rubber compound is composed of 100 parts of amidoxime-modified nitrile rubber raw rubber, 0.5 parts of vulcanization accelerator and 50 parts of filler, the TC90 is 29.45min.

[0028] When the amidoamine modified nitrile rubber compound is composed of amidoamine modified nitrile rubber raw rubber 100 parts, vulcanization accelerator 1 part, and filler 50 parts, the TC90 is 18.44 min;

[0029] When the amidoamine modified nitrile rubber compound is composed of amidoamine modified nitrile rubber raw rubber 100 parts, vulcanization accelerator 2 parts, and filler 50 parts, the TC90 is 10.58 min;

[0030] When the amidoamine modified nitrile rubber compound is composed of amidoamine modified nitrile rubber raw rubber 100 parts, vulcanization accelerator 3 parts, and filler 50 parts, the TC90 is 10.45 min;

[0031] When the amidoamine modified nitrile rubber compound is composed of amidoamine modified nitrile rubber raw rubber 100 parts, vulcanization accelerator 4 parts, and filler 50 parts, the TC90 is 9.42 min.

[0032] The application also provides a use of the amidoamine modified nitrile rubber compound in preparing materials in the fields of automobiles, aerospace, environmental remediation, biomedicine, and electronics.

[0033] The application has the following beneficial effects:

[0034] The amidoamine modified nitrile rubber can be quickly vulcanized and has excellent mechanical properties through improvement of the amidoamine modified nitrile rubber mixing process. The application simplifies the production process, improves production efficiency, and has significant industrial application value. The amidoamine modified nitrile rubber material has broad application prospects in the fields of environmental remediation, biomedicine, and electronics.

[0035] Compared with the nitrile rubber material in the patent application document CN117659228A, the tensile strength of the amidoamine modified nitrile rubber is better, up to 33.64 MPa, while the tensile strength of the nitrile rubber material in the patent application document CN117659228A is only up to 28.3 MPa at most. In addition, the vulcanization rate of the preparation method is faster, and the vulcanization time of the preferred (Example 3) is only 15 min; while the vulcanization time in the patent application document CN117659228A is all above 30 min, and the vulcanization rate is too slow.

[0036] Obviously, according to the above content of the application, according to the ordinary technical knowledge and common means in the art, other various forms of modifications, replacements or changes can be made without departing from the above basic technical ideas of the application.

[0037] The above mentioned subject matter of the present application will be further explained in details by way of specific embodiments in the form of examples. However, it should not be construed that the scope of the above mentioned subject matter of the present application is limited to the following examples only. Any technology realized based on the above mentioned subject matter of the present application falls within the scope of the present application. DETAILED DESCRIPTION

[0038] The raw materials and equipment used in the present application are known products, which are obtained by purchasing commercially available products.

[0039] "Room temperature" as used in the present application means 23±1°C. The hydrogenated nitrile rubber used in the examples and comparative examples of the present application is Therban 3406 hydrogenated nitrile rubber (the content of acrylonitrile in the rubber is 34±1 wt%) of Arlanxeo.

[0040] Example 1, Preparation of the Ammoxime-modified hydrogenated nitrile rubber compound

[0041] Formulation: Ammoxime-modified hydrogenated nitrile rubber 100 parts, stearic acid 0.5 parts, carbon black N550 50 parts.

[0042] Preparation method:

[0043] (1) Preparation of ammoxime-modified hydrogenated nitrile rubber

[0044] The hydrogenated nitrile rubber containing acrylonitrile is used as raw material, which is dissolved (solvent: tetrahydrofuran, solvent amount: 10 ml / g of hydrogenated nitrile rubber) to prepare a solution with a mass fraction of 10%. Under a nitrogen protective atmosphere, stoichiometrically (the molar ratio of acrylonitrile units to hydroxylamine hydrochloride to base is 1:1:1.1) hydroxylamine hydrochloride is added to the solution, which is stirred uniformly, then a mass fraction of 17.4% base solution (the base solution is a methanol solution of potassium hydroxide, solvent amount: 6 ml / g of potassium hydroxide) is slowly added dropwise, the dropwise speed is controlled at 2 mL / min, the reaction temperature is maintained at 40-80°C, and the reaction time is 2-24 h. After the reaction is completed, the reaction liquid is poured into a large amount of deionized water to precipitate the modified rubber, which is washed with water for several times until it is neutral, then dried in a vacuum drying oven at 55°C to constant weight to obtain the ammoxime-modified hydrogenated nitrile rubber.

[0045] (2) Preparation of ammoxime-modified hydrogenated nitrile rubber

[0046] The ammoxime-modified hydrogenated nitrile rubber is added to a two-roll open mill, which is plasticized at room temperature for 2-3 min, the roller speed is 40 r·min -1, add carbon black N550 and stearic acid, keep the roller speed unchanged, after mixing evenly, adjust the roll gap to 1 mm below the roll, thin pass triangle package and roll, finally adjust the roll gap to 2 mm out of the sheet, to prepare the mixing rubber. The mixing rubber is placed in the mold, the pressure is controlled to 10 MPa, the temperature is 180℃, the vulcanization time is 1.2 times TC90+3min (TC90 is shown in Table 1), and the amine oxime modified hydrogenated nitrile rubber mixing rubber is obtained.

