CN106317530B - A kind of heat resistant hydro-expansive rubber and preparation method thereof - Google Patents
A kind of heat resistant hydro-expansive rubber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of heat resistant hydro-expansive rubbers.Heat resistant hydro-expansive rubber provided by the invention includes following component: hydrogenated nitrile-butadiene rubber, high hydroscopic resin, sulphur, vulcanization accelerator and peroxide vulcanizing agent.Heat resistant hydro-expansive rubber of the invention uses hydrogenated nitrile-butadiene rubber as hydro-expansive rubber matrix, improves the high temperature resistance of rubber, especially high temperature water absorbing properties.In addition, the present invention uses peroxide vulcanizing agent and the compound vulcanizing system of sulphur, to improve the ageing-resistant performance and high temperature water absorbing properties of rubber.
Description
Technical field
The present invention relates to a kind of functional polymer material, in particular to a kind of heat resistant hydro-expansive rubber and its system
Preparation Method.
Background technique
Hydro-expansive rubber (WSR) is a kind of new functional macromolecule material.It is by hydrophilic material and elastomer alloy
Change, form it into a kind of elasticity and intensity with rubber, while having and can be retained in the case of water swelling, extruding, reaches both
Structure change is adapted to, and has water swelling with the dual water stopping function material of water sealing.
According to a large amount of practice and the study found that most blend polymers are incompatible or partially compatible.It is real
On border, polyblend is all the mixture of multi-phase multi-component structure, and there is phase interfaces and Phase Morphology difference to be produced
Raw performance weakness problem.For polyblend often because of poor compatibility, two interphase interfaces can be high, and interface binding power is low and causing property
It can decline.Rubber is used after cross-linking vulcanized, resin be present in cross-linked network could only expand after absorbing water without from
It is lost in rubber.Sulfur cross-linking is mainly used in ordinary rubber, cross-bond C-S key and uncrosslinked double bond are easy in hot environment
In be destroyed rubber molecular chain caused to be destroyed, reduce the resistance to ag(e)ing in actual use.It is resistance to due to unsaturated rubber itself
Aging problem, so the resistance to ag(e)ing of enhancing hydro-expansive rubber is exactly to prepare a main problem of hydro-expansive rubber.
The conventional method for preparing hydro-expansive rubber is: with hydrophilic water-absorbing resin and hydrophobic unsaturated rubber into
Row physical blending exists between water-absorbing resin and rubber in " island " shape, it is difficult to form biggish affinity, water-absorbing resin cannot be very
Good is dispersed in rubber phase, and long period of soaking is easily precipitated, especially in the high temperature environment, due in the rubber that can accelerate the failure in this way
Unstable double bond and C-S key, make molecular chain rupture, water-absorbing resin is not easy to be wrapped in rubber network, water-absorbing resin stream
It loses, reduces water absorbing properties, mechanical property, long-term water-retaining property and the reusability of rubber.Mo Yiting, Yang Linde etc. utilize poly- ammonia
The mixture of ester chlorination buna and natural rubber vulcanization made of hydro-expansive rubber, 85 DEG C of heat ageings for 24 hours after, tensile strength
Decline 8.9%, elongation at break decline 5.6%, expansion rate of water absorption decline 8%, although opposite generally mix with type water-swellable rubber
Glue ageing-resistant performance increases, but properties all continue to decline after high temperature ageing more days, cannot be used for a long time.
For this reason, the present inventor is studied, it is therefore an objective to it is sudden and violent to solve related fields prior art institute
The problem of exposing is intended to provide a kind of ageing-resistant performance and the preferable hydro-expansive rubber of high temperature water absorbing properties and its preparation
Method.
Summary of the invention
In view of the above the deficiencies in the prior art, it is an object of the present invention to provide a kind of heat resistant water-swellables
Rubber uses hydrogenated nitrile-butadiene rubber as hydro-expansive rubber matrix, improves the high temperature resistance of rubber, especially high temperature and inhale
Aqueous energy.In addition, the present invention uses peroxide vulcanizing agent and the compound vulcanizing system of sulphur, so as to further increase rubber
The ageing-resistant performance and high temperature water absorbing properties of glue.
