CN110862593B - Hydrogenated nitrile rubber masterbatch and preparation method and application thereof - Google Patents

Hydrogenated nitrile rubber masterbatch and preparation method and application thereof Download PDF

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CN110862593B
CN110862593B CN201911142710.7A CN201911142710A CN110862593B CN 110862593 B CN110862593 B CN 110862593B CN 201911142710 A CN201911142710 A CN 201911142710A CN 110862593 B CN110862593 B CN 110862593B
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hydrogenated nitrile
nitrile rubber
leather
emulsion
hydrogenated
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CN110862593A (en
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岳冬梅
谢飞
孙昊楠
徐蒽云
刘显魁
张立群
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Beijing University of Chemical Technology
China Leather and Footwear Research Institute Co Ltd
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Beijing University of Chemical Technology
China Leather and Footwear Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2315/00—Characterised by the use of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2415/00—Characterised by the use of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2489/00—Characterised by the use of proteins; Derivatives thereof

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Abstract

The invention relates to the field of chemical products, in particular to a hydrogenated nitrile butadiene rubber masterbatch and a preparation method and application thereof. The hydrogenated nitrile butadiene rubber master batch comprises leather and hydrogenated nitrile butadiene rubber emulsion, wherein the mass ratio of the leather to the hydrogenated nitrile butadiene rubber emulsion is (1-6): 20; the preparation method of the hydrogenated nitrile rubber master batch comprises the following steps: carrying out ultrasonic treatment on leather and hydrogenated nitrile-butadiene rubber emulsion at the temperature of 20-80 ℃, and then carrying out demulsification and rubber precipitation under the action of a demulsifier; compared with other hydrogenated nitrile rubbers, the hydrogenated nitrile rubber composite material prepared by using the hydrogenated nitrile rubber master batch has the advantages that the cost is greatly reduced, and the static mechanical properties such as stretching, tearing and wear resistance are good.

Description

Hydrogenated nitrile rubber masterbatch and preparation method and application thereof
Technical Field
The invention relates to the field of chemical products, in particular to a hydrogenated nitrile butadiene rubber masterbatch and a preparation method and application thereof.
Background
Nitrile Butadiene Rubber (NBR) has unsaturated C ═ C bonds in the molecular chain, and is easily oxidized at high temperature to break the molecular chain, limiting its application in many fields. Due to the requirement of practical application, people hydrogenate and modify the nitrile rubber to obtain hydrogenated nitrile rubber (HNBR) with a highly saturated molecular chain, and the HNBR still retains nitrile groups on the molecular chain and has good oil resistance because the hydrogenation process is selective hydrogenation. When the hydrogenation degree reaches more than 90 percent, the thermal decomposition temperature of the hydrogenated nitrile-butadiene rubber is 30 to 40 ℃ higher than that of the nitrile-butadiene rubber and exceeds 150 ℃. The hydrogenated nitrile rubber has good medium resistance, and is mainly characterized by having good medium resistance to various media such as organic acid, hot water, inorganic acid, alkali, salt, alcohol, aliphatic hydrocarbon and the like. Nowadays, HNBR is widely used in the fields of aerospace, automotive manufacturing, oil industry, printing, etc. The current production process mainly adopts noble metal catalytic high-pressure hydrogen hydrogenation, and the companies for realizing HNBR industrial production and commercial sale are mainly Lanxess company in Germany and Zeon company in Japan, both use nitrile rubber solution as a substrate, and NBR solution hydrogenation can be divided into homogeneous catalytic hydrogenation and heterogeneous catalytic hydrogenation according to whether a catalyst and the substrate are in the same phase. Because of international monopolies, expensive catalysts and harsh reaction conditions, the price of HNBR remains high, and how to reduce the price of HNBR is a problem to be solved urgently by the people in the field.
