CN102766271B - Method for conducting chemical modification on nitrile butadiene rubber surface by using oxidation solution - Google Patents
Method for conducting chemical modification on nitrile butadiene rubber surface by using oxidation solution Download PDFInfo
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- CN102766271B CN102766271B CN201210283766.6A CN201210283766A CN102766271B CN 102766271 B CN102766271 B CN 102766271B CN 201210283766 A CN201210283766 A CN 201210283766A CN 102766271 B CN102766271 B CN 102766271B
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Abstract
The invention relates to a method for conducting chemical modification on a nitrile butadiene rubber surface by using an oxidation solution. The method includes the following steps: (1) surface processing: soaking nitrile butadiene rubber in a mixed solution containing 30-60% of sulfuric acid, 10-15% of potassium iodide and 5-10% of potassium bromide (mass percentage) for 3-7 days; and (2) drying processing: placing the nitrile butadiene rubber in a dry environment at the temperature of 100-110 DEG C for 1-2 hours. By conducting chemical modification on the nitrile butadiene rubber surface, a molecular structure of the nitrile butadiene rubber surface is changed so that polarity and hardness of the nitrile butadiene rubber surface are improved, mechanical performance, antifriction performance and abrasion resistance are improved, and service life of rubber products is greatly prolonged. The method is simple in process and low in cost.
Description
Technical field
The present invention relates to a kind of paracril surface oxidation chemical modification method, belong to material surface modifying technology field, employing the method increases substantially the oil-proofness of rubber, anti-friction wear-resistant after processing.
Background technology
In oil production, oil refining, aerospace, automobile, machinofacture and other industrial production, need a large amount of rubber items, and along with the development of industrialized level, more and more harsh to the requirement of the mechanical property of rubber item and frictional behaviour.
Paracril (NBR) is the multipolymer of divinyl and vinyl cyanide.Owing to containing itrile group in NBR molecular structure, thereby there is good oil-proofness.But simultaneously again because the bond energy of itrile group is large not, content is restricted again, so paracril has certain limitation aspect oil-proofness.In addition, as paracril application key areas---dynamic seal goods also require material to have good tribological property.The variation of material in medium and friction always start from surface, thereby closely related with surperficial performance, people have proposed the method for kinds of surface modification to paracril for this reason, as surface chemical modification (halogenation, sulfonation etc.) and surface physics modification (top coat, plasma technology, surface grafting polymerization etc.).
Halogenation modification is exactly with processing rubber items such as metal halide, interhalogen compound and the gases of fluorine, chlorine, bromine, iodine.By factors such as controlled concentration, time, temperature, make that rubber surface is oxidized, addition reaction, form the approximately several microns of surface-modification structures layers to tens micron thickness, though can improve to a certain degree the anti-attrition wear resisting property of rubber item, but because of modified layer thinner thickness, hardness improves little, and mechanical property declines to some extent, and these have all affected its modified effect.Because halogenation gas toxicity is very strong, very high to processing units and processing requirement in addition.Rubber surface sulfonation is used the vitriol oil or sulfide that its surperficial carbon-carbon bond is opened conventionally, carbon atom oxidation generates carbonyl, hydroxyl and carboxyl isopolarity group, chemically inert surface becomes the surface that has polar group, thereby makes rubber surface activation or polar.Sulfonation can make rubber surface free energy improve, and it is excellent that wetting property becomes, and is conducive to improve bond strength; But can make rubber surface form trickle slight crack, during production in enormous quantities, degree for the treatment of is difficult for grasping simultaneously, and a large amount of concentrated acid can be to environment.Surface physics modification technology is as plasma treatment, graft copolymerization, bionic coating etc. exist modified layer thin thickness, easily peel off, poor stability, complete processing is loaded down with trivial details wait not enough.