It is another object of the present invention to provide a kind of methods for preparing the heat resistant hydro-expansive rubber.
According to an aspect of the present invention, the present invention provides a kind of heat resistant hydro-expansive rubbers comprising such as
Lower component: hydrogenated nitrile-butadiene rubber, high hydroscopic resin, sulphur, vulcanization accelerator and peroxide vulcanizing agent.
A specific embodiment according to the present invention, the hydrogenated nitrile-butadiene rubber are selected from the hydrogenation that saturation degree is 85~95%
The hydrogenated nitrile-butadiene rubber that nitrile rubber, preferably saturation degree are 90%.
In the present invention, saturated bond accounts for total molecule after the saturation degree of the hydrogenated nitrile-butadiene rubber refers to chemigum hydrogenation
The ratio of main chain key.
Hydro-expansive rubber of the invention uses hydrogenated nitrile-butadiene rubber as matrix, improves the resistance to old of hydro-expansive rubber
Change performance, reduce the turnover rate of hydro-expansive rubber absorbent composition in the hot water, the performance for improving material after heat ageing is stablized
Property.
A specific embodiment according to the present invention, the high hydroscopic resin are selected from polyacrylate, polyvinyl alcohol, polyethers
With acrylates-methacrylate copolymers resin, it is preferably selected from polyacrylate and acrylates-methacrylate copolymers
Resin is more preferably selected from Sodium Polyacrylate and sodium acrylate-lauryl methacrylate copolymer resins.
(Superabsorbent polymers, abbreviation SAP also make high-hydroscopicity high to super absorbent resin of the present invention
Molecule, super-strong moisture absorbing machine or high water absorbency polymer) it is a kind of containing strongly hydrophilics groups such as carboxyl, hydroxyls and with low cross-linking
The water-swellable type high molecular polymer of degree or partially crystallizable.
A specific embodiment according to the present invention, the peroxide vulcanizing agent are selected from cumyl peroxide, tertiary fourth
Base dicumyl peroxide, dibenzoyl peroxide, peroxidized t-butyl perbenzoate, 1,4- dual-tert-butyl peroxide diisopropyl benzene,
Bis- (di-t-butyl the peroxy) -3,3,5- trimethyl-cyclohexanes of 1,1-, 2,5- dimethyl -2,5- two (benzoyl peroxide) base hexane
With 2,5- dimethyl -2,5- two (t-butylperoxy) -3- hexin.
Hydro-expansive rubber of the invention, the saturation hydrogenated nitrile-butadiene rubber being crosslinked using peroxide vulcanizing agent, is effectively changed
The ageing-resistant performance of rubber has been apt to it, hence it is evident that the loss that falls off for reducing water-absorbing resin enhances hydro-expansive rubber in the hot water
Water-swelling property and aging after mechanical strength.
The mass ratio of a specific embodiment according to the present invention, sulphur and vulcanization accelerator is 1:2~2:1, preferably
1:1.The purpose being implemented is can to increase rubber to make the unsaturated double-bond in rubber be crosslinked the weak bond reduced in rubber
The degree of cross linking.
A specific embodiment according to the present invention, based on parts by weight, the hydro-expansive rubber include: 100 parts of hydrogen
Change nitrile rubber, 30~70 parts of high hydroscopic resins, 0.1~1.5 part of sulphur, 0.1~1.5 part of vulcanization accelerator and 1~4 part of mistake
Oxide curative agent.
A specific embodiment according to the present invention, the hydro-expansive rubber further include PEG, anti-aging agent and reinforcing agent；
Wherein, the reinforcing agent is silane coupler modified white carbon black, and the anti-aging agent is selected from N- isopropyl-N '-phenyl to benzene two
Amine, N- phenyl-N '-diphenyl-para-phenylene diamine and N- phenyl-N '-cyclohexyl p-phenylenediamine.
In the present invention, the effect of PEG is to increase the compatibility of high hydroscopic resin, white carbon black and rubber, can be less
The free rubber out of rubber functional stuffing in water suction.
In the present invention, the effect of reinforcing agent is enhancing rubber mechanical property, wherein silane coupler modified white carbon black
It can be further improved the compatibility of reinforcing agent and rubber.
