阅读说明：本技术 一种增强改性橡胶及其制备工艺 (Reinforced modified rubber and preparation process thereof ) 是由 范敏敏 张明华 张熙 王克 于 2020-07-27 设计创作，主要内容包括：本发明属于橡胶的处理或化学改性领域,具体地,本发明公开了一种增强改性橡胶及其制备工艺。本发明的增强改性橡胶是由包括以下重量份数的原料制得的：橡胶100份,活性剂4～6份,软化剂0.5～1.5份,引发剂0.5～1.5份,防老剂0.5～1.5份,促进剂0.1～1.0份,助交联剂0.5～1.5份,交联剂2～5份,侧链修饰试剂5～60份,补强剂0～150份；所述侧链修饰试剂为4-叔丁基苯乙烯。该增强改性橡胶是一种吸油膨胀橡胶,该吸油膨胀橡胶不仅具有良好的热稳定性,而且具有优异的吸油性能和力学性能,可以用作在油田高温条件下使用的密封材料(比如自膨胀封隔器),应用前景广阔。本发明增强改性橡胶的制备过程条件温和,操作简单,生产成本低,适合工业化生产。(The invention belongs to the field of rubber treatment or chemical modification, and particularly discloses reinforced modified rubber and a preparation process thereof. The reinforced modified rubber is prepared from the following raw materials in parts by weight: 100 parts of rubber, 4-6 parts of an active agent, 0.5-1.5 parts of a softening agent, 0.5-1.5 parts of an initiator, 0.5-1.5 parts of an anti-aging agent, 0.1-1.0 part of an accelerator, 0.5-1.5 parts of a cross-linking aid, 2-5 parts of a cross-linking agent, 5-60 parts of a side chain modification reagent and 0-150 parts of a reinforcing agent; the side chain modification reagent is 4-tert-butyl styrene. The reinforced modified rubber is oil-absorbing expansion rubber which not only has good thermal stability, but also has excellent oil-absorbing performance and mechanical performance, can be used as a sealing material (such as a self-expansion packer) used under the high-temperature condition of an oil field, and has wide application prospect. The preparation process of the reinforced modified rubber has mild conditions, simple operation and low production cost, and is suitable for industrial production.)

1. A reinforced modified rubber, which is characterized in that: the reinforced modified rubber is prepared from the following raw materials in parts by weight:

100 parts of rubber, 4-6 parts of an active agent, 0.5-1.5 parts of a softening agent, 0.5-1.5 parts of an initiator, 0.5-1.5 parts of an anti-aging agent, 0.1-1.0 part of an accelerator, 0.5-1.5 parts of a cross-linking aid, 2-5 parts of a cross-linking agent, 5-60 parts of a side chain modification reagent and 0-150 parts of a reinforcing agent; the side chain modification reagent is 4-tert-butyl styrene.

2. The reinforced modified rubber according to claim 1, wherein: the reinforced modified rubber is prepared from the following raw materials in parts by weight:

100 parts of rubber, 5 parts of an active agent, 1 part of a softening agent, 1 part of an initiator, 1 part of an anti-aging agent, 0.5 part of an accelerator, 1 part of an auxiliary crosslinking agent, 3 parts of a crosslinking agent, 10-50 parts of 4-tert-butylstyrene and 0-120 parts of a reinforcing agent.

3. The reinforced modified rubber according to claim 2, wherein: the reinforced modified rubber is prepared from the following raw materials in parts by weight:

100 parts of rubber, 5 parts of an active agent, 1 part of a softening agent, 1 part of an initiator, 1 part of an anti-aging agent, 0.5 part of an accelerator, 1 part of an auxiliary crosslinking agent, 3 parts of a crosslinking agent, 10-50 parts of 4-tert-butylstyrene and 30 parts of a reinforcing agent; preferably, the content of the 4-tert-butyl styrene is 20-40 parts, and more preferably 20 parts or 40 parts.

4. The reinforced modified rubber according to claim 2, wherein: the reinforced modified rubber is prepared from the following raw materials in parts by weight:

100 parts of rubber, 5 parts of an active agent, 1 part of a softening agent, 1 part of an initiator, 1 part of an anti-aging agent, 0.5 part of an accelerator, 1 part of an auxiliary crosslinking agent, 3 parts of a crosslinking agent, 30 parts of 4-tert-butylstyrene and 0-120 parts of a reinforcing agent; preferably, the reinforcing agent is 30-120 parts.

