CN112126104A - Method for chemically modifying surface of nitrile rubber by using strong acid salt oxidation solution - Google Patents
Method for chemically modifying surface of nitrile rubber by using strong acid salt oxidation solution Download PDFInfo
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- CN112126104A CN112126104A CN202010998714.1A CN202010998714A CN112126104A CN 112126104 A CN112126104 A CN 112126104A CN 202010998714 A CN202010998714 A CN 202010998714A CN 112126104 A CN112126104 A CN 112126104A
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
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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
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/02—Copolymers with acrylonitrile
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Abstract
The invention discloses a method for chemically modifying the surface of nitrile rubber by using a strong acid salt oxidizing solution, and relates to a method for modifying the surface of a rubber material, which comprises the following steps: 1) surface treatment: soaking nitrile rubber in a mixed solution containing 8-16% of KIO4, 5-8% of sulfuric acid and 5-10% of zinc fluosilicate (in percentage by mass) at room temperature for 3-7 days; 2) and (3) drying treatment: the nitrile rubber treated in the above way is placed in a drying environment at 100-110 ℃ for 1-2 hours. The invention chemically modifies the surface of the nitrile rubber, changes the molecular structure of the surface of the nitrile rubber, enhances the polarity and hardness of the surface of the nitrile rubber, improves the mechanical property, the antifriction and wear resistance, and greatly prolongs the service life of rubber products. The invention has simple process and low cost.
Description
Technical Field
The invention relates to a surface modification method of a rubber material, in particular to a method for chemically modifying the surface of nitrile rubber by using a strong acid salt oxidation solution.
Background
In oil extraction, oil refining, aerospace, automobiles, machinery manufacturing and other industrial production, a large number of rubber products are needed, and with the continuous development of the industrialization level, the requirements on the mechanical property and the friction property of the rubber products are more and more strict.
Nitrile rubber (NBR) is a copolymer of butadiene and acrylonitrile. The NBR has better oil resistance because the molecular structure contains nitrile groups. But at the same time, the nitrile rubber has a certain limitation in oil resistance because the bond of the nitrile group is not large enough and the content is limited. In addition, dynamic sealing products, which are important fields of nitrile rubber application, also require materials with good tribological properties. The change and friction of the material in the medium always start from the surface and are thus closely related to the properties of the surface, and various surface modification methods such as surface chemical modification (halogenation, sulfonation, etc.) and surface physical modification (surface coating, plasma technology, surface graft polymerization, etc.) have been proposed for nitrile rubbers.
The halogenation modification is to treat the rubber product with metal halides, interhalides, gases and the like of fluorine, chlorine, bromine and iodine. By controlling the factors such as concentration, time, temperature and the like, the rubber surface is oxidized and subjected to addition reaction to form a surface modified structure layer with the thickness of about several microns to dozens of microns, and although the abrasion reduction and wear resistance of the rubber product can be improved to a certain degree, the modification effect is influenced because the modified layer is thin, the hardness is not greatly improved, and the mechanical property is reduced to a certain extent. In addition, the halogen gas has strong toxicity, so the requirements on processing equipment and technology are high. The surface sulfonation of rubber usually uses concentrated sulfuric acid or sulfide to open the carbon-carbon bond on the surface, the carbon atom is oxidized to generate carbonyl, hydroxyl and carboxyl polar groups, the chemically inert surface is changed into the surface with polar groups, and the surface of rubber is activated or polarized. The sulfonation can improve the free energy of the rubber surface, the wetting property becomes excellent, and the improvement of the bonding strength is facilitated; but at the same time, the rubber surface will form fine cracks, the processing degree is not easy to be controlled in mass production, and a large amount of concentrated acid will pollute the environment. The surface physical modification technology such as plasma treatment, graft copolymerization, bionic coating and the like has the defects of thin thickness of the modified layer, easy peeling, poor stability, complex processing technology and the like.
Disclosure of Invention
The invention aims to provide a method for chemically modifying the surface of nitrile rubber by using a strong acid salt oxidation solution, the tissue structure of the surface of the nitrile rubber treated by the method is changed to generate polar groups, the mechanical and tribological properties are greatly improved, and the service life is prolonged; the nitrile rubber surface modified film can not be peeled from the matrix, and the surface modification does not influence the property of the material body.
