阅读说明：本技术 一种石墨烯天然橡胶耐油混合发泡材料及其制备方法 (Graphene natural rubber oil-resistant mixed foam material and preparation method thereof ) 是由 丁天宁 丁德材 丁幼丝 于 2019-10-14 设计创作，主要内容包括：本发明公开了一种石墨烯天然橡胶耐油混合发泡材料及其制备方法,由包括以下重量份的原料制成：天然橡胶36～44份、丁腈橡胶28～33份、顺丁橡胶8.5～11.5份、聚氯乙烯树脂14～16份、白炭黑4～6份、硅酮油1.2～1.5份、氧化锌1.7～2.1份、硬脂酸锌1.4～1.8份、硬脂酸1.3～1.6份、交联剂2.3～2.9份、石墨烯2.5～3.5份、发泡剂1.9～2.5份、流动助剂1.8～2.4份。本发明的产品在烃类油溶剂(如丙烯酸丁酯)中浸泡后,仍然保持高的拉伸强度和大的断裂伸长率,不易与烃类油溶剂发生作用,耐油性能好,力学性能好；压缩永久变形率,回弹性好,力学性能好；耐磨性能好。(The invention discloses a graphene natural rubber oil-resistant mixed foaming material and a preparation method thereof, wherein the graphene natural rubber oil-resistant mixed foaming material is prepared from the following raw materials in parts by weight: 36-44 parts of natural rubber, 28-33 parts of nitrile rubber, 8.5-11.5 parts of butadiene rubber, 14-16 parts of polyvinyl chloride resin, 4-6 parts of white carbon black, 1.2-1.5 parts of silicone oil, 1.7-2.1 parts of zinc oxide, 1.4-1.8 parts of zinc stearate, 1.3-1.6 parts of stearic acid, 2.3-2.9 parts of a cross-linking agent, 2.5-3.5 parts of graphene, 1.9-2.5 parts of a foaming agent and 1.8-2.4 parts of a flow assistant. After the product of the invention is soaked in hydrocarbon oil solvent (such as butyl acrylate), high tensile strength and large elongation at break are still maintained, the product is not easy to react with the hydrocarbon oil solvent, and the oil resistance and the mechanical property are good; the compression set rate, the rebound resilience and the mechanical property are good; the wear resistance is good.)

1. The oil-resistant graphene natural rubber mixed foam material is characterized by being prepared from the following raw materials in parts by weight: 36-44 parts of natural rubber, 28-33 parts of nitrile rubber, 8.5-11.5 parts of butadiene rubber, 14-16 parts of polyvinyl chloride resin, 4-6 parts of white carbon black, 1.2-1.5 parts of silicone oil, 1.7-2.1 parts of zinc oxide, 1.4-1.8 parts of zinc stearate, 1.3-1.6 parts of stearic acid, 2.3-2.9 parts of a cross-linking agent, 2.5-3.5 parts of graphene, 1.9-2.5 parts of a foaming agent and 1.8-2.4 parts of a flow assistant; the cross-linking agent is a mixture of sulfur, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and N, N' -p-phenyl bismaleimide; the graphene is edge graphene oxide.

2. The graphene natural rubber oil-resistant hybrid foam material according to claim 1, wherein the graphene natural rubber oil-resistant hybrid foam material is prepared from the following raw materials in parts by weight: 42 parts of natural rubber, 31.5 parts of nitrile rubber, 10.8 parts of butadiene rubber, 15.4 parts of polyvinyl chloride resin, 5.2 parts of white carbon black, 1.42 parts of silicone oil, 1.88 parts of zinc oxide, 1.71 parts of zinc stearate, 1.55 parts of stearic acid, 2.7 parts of a cross-linking agent, 3.2 parts of graphene, 2.35 parts of a foaming agent and 2.25 parts of a flow aid.

3. The graphene natural rubber oil-resistant hybrid foam material according to claim 1, wherein the graphene natural rubber oil-resistant hybrid foam material is prepared from the following raw materials in parts by weight: 40 parts of natural rubber, 30 parts of nitrile rubber, 10 parts of butadiene rubber, 15 parts of polyvinyl chloride resin, 5 parts of white carbon black, 1.35 parts of silicone oil, 1.9 parts of zinc oxide, 1.6 parts of zinc stearate, 1.45 parts of stearic acid, 2.6 parts of a cross-linking agent, 3 parts of graphene, 2.2 parts of a foaming agent and 2.1 parts of a flow aid.