Summary of the invention
Goal of the invention
The present invention is a kind of method of oxidizing solution to paracril surface chemical modification of utilizing, its objective is the paracril surface microstructure making after the method the is processed polarization group that changes, mechanics, tribological property increase substantially, and increase the service life; In addition, paracril surface modified membrane can not produce and to peel off with matrix, and surface modification do not affect the character of material body, and technique is simple, with low cost.
Technical scheme
A kind of method of oxidizing solution to paracril surface chemical modification of utilizing, it is characterized in that: described surface modifying method is surface oxidation method, oxidizing solution is to contain by mass percentage the mixing solutions of 30%-60% sulfuric acid, 10%-15% potassiumiodide, 5%-10% Potassium Bromide, and step is as follows:
(1), surface treatment: paracril is soaked in the mixing solutions containing 30%-60% sulfuric acid, 10%-15% potassiumiodide, 5%-10% Potassium Bromide at ambient temperature, and soak time is 3-7 days;
(2), drying treatment: the paracril after above-mentioned surface treatment is positioned over to 1-2 hour in the dry environment of 100-110 ℃.
Oxidizing solution is to contain by mass percentage the mixing solutions of 50% sulfuric acid, 10% potassiumiodide, 5% Potassium Bromide, and at room temperature soak time is 3 days.
It is that 95% acetone, the volume fraction industrial spirit that is 98%, deionized water are as medium that pending paracril all needs successively by volume fraction before surface treatment and after surface treatment, in ultrasonic washing instrument, clean 3 ~ 7 minutes, remove paracril surface and oil contaminant and impurity.
In ultrasonic washing instrument, clean 5 minutes.
Advantage and effect
The present invention is a kind of method of oxidizing solution to paracril surface chemical modification of utilizing, and has the following advantages and beneficial effect:
(1), surface modifying treatment of the present invention, make rubber surface produce carbonyl, hydroxyl and carboxyl isopolarity group, thereby the polarity of making, wetting property become excellent, oil-proofness significantly promotes; Hardness increases, and mechanics and tribological property increase substantially;
(2), adopt process for surface oxidation to carry out surface modification to paracril, will overcome existing surface modification polarity technology as the existence such as plasma treatment, graft copolymerization, bionic coating are peeled off, the deficiency such as poor stability, technique be loaded down with trivial details;
(3), technique of the present invention is simple, with low cost.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope image of untreated paracril;
Fig. 2 is the scanning electron microscope image of embodiment 1 gained paracril;
Fig. 3 is the scanning electron microscope image of embodiment 2 gained paracrils;
Fig. 4 is the scanning electron microscope image of embodiment 3 gained paracrils;
Fig. 5 is the scanning electron microscope image of embodiment 4 gained paracrils;
Fig. 6 is the scanning electron microscope image of embodiment 5 gained paracrils;
Fig. 7 is the scanning electron microscope image of embodiment 6 gained paracrils;
Fig. 8 is untreated paracril surface infrared spectrum image;
Fig. 9 is embodiment 1 gained paracril surface infrared spectrum image;
Figure 10 is embodiment 2 gained paracril surface infrared spectrum images;
Figure 11 is embodiment 3 gained paracril surface infrared spectrum images;
Figure 12 is embodiment 4 gained paracril surface infrared spectrum images;
Figure 13 is embodiment 5 gained paracril surface infrared spectrum images;
Figure 14 is embodiment 6 gained paracril surface infrared spectrum images;
Figure 15 is the hardness value curve over time of untreated, embodiment 1,2,3;
Figure 16 is the mechanical properties value curve over time of untreated, embodiment 1,2,3;
Figure 17 is the change curve in time of frictional coefficient of untreated, embodiment 1,2,3;
Figure 18 is the abrasion loss curve over time of untreated, embodiment 1,2,3.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention is described further:
The present invention adopt acid with strong oxidizing property---the vitriol oil is opened the C-C key on paracril surface, carbon atom oxidation generates carbonyl, hydroxyl and carboxyl isopolarity group, chemically inert surface becomes polar group surface, thereby makes surface active or polar.Oxidation can make surface free energy improve, and it is excellent that wetting property becomes, and makes better tribological property improve.