In the present invention, the effect of anti-aging agent is to absorb the oxidants such as oxygen to react with it, and the resistance to of rubber can be improved
Ageing properties.
A specific embodiment according to the present invention, based on parts by weight, based on parts by weight, the hydro-expansive rubber
It include: 100 parts of hydrogenated nitrile-butadiene rubbers, 2~6 parts of PEG, 2~4 parts of anti-aging agents and 20~60 portions of reinforcing agents.
A specific embodiment according to the present invention, the hydro-expansive rubber further include zinc oxide, stearic acid and softening
Agent.Wherein, zinc oxide is inorganic sulphide activator, and curingprocess rate can be improved；Stearic acid is organic sulfide activator, can be with
It improves vulcanizing agent and is passivated curing efficiency；The effect of softening agent is to increase rubber processing plasticity, can solve gum filler filling
The technical issues of relative difficulty.
According to another aspect of the present invention, a kind of heat resistant chance water is prepared the present invention also provides a kind of
The method of expanded rubber comprising following steps:
(1) hydrogenated nitrile-butadiene rubber progress room temperature in mixer or open mill is put into plasticate；
(2) zinc oxide, stearic acid, anti-aging agent, reinforcing agent, softening agent, PEG and high hydroscopic resin are sequentially added, in room temperature
Lower mixing；
(3) after natural cooling, white carbon black, sulphur, vulcanization accelerator and peroxide vulcanizing agent is added and continues to mix
Refining, obtains rubber compound；
(4) finally rubber compound is put into mold and is pressed and molded.
The present invention proposes to use peroxidating using saturation oil resistant hydrogenated nitrile-butadiene rubber as hydro-expansive rubber complex matrix
Object vulcanizing agent and the compound vulcanizing system rubber of sulphur, to significantly improve the ageing-resistant performance and high temperature water imbibition of rubber
Energy.Method and process of the invention is simple and convenient, and equipment requirement is low.The ageing-resistant performance and height of the hydro-expansive rubber of preparation is blended
Warm water absorbing properties are preferable.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Embodiment 1
The hydrogenated nitrile-butadiene rubber that the saturation degree that 100 parts are added first in open mill is 90%, room temperature are plasticated 2min；Then
It is different to sequentially add 65 parts of Sodium Polyacrylates, 5 parts of zinc oxide, 1.5 parts of stearic acid, 30 parts of reinforcing agent white carbon blacks, 6 parts of PEG, 2 parts of N-
Propyl-N '-diphenyl-para-phenylene diamine and 4 parts of softening agents, room temperature are kneaded 10min；After rubber places cooling naturally, 0.5 is added
Part sulphur, 0.5 part of 2,2'- dithio-bis-benzothiazole and 1.5 parts of cumyl peroxides, are kneaded under 25 DEG C of blending temperature
2min discharges, cooling；Finally rubber compound is put into mold again, is molded under 160 DEG C of temperature, pressure 10MPa conditions of vulcanization
A kind of high-temperature-rusistance water-expansible rubber of the invention can be obtained in type.
It takes the 1g high-temperature-rusistance water-expansible rubber to immerse in 25 DEG C of fresh water water-baths, water suction balance is reached after 15 days or so,
Rapid taking-up wipes moisture weighing with filter paper, and calculating gained water-swellable multiplying power is 1830%.It absorbs water in 60 DEG C of fresh water, 2 days
After reach water suction balance, wipe the weighing of surface water, calculate gained water-swellable multiplying power and still there was only 420%, water-absorbing resin be precipitated compared with
Seriously.Hydro-expansive rubber tensile strength is 7.6MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours,
The tensile strength of test rubber still maintains tensile strength 7.6MPa or more before ageing, increases 10%.