The purpose of the invention is realized by the following technical scheme:
a method for chemically modifying the surface of nitrile rubber by using a strong acid salt oxidation solution is a surface oxidation method, wherein the oxidation solution is a mixed solution containing 8-16% of KIO4, 5-8% of sulfuric acid and 5-10% of zinc fluosilicate in percentage by mass, and the method comprises the following steps:
(1) and surface treatment: soaking nitrile rubber in a mixed solution containing 8-16% of KIO4, 5-8% of sulfuric acid and 5-10% of zinc fluosilicate at room temperature for 3-7 days;
(2) and (3) drying treatment: the nitrile rubber after the surface treatment is placed in a drying environment at the temperature of 100-110 ℃ for 1-2 hours.
The method for chemically modifying the surface of the nitrile rubber by using the strong acid salt oxidation solution is characterized in that the oxidation solution is a mixed solution containing 10% of KIO4, 5% of sulfuric acid and 8% of zinc fluosilicate in percentage by mass, and the soaking time is 3 days at room temperature.
According to the method for chemically modifying the surface of the nitrile rubber by using the strong acid salt oxidation solution, the nitrile rubber to be treated needs to be washed for 5-10 minutes in an ultrasonic cleaner by using acetone with the volume fraction of 95%, industrial alcohol with the volume fraction of 98% and deionized water as media before and after surface treatment, so that oil stains and impurities on the surface of the nitrile rubber are removed.
The method for chemically modifying the surface of the nitrile rubber by using the oxidizing solution is used for cleaning for 8 minutes in an ultrasonic cleaning instrument.
The invention has the following advantages and beneficial effects:
(1) the surface modification treatment method of the invention can generate carbonyl, hydroxyl, carboxyl and other polar groups on the surface of the rubber, thereby ensuring excellent polarity and wettability and greatly improving oil resistance; the hardness is increased, and the mechanical and tribological properties are greatly improved;
(2) the nitrile rubber is subjected to surface modification by adopting a surface oxidation method, so that the defects of stripping, poor stability, complex process and the like in the conventional surface modification polarity technology such as plasma treatment, graft copolymerization, bionic coating and the like are overcome;
(3) the invention has simple process and low cost.
Drawings
FIG. 1 is a scanning electron microscope image of untreated nitrile rubber;
FIG. 2 is a scanning electron microscope image of the nitrile rubber obtained in example 1;
FIG. 3 is a scanning electron microscope image of the nitrile rubber obtained in example 2;
FIG. 4 is a scanning electron microscope image of the nitrile rubber obtained in example 3;
FIG. 5 is a scanning electron microscope image of the nitrile rubber obtained in example 4;
FIG. 6 is a scanning electron microscope image of the nitrile rubber obtained in example 5;
FIG. 7 is a scanning electron microscope image of the nitrile rubber obtained in example 6;
FIG. 8 is an image of the surface IR spectrum of untreated nitrile rubber;
FIG. 9 is an image of the surface IR spectrum of the nitrile rubber obtained in example 1;
FIG. 10 is an image of the surface IR spectrum of the nitrile rubber obtained in example 2;
FIG. 11 is an image of the surface IR spectrum of the nitrile rubber obtained in example 3;
FIG. 12 is an image of the surface IR spectrum of the nitrile rubber obtained in example 4;
FIG. 13 is an image of the surface IR spectrum of the nitrile rubber obtained in example 5;
FIG. 14 is an image of the surface IR spectrum of the nitrile rubber obtained in example 6;
FIG. 15 is a plot of hardness values over time for untreated, examples 1, 2, and 3;
FIG. 16 is a graph of the mechanical property values of untreated, examples 1, 2, 3 over time;
FIG. 17 is a graph of the coefficient of friction versus time for untreated, examples 1, 2, and 3;
FIG. 18 is a graph showing the change of the abrasion loss with time in untreated examples 1, 2 and 3.
Detailed Description
The invention will be further described with reference to the following drawings and specific examples:
the strong acid salt adopted by the invention oxidizes strong oxidizing acid in the solution, namely concentrated sulfuric acid, to open the C-C bond on the surface of the nitrile rubber, oxidize carbon atoms to generate polar groups such as carbonyl, hydroxyl, carboxyl and the like, and change the chemical inert surface into the surface of the polar group, thereby activating or polarizing the surface. Oxidation can improve the surface free energy, the wetting property becomes excellent, and the tribological property is better improved. The fluosilicic acid generated in the solution can perform fluorination treatment on the surface of the nitrile rubber product, can inhibit cracking and corrosion, and the zinc fluosilicate can also be used as a hardening surface layer of the nitrile rubber to improve the wear resistance and prevent the aging of the nitrile rubber product.