The present invention relates to a kind of method of oxidizing solution to paracril surface chemical modification of utilizing, it is characterized in that: described surface modifying method is surface oxidation method, oxidizing solution is the mixing solutions of sulfuric acid, potassiumiodide, Potassium Bromide, by mass percentage containing 30%-60% sulfuric acid, 10%-15% potassiumiodide, 5%-10% Potassium Bromide, all the other are deionized water; Concrete steps are as follows:
(1), surface treatment: paracril is soaked at ambient temperature containing 30%-60% sulfuric acid (H
2sO
4, analytical pure, the vitriol oil that is 98% by solute massfraction is prepared), in the mixing solutions of 10%-15% potassiumiodide (KI, analytical pure), 5%-10% Potassium Bromide (KBr, analytical pure), soak time is 3-7 days;
(2), drying treatment: the paracril after above-mentioned surface treatment is positioned over to 1-2 hour in the dry environment of 100-110 ℃.
Above-mentioned oxidizing solution is to contain by mass percentage the mixing solutions of 50% sulfuric acid, 10% potassiumiodide, 5% Potassium Bromide, and at room temperature soak time is 3 days, and now effect is better.
Above-mentioned pending paracril is before surface treatment and after surface treatment (before soaking with oxidizing solution, afterwards) all needing successively to use respectively concentration (volume fraction) is 95% acetone, the industrial spirit that concentration (volume fraction) is 98%, deionized water is as medium, in ultrasonic washing instrument, cleaning 3 ~ 7 minutes (is that medium cleans 3 ~ 7 minutes in ultrasonic washing instrument with the acetone of volume fraction 95%, the industrial spirit that is 98% by volume fraction is again that medium cleans 3 ~ 7 minutes in ultrasonic washing instrument, with deionized water, be finally that medium cleans 3 ~ 7 minutes in ultrasonic washing instrument), scavenging period is advisable with about 5 minutes, to remove paracril surface and oil contaminant and other impurity, thereby guarantee the degree of cleaning of pending paracril.
Paracril is soaked in to the mixing solutions containing 50% sulfuric acid, 10% potassiumiodide, 5% Potassium Bromide (mass percent), and at room temperature soak time is 3 days; Then be positioned in the dry environment of 100 ℃ 1 hour, can obtain the polarity paracril that hardness is high, anti-friction wear-resistant is good.Wherein paracril before surface treatment and after surface treatment, all need successively with concentration (volume fraction) be 95% acetone, concentration (volume fraction) industrial spirit that is 98% and deionized water as medium, in ultrasonic washing instrument, clean 5 minutes.
Paracril is soaked in to the mixing solutions containing 50% sulfuric acid, 10% potassiumiodide, 5% Potassium Bromide (mass percent), and at room temperature soak time is 5 days; Then be positioned in the dry environment of 100 ℃ 1 hour, can obtain the polarity paracril that hardness is high, anti-friction wear-resistant is good.Wherein paracril before surface treatment and after surface treatment, all need successively with concentration (volume fraction) be 95% acetone, concentration (volume fraction) industrial spirit that is 98% and deionized water as medium, in ultrasonic washing instrument, clean 5 minutes.
Embodiment 3
Paracril is soaked in to the mixing solutions containing 50% sulfuric acid, 10% potassiumiodide, 5% Potassium Bromide (mass percent), and at room temperature soak time is 7 days; Then be positioned in the dry environment of 100 ℃ 1 hour, can obtain the polarity paracril that hardness is high, anti-friction wear-resistant is good.Wherein paracril before surface treatment and after surface treatment, all need successively with concentration (volume fraction) be 95% acetone, concentration (volume fraction) industrial spirit that is 98% and deionized water as medium, in ultrasonic washing instrument, clean 5 minutes.