Embodiment 2
It is added the hydrogenated nitrile-butadiene rubber that 100 parts of saturation degrees are 90% first in open mill, room temperature is plasticated 3min；Then
Sequentially add 65 parts of sodium acrylate-lauryl methacrylate copolymer resins, 5 parts of zinc oxide, 1 part of stearic acid, 50 parts of silane idols
Join agent modified white carbon black, 4 parts of PEG, 2 parts of N- phenyl-N '-diphenyl-para-phenylene diamines and 6 parts of softening agents, room temperature is kneaded 10min；To
After rubber places cooling naturally, it is different to add 0.5 part of sulphur, 0.5 part of 2,2'- dithio-bis-benzothiazole and 2 parts of peroxidating two
Propyl benzene is kneaded 2min under 25 DEG C of blending temperature, discharges, cooling；Finally rubber compound is put into mold again, in temperature 160
DEG C, it is pressed and molded under pressure 10MPa conditions of vulcanization, a kind of high-temperature-rusistance water-expansible rubber of the invention can be obtained.
It takes the 1g high-temperature-rusistance water-expansible rubber to immerse in 25 DEG C of fresh water water-baths, water suction balance is reached after 5 days or so, it is fast
Fast taking-up wipes moisture weighing with filter paper, and calculating gained water-swellable multiplying power is 1443%.It absorbs water in 60 DEG C of fresh water, after 2 days
Reach water suction balance, wipe the weighing of surface water, calculating gained water-swellable multiplying power still has 1249%, water-absorbing resin be precipitated compared with
It is few.Hydro-expansive rubber tensile strength is 7.07MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours,
The tensile strength of test rubber still maintains tensile strength 7.07MPa or so before ageing, reduces 4.2%.
Embodiment 3
It is added the hydrogenated nitrile-butadiene rubber that 100 parts of saturation degrees are 90% first in open mill, room temperature is plasticated 3min；Then
Sequentially add 65 parts of Sodium Polyacrylates, 5 parts of zinc oxide, 1 part of stearic acid, 50 parts of silane coupler modified white carbon blacks, 2 parts of PEG,
2 parts of N- phenyl-N '-cyclohexyl p-phenylenediamine and 10 parts of softening agents, room temperature are kneaded 10min；After rubber places cooling naturally, then
0.5 part of sulphur, 0.5 part of 2,2'- dithio-bis-benzothiazole and 2 parts of cumyl peroxides are added, in 25 DEG C of blending temperature
Lower mixing 2min discharges, cooling；Finally rubber compound is put into mold again, under 160 DEG C of temperature, pressure 10MPa conditions of vulcanization
Compression molding, can be obtained a kind of high-temperature-rusistance water-expansible rubber of the invention.
It takes the 1g hydro-expansive rubber to immerse in 25 DEG C of fresh water water-baths, water suction balance is reached after 10 days or so, is taken rapidly
Moisture weighing is wiped with filter paper out, calculating gained water-swellable multiplying power is 1415%.It absorbs water in 60 DEG C of fresh water, reaches after 3 days
Water suction balance wipes the weighing of surface water, and calculating gained water-swellable multiplying power still has 1268%, and water-absorbing resin is precipitated less.It meets
Water-expansible rubber tensile strength is 6.3MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours, tests rubber
The tensile strength of glue is more more than tensile strength 6.3MPa increase before aging, increases 25%.
Embodiment 4
It is added the hydrogenated nitrile-butadiene rubber that 100 parts of saturation degrees are 90% first in open mill, room temperature is plasticated 3min；Then
Sequentially add 65 parts of Sodium Polyacrylates, 5 parts of zinc oxide, 1 part of stearic acid, 30 parts of silane coupler modified white carbon blacks, 2 parts of PEG,
2 parts of N- isopropyl-N '-diphenyl-para-phenylene diamines and 5 parts of softening agents, room temperature are kneaded 10min；After rubber places cooling naturally, then
0.5 part of sulphur, 0.5 part of 2,2'- dithio-bis-benzothiazole and 2 parts of 2,5- dimethyl -2,5- two (benzoyl peroxide) bases are added
Hexane is kneaded 2min under 25 DEG C of blending temperature, discharges, cooling；Finally rubber compound is put into mold again, in temperature 160
DEG C, it is pressed and molded under pressure 10MPa conditions of vulcanization, a kind of high-temperature-rusistance water-expansible rubber of the invention can be obtained.