The invention relates to a method for chemically modifying the surface of nitrile rubber by using a strong acid salt oxidation solution, which is characterized by comprising the following steps: the surface modification method is a surface oxidation method, the oxidation solution is a mixed solution of sulfuric acid, potassium periodate and zinc fluosilicate, and the mixed solution comprises 8-16% of sulfuric acid, 5-8% of sulfuric acid, 5-10% of zinc fluosilicate and the balance of deionized water by mass percent; the method comprises the following specific steps:
(1) and surface treatment: immersing nitrile rubber in 5-8% sulfuric acid (H) at room temperature2SO4Analytically pure, prepared by concentrated sulfuric acid with solute mass percent of 98%), 5% -10% potassium periodate (KIO 4, analytically pure) and 5% -10% zinc fluosilicate (ZnSiF 6.6H 2O, analytically pure) for 3-7 days;
(2) and (3) drying treatment: the nitrile rubber after the surface treatment is placed in a drying environment at the temperature of 100-110 ℃ for 1-2 hours.
The oxidizing solution is a mixed solution containing 10% of KIO4, 5% of sulfuric acid and 8% of zinc fluosilicate in percentage by mass, and the soaking time is 3 days at room temperature, so that the effect is better.
Before and after the surface treatment (i.e. before and after soaking in the oxidizing solution), the nitrile rubber to be treated is washed in an ultrasonic washer for 5-10 minutes by using acetone with the concentration (volume fraction) of 95%, industrial alcohol with the concentration (volume fraction) of 98% and deionized water as media (i.e. acetone with the volume fraction of 95% as a medium is washed in the ultrasonic washer for 5-10 minutes, then the industrial alcohol with the volume fraction of 98% is used as a medium for 5-10 minutes, and finally the deionized water is used as a medium for 5-10 minutes), wherein the washing time is about 8 minutes, so that oil stains and other impurities on the surface of the nitrile rubber are removed, and the cleanliness of the nitrile rubber to be treated is ensured.
Example 1
Soaking the nitrile rubber in a mixed solution (in percentage by mass) containing 10% of KIO4, 5% of sulfuric acid and 8% of zinc fluosilicate for 3 days at room temperature; then placing the mixture in a drying environment at 100 ℃ for 1 hour to obtain the polar nitrile rubber with high hardness and good antifriction and wear resistance. Wherein, before and after the surface treatment, the nitrile rubber is washed for 8 minutes in an ultrasonic cleaner by using acetone with the concentration (volume fraction) of 95 percent, industrial alcohol with the concentration (volume fraction) of 98 percent and deionized water as media in sequence.
Example 2
Soaking nitrile rubber in a mixed solution of 10% of KIO4, 5% of sulfuric acid and 8% of zinc fluosilicate for 5 days at room temperature; then placing the mixture in a drying environment at 100 ℃ for 1 hour to obtain the polar nitrile rubber with high hardness and good antifriction and wear resistance. Wherein, before and after the surface treatment, the nitrile rubber is washed for 8 minutes in an ultrasonic cleaner by using acetone with the concentration (volume fraction) of 95 percent, industrial alcohol with the concentration (volume fraction) of 98 percent and deionized water as media in sequence.
Example 3
Soaking nitrile rubber in a mixed solution containing 10% of KIO4, 5% of sulfuric acid and 8% of zinc fluosilicate (in percentage by mass), and soaking for 7 days at room temperature; then placing the mixture in a drying environment at 100 ℃ for 1 hour to obtain the polar nitrile rubber with high hardness and good antifriction and wear resistance. Wherein, before and after the surface treatment, the nitrile rubber is washed for 5 minutes in an ultrasonic cleaner by using acetone with the concentration (volume fraction) of 95 percent, industrial alcohol with the concentration (volume fraction) of 98 percent and deionized water as media in sequence.