Paracril is soaked in to the mixing solutions containing 30% sulfuric acid, 15% potassiumiodide, 10% Potassium Bromide (mass percent), and at room temperature soak time is 6 days; Then be positioned in the dry environment of 100 ℃ 1 hour, can obtain the polarity paracril that hardness is high, anti-friction wear-resistant is good.Wherein paracril before surface treatment and after surface treatment, all need successively with concentration (volume fraction) be 95% acetone, concentration (volume fraction) industrial spirit that is 98% and deionized water as medium, in ultrasonic washing instrument, clean 3 minutes.
Paracril is soaked in to the mixing solutions containing 60% sulfuric acid, 12% potassiumiodide, 8% Potassium Bromide (mass percent), and at room temperature soak time is 4 days; Then be positioned in the dry environment of 110 ℃ 2 hours, can obtain the polarity paracril that hardness is high, anti-friction wear-resistant is good.Wherein paracril before surface treatment and after surface treatment, all need successively with concentration (volume fraction) be 95% acetone, concentration (volume fraction) industrial spirit that is 98% and deionized water as medium, in ultrasonic washing instrument, clean 7 minutes.
Paracril is soaked in to the mixing solutions containing 40% sulfuric acid, 13% potassiumiodide, 7% Potassium Bromide (mass percent), and at room temperature soak time is 7 days; Then be positioned in the dry environment of 105 ℃ 1.5 hours, can obtain the polarity paracril that hardness is high, anti-friction wear-resistant is good.Wherein paracril before surface treatment and after surface treatment, all need successively with concentration (volume fraction) be 95% acetone, concentration (volume fraction) industrial spirit that is 98% and deionized water as medium, in ultrasonic washing instrument, clean 5 minutes.
The modified butadiene acrylonitrile rubber of above-described embodiment 1 ~ 6 gained is carried out to various performance tests, and result is as follows:
As shown in Figures 1 to 7, the paracril of above-mentioned six embodiment gained is analyzed by scanning electron microscope, under 5000 times of magnifications, observe, and compare with the paracril that does not carry out surface modification, find that surface topography occurs obviously to change, along with the prolongation of soak time, surface is Paint Gloss, shows that the wetting property of rubber becomes excellent.
As shown in Fig. 8 to Figure 14, the paracril of above-mentioned six embodiment gained is observed with infrared spectra, and compare with the paracril that does not carry out surface modification, find that surface microstructure occurs obviously to change, prolongation along with soak time, polar group increases, and shows that rubber oil-proofness becomes excellent.
As shown in figure 15, hardness test is carried out in the paracril surface of above-described embodiment 1,2,3 gained, adopt LX-A type durometer.And compare with the paracril that does not carry out surface modification, find that hardness occurs obviously to change, along with the prolongation of soak time, hardness increases gradually.
As shown in figure 16, mechanical test is carried out in the paracril surface of above-described embodiment 1,2,3 gained, press GB/T528-92 standard, sample is cut to dumb-bell shape, tensile property at the TCS-2000 type pulling force aircraft measurements sample of Taiwan High Speed Rail Testing Instruments company limited, gauge length 20mm, draw speed is 500mm/min.And compare with the paracril that does not carry out surface modification, find that mechanical property occurs obviously to change, along with the prolongation of soak time, intensity increases gradually.
As shown in figure 17, PVvalue testing is carried out in the paracril surface of above-described embodiment 1,2,3 gained, use the reciprocation type microcomputer control wear tester of Jinan Pu Ye mechanical & electrical technology company limited to carry out dry friction and wear experiment to paracril, load 98N, reciprocating frequence 1Hz, reciprocal distance 0.02m, wearing-in period 3600s.And compare with the paracril that does not carry out surface modification, find that frictional coefficient occurs obviously to change, along with the prolongation of soak time, frictional coefficient reduces gradually.