The literature reports that diimide generated by preparing hydrogenated nitrile rubber emulsion hydrogen peroxide and hydrazine hydrate can be directly hydrogenated nitrile rubber latex to obtain hydrogenated nitrile rubber. The biggest problem of the hydrogenated nitrile latex by the diamine coupling method is that the latex particles are subjected to crosslinking reaction due to free radicals generated by gel, diamine disproportionation or hydrogen peroxide decomposition. The adoption of nitrile latex hydrogenation is a focus of recent years, and has the advantages of low cost, mild conditions, environmental friendliness and the like, but the application of a hydrogenation product of gel is greatly limited.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a hydrogenated nitrile rubber master batch; the hydrogenated nitrile rubber master batch is prepared by impregnating leather waste with self-crosslinked hydrogenated nitrile rubber.
Specifically, the hydrogenated nitrile rubber master batch comprises leather and hydrogenated nitrile rubber emulsion, wherein the mass ratio of the leather to the hydrogenated nitrile rubber emulsion is (1-6): 20.
preferably, the leather is leather waste after processing or shaving in industry.
Leather is a natural polymer composed of collagen fibers cross-linked in a three-dimensional structure, but Leather Waste (LW) generated after edge trimming and shaving is difficult to reuse. The waste produced by the leather industry poses a significant environmental challenge, with the leather industry producing about 140 million tons of solid waste per year, with about 60% of the leather being lost after being trimmed and shaved. The leather waste is added into the nitrile rubber, so that the waste discharge and the environmental pollution can be reduced to a certain extent; in order to further improve the performance of the hydrogenated nitrile rubber master batch, the leather is preferably subjected to digestion treatment in advance: carrying out digestion reaction on leather in an alkaline solution, wherein the mass fraction of the alkaline solution is 0.1-15%;
and the weight volume ratio of the leather to the alkaline solution is 1-10: 150 in g/ml.
The hydrogenated nitrile rubber master batch prepared from the digested leather and the hydrogenated nitrile rubber emulsion has excellent performance; however, the invention discovers that leather is digested in different alkaline solutions, which have unexpected influence on the performance of the hydrogenated nitrile rubber master batch, and in order to further optimize the hydrogenated nitrile rubber master batch, the alkaline solution is preferably selected from one or more of aqueous urea solution, aqueous sodium formate solution and aqueous gamma-aminopropyltriethoxysilane solution;
in a preferred embodiment, the alkaline solution is an aqueous solution of sodium formate; when the leather is digested in the sodium formate water solution, the chromium and the acidic substances in the leather are separated from the leather fibers and the leather fibers are retained.
Preferably, the digestion reaction is refluxed for 1-5 h at 80-120 ℃.
Preferably, the preparation method of the hydrogenated nitrile rubber emulsion comprises the following steps: the modified nitrile butadiene rubber is prepared by taking carboxyl nitrile butadiene rubber emulsion, hydrazine hydrate, hydrogen peroxide and boric acid as raw materials and reacting at the temperature of 20-80 ℃.
Preferably, the molar ratio of the carbon-carbon double bond in the carboxylated nitrile rubber emulsion to the hydrazine hydrate, the hydrogen peroxide and the boric acid is 1: 1-3: 1.5-3: 0.02 to 0.2; preferably 1: 2-3: 1.5-1.8: 0.12 to 0.18.
Preferably, the hydrogenation degree of the hydrogenated nitrile-butadiene rubber emulsion is 90-100%.
The invention also provides a preparation method of the hydrogenated nitrile rubber masterbatch, which is characterized in that leather and hydrogenated nitrile rubber emulsion are subjected to ultrasonic treatment at the temperature of 20-80 ℃, and then demulsification and rubber precipitation are carried out under the action of a demulsifier.
Preferably, the demulsifier is selected from one or more of ethanol, isopropanol, acetone, hydrochloric acid, calcium chloride and calcium nitrate; calcium chloride is preferred.
The preparation method of the hydrogenated nitrile butadiene rubber master batch is simple in process flow and environment-friendly in process.
