CN106349410B - A kind of extraordinary hydrogenated nitrile-butadiene rubber for compressing cold resistance and preparation method thereof - Google Patents
A kind of extraordinary hydrogenated nitrile-butadiene rubber for compressing cold resistance and preparation method thereof Download PDFInfo
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- CN106349410B CN106349410B CN201610780936.XA CN201610780936A CN106349410B CN 106349410 B CN106349410 B CN 106349410B CN 201610780936 A CN201610780936 A CN 201610780936A CN 106349410 B CN106349410 B CN 106349410B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/04—Oxidation
- C08C19/06—Epoxidation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08C19/02—Hydrogenation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
- C08C19/40—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with epoxy radicals
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Abstract
The present invention relates to a kind of extraordinary hydrogenated nitrile-butadiene rubber for compressing cold resistance and preparation method thereof, epoxide group is contained in its rubber backbone, the part epoxide group is further connected with ester group side base；The ester group side base is generated by C6 C24 acid anhydrides with the epoxide group ring-opening reaction.Preparation method, which is included in rubber molecule main chain, introduces epoxide group, so by the part epoxide group under catalyst action with anhydride reaction, introduce ester group, obtain the extraordinary hydrogenated nitrile-butadiene rubber containing epoxide group and ester group.Extraordinary hydrogenated nitrile-butadiene rubber proposed by the present invention has relatively low glass transition temperature, and crystal region is not present, and compresses cold-resistant coefficient and can reach 0.4, compresses the excellent specific rubber of cold tolerance to be a kind of.Epoxide group and ester group are introduced in rubber, while its compression cold tolerance is improved, ensure that excellent oil resistance.
Description
Technical field
The invention belongs to high-molecular organic material technical field, and in particular to a kind of extraordinary hydrogenated butyronitrile for compressing cold resistance
Rubber and preparation method thereof.
Background technology
Hydrogenated nitrile-butadiene rubber (HNBR) is a kind of elastomeric material of excellent combination property, by nitrile rubber (NBR)
Middle carbon-carbon double bond Hydrogenation obtains, and HNBR not only remains the original excellent oil resistances of NBR, and hydrogenated nitrile-butadiene rubber (HNBR)
With excellent high temperature resistant and ageing-resistant performance etc..But the nitrile rubber backbone structure after being hydrogenated with is by-CH2-CH2=CH2-CH2
It is converted into-the CH for being more easy to stacked arrangement2-CH2-CH2-CH2- structure, material form crystal region, and glass transition temperature (Tg)
Rise, influences its performance in low temperature environment.And the itrile group of decision rubber oil-resistant performance is strong pole in HNBR strands
Property group, largely have impact on HNBR cryogenic property, so the cryogenic property of the hydrogenated nitrile-butadiene rubber of high oil resistant shows
It is worse.
The cold-resistant coefficient of compression is to be characterized by determining the degree of sample elastic reduction before and after freezing as glue lower temperature resistance
The quality of energy, it is to weigh the rubber low temperature under low temperature compression state, undertaking the effects such as damping, sealing, buffering for a long time
One important indicator of performance.Hydrogenated butyronitrile nitrile rubber product is usually used in oil pipe under low temperature environment, oil circuit, hydraulic packing, because
It is of equal importance with improving oil resistance that this improves its low temperature compression performance in this case.
Generally speaking, improving hydrogenated nitrile-butadiene rubber low temperature compression performance is gone out from destruction crystallization and reduction by two angles of Tg
Hair, the method used more is that Third monomer is added during HNBR is synthesized, and the ordered structure of saboteur hinders to crystallize, and the
Three monomers generally have flexible side group can reduce Tg, also have part research be by molecular structure be modified introduce functional group come
The order of saboteur's chain.Early in 1993, Susmita Bhattacharjee et al. were proposed in the natural rubber of hydrogenation
Epoxide group is introduced to form crystalline texture after preventing natural rubber repeated hydrogenation, but unfortunately hydrogenated nitrile-butadiene rubber strand has
Sequence degree is higher than the natural rubber of hydrogenation, and it is difficult to destroy its crystalline texture completely to only rely on epoxide group.