4. The graphene natural rubber oil-resistant hybrid foam material according to any one of claims 1 to 3, wherein the mixture of sulfur, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and N, N '-p-phenylene bismaleimide has a ratio of the mass of sulfur, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and N, N' -p-phenylene bismaleimide of 10: (19-22): (6-7).

5. The graphene natural rubber oil-resistant hybrid foam material according to any one of claims 1 to 3, wherein the relative content of sulfonic acid groups in the edge graphene oxide is 14.4-16.9%.

6. The graphene natural rubber oil resistant hybrid foam material according to any one of claims 1 to 3, wherein the zinc oxide is active zinc oxide.

7. The graphene natural rubber oil resistant hybrid foam material according to any one of claims 1 to 3, wherein the foaming agent is azodicarbonamide.

8. The graphene natural rubber oil resistant hybrid foam material according to any one of claims 1 to 3, wherein the flow aid is beeswax.

9. The preparation method of the graphene natural rubber oil-resistant mixed foam material as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:

A. respectively weighing natural rubber, nitrile rubber, butadiene rubber, polyvinyl chloride resin, white carbon black, silicone oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, graphene, a foaming agent and a flow aid in parts by weight;

B. feeding natural rubber into an internal mixer, masticating for 12-14 min at the temperature of 144-148 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 48h for later use;

C. b, feeding the natural rubber subjected to the mastication treatment in the step B, nitrile rubber, butadiene rubber, polyvinyl chloride resin, white carbon black, silicone oil, zinc oxide, zinc stearate, stearic acid and graphene into an internal mixer, and internally mixing for 11-14 min at 86-92 ℃; then banburying for 9-12 min at the temperature of 108-112 ℃; then adding a cross-linking agent, a foaming agent and a flow aid, banburying at 119-122 ℃ for 8-10 min, and discharging to obtain a banburying rubber mixture;

D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2-4 times on the open mill, and discharging to obtain an open mill rubber mixture;

and finally, feeding the open mill rubber mixture into a mold for hot-pressing foaming, cooling and molding, and cutting a sample to obtain the graphene natural rubber oil-resistant mixed foaming material.

Technical Field

The invention relates to the technical field of rubber products, and particularly relates to a graphene natural rubber oil-resistant mixed foam material and a preparation method thereof.

Background

Natural Rubber (NR) is a natural polymer compound containing cis-1, 4-polyisoprene as a main component, 91 to 94% of which is rubber hydrocarbon (cis-1, 4-polyisoprene), and the balance of which is non-rubber substances such as protein, fatty acid, ash, saccharides and the like. The material is generally a flaky solid, has the relative density of 0.94, the refractive index of 1.522 and the elastic modulus of 2-4 MPa, is softened at 130-140 ℃, is sticky and soft at 150-160 ℃, and begins to degrade at 200 ℃. Has high elasticity and slight plasticity at normal temperature and is crystallized and hardened at low temperature. Has better alkali resistance but does not resist strong acid. Is insoluble in water, lower ketones and alcohols, and can swell in nonpolar solvents such as chloroform, carbon tetrachloride, etc.

The natural rubber mainly has a macromolecular chain structure, the molecular weight, the distribution and aggregation structure of the molecular weight, the macromolecular chain structural unit of the natural rubber is isoprene, the macromolecular chain is mainly composed of polyisoolefine, the content of the rubber accounts for more than ninety-seven percent, aldehyde groups are arranged on the molecular chain, one aldehyde group is arranged on each macromolecular chain on average, just condensation or reaction with a protein decomposition product is carried out on the aldehyde groups to form branching and crosslinking, so that the viscosity of the rubber in storage is increased, and epoxy groups are arranged on the macromolecular chains of the natural rubber and are more active. The macromolecule end of the natural rubber is generally inferred to be dimethylallyl, the other end of the natural rubber is pyrophosphate, a terminal group, aldehyde group of a molecular chain and polymeric elements are few, the molecular weight range of the natural rubber is wide in the aspects of the molecular weight and the distribution of the molecular weight, the vast majority of the molecular weight is about thirty thousand according to the report from abroad, the strength of the natural raw rubber, the rubber compound and the vulcanized rubber is higher, and the strength of the general natural rubber can reach three megapascals. The main reason for the high mechanical strength of natural rubber is that it is a self-reinforcing rubber series, which, when stretched, orients the macromolecular chains in the direction of stress to form crystals, which act as reinforcement in the amorphous macromolecular fraction, and the same high strength as that without expansion is due to the close agglomeration of the tiny particles in its internal structure.