Example 4
Soaking nitrile rubber in a mixed solution containing 15% of KIO4, 8% of sulfuric acid and 10% of zinc fluosilicate (in percentage by mass) at room temperature for 6 days; then placing the mixture in a drying environment at 100 ℃ for 1 hour to obtain the polar nitrile rubber with high hardness and good antifriction and wear resistance. Wherein, before and after the surface treatment, the nitrile rubber is washed for 5 minutes in an ultrasonic cleaner by using acetone with the concentration (volume fraction) of 95 percent, industrial alcohol with the concentration (volume fraction) of 98 percent and deionized water as media in sequence.
Example 5
Soaking nitrile rubber in a mixed solution containing 15% of KIO4, 8% of sulfuric acid and 10% of zinc fluosilicate (in percentage by mass) at room temperature for 4 days; then placing the mixture in a drying environment at 110 ℃ for 2 hours to obtain the polar nitrile rubber with high hardness and good antifriction and wear resistance. Wherein, before and after the surface treatment, the nitrile rubber is washed for 7 minutes in an ultrasonic cleaner by using acetone with the concentration (volume fraction) of 95 percent, industrial alcohol with the concentration (volume fraction) of 98 percent and deionized water as media in sequence.
Example 6
Soaking nitrile rubber in a mixed solution containing 8% of KIO4, 9% of sulfuric acid and 10% of zinc fluosilicate (in percentage by mass), and soaking for 7 days at room temperature; then placing the mixture in a drying environment at 105 ℃ for 1.5 hours to obtain the polar nitrile rubber with high hardness and good antifriction and wear resistance. Wherein, before and after the surface treatment, the nitrile rubber is washed for 8 minutes in an ultrasonic cleaner by using acetone with the concentration (volume fraction) of 95 percent, industrial alcohol with the concentration (volume fraction) of 98 percent and deionized water as media in sequence.
The modified nitrile rubbers obtained in examples 1 to 6 were subjected to various performance tests, and the results were as follows:
as shown in fig. 1 to 7, the nitrile rubbers obtained in the above six examples were analyzed by a scanning electron microscope, observed under a magnification of 5000 times, and compared with the nitrile rubbers without surface modification, it was found that the surface morphology was significantly changed, and as the soaking time was prolonged, the surface was smoother, indicating that the wettability of the rubbers was superior.
As shown in FIGS. 8 to 14, the nitrile rubbers obtained in the above six examples were observed by infrared spectroscopy, and compared with the nitrile rubbers without surface modification, it was found that the surface texture was significantly changed, and as the soaking time was prolonged, the polar groups were increased, indicating that the oil resistance of the rubbers was excellent.
As shown in FIG. 15, the nitrile rubber surfaces obtained in examples 1, 2 and 3 were subjected to a hardness test using an LX-A type rubber durometer. Compared with nitrile rubber which is not subjected to surface modification, the hardness of the modified nitrile rubber is obviously changed, and the hardness is gradually increased along with the prolonging of the soaking time.
As shown in FIG. 16, the nitrile rubber obtained in examples 1, 2 and 3 was subjected to mechanical testing, and the tensile properties of the test specimens cut into dumbbell shapes according to GB/T528-92 standard were measured on a model TCS-2000 tensile machine of Taiwan high-speed rail testing apparatus Co., Ltd. at a gauge length of 20mm and at a tensile speed of 500 mm/min. Compared with nitrile rubber which is not subjected to surface modification, the mechanical property of the nitrile rubber is obviously changed, and the strength of the nitrile rubber is gradually increased along with the prolonging of the soaking time.
As shown in fig. 17, the surface of the nitrile rubber obtained in examples 1, 2 and 3 was subjected to a friction coefficient test, and a dry friction and wear test was performed on the nitrile rubber using a reciprocating microcomputer-controlled wear tester manufactured by the jen general electromechanical technology ltd, wherein the load was 98N, the reciprocating frequency was 1Hz, the reciprocating distance was 0.02m, and the wear time was 3600 s. And compared with the nitrile rubber without surface modification, the friction coefficient is obviously changed, and gradually reduced along with the prolonging of the soaking time.
As shown in fig. 18, the surface wear amount of the nitrile rubber obtained in examples 1, 2 and 3 was measured, and the nitrile rubber was subjected to a dry friction wear test using a reciprocating microcomputer-controlled wear tester manufactured by the jen general electromechanical technology ltd, under a load of 98N, a reciprocating frequency of 1Hz, a reciprocating distance of 0.02m and a wear time of 3600 s. Compared with nitrile rubber which is not subjected to surface modification, the abrasion loss is obviously changed, and the abrasion loss is gradually reduced along with the prolonging of the soaking time.