The content of the invention
Present invention aims at a kind of extraordinary hydrogenated nitrile-butadiene rubber for compressing cold resistance is provided, contain epoxy in rubber backbone
Group, ester group side base is further connected with epoxide group.Raising of the presence of epoxide group to oil resistivity plays key effect, ester group side
The presence of base improves to compression cold tolerance and serves decisive role.The present invention can be by adjusting epoxy group content come real
Now to the controllable of oil resistance, access hydrogenated nitrile-butadiene rubber strand is adjusted by controlling the length of Ring Opening Reagent acid anhydrides carbochain
The length of middle ester group side base, so as to realize the regulation and control to hydrogenated nitrile-butadiene rubber compression cold tolerance.
Technical solution of the present invention is as follows：
A kind of extraordinary hydrogenated nitrile-butadiene rubber for compressing cold resistance, contains epoxide group, the part ring in its rubber backbone
Oxygen groups are further connected with ester group side base；The epoxy content of the rubber is 1-45%, acid anhydrides and institute of the ester group side base by C6-C24
Stating the generation of epoxide group ring-opening reaction, (i.e. C6-C24 acid anhydrides is grafted to rubber backbone with the epoxide group ring-opening reaction
On.).
Preferably, the epoxy content of the rubber is 10-30%.
Preferably, the ester group side base is generated by C10-C20 acid anhydrides with the epoxide group ring-opening reaction.
Preferably, acrylonitrile content is 15-30wt%, more preferably 19wt% in the hydrogenated nitrile-butadiene rubber.
Preferably, the glass transition temperature of the extraordinary hydrogenated nitrile-butadiene rubber is -36.4 to -26.3 DEG C, and compression is cold-resistant
Coefficient is 0.22-0.4, and crystal region is not present.
The present invention can be by adjusting ester group side base (i.e. acid anhydrides carbochain) length, to adjust access hydrogenated nitrile-butadiene rubber side base
Ester group length, with realize to compress cold tolerance regulation；Ensure oil resistance, real meaning by adjusting epoxy content
On realize hydrogenated nitrile-butadiene rubber resist cold controllable and oil resistant of compression it is controllable.
The present invention also provides a kind of preparation method for the extraordinary hydrogenated nitrile-butadiene rubber for compressing cold resistance, is included in rubber molecule
Introduce epoxide group in main chain, so by the part epoxide group under catalyst action with anhydride reaction, introduce ester group, obtain
The extraordinary hydrogenated nitrile-butadiene rubber containing epoxide group and ester group into a kind of strand.
Specifically, above-mentioned preparation method comprises the following steps：
Epoxidation reaction：Nitrile rubber is dissolved in organic solvent, nitrile rubber solution is made, sequentially adds second thereto
Acid and hydrogen peroxide, epoxidation reaction is carried out, the Epoxy acrylonitrile-butadirubber rubber that epoxy content is 10~50% is made；
Hydrogenation：Obtained Epoxy acrylonitrile-butadirubber rubber is dissolved in organic solvent, it is molten that Epoxy acrylonitrile-butadirubber rubber is made
Liquid, add thereto Wilkinson catalyst [Wilkinson's catalyst, i.e. chlorination three (triphenylphosphine) close rhodium (I)] and
Ligand triphenylphosphine, hydrogenation reaction is carried out, the epoxidation hydrogenated nitrile-butadiene rubber of degree of hydrogenation more than 90% is made；
Open loop graft reaction：Acid anhydrides and epoxide group open loop catalysis are added into obtained epoxidation hydrogenated nitrile-butadiene rubber
Agent, (i.e. Ring Opening Reagent acid anhydrides reacts heating response with the epoxide group in epoxidation hydrogenated nitrile-butadiene rubber, in rubber molecular chain
Introduce ester group), reacted mixed liquor is subjected to precipitating, washed, drying, the hydrogenated nitrile-butadiene rubber containing ester group side base is made；
Wherein described acid anhydrides is C6-C24 acid anhydrides；The epoxide group open loop rate is 10%~90%.