Natural rubber is used as a general material and is commonly used in various tire products, medical supplies, aerospace materials, rubber tubes, gloves, waterproof materials and the like. NR, while having good balance of properties, is an unsaturated, nonpolar rubber. Active chemical property, ageing resistance and poor heat resistance, and is easy to react with hydrocarbon oil solvent. Therefore, in order to improve the performance defects, the NR is usually modified by blending and the like, so that various performances, service life and application range of the NR are improved.

However, the natural rubber foam materials used at present have the following problems:

1. the product is easy to react with hydrocarbon oil solvent, so that the tensile strength is greatly reduced, the elongation at break is reduced, and the mechanical property is poor, namely the oil resistance is poor;

2. the compression set rate is high, and the rebound resilience is poor;

3. the wear resistance and other comprehensive use performances are poor.

Disclosure of Invention

Based on the above situation, the invention aims to provide a graphene natural rubber oil-resistant mixed foam material and a preparation method thereof, which can effectively solve the above problems.

In order to solve the technical problems, the technical scheme provided by the invention is as follows:

the graphene natural rubber oil-resistant mixed foaming material is prepared from the following raw materials in parts by weight: 36-44 parts of natural rubber, 28-33 parts of nitrile rubber, 8.5-11.5 parts of butadiene rubber, 14-16 parts of polyvinyl chloride resin, 4-6 parts of white carbon black, 1.2-1.5 parts of silicone oil, 1.7-2.1 parts of zinc oxide, 1.4-1.8 parts of zinc stearate, 1.3-1.6 parts of stearic acid, 2.3-2.9 parts of a cross-linking agent, 2.5-3.5 parts of graphene, 1.9-2.5 parts of a foaming agent and 1.8-2.4 parts of a flow assistant; the cross-linking agent is a mixture of sulfur, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and N, N' -p-phenyl bismaleimide; the graphene is edge graphene oxide.

Preferably, the graphene natural rubber oil-resistant mixed foaming material is prepared from the following raw materials in parts by weight: 42 parts of natural rubber, 31.5 parts of nitrile rubber, 10.8 parts of butadiene rubber, 15.4 parts of polyvinyl chloride resin, 5.2 parts of white carbon black, 1.42 parts of silicone oil, 1.88 parts of zinc oxide, 1.71 parts of zinc stearate, 1.55 parts of stearic acid, 2.7 parts of a cross-linking agent, 3.2 parts of graphene, 2.35 parts of a foaming agent and 2.25 parts of a flow aid.

Preferably, the graphene natural rubber oil-resistant mixed foaming material is prepared from the following raw materials in parts by weight: 40 parts of natural rubber, 30 parts of nitrile rubber, 10 parts of butadiene rubber, 15 parts of polyvinyl chloride resin, 5 parts of white carbon black, 1.35 parts of silicone oil, 1.9 parts of zinc oxide, 1.6 parts of zinc stearate, 1.45 parts of stearic acid, 2.6 parts of a cross-linking agent, 3 parts of graphene, 2.2 parts of a foaming agent and 2.1 parts of a flow aid.

Preferably, the mass ratio of the sulfur, the 1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and the N, N '-p-phenyl bismaleimide in the mixture of the sulfur, the 1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and the N, N' -p-phenyl bismaleimide is 10: (19-22): (6-7).

Preferably, the relative content of the sulfonic acid group in the edge graphene oxide is 14.4-16.9%.