It takes the 1g hydro-expansive rubber to immerse in 25 DEG C of fresh water water-baths, water suction balance is reached after 21 days or so, is taken rapidly
Moisture weighing is wiped with filter paper out, calculating gained water-swellable multiplying power is 2526%.It absorbs water in 60 DEG C of fresh water, reaches after 4 days
Water suction balance wipes the weighing of surface water, and calculating gained water-swellable multiplying power still has 1265%, there is water-absorbing resin precipitation.Meet water
Expanded rubber tensile strength is 6.7MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours, tests rubber
Tensile strength keep tensile strength 6.7MPa or more before ageing, increase 7.3%.
Embodiment 5
It is added the hydrogenated nitrile-butadiene rubber that 100 parts of saturation degrees are 90% first in open mill, room temperature is plasticated 3min；Then
Sequentially add 30 parts of sodium acrylate-lauryl methacrylate copolymer resins, 5 parts of zinc oxide, 1 part of stearic acid, 40 parts of silane idols
Join agent modified white carbon black, 5 parts of PEG, 2 parts of N- isopropyl-N '-diphenyl-para-phenylene diamines and 5 parts of softening agents, room temperature is kneaded 10min；
After rubber places cooling naturally, 0.5 part of sulphur, 0.5 part of 2,2'- dithio-bis-benzothiazole and 2 parts of 2,5- diformazans are added
Base -2,5- bis- (t-butylperoxy) -3- hexin, is kneaded 2min under 25 DEG C of blending temperature, discharges, cooling；Finally again will
Rubber compound is put into mold, is pressed and molded under 160 DEG C of temperature, pressure 10MPa conditions of vulcanization, one kind of the invention can be obtained
High-temperature-rusistance water-expansible rubber.
It takes the 1g hydro-expansive rubber to immerse in 25 DEG C of fresh water water-baths, water suction balance is reached after 16 days or so, is taken rapidly
Moisture weighing is wiped with filter paper out, calculating gained water-swellable multiplying power is 783%.It absorbs water in 60 DEG C of fresh water, reaches after 11 days
Water suction balance wipes the weighing of surface water, and calculating gained water-swellable multiplying power still has 378%, there is water-absorbing resin precipitation.It is swollen to meet water
Swollen rubber tensile intensity is 11.41MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours, tests rubber
Tensile strength compared with before aging tensile strength 11.41MPa increase it is more, increase 39.6%.
Embodiment 6
It is added the hydrogenated nitrile-butadiene rubber that 100 parts of saturation degrees are 90% first in open mill, room temperature is plasticated 3min；Then
Sequentially add 60 parts of Sodium Polyacrylates, 5 parts of zinc oxide, 1 part of stearic acid, 25 parts of silane coupler modified white carbon blacks, 5 parts of PEG,
2 parts of N- phenyl-N '-diphenyl-para-phenylene diamines and 4 parts of softening agents, room temperature are kneaded 10min；After rubber places cooling naturally, then plus
Enter 0.5 part of sulphur, 0.5 part of 2,2'- dithio-bis-benzothiazole and 2 parts of cumyl peroxides, under 25 DEG C of blending temperature
It is kneaded 2min, is discharged, it is cooling；Finally rubber compound is put into mold again, at 160 DEG C of temperature, pressure 10MPa conditions of vulcanization lower die
It is molded, a kind of high-temperature-rusistance water-expansible rubber of the invention can be obtained.
It takes the 1g hydro-expansive rubber to immerse in 25 DEG C of fresh water water-baths, water suction balance is reached after 14 days or so, is taken rapidly
Moisture weighing is wiped with filter paper out, calculating gained water-swellable multiplying power is 1123%.It absorbs water in 60 DEG C of fresh water, reaches after 13 days
Water suction balance wipes the weighing of surface water, and calculating gained water-swellable multiplying power still has 998%, almost without water-absorbing resin precipitation.
Hydro-expansive rubber tensile strength is 8.99MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours, is tested
The tensile strength of rubber is more compared with tensile strength 8.99MPa increase before aging, increases 23%.
Comparative example 1
With embodiment 1, difference is only that using natural rubber be substrate, instead of hydrogenated nitrile-butadiene rubber, thus the system of processing
It is standby to obtain a kind of Water Swelling Rubber Made by Blending.