Or above-mentioned preparation method comprises the following steps：
Epoxidation reaction：Nitrile rubber is dissolved in organic solvent, nitrile rubber solution is made, sequentially adds second thereto
Acid and hydrogen peroxide, epoxidation reaction is carried out, the Epoxy acrylonitrile-butadirubber rubber that epoxy content is 10~50% is made；
Open loop graft reaction：Acid anhydrides and epoxide group ring opening catalyst are added into obtained Epoxy acrylonitrile-butadirubber rubber,
(i.e. Ring Opening Reagent acid anhydrides is reacted heating response with the epoxide group in Epoxy acrylonitrile-butadirubber rubber, and ester is introduced in rubber molecular chain
Base), reacted mixed liquor is subjected to precipitating, washed, drying, the nitrile rubber containing ester group side base is made；Wherein described acid
Acid anhydride is C6-C24 acid anhydrides；The epoxide group open loop rate is 10%~90%；
Hydrogenation：The obtained nitrile rubber containing ester group side base is dissolved in organic solvent, is made containing ester group
The nitrile rubber solution of side base, Wilkinson catalyst [Wilkinson's catalyst, i.e. chlorination three (three are added thereto
Phenylphosphine) close rhodium (I)] and ligand triphenylphosphine, carry out hydrogenation reaction, be made degree of hydrogenation more than 90% containing ester group side base
Hydrogenated nitrile-butadiene rubber.
Above-mentioned preparation method also includes further being kneaded hydrogenated nitrile-butadiene rubber of the gained containing ester group side base and sulphur
The step of change, the extraordinary hydrogenated nitrile-butadiene rubber of the compression cold resistance is finally made.
In above-mentioned preparation method,
Acrylonitrile content is 15-30wt% in nitrile rubber described in step epoxidation reaction；Preferably, the nitrile rubber
Middle acrylonitrile content is 19wt%.
The mass concentration of nitrile rubber solution described in step epoxidation reaction is 3-15wt%, preferably 8wt%.
Step epoxidation reaction is used as epoxidation reagent using acetic acid and hydrogen peroxide, it is preferable that mole of acetic acid and hydrogen peroxide
Than for 1.0：1.0~1.5, more preferably 1.0:1.2~1.3.
The molar ratio ratio of carbon-carbon double bond and acetic acid is 1.0 in nitrile rubber described in step epoxidation reaction:0.5-
1.5, preferably 1.0:0.8-1.2.
Reaction temperature described in step epoxidation reaction is 40~80 DEG C, and the time is 2~15h.
The epoxy content of Epoxy acrylonitrile-butadirubber rubber is preferably 10-30% described in step epoxidation reaction.
Epoxy acrylonitrile-butadirubber rubber solution described in step hydrogenation or the nitrile rubber solution containing ester group side base
Mass concentration is 2~12%；Preferably 5%.
Wilkinson catalyst described in step hydrogenation accounts for the Epoxy acrylonitrile-butadirubber rubber or described containing ester group side base
Nitrile rubber quality 0.5~1.2%, preferably 0.8%.
The mass ratio of Wilkinson catalyst and ligand triphenylphosphine described in step hydrogenation is 1:1~1:8, be preferably
1:3。
Hydrogenation reaction temperature described in step hydrogenation is 70~140 DEG C, 3~15 hours reaction time；It is preferred that hydrogen pressure
1~5MPa of power.
Epoxide group described in step open loop graft reaction not necessarily reacts completely, and the open loop rate of epoxide group can be 10%
~90%, best open loop rate can obtain preferable resistance to low temperature in 40%-60%.
The open loop rate of epoxide group of the present invention refers in step open loop graft reaction, participate in the epoxide group of reaction with
The mol ratio of total epoxide group before reaction, can be calculated by proton nmr spectra.