Therefore, the graphene natural rubber oil-resistant mixed foaming material has better identity with other components in a raw material system, is easy to disperse uniformly, and better maintains the performance of graphene (the whole multilayer structure is not damaged).

Preferably, the zinc oxide is activated zinc oxide.

Preferably, the blowing agent is azodicarbonamide.

Preferably, the flow aid is beeswax.

The beeswax has various polarities, and can play a better lubricating role and increase the processing fluidity by being matched with other components in the raw material system of the graphene natural rubber oil-resistant mixed foaming material.

The invention also provides a preparation method of the graphene natural rubber oil-resistant mixed foam material, which comprises the following steps:

A. respectively weighing natural rubber, nitrile rubber, butadiene rubber, polyvinyl chloride resin, white carbon black, silicone oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, graphene, a foaming agent and a flow aid in parts by weight;

B. feeding natural rubber into an internal mixer, masticating for 12-14 min at the temperature of 144-148 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 48h for later use;

C. b, feeding the natural rubber subjected to the mastication treatment in the step B, nitrile rubber, butadiene rubber, polyvinyl chloride resin, white carbon black, silicone oil, zinc oxide, zinc stearate, stearic acid and graphene into an internal mixer, and internally mixing for 11-14 min at 86-92 ℃; then banburying for 9-12 min at the temperature of 108-112 ℃; then adding a cross-linking agent, a foaming agent and a flow aid, banburying at 119-122 ℃ for 8-10 min, and discharging to obtain a banburying rubber mixture;

D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2-4 times on the open mill, and discharging to obtain an open mill rubber mixture;

E. and finally, feeding the open mill rubber mixture into a mold for hot-pressing foaming, cooling and forming, and cutting a sample to obtain the graphene natural rubber oil-resistant mixed foaming material.

Compared with the prior art, the invention has the following advantages and beneficial effects:

the graphene natural rubber oil-resistant mixed foaming material disclosed by the invention is prepared by selecting raw materials, optimizing the content of each raw material, and selecting natural rubber, nitrile rubber, butadiene rubber, polyvinyl chloride resin, white carbon black, silicone oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, graphene, a foaming agent and a flow aid in a proper ratio, so that the advantages of the raw materials are fully exerted, the raw materials are mutually supplemented and mutually promoted, and the quality stability of a product is improved; the compression set rate, the rebound resilience and the mechanical property are good; the wear resistance is good.

The graphene natural rubber oil-resistant mixed foaming material is added with natural rubber, nitrile rubber and butadiene rubber in a proper proportion, and polyvinyl chloride resin in a proper proportion is reasonably prepared, and is used as a main raw material of the graphene natural rubber oil-resistant mixed foaming material, so that the graphene natural rubber oil-resistant mixed foaming material still keeps high tensile strength and large elongation at break after being soaked in a hydrocarbon oil solvent (such as butyl acrylate), is not easy to react with the hydrocarbon oil solvent (such as butyl acrylate), has good oil resistance and mechanical property, and also ensures low compression permanent deformation rate and good resilience.

The proper proportion of the white carbon black and the graphene are added into the graphene natural rubber oil-resistant mixed foaming material and are matched with other components, so that the graphene natural rubber oil-resistant mixed foaming material has good compatibility with base materials such as natural rubber, nitrile rubber and butadiene rubber, and the mechanical properties such as strength and the like of the graphene natural rubber oil-resistant mixed foaming material are further improved.

In the oil-resistant graphene natural rubber mixed foaming material, the cross-linking agent is a mixture of sulfur, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and N, N' -p-phenyl bismaleimide, so that the oil-resistant graphene natural rubber mixed foaming material is quickly cross-linked, is moderate in cross-linking and uniform in cross-linking area distribution, can greatly improve the mechanical properties such as tensile strength, elongation at break and the like, and greatly improves the oil resistance, and in addition, the compression permanent deformation rate is reduced, and the resilience performance is increased; the graphene is edge oxidized graphene, has good identity with other components, is easy to disperse uniformly, is only partially oxidized, and keeps good performance of the graphene.

The preparation method has simple process and simple and convenient operation, and saves manpower and equipment cost.

Detailed Description

In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.

The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.