The invention also provides a hydrogenated nitrile-butadiene rubber composite material, which contains the hydrogenated nitrile-butadiene rubber master batch; preferably, the hydrogenated nitrile butadiene rubber master batch accounts for 12-29% of the hydrogenated nitrile butadiene rubber composite material.
The invention also provides a preparation method of the hydrogenated nitrile-butadiene rubber composite material, which comprises the step of carrying out hot press molding on the hydrogenated nitrile-butadiene rubber master batch, the hydrogenated nitrile-butadiene rubber, the plasticizer, the anti-aging agent and the vulcanizing agent at 160-180 ℃.
The invention has the beneficial effects that:
(1) the invention makes full use of the leather waste; further, digesting the leather waste and then preparing hydrogenated nitrile-butadiene rubber master batch with hydrogenated nitrile-butadiene rubber emulsion; not only can effectively utilize the self-crosslinking hydrogenation product, but also can realize the filling of the leather waste into the rubber matrix.
(2) The preparation method of the hydrogenated nitrile rubber masterbatch provided by the invention is simple and low in cost; and then the hydrogenated nitrile rubber composite material is prepared from the hydrogenated nitrile rubber master batch with low cost, the obtained hydrogenated nitrile rubber composite material has good static mechanical properties such as tensile property, tearing property and wear resistance, and Dynamic Mechanical Thermal Analysis (DMTA) proves that the loss angle of the composite material is reduced.
(3) Compared with other hydrogenated nitrile rubbers, the hydrogenated nitrile rubber composite material provided by the invention has the advantage that the cost is greatly reduced.
Drawings
FIG. 1 is a scanning electron micrograph of a hydrogenated nitrile rubber composite prepared according to comparative example 3.
FIG. 2 is a scanning electron micrograph of the hydrogenated nitrile rubber composite obtained in example 8.
FIG. 3 is a scanning electron micrograph of the hydrogenated nitrile rubber composite obtained in example 9.
FIG. 4 is a DMTA chart of the hydrogenated nitrile rubber composites prepared in examples 6-9 and comparative example 3.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
This example provides a hydrogenated nitrile rubber masterbatch, which is prepared by the following method:
(1) preparing hydrogenated nitrile-butadiene rubber emulsion: weighing 100g of carboxyl nitrile rubber emulsion (45 mass percent of carboxyl nitrile rubber and about 70 mass percent of butadiene chain segment), and adding 93.80g of hydrazine hydrate solution (80 mass percent of hydrazine hydrate); dissolving 5.82g of boric acid in 113.45g of hydrogen peroxide solution (30% by mass of hydrogen peroxide), and then dropwise adding the solution into a mixed solution of the carboxyl nitrile rubber emulsion and hydrazine hydrate at a constant speed; reacting for 8 hours at the temperature of 50 ℃ to obtain hydrogenated nitrile-butadiene rubber emulsion with the hydrogenation degree of 95 percent;
(2) carrying out digestion treatment on leather: adding 10g of leather waste and 150ml of sodium formate aqueous solution with the mass fraction of 1.5% into a 500ml three-neck round-bottom flask, stirring for 5 hours at 110 ℃, condensing, refluxing, washing and drying after the reaction is finished to obtain leather fibers;
(3) preparing a hydrogenated nitrile rubber master batch: and (3) placing 10g of the leather fiber prepared in the step (2) into 100g of the hydrogenated nitrile-butadiene rubber emulsion prepared in the step (1) (the solid content is 10%), performing 500W ultrasonic treatment at 30 ℃ for 2h, performing emulsion breaking and rubber precipitation by using a 5% calcium chloride solution, and drying to obtain the hydrogenated nitrile-butadiene rubber master batch.
Example 2
This example provides a hydrogenated nitrile rubber masterbatch which differs from example 1 only in the method of preparation: in the step (3), 5g of the leather fiber prepared in the step (2) is placed in 100g of the hydrogenated nitrile-butadiene rubber emulsion prepared in the step (1).