The acid anhydrides that step open loop graft reaction is added and the epoxidation hydrogenated nitrile-butadiene rubber or the epoxidation butyronitrile
The mol ratio of rubber epoxide epoxy group group is 1.0~5.0:1, preferably 2~4:1, more preferably 2.5-3:1.
Ring opening catalyst described in step open loop graft reaction can be the epoxy such as N, accelerine, tetrabutylammonium chloride
The one or more of group ring opening catalyst, preferably tetrabutylammonium chloride.
Ring opening catalyst described in step open loop graft reaction and the epoxidation hydrogenated nitrile-butadiene rubber or the epoxidation fourth
The mol ratio of nitrile rubber epoxide epoxy group group is 5~20: 100, preferably 10~15: 100.
Acid anhydrides described in step open loop graft reaction includes propionic andydride, butyric anhydride, valeric anhydride, caproic anhydride, heptanoic anhydride or octanoic acid
Acid anhydride；More preferably C10-C20 acid anhydrides.
Reaction is carried out in nitrogen scope described in step open loop graft reaction.
Reaction temperature described in step open loop graft reaction is 80-150 DEG C, reaction time 3-10h；Preferably, reaction temperature
Spend for 110 DEG C, reaction time 8h.
Organic solvent of the present invention prepares the nitrile rubber solution, Epoxy acrylonitrile-butadirubber rubber solution, contains ester group
The organic solvent of the nitrile rubber solution of side base includes the one or more in toluene, chlorobenzene, dimethylbenzene etc.；Preferably diformazan
Benzene.
More specifically, above-mentioned preparation method comprises the following steps：
Epoxidation reaction：Nitrile rubber is dissolved in dimethylbenzene, it is molten that the nitrile rubber that mass concentration is 3-15wt% is made
Liquid, acetic acid and hydrogen peroxide are sequentially added thereto, in 40~80 DEG C of 2~15h of epoxidation reaction, it is 10~50% that epoxy content, which is made,
Epoxy acrylonitrile-butadirubber rubber；Acrylonitrile content is 15-30wt% in the nitrile rubber；The mol ratio of the acetic acid and hydrogen peroxide
For 1.0：1.0~1.5；The molar ratio ratio of carbon-carbon double bond and acetic acid is 1.0 in the nitrile rubber:0.5-1.5；
Hydrogenation：Obtained Epoxy acrylonitrile-butadirubber rubber is dissolved in dimethylbenzene, it is 2~12% that mass concentration, which is made,
Epoxy acrylonitrile-butadirubber rubber solution, Wilkinson catalyst and ligand triphenylphosphine is added thereto, in 70~140 DEG C of temperature, hydrogen
Under 1~5MPa of atmospheric pressure, 3~15h of hydrogenation reaction, the epoxidation hydrogenated nitrile-butadiene rubber of obtained degree of hydrogenation more than 90%；The prestige
The mass ratio of Er Jinsen catalyst and ligand triphenylphosphine is 1:1~1:8；
Open loop graft reaction：Acid anhydrides and epoxide group open loop catalysis are added into obtained epoxidation hydrogenated nitrile-butadiene rubber
Agent, heating response under nitrogen atmosphere, reacted mixed liquor is subjected to precipitating, washed, drying, the hydrogen containing ester group side base is made
Change nitrile rubber；The mol ratio of the acid anhydrides and the epoxidation hydrogenated nitrile-butadiene rubber epoxide epoxy group group is 1.0~5.0:1；Institute
It is N, accelerine or tetrabutylammonium chloride to state ring opening catalyst；The ring opening catalyst and the epoxidation hydrogenated butyronitrile
The mol ratio of rubber epoxide epoxy group group is 5~20: 100；The epoxide group open loop rate is 40%~60%；The acid anhydrides propionic acid
Acid anhydride, butyric anhydride, valeric anhydride, caproic anhydride, heptanoic anhydride or caprylic anhydride；The reaction temperature is 80-150 DEG C, reaction time 3-
10h。
The order of hydrogenation and open loop graft reaction can exchange described in the above-mentioned preparation method of the present invention, i.e., to double bond
Hydrogenation and acid anhydrides do not influence on the order of epoxide group open loop on end-product.