5. The reinforced modified rubber according to any one of claims 1 to 4, wherein: the rubber is butadiene cyanide rubber, chloroprene rubber, natural rubber or ethylene propylene rubber, preferably ethylene propylene rubber; the ethylene propylene rubber is preferably ethylene propylene diene monomer, and the grade of the ethylene propylene diene monomer is preferably EPDM 7001;

and/or the active agent is a metal oxide active agent, preferably one or the combination of two of zinc oxide and magnesium oxide;

and/or the softening agent is one or more of stearic acid, naphthenic oil, dibutyl phthalate and dioctyl phthalate in combination, preferably stearic acid;

and/or the initiator is a peroxide initiator, preferably di-tert-butyl dicumyl peroxide;

and/or the anti-aging agent is one or more of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, N-cyclohexyl-N '-phenyl-p-phenylenediamine and N-isopropyl-N' -phenyl-p-phenylenediamine, preferably 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer;

and/or the accelerator is one or more of dibenzothiazyl disulfide, tetramethylthiuram disulfide and N-cyclohexyl-2-benzothiazole sulfonamide, preferably dibenzothiazyl disulfide;

and/or the auxiliary crosslinking agent is triallyl isocyanurate;

and/or the cross-linking agent is an alkene monomer, preferably divinylbenzene.

6. The reinforced modified rubber according to claim 5, wherein: the reinforcing agent is one or the combination of two of carbon black and white carbon black.

7. An oil-absorbing expandable rubber, characterized in that: the rubber is prepared from the reinforced modified rubber as described in any one of claims 1 to 6.

8. A process for producing the reinforced modified rubber as claimed in any one of claims 1 to 6, wherein: the method comprises the following steps:

(1) mixing of rubber: mixing rubber by using an open mill, thinly passing the rubber, wrapping the rubber by using a roller, then adding an active agent, a softening agent, an initiator, an anti-aging agent, an accelerator, an auxiliary crosslinking agent and a reinforcing agent, thinly passing the rubber again, uniformly mixing the rubber and the reinforcing agent, and then discharging the rubber sheet; then dipping the mixed rubber after the sheet feeding into a mixed system of a cross-linking agent and a side chain modification reagent, taking out and drying to obtain a mixed rubber material;

(2) and (3) vulcanization of rubber: and (2) adding the mixed rubber material obtained in the step (1) into a mold, and vulcanizing by using a flat vulcanizing machine to obtain the rubber material.

9. The process according to claim 8, characterized in that: in the step (1), the open mill is a double-roller open mill; the roller temperature during mixing is 60-100 ℃, and preferably 80 ℃; and/or, in the mixed system, the mass ratio of the cross-linking agent and the side chain modification agent is as defined in any one of claims 1 to 6.

10. The process according to claim 8 or 9, characterized in that: in the step (2), the mould is preheated, the preheating temperature is 160-200 ℃, and preferably 170-180 ℃;

and/or, the vulcanization conditions are as follows: hot pressing at 170-180 ℃ for 30-300 seconds under 15-25 MPa, and then cold pressing at 8-12 MPa and normal temperature-50 ℃ for 1-5 minutes; preferably, the vulcanization conditions are as follows: hot pressing at 180 deg.C under 20MPa for 180 s, and cold pressing at 40 deg.C under 10MPa for 3 min.

Technical Field

The invention belongs to the field of rubber treatment or chemical modification, and particularly relates to reinforced modified rubber and a preparation process thereof.

Background

In recent years, with the rapid development of the industry in China, the living standard of people is increasingly improved, the demand of people for petroleum is increasingly increased, and the dependence degree of economic development on petroleum is increasingly enhanced. With the continuous innovation of oil field exploitation technology, a novel self-expansion oil seal technology is gradually valued by people, and oil absorption expansion rubber has attracted attention.

The oil-absorbing expandable rubber (OSR) is a rubber material capable of self-expanding after meeting oil products, is prepared by introducing lipophilic functional groups into a rubber matrix by a chemical method or blending the lipophilic functional groups with a lipophilic component, and is a combination of the rubber matrix and a non-polar lipophilic component. The oil-absorbing expansion rubber not only maintains the good high elasticity and compression deformation resistance of the rubber, but also can rapidly expand after absorbing oil, has stable oil-retaining characteristic under certain pressure, is the most ideal leak-stopping sealing material at present, can be widely applied to various industries, and is most reported to be used as a self-expansion packer for oil wells at present. In practical applications, the oil-absorbing swelling rubber is used under closed conditions, and the oil-absorbing swelling rate cannot be maximized, so that the contact pressure between the swelling rubber and the constraining body is generated. By means of the contact pressure, the oil absorption expansion rubber can play a role in leakage stopping and sealing, so that the layered mining in the oil field mining process is realized.