Example 3
This example provides a hydrogenated nitrile rubber masterbatch which differs from example 1 only in the method of preparation: in the step (3), 20g of the leather fiber prepared in the step (2) is placed in 100g of the hydrogenated nitrile-butadiene rubber emulsion prepared in the step (1).
Example 4
This example provides a hydrogenated nitrile rubber masterbatch which differs from example 1 only in the method of preparation: in the step (3), 30g of the leather fiber prepared in the step (2) is placed in 100g of the hydrogenated nitrile-butadiene rubber emulsion prepared in the step (1).
Example 5
This example provides a hydrogenated nitrile rubber masterbatch which differs from example 1 only in the method of preparation: replacing the sodium formate aqueous solution in the step (2) with urea aqueous solution.
Example 6
This example provides a hydrogenated nitrile rubber composite, which was formed from 15g of the hydrogenated nitrile rubber masterbatch obtained in example 2, 90g of hydrogenated nitrile rubber, 1g of stearic acid, 5g of zinc oxide, 1g of N-isopropyl-N' -phenyl-p-phenylenediamine, and 5g of dicumyl peroxide by hot pressing at 170 ℃ for 12 min.
Example 7
This example provides a hydrogenated nitrile rubber composite, which was molded from 20g of the hydrogenated nitrile rubber masterbatch obtained in example 1, 90g of hydrogenated nitrile rubber, 1g of stearic acid, 5g of zinc oxide, 1g of N-isopropyl-N' -phenyl-p-phenylenediamine, and 5g of dicumyl peroxide at 170 ℃ for 12min under hot pressing.
Example 8
This example provides a hydrogenated nitrile rubber composite (see FIG. 2 in scanning electron microscope), which was molded from 30g of the hydrogenated nitrile rubber masterbatch obtained in example 3, 90g of hydrogenated nitrile rubber, 1g of stearic acid, 5g of zinc oxide, 1g of N-isopropyl-N' -phenyl-p-phenylenediamine, and 5g of dicumyl peroxide by hot pressing at 170 ℃ for 12 min.
Example 9
This example provides a hydrogenated nitrile rubber composite (see FIG. 3 in scanning electron microscope), which was molded from 40g of the hydrogenated nitrile rubber masterbatch obtained in example 4, 90g of hydrogenated nitrile rubber, 1g of stearic acid, 5g of zinc oxide, 1g of N-isopropyl-N' -phenyl-p-phenylenediamine, and 5g of dicumyl peroxide by hot pressing at 170 ℃ for 12 min.
Example 10
This example provides a hydrogenated nitrile rubber composite, which was molded from 20g of the hydrogenated nitrile rubber masterbatch obtained in example 5, 90g of hydrogenated nitrile rubber, 1g of stearic acid, 5g of zinc oxide, 1g of N-isopropyl-N' -phenyl-p-phenylenediamine, and 5g of dicumyl peroxide at 170 ℃ for 12min under hot pressing.
Comparative example 1
This comparative example provides a hydrogenated nitrile rubber masterbatch which was prepared by a method which differs from that of example 1 only in that: the leather waste is not subjected to digestion treatment.
Comparative example 2 leather was not digested
The comparative example provides a hydrogenated nitrile rubber composite material, and the hydrogenated nitrile rubber masterbatch prepared in the comparative example 1 is formed by hot pressing 20g, 90g, 1g, zinc oxide 5g, N-isopropyl-N' -phenyl-p-phenylenediamine 1g and dicumyl peroxide 5g at 170 ℃ for 12 min.
Comparative example 3
This comparative example provides a hydrogenated nitrile rubber composite (shown in FIG. 1 in the scanning electron microscope), which is formed from 100g of hydrogenated nitrile rubber, 1g of stearic acid, 5g of zinc oxide, 1g of N-isopropyl-N' -phenyl-p-phenylenediamine, and 5g of dicumyl peroxide by hot pressing at 170 ℃ for 12 min.