[0047] Example 2, preparation of amine oxime modified hydrogenated nitrile rubber mixing rubber

[0048] Formula: amine oxime modified hydrogenated nitrile rubber 100 parts, stearic acid 1 part, carbon black N550 50 parts.

[0049] Preparation method: as described in example 1.

[0050] Example 3, preparation of amine oxime modified hydrogenated nitrile rubber mixing rubber

[0051] Formula: amine oxime modified hydrogenated nitrile rubber 100 parts, stearic acid 2 parts, carbon black N550 50 parts.

[0052] Preparation method: as described in example 1.

[0053] Example 4, preparation of amine oxime modified hydrogenated nitrile rubber mixing rubber

[0054] Formula: amine oxime modified hydrogenated nitrile rubber 100 parts, stearic acid 3 parts, carbon black N550 50 parts.

[0055] Preparation method: as described in example 1.

[0056] Example 5, preparation of amine oxime modified hydrogenated nitrile rubber mixing rubber

[0057] Formula: amine oxime modified hydrogenated nitrile rubber 100 parts, stearic acid 4 parts, carbon black N550 50 parts.

[0058] Preparation method: as described in example 1.

[0059] The following comparative examples are prepared for comparison with the samples.

[0060] Comparative example 1, preparation of amine oxime modified hydrogenated nitrile rubber mixing rubber

[0061] Formula: amine oxime modified hydrogenated nitrile rubber 100 parts, stearic acid 0 parts, carbon black N550 50 parts.

[0062] Preparation method: as described in example 1.

[0063] Comparative example 2, preparation of hydrogenated nitrile rubber mixing rubber without amine oxime modification

[0064] Formulation: hydrogenated nitrile raw rubber 100 parts, stearic acid 0 parts, carbon black N550 50 parts, BIBP 2 parts, TAIC 4 parts.

[0065] Preparation method: as described in Example 1.

[0066] Preparation of non-amidoxime-modified hydrogenated nitrile rubber of Comparative Example 3

[0067] Formulation: hydrogenated nitrile raw rubber 100 parts, stearic acid 2 parts, N550 50 parts, BIBP 2 parts, TAIC 4 parts.

[0068] Preparation method: as described in Example 1.

[0069] The beneficial effects of the present application are demonstrated by the following experimental examples.

[0070] Experimental Example 1, testing the properties of the amidoxime-modified hydrogenated nitrile rubber compound and the non-amidoxime-modified hydrogenated nitrile rubber compound

[0071] 1. Experimental method

[0072] The samples of Examples 1-5 and Comparative Examples 1-3 were subjected to vulcanization testing, testing standard: GB / T 16584-1996, testing conditions: testing equipment GT-M3000A, conditions MDR 180℃@60min, Arc 0.5.

[0073] Tensile strength and elongation at break were tested according to the national standard GB / T 528-2009.

[0074] 2. Experimental results

[0075] Table 1 is the vulcanization test results of the samples.

[0076] Table 1 is the vulcanization test results of the samples.

[0077] MH ML TS2 TC90 Example 1 26.45 3.35 0.57 29.45 Example 2 24.48 3.32 0.43 18.44 Example 3 20.25 2.46 0.47 10.58 Example 4 18.74 2.20 0.36 10.45 Example 5 17.74 1.80 0.35 9.42 Comparative Example 1 29.45 3.45 1.26 37.27 Comparative Example 2 28.84 1.2 0.28 5.34 Comparative Example 3 24.84 0.98 0.40 5.40

[0078] Wherein, ML: minimum torque, N·m (kgf·cm), indicating the flowability of the compound, the lower the ML, the better the flowability, otherwise, the worse

[0079] MH: maximum torque N·m (kgf·cm), indicating the shear modulus and crosslinking density of the compound, MH depends on the filler and vulcanization system, wherein MH-ML (maximum and minimum torque difference) reflects the crosslinking degree (density);

[0080] TS2: the time when the torque of the rubber compound reaches (minimum torque + 2, min), at which time the vulcanization of the rubber compound reaches a certain rate, which can be indirectly considered as the time when the rubber compound is basically shaped, and which represents the operation safety of the rubber compound. The shorter the TS2, the more likely the rubber compound is to scorch, and the flowability of the rubber compound after scorching is significantly reduced, and even the rubber compound cannot flow, so that the subsequent processing procedures cannot be normally operated. On the contrary, the longer the TS2, the longer the operation safety processing time, but the production efficiency is low, and the cost is increased.

[0081] TC90: process curing time (min), the time required from the start of heating of the rubber compound to the torque reaching 90% of the maximum torque. TC90 is mainly used to evaluate the one-time curing conditions of the rubber compound in the molding production, and a longer TC90 indicates that the vulcanization speed is relatively slow, and the production efficiency is low.