Ethylene Propylene Diene Monomer (EPDM) is an amorphous elastomer, and is a terpolymer composed of Ethylene, Propylene and a third Monomer (usually non-conjugated Diene), and the main chain of the terpolymer is saturated olefin, and the side chain of the terpolymer contains a small amount of unsaturated bonds, so that the terpolymer can maintain chemical activity and has excellent heat resistance, light resistance, oxygen resistance and ozone resistance, and therefore, the EPDM is widely applied to the fields of automobiles, ships, buildings, electrical appliances and the like, and also has wide attention in the field of oil-absorbing expansion rubber.

However, as the mechanical properties of the oil-absorbing expandable rubber as a sealing material directly determine the sealing performance, researchers have improved the mechanical properties of the oil-absorbing expandable rubber by adding a reinforcing agent (such as carbon black). However, the research shows that although the mechanical strength of the oil-absorbing rubber can be improved by adding the reinforcing agent, the oil-absorbing performance of the oil-absorbing swelling rubber is seriously reduced.

Therefore, it is necessary to develop an oil-absorbing expandable rubber having both excellent mechanical properties and oil absorption properties.

Disclosure of Invention

The invention aims to provide a reinforced modified rubber and an oil-absorbing expansion rubber which have excellent mechanical property and oil-absorbing property.

The invention provides reinforced modified rubber which is prepared from the following raw materials in parts by weight:

100 parts of rubber, 4-6 parts of an active agent, 0.5-1.5 parts of a softening agent, 0.5-1.5 parts of an initiator, 0.5-1.5 parts of an anti-aging agent, 0.1-1.0 part of an accelerator, 0.5-1.5 parts of a cross-linking aid, 2-5 parts of a cross-linking agent, 5-60 parts of a side chain modification reagent and 0-150 parts of a reinforcing agent; the side chain modification reagent is 4-tert-butyl styrene.

Further, the reinforced modified rubber is prepared from the following raw materials in parts by weight:

100 parts of rubber, 5 parts of an active agent, 1 part of a softening agent, 1 part of an initiator, 1 part of an anti-aging agent, 0.5 part of an accelerator, 1 part of an auxiliary crosslinking agent, 3 parts of a crosslinking agent, 10-50 parts of 4-tert-butylstyrene and 0-120 parts of a reinforcing agent.

Further, the reinforced modified rubber is prepared from the following raw materials in parts by weight:

100 parts of rubber, 5 parts of an active agent, 1 part of a softening agent, 1 part of an initiator, 1 part of an anti-aging agent, 0.5 part of an accelerator, 1 part of an auxiliary crosslinking agent, 3 parts of a crosslinking agent, 10-50 parts of 4-tert-butylstyrene and 30 parts of a reinforcing agent; preferably, the content of the 4-tert-butyl styrene is 20-40 parts, and more preferably 20 parts or 40 parts.

Further, the reinforced modified rubber is prepared from the following raw materials in parts by weight:

100 parts of rubber, 5 parts of an active agent, 1 part of a softening agent, 1 part of an initiator, 1 part of an anti-aging agent, 0.5 part of an accelerator, 1 part of an auxiliary crosslinking agent, 3 parts of a crosslinking agent, 30 parts of 4-tert-butylstyrene and 0-120 parts of a reinforcing agent; preferably, the reinforcing agent is 30-120 parts.

Further, the rubber is butadiene cyanide rubber, chloroprene rubber, natural rubber or ethylene propylene rubber, preferably ethylene propylene rubber; the ethylene propylene rubber is preferably ethylene propylene diene monomer, and the grade of the ethylene propylene diene monomer is preferably EPDM 7001;

and/or the active agent is a metal oxide active agent, preferably one or the combination of two of zinc oxide and magnesium oxide;

and/or the softening agent is one or more of stearic acid, naphthenic oil, dibutyl phthalate and dioctyl phthalate in combination, preferably stearic acid;

and/or the initiator is a peroxide initiator, preferably di-tert-butyl dicumyl peroxide;

and/or the anti-aging agent is one or more of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, N-cyclohexyl-N '-phenyl-p-phenylenediamine and N-isopropyl-N' -phenyl-p-phenylenediamine, preferably 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer;

and/or the accelerator is one or more of dibenzothiazyl disulfide, tetramethylthiuram disulfide and N-cyclohexyl-2-benzothiazole sulfonamide, preferably dibenzothiazyl disulfide;

and/or the auxiliary crosslinking agent is triallyl isocyanurate;

and/or the cross-linking agent is an alkene monomer, preferably divinylbenzene.

Further, the reinforcing agent is one or a combination of two of carbon black and white carbon black.

The invention also provides oil-absorbing expansion rubber which is prepared from the reinforced modified rubber.