Table 1 shows the test values of various properties of examples 4, 5 and 6, and as shown in table 1, the hardness, the friction coefficient and the abrasion loss of the nitrile rubber surfaces obtained in examples 4, 5 and 6 were measured, and compared with the nitrile rubber which was not surface-modified, it was found that the properties of each test were significantly improved, the hardness was increased, the friction coefficient was decreased and the abrasion loss was decreased as the oxidation property of the solution was increased and the soaking time was prolonged.
Table 1 below shows the measured values of the various properties of examples 4, 5 and 6.
The invention adopts a strong acid salt mixed solution oxidation method, and the components are prepared into an oxidation solution according to a certain proportion. The method makes the rubber surface generate oxidation and addition reaction to form a millimeter-grade surface modified structure layer, greatly improves the hardness, mechanical property and tribological property, prolongs the service life and enlarges the application range. In addition, the nitrile rubber surface modified film can not be peeled from the matrix, and the surface modification does not influence the property of the material body, so the process is simple and the cost is low.
Claims (4)
1. A method for chemically modifying the surface of nitrile rubber by using a strong acid salt oxidation solution is characterized in that the surface modification method is a surface oxidation method, the oxidation solution is a mixed solution containing 8-16% of KIO4, 5-8% of sulfuric acid and 5-10% of zinc fluosilicate in percentage by mass, and the method comprises the following steps:
(1) and surface treatment: soaking nitrile rubber in a mixed solution containing 8-16% of KIO4, 5-8% of sulfuric acid and 5-10% of zinc fluosilicate at room temperature for 3-7 days;
(2) and (3) drying treatment: the nitrile rubber after the surface treatment is placed in a drying environment at the temperature of 100-110 ℃ for 1-2 hours.
2. The method for chemically modifying the surface of nitrile rubber according to claim 1, wherein the oxidizing solution is a mixture of 10% by mass of KIO4, 5% by mass of sulfuric acid, and 8% by mass of zinc fluorosilicate, and the soaking time is 3 days at room temperature.
3. The method for chemically modifying the surface of the nitrile rubber by using the strong acid salt oxidation solution according to claim 1, wherein the nitrile rubber to be treated is washed in an ultrasonic washer for 5-10 minutes by using acetone with a volume fraction of 95%, industrial alcohol with a volume fraction of 98% and deionized water as media before and after surface treatment to remove oil stains and impurities on the surface of the nitrile rubber.
4. The method for chemically modifying the surface of nitrile rubber using an oxidizing solution according to claim 3, wherein the cleaning is performed in an ultrasonic cleaning apparatus for 8 minutes.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219606A (en) * | 1997-10-31 | 1999-06-16 | 铃木株式会社 | Surface treatment method, sliding member and piston |
| JP2000290781A (en) * | 1999-04-07 | 2000-10-17 | Saafeisutekkusu:Kk | Surface treating solution for metallic sliding parts, and surface treating method for metallic sliding parts |
| CN102766271A (en) * | 2012-08-10 | 2012-11-07 | 沈阳工业大学 | Method for conducting chemical modification on nitrile butadiene rubber surface by using oxidation solution |
| CN110204762A (en) * | 2019-06-20 | 2019-09-06 | 合肥汉甲陶瓷科技有限公司 | A kind of preparation method of high intensity automatically cleaning organic glass |
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2020
- 2020-09-22 CN CN202010998714.1A patent/CN112126104A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219606A (en) * | 1997-10-31 | 1999-06-16 | 铃木株式会社 | Surface treatment method, sliding member and piston |
| JP2000290781A (en) * | 1999-04-07 | 2000-10-17 | Saafeisutekkusu:Kk | Surface treating solution for metallic sliding parts, and surface treating method for metallic sliding parts |
| CN102766271A (en) * | 2012-08-10 | 2012-11-07 | 沈阳工业大学 | Method for conducting chemical modification on nitrile butadiene rubber surface by using oxidation solution |
| CN110204762A (en) * | 2019-06-20 | 2019-09-06 | 合肥汉甲陶瓷科技有限公司 | A kind of preparation method of high intensity automatically cleaning organic glass |
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