[0082] It can be seen from the comparison of the vulcanization test results of Examples 1-5 and Comparative Examples 1-3 that the addition of stearic acid to the amminoxime hydrogenated nitrile vulcanizing system in Examples 1-5 can effectively improve the vulcanization rate and promote crosslinking.

[0083] Further comparison of Examples 1-5 and Comparative Example 1 shows that the technical scheme of using stearic acid as a promoter of the amminoxime hydrogenated nitrile vulcanizing system significantly improves the vulcanization rate; compared with Comparative Examples 2 and 3, the technical scheme of using stearic acid as a promoter of the amminoxime hydrogenated nitrile vulcanizing system in Examples 1-5 is only directed to the amminoxime hydrogenated nitrile rubber.

[0084] Table 2 shows the mechanical property test results of the samples.

[0085] Table 2 shows the mechanical property test results of the samples.

[0086]

[0087] Further comparison of the mechanical properties of Examples 1-5 shows that the tensile strength obtained by using 2 parts of stearic acid as a promoter of the amminoxime hydrogenated nitrile vulcanizing system in Example 3 is optimal, and an unexpected technical effect is achieved.

[0088] In summary, the present application provides a kind of amminoxime modified nitrile rubber of rapid vulcanization and its preparation method and application.The amminoxime modified nitrile rubber prepared by the present application is prepared from the following weight parts of raw materials:100 parts of amminoxime modified nitrile rubber raw rubber, 0.1-5 parts of vulcanization accelerator, 20-50 parts of filler.The amminoxime modified nitrile rubber of the present application can be rapidly vulcanized, and has excellent mechanical properties by improving the mixing process of the amminoxime modified nitrile rubber.The present application simplifies the production process, improves the production efficiency, and has significant industrial application value.The amminoxime modified nitrile rubber material of the present application has wide application prospects in the fields of environmental remediation, biological medicine, electronics, etc.

Claims

1. An amidoxime-modified nitrile rubber compound, characterized by, It comprises the following raw materials by weight: 100 parts of amidoxime modified nitrile rubber raw rubber, 2 parts of stearic acid, 50 parts of carbon black; the amidoxime modified nitrile rubber raw rubber is obtained by reacting nitrile-containing nitrile rubber with hydroxylamine hydrochloride.

2. The amine-oxime modified nitrile rubber mix according to claim 1, characterized in that, The amidoxime modified nitrile rubber raw rubber also comprises any one or mixture of any several of vulcanizing agent, vulcanizing aid, acid absorber, pigment, plasticizer, release agent, metal oxide.

3. The amine-oxime modified nitrile rubber mix of claim 1, wherein, The preparation method of the amidoxime modified nitrile rubber raw rubber comprises the following steps: reacting nitrile-containing nitrile rubber solution, hydroxylamine hydrochloride and alkali solution, and then obtaining.

4. The amidoxime-modified nitrile rubber mix of claim 3, wherein the amidoxime-modified nitrile rubber mix has a Mooney viscosity ML (1+10) at 100 °C of 30 to 60. The content of acrylonitrile in the nitrile rubber is 1-60 wt%; the nitrile rubber is ordinary nitrile rubber, carboxyl nitrile rubber or hydrogenated nitrile rubber; The mass fraction of the nitrile-containing nitrile rubber solution is 5-15 %; The mass fraction of the alkali solution is 5-20 %.

5. The amine-oxime modified nitrile rubber mix according to claim 4, characterized in that, The nitrile rubber is hydrogenated nitrile rubber; The mass fraction of the nitrile-containing nitrile rubber solution is 10 %; The mass fraction of the alkali solution is 17-18 %.

6. The amine-oxime modified nitrile rubber mix of claim 3, wherein the amine-oxime modified nitrile rubber mix has a Mooney viscosity ML (1+10) at 100 °C of 30 to 60. The molar ratio of acrylonitrile unit in the nitrile-containing nitrile rubber, hydroxylamine hydrochloride and alkali is 1:1:1-1.5; the solvent in the nitrile-containing nitrile rubber solution is tetrahydrofuran, toluene, xylene, dichloromethane, dichloroethane, trichloromethane or acetonitrile; the alkali is sodium hydroxide, potassium hydroxide, lithium hydroxide or anhydrous sodium carbonate; the solvent in the alkali solution is methanol, ethanol or isopropyl alcohol; the reaction conditions are as follows: under inert gas atmosphere, at 30-90℃ for 1-25h.

7. A process for preparing the amidoxime-modified nitrile rubber mix according to any one of claims 1 to 6, characterized in that The method comprises the following steps: masticating the amidoxime modified nitrile rubber raw rubber, then adding and mixing the remaining raw materials uniformly, and then vulcanizing, and then obtaining.

8. The method of claim 7, wherein, The mastication conditions are as follows: masticating at 10-40℃ for 1-5min; the vulcanization conditions are as follows: vulcanizing at 5-25MPa pressure and 160-200℃ for 1-60min.

9. Use of the amidoxime modified nitrile rubber raw rubber in the preparation of materials in the fields of automobile, aerospace, environmental remediation, biomedicine and electronics.

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