Further, the method comprises the steps of:

(1) mixing of rubber: mixing rubber by using an open mill, thinly passing the rubber, wrapping the rubber by using a roller, then adding an active agent, a softening agent, an initiator, an anti-aging agent, an accelerator, an auxiliary crosslinking agent and a reinforcing agent, thinly passing the rubber again, uniformly mixing the rubber and the reinforcing agent, and then discharging the rubber sheet; then dipping the mixed rubber after the sheet feeding into a mixed system of a cross-linking agent and a side chain modification reagent, taking out and drying to obtain a mixed rubber material;

(2) and (3) vulcanization of rubber: and (2) adding the mixed rubber material obtained in the step (1) into a mold, and vulcanizing by using a flat vulcanizing machine to obtain the rubber material.

Further, in the step (1), the open mill is a two-roll open mill; the roller temperature during mixing is 60-100 ℃, and preferably 80 ℃; and/or, in the mixed system, the mass ratio of the cross-linking agent and the side chain modifying agent is as described above.

Further, in the step (2), the die is a preheated die, and the preheating temperature is 160-200 ℃, preferably 170-180 ℃;

and/or, the vulcanization conditions are as follows: hot pressing at 170-180 ℃ for 30-300 seconds under 15-25 MPa, and then cold pressing at 8-12 MPa and normal temperature-50 ℃ for 1-5 minutes; preferably, the vulcanization conditions are as follows: hot pressing at 180 deg.C under 20MPa for 180 s, and cold pressing at 40 deg.C under 10MPa for 3 min.

Ethylene-propylene-diene monomer (EPDM), which is a copolymer polymerized from ethylene, propylene, and a small amount of a third monomer, typically a non-conjugated diene, is one type of ethylene-propylene rubber.

In the invention, the EPDM-based oil-absorbing expandable rubber is abbreviated as ESA.

In the present invention, the normal temperature means 25. + -. 2 ℃.

Experimental results show that the reinforced modified rubber provided by the invention is EPDM-based oil-absorbing expansion rubber, and the oil-absorbing expansion rubber not only has good thermal stability, but also has excellent oil absorption performance and mechanical property, can be used as a sealing material (such as a self-expansion packer) used under the high-temperature condition of an oil field, and has a wide application prospect.

The preparation process of the reinforced modified rubber is an in-situ reaction compression molding method, has mild reaction conditions, simple operation and low production cost, and is suitable for industrial production.

Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.

The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.

Drawings

FIG. 1 is a schematic diagram of an in-situ reaction compression molding method for preparing EPDM-based oil-absorbing expansive rubber.

Fig. 2 dynamic mechanical property-temperature spectra of ESA0, ESA10, ESA20, ESA30, ESA40 and ESA 50.

FIG. 3 mechanical loss vs. temperature curve (A) and glass transition temperature (B) for each ESA (prepared in example 2).

FIG. 4 TG and DTG curves for ESA (from example 1) for different carbon black contents.

FIG. 5 TG and DTG curves for ESA (made in example 2) at different t-BS contents.

FIG. 6 TG and DTG curves of ESA with different strengthening agents added.

FIG. 7 is a cross-sectional profile of ESA without reinforcing agent (A, sample 1 from example 1), carbon black reinforced ESA (B, ESA20 from example 2), and white carbon black reinforced ESA (C, sample 1 from example 3).

Fig. 8 oil absorption test results for each ESA: a is the oil absorption test results for different solvents for ESA samples (prepared in example 1, with a t-BS unit content of 30phr) with different carbon black contents; b is the oil absorption test result for different solvents for ESA samples (prepared in example 2, carbon black content 30phr) with different t-BS contents.

Fig. 9 results of oil retention test for each ESA: a is the result of the oil retention test of ESA samples with different carbon black contents (prepared in example 1, the content of t-BS structural unit is 30phr) on different solvents; b is the results of the oil retention tests of ESA samples (prepared in example 2, with a carbon black content of 30phr) with different t-BS contents and different solvents.

FIG. 10 tensile strength and elongation at break for ESA samples of varying t-BS content (made in example 2).

FIG. 11 hardness of ESA samples (made in example 2) of varying t-BS content.

FIG. 12 tensile strength and elongation at break for ESA samples (made in example 1) of varying carbon black content.

FIG. 13 hardness of ESA samples (made in example 1) of different carbon black content.

Detailed Description

The raw materials and equipment used in the invention are known products and are obtained by purchasing commercial products.

The ethylene propylene diene monomer is EPDM for short, t-BS for short, DVB for short, bis (tert-butyl) peroxydiisopropylbenzene (BIBP) for short, SA for short, ZnO for short, antioxidant RD for short, accelerator DM for short, TAIC for short, and N550 for short.