It takes the 1g Water Swelling Rubber Made by Blending to immerse in 25 DEG C of fresh water water-baths, reaches within 12 days water suction balance, take rapidly
Moisture weighing is wiped with filter paper out, calculating gained water-swellable multiplying power is 856%.It absorbs water in 60 DEG C of fresh water, suction is reached after 8 days
Water balance wipes the weighing of surface water, calculates gained water-swellable multiplying power and there was only 316%, there is water-absorbing resin precipitation.Water-swellable rubber
Glue tensile strength is 9.70MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours, tests the stretching of rubber
Intensity is more compared with tensile strength 9.7MPa reduction before aging, reduces 52%.
Prepared high-temperature-rusistance water-expansible in the Water Swelling Rubber Made by Blending and embodiment 1 that this comparative example is prepared
Rubber phase ratio, room temperature expansion rate of water absorption is much smaller, and ageing-resistant performance is also relatively poor.
Comparative example 2
With embodiment 1, difference is only that using nitrile rubber be substrate, instead of hydrogenated nitrile-butadiene rubber, thus the system of processing
It is standby to obtain a kind of Water Swelling Rubber Made by Blending.
It takes the 1g Water Swelling Rubber Made by Blending to immerse in 25 DEG C of fresh water water-baths, reaches within 10 days water suction balance, take rapidly
Moisture weighing is wiped with filter paper out, calculating gained water-swellable multiplying power is 776%.It absorbs water in 60 DEG C of fresh water, suction is reached after 8 days
Water balance wipes the weighing of surface water, calculates gained water-swellable multiplying power and there was only 385%, there is water-absorbing resin precipitation.Water-swellable rubber
Glue tensile strength is 4.89MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours, tests the stretching of rubber
Intensity is more compared with tensile strength 4.89MPa reduction before aging, reduces 40.5%.
Prepared high-temperature-rusistance water-expansible in the Water Swelling Rubber Made by Blending and embodiment 1 that this comparative example is prepared
Rubber phase ratio, room temperature expansion rate of water absorption is much smaller, and mechanical property, ageing-resistant performance are also relatively poor.
Comparative example 3
With embodiment 1, the hydrogenated nitrile-butadiene rubber that it is 75% using saturation degree that difference, which is only that, so that processing is prepared
A kind of water swelling rubber.
It takes the 1g water swelling rubber to immerse in 25 DEG C of fresh water water-baths, reaches within 16 days water suction balance, take out rapidly with filter
Paper wipes moisture weighing, and calculating gained water-swellable multiplying power is 1235%.It absorbs water in 60 DEG C of fresh water, it is flat that water suction is reached after 3 days
Weighing apparatus wipes the weighing of surface water, calculates gained water-swellable multiplying power and there was only 565%, there is water-absorbing resin precipitation.Hydro-expansive rubber is drawn
Stretching intensity is 8.29MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours, tests the tensile strength of rubber
It decreases compared with tensile strength 8.29MPa before aging, reduces 5.5%.
The water swelling rubber that this comparative example is prepared and high-temperature-rusistance water-expansible rubber phase prepared in embodiment 1
Than room temperature expansion rate of water absorption is slightly smaller, and mechanical property is preferable, but ageing-resistant performance is relatively poor.
Comparative example 4
With embodiment 1, the hydrogenated nitrile-butadiene rubber that it is 95% using saturation degree that difference, which is only that, so that processing is prepared
A kind of water swelling rubber.
It takes the 1g water swelling rubber to immerse in 25 DEG C of fresh water water-baths, reaches within 18 days water suction balance, take out rapidly with filter
Paper wipes moisture weighing, and calculating gained water-swellable multiplying power is 991%.It absorbs water in 60 DEG C of fresh water, it is flat that water suction is reached after 4 days
Weighing apparatus wipes the weighing of surface water, calculates gained water-swellable multiplying power and there was only 665%, there is water-absorbing resin precipitation.Hydro-expansive rubber is drawn
Stretching intensity is 10.19MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours, and the stretching for testing rubber is strong
Degree decreases compared with tensile strength 10.19MPa before aging, improves 1.5%.
The water swelling rubber that this comparative example is prepared and high-temperature-rusistance water-expansible rubber phase prepared in embodiment 1
Than room temperature expansion rate of water absorption is slightly smaller, and ageing-resistant performance, mechanical property are preferable.