As shown in figure 18, abrasion loss test is carried out in the paracril surface of above-described embodiment 1,2,3 gained, use the reciprocation type microcomputer control wear tester of Jinan Pu Ye mechanical & electrical technology company limited to carry out dry friction and wear experiment to paracril, load 98N, reciprocating frequence 1Hz, reciprocal distance 0.02m, wearing-in period 3600s.And compare with the paracril that does not carry out surface modification, find that abrasion loss occurs obviously to change, along with the prolongation of soak time, abrasion loss reduces gradually.
Table 1 is the test value of the various performances of embodiment 4,5,6, as shown in table 1, hardness test, PVvalue testing, abrasion loss test are carried out in the paracril surface of above-described embodiment 4,5,6 gained, and compare with the paracril that does not carry out surface modification, discovery is along with the oxidation susceptibility enhancing of solution and the prolongation of soak time, and each test performance occurs obviously to improve, and hardness increases, frictional coefficient reduces, and abrasion loss reduces.
Following table 1 is the test value of the various performances of embodiment 4,5,6.
The present invention adopts mixing solutions oxidation style, and each composition is made oxidizing solution according to a certain percentage.The method makes that rubber surface is oxidized, addition reaction, forms millimetre-sized surface-modification structures layer, and its hardness, mechanical property, tribological property are increased substantially, and extends its work-ing life, expands its scope of application.In addition, paracril surface modified membrane can not produce and to peel off with matrix, and surface modification do not affect the character of material body, and technique is simple, with low cost.
Claims (3)
1. one kind is utilized the method for oxidizing solution to paracril surface chemical modification, it is characterized in that: described surface modifying method is surface oxidation method, oxidizing solution is to contain by mass percentage the mixing solutions of 30%-60% sulfuric acid, 10%-15% potassiumiodide, 5%-10% Potassium Bromide, and step is as follows:
(1), surface treatment: paracril is soaked in the mixing solutions containing 30%-60% sulfuric acid, 10%-15% potassiumiodide, 5%-10% Potassium Bromide at ambient temperature, and soak time is 3-7 days;
(2), drying treatment: the paracril after above-mentioned surface treatment is positioned over to 1-2 hour in the dry environment of 100-110 ℃;
It is that 95% acetone, the volume fraction industrial spirit that is 98%, deionized water are as medium that pending paracril all needs successively by volume fraction before surface treatment and after surface treatment, in ultrasonic washing instrument, clean 3 ~ 7 minutes, remove paracril surface and oil contaminant and impurity.
2. a kind of method of oxidizing solution to paracril surface chemical modification of utilizing according to claim 1, it is characterized in that: oxidizing solution is for by mass percentage containing the mixing solutions of 50% sulfuric acid, 10% potassiumiodide, 5% Potassium Bromide, and at room temperature soak time is 3 days.
3. a kind of method of oxidizing solution to paracril surface chemical modification of utilizing according to claim 1, is characterized in that: in ultrasonic washing instrument, clean 5 minutes.
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| CN113045834A (en) * | 2021-03-16 | 2021-06-29 | 徐州工业职业技术学院 | Rubber composite material for cable and preparation method and application thereof |
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| CN104311865B (en) * | 2014-10-13 | 2017-04-05 | 重庆交通大学 | A kind of rubber surface method of modifying |
| CN109081967A (en) * | 2018-08-02 | 2018-12-25 | 佛山市高明区爪和新材料科技有限公司 | A kind of preparation method of high-wearing feature rubber slab |
| CN112126104A (en) * | 2020-09-22 | 2020-12-25 | 沈阳化工大学 | Method for chemically modifying surface of nitrile rubber by using strong acid salt oxidation solution |
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| CN1324699A (en) * | 2000-05-24 | 2001-12-05 | 王祥华 | Rubber surface treating process |
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Application publication date: 20121107 Assignee: Rong Shi international (investment) Beijing Co., Ltd. Assignor: Shenyang University of Technology Contract record no.: 2015990000153 Denomination of invention: Method for conducting chemical modification on nitrile butadiene rubber surface by using oxidation solution Granted publication date: 20140319 License type: Exclusive License Record date: 20150401 |
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