Test example 1
The performance of the hydrogenated nitrile rubber composite materials prepared in examples 6 to 10 and comparative examples 2 to 3 was tested in this test example and is shown in table 1;
TABLE 1 Performance testing of hydrogenated nitrile rubber composites prepared in examples 6 to 10 and comparative examples 2 to 3
Figure BDA0002281388300000081
FIG. 4 is a DMTA chart of the hydrogenated nitrile rubber composites prepared in examples 6-9 and comparative example 3.
Test example 2
The test examples tested the vulcanization characteristics of the hydrogenated nitrile rubber composites prepared in examples 6 to 10 and comparative examples 2 to 3, as shown in Table 2;
TABLE 2 vulcanization characteristics of the hydrogenated nitrile rubber composites obtained in examples 6 to 10 and comparative examples 2 to 3
Figure BDA0002281388300000091
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. The hydrogenated nitrile rubber master batch is characterized by comprising leather and hydrogenated nitrile rubber emulsion, wherein the mass ratio of the leather to the hydrogenated nitrile rubber emulsion is (1-6): 20;
the leather is subjected to digestion treatment in advance: carrying out digestion reaction on leather in an alkaline solution, wherein the mass fraction of the alkaline solution is 0.1-15%;
the weight volume ratio of the leather to the alkaline solution is 1-10: 150 in g/ml;
the alkaline solution is selected from one or more of urea aqueous solution, sodium formate aqueous solution and gamma-aminopropyltriethoxysilane aqueous solution;
and refluxing the digestion reaction for 1-5 h at 80-120 ℃.
2. A hydrogenated nitrile rubber masterbatch according to claim 1, characterised in that said alkaline solution is an aqueous solution of sodium formate.
3. A hydrogenated nitrile rubber masterbatch according to claim 1, characterized in that said hydrogenated nitrile rubber emulsion is prepared by the following process: the modified nitrile butadiene rubber is prepared by taking carboxyl nitrile butadiene rubber emulsion, hydrazine hydrate, hydrogen peroxide and boric acid as raw materials and reacting at the temperature of 20-80 ℃.
4. A hydrogenated nitrile rubber masterbatch according to claim 3, wherein the molar ratio of carbon-carbon double bonds in said carboxylated nitrile rubber emulsion to hydrazine hydrate, hydrogen peroxide and boric acid is 1: 1-3: 1.5-3: 0.02 to 0.2.
5. A hydrogenated nitrile rubber masterbatch according to claim 4, wherein the molar ratio of carbon-carbon double bonds in said carboxylated nitrile rubber emulsion to hydrazine hydrate, hydrogen peroxide and boric acid is 1: 2-3: 1.5-1.8: 0.12 to 0.18.
6. The method for producing a hydrogenated nitrile rubber masterbatch according to any one of claims 1 to 5, wherein the leather and the hydrogenated nitrile rubber emulsion are subjected to ultrasonic treatment at 20 to 80 ℃ and then to demulsification and precipitation by the action of a demulsifier.
7. The preparation method according to claim 6, wherein the demulsifier is selected from one or more of ethanol, isopropanol, acetone, hydrochloric acid, calcium chloride and calcium nitrate.
8. A hydrogenated nitrile rubber composite material comprising the hydrogenated nitrile rubber masterbatch according to any one of claims 1 to 5.
9. The hydrogenated nitrile rubber composite according to claim 8, wherein the hydrogenated nitrile rubber masterbatch comprises 12 to 29% of the hydrogenated nitrile rubber composite.
10. The method for preparing a hydrogenated nitrile rubber composite material according to claim 8 or 9, wherein the hydrogenated nitrile rubber masterbatch, the hydrogenated nitrile rubber, the plasticizer, the anti-aging agent and the vulcanizing agent are subjected to hot press molding at 160 to 180 ℃.
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US3542705A (en) * 1966-11-21 1970-11-24 Polymer Corp Reconstituted leatherboard comprising leather fibers and alkyl-substituted nitrile/carboxyl containing rubber
US5506308A (en) * 1995-04-11 1996-04-09 Interface, Inc. Precure retardation of free radical cured elastomers

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