Comparative example 5
With embodiment 1, difference is only that the mass ratio of the sulphur and vulcanization accelerator that use is 1:3, thus the system of processing
It is standby to obtain a kind of water swelling rubber.
It takes the 1g water swelling rubber to immerse in 25 DEG C of fresh water water-baths, reaches within 8 days water suction balance, take out use filter paper rapidly
Moisture weighing is wiped, calculating gained water-swellable multiplying power is 1621%.It absorbs water in 60 DEG C of fresh water, water suction balance is reached after 3 days,
The weighing of surface water is wiped, gained water-swellable multiplying power is calculated and there was only 226%, there are a large amount of water-absorbing resins to be precipitated.Hydro-expansive rubber
Tensile strength is 4.20MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours, and the stretching for testing rubber is strong
Degree decreases compared with tensile strength 4.2MPa before aging, reduces 12.6%.
The water swelling rubber that this comparative example is prepared and high-temperature-rusistance water-expansible rubber phase prepared in embodiment 1
Than high temperature expansion rate of water absorption is much smaller, and ageing-resistant performance, mechanical property are all poor.
Comparative example 6
With embodiment 1, difference is only that the mass ratio of the sulphur and vulcanization accelerator that use is 3:1, thus the system of processing
It is standby to obtain a kind of water swelling rubber.
It takes the 1g water swelling rubber to immerse in 25 DEG C of fresh water water-baths, reaches within 9 days water suction balance, take out use filter paper rapidly
Moisture weighing is wiped, calculating gained water-swellable multiplying power is 1921%.It absorbs water in 60 DEG C of fresh water, water suction balance is reached after 3 days,
The weighing of surface water is wiped, gained water-swellable multiplying power is calculated and there was only 329.5%, there are a large amount of water-absorbing resins to be precipitated.Water-swellable rubber
Glue tensile strength is 3.90MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours, tests the stretching of rubber
Intensity decreases compared with tensile strength 3.90MPa before aging, reduces 16.7%.
The water swelling rubber that this comparative example is prepared and high-temperature-rusistance water-expansible rubber phase prepared in embodiment 1
Than high temperature expansion rate of water absorption is much smaller, and ageing-resistant performance, mechanical property are all poor.
Comparative example 7
With embodiment 1, difference, which is only that using conventional absorbent paper polypropylene amide, replaces super absorbent resin poly-
Sodium acrylate, so that a kind of conventional absorbent paper expanded rubber is prepared in processing.
It takes the 1g water swelling rubber to immerse in 25 DEG C of fresh water water-baths, reaches within 16 days water suction balance, take out rapidly with filter
Paper wipes moisture weighing, and calculating gained water-swellable multiplying power is 685.5%.It absorbs water in 60 DEG C of fresh water, it is flat that water suction is reached after 3 days
Weighing apparatus wipes the weighing of surface water, calculates gained water-swellable multiplying power and there was only 429.5%, has a large amount of water-absorbing resins to be precipitated.Water-swellable
Rubber tensile intensity is 9.87MPa, and rubber continuous ageing in 150 DEG C of hot air aging casees is taken out afterwards for 24 hours, tests the drawing of rubber
It stretches intensity to decrease compared with tensile strength 9.87MPa before aging, improves 8.91%.
Prepared high-temperature-rusistance water-expansible rubber in the conventional absorbent paper expanded rubber and embodiment 1 that this comparative example is prepared
Glue is compared: the room temperature expansion rate of water absorption of comparative example is more much smaller than embodiment 1, and ageing-resistant performance, mechanical property are all relatively good.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (10)
1. a kind of heat resistant hydro-expansive rubber comprising following component: hydrogenated nitrile-butadiene rubber, high hydroscopic resin, sulphur,
Vulcanization accelerator and peroxide vulcanizing agent；The hydrogenated nitrile-butadiene rubber is selected from the hydrogenated butyronitrile rubber that saturation degree is 85 ~ 95%
Glue；
The high hydroscopic resin is selected from polyacrylate, polyvinyl alcohol, polyethers and acrylates-methacrylate copolymers tree
Rouge；
Based on parts by weight, the hydro-expansive rubber includes: 100 parts of hydrogenated nitrile-butadiene rubbers, 60 ~ 70 parts of high hydroscopic resins, 0.1
~ 1.5 parts of sulphur, 0.1 ~ 1.5 part of vulcanization accelerator and 1 ~ 4 portion of peroxide vulcanizing agent；
The mass ratio of sulphur and vulcanization accelerator is 1:2 ~ 1:1；
The hydro-expansive rubber further includes PEG, anti-aging agent and reinforcing agent；Wherein, the reinforcing agent is silane coupler modified
White carbon black.
2. heat resistant hydro-expansive rubber according to claim 1, which is characterized in that the hydrogenated nitrile-butadiene rubber is
The hydrogenated nitrile-butadiene rubber that saturation degree is 90%.
3. heat resistant hydro-expansive rubber according to claim 1 or 2, which is characterized in that the high hydroscopic resin
Selected from selected from polyacrylate and acrylates-methacrylate copolymers resin.
4. heat resistant hydro-expansive rubber according to claim 3, which is characterized in that the high hydroscopic resin is selected from
Sodium Polyacrylate and sodium acrylate-lauryl methacrylate copolymer resins.
5. heat resistant hydro-expansive rubber according to claim 1 or 2, which is characterized in that the peroxide sulphur
Agent be selected from cumyl peroxide, cumyl t-butyl peroxide, dibenzoyl peroxide, peroxidized t-butyl perbenzoate,
Bis- (di-t-butyl the peroxy) -3,3,5- trimethyl-cyclohexanes of 1,4- dual-tert-butyl peroxide diisopropyl benzene, 1,1-, 2,5- diformazan
(benzoyl peroxide) the base hexane of base -2,5- two and 2,5- dimethyl -2,5- two (t-butylperoxy) -3- hexin.
6. heat resistant hydro-expansive rubber according to claim 1, which is characterized in that sulphur and vulcanization accelerator
Mass ratio is 1:1.
7. heat resistant hydro-expansive rubber according to claim 1 or 2, which is characterized in that the anti-aging agent is selected from
N- isopropyl-N '-diphenyl-para-phenylene diamine, N- phenyl-N '-diphenyl-para-phenylene diamine and N- phenyl-N '-cyclohexyl p-phenylenediamine.
8. heat resistant hydro-expansive rubber according to claim 1 or 2, which is characterized in that the water-swellable rubber
In glue, PEG is 2 ~ 6 parts, anti-aging agent is 2 ~ 4 parts and reinforcing agent is 20 ~ 60 parts.
9. according to claim 1 or 2 kind of heat resistant hydro-expansive rubber, which is characterized in that the water-swellable
Rubber further includes zinc oxide, stearic acid and softening agent.
10. a kind of method for preparing a kind of heat resistant hydro-expansive rubber as claimed in claim 9 comprising following step
It is rapid:
(1) hydrogenated nitrile-butadiene rubber progress room temperature in mixer or open mill is put into plasticate；
(2) zinc oxide, stearic acid, anti-aging agent, reinforcing agent, softening agent, PEG and high hydroscopic resin are sequentially added, is mixed at normal temperature
Refining；
(3) after natural cooling, sulphur, vulcanization accelerator and peroxide vulcanizing agent is added and continues to be kneaded, is kneaded
Glue；
(4) finally rubber compound is put into mold and is pressed and molded.
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| CN107641274B (en) * | 2017-09-30 | 2020-06-09 | 咸阳橡胶工业制品研究所有限公司 | Time-controlled high-temperature-resistant water-swelling rubber composite sealing material and preparation method thereof |
| CN108300436B (en) * | 2018-01-15 | 2020-08-28 | 中国石油化工股份有限公司西北油田分公司石油工程技术研究院 | Oil-water selective self-expansion rubber plugging agent for fracture-cavity oil reservoir, and preparation method and application thereof |
| CN110078986B (en) * | 2018-01-26 | 2021-07-30 | 中石化石油工程技术服务有限公司 | Preparation method of difunctional expandable elastomer material |
| CN111269477A (en) * | 2018-11-20 | 2020-06-12 | 中国石油化工股份有限公司 | Rubber composite material and preparation method thereof |
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