The extraordinary hydrogenated nitrile-butadiene rubber of the compression cold resistance prepared present invention additionally comprises the above method.
Epoxy content of the present invention refer to product epoxide epoxy group group molal quantity and carbon-carbon double bond and epoxide group molal quantity it
The ratio of sum.
The assay method of the epoxy content is conventional proton nmr spectra computational methods.
Degree of unsaturation before degree of hydrogenation of the present invention=(degree of unsaturation after degree of unsaturation-hydrogenation before hydrogenation)/hydrogenation ×
100%.This area routine proton nmr spectra can be used to calculate.
The present invention first using in HNBR introducing epoxide group come largely in the crystalline texture of hydrogenated nitrile-butadiene rubber,
Epoxide group is recycled to introduce ester group, the presence of epoxide group and ester group in strand as the group with anhydride reaction
Crystalline texture thoroughly is destroyed, and oil resistivity is greatly improved, the presence of flexible ester-group significantly reduces Tg, so as to obtain one
The hydrogenated nitrile-butadiene rubber of the low temperature compression excellent performance of the high oil resistant of kind.The extraordinary hydrogenated nitrile-butadiene rubber of the present invention has relatively low glass
Change transition temperature, and crystal region is not present, compress cold-resistant coefficient and can reach 0.4, compress the excellent spy of cold tolerance to be a kind of
Kind rubber.Epoxide group and ester group are introduced in rubber, while its compression cold tolerance is improved, ensure that excellent oil resistant
Performance.
Advantage of the invention compared with existing NBR catalytic hydrogenations is：
1. being used as intermediate reaction group by introducing epoxide group in the molecular structure, reacted, divided using acid anhydrides
Ester group is introduced in subchain.Only the presence of epoxide group can largely destroy the crystalline texture of hydrogenated nitrile-butadiene rubber, be re-introduced into
Ester group not only can thoroughly destroy crystallization, and this flexible side group can be remarkably decreased Tg, resistance to from making rubber obtain excellent compression
Cold energy.
2. the epoxide group not reacted completely in strand as highly polar group, makes the oil resistant of hydrogenated nitrile-butadiene rubber again
Property be improved, it is possible to by controlling epoxy group content in strand to control oil resistivity.Ester group in strand
Carbochain length directly determine the compression cold tolerance of hydrogenated nitrile-butadiene rubber, and the carbochain length of ester group is decided by acid anhydrides,
So the compression cold tolerance of hydrogenated nitrile-butadiene rubber can be controlled by selecting different Ring Opening Reagents, it is cold-resistant to realize compression
Performance is controllable, oil resistant is controllable, has greatly widened the application field of hydrogenated nitrile-butadiene rubber.
Brief description of the drawings
Fig. 1 is HNBR, epoxidation HNBR and the epoxidation HNBR containing ester group infrared absorption spectra in experimental example 2.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.It is unreceipted specific in embodiment
Technology or condition person, carried out according to the technology or condition described by document in the art, or according to product description.It is used
Reagent or the unreceipted production firm person of instrument, it is the conventional products that can be commercially available by regular distributor.
The detection method of epoxy content as described below is conventional proton nmr spectra computational methods.
Embodiment 1
(1) acrylonitrile content 19wt% nitrile rubbers are taken to be dissolved in dimethylbenzene, it is 8wt%'s to be configured to concentration of polymer solution
Nitrile rubber solution.The above-mentioned glues of 300g are taken in 500ml there-necked flasks, add 21.6g acetic acid, then that dioxygen is added dropwise is water-soluble
Liquid, reaction stirring 10h, obtains mixed liquor at 65 DEG C.Reacted mixed liquor is subjected to precipitating, washed, drying, obtains epoxidation
Nitrile rubber.Calculated through nuclear magnetic spectrogram, epoxy content E%=32%；
(2) Epoxy acrylonitrile-butadirubber rubber is dissolved in dimethylbenzene, is configured to the solution that concentration of polymer solution is 5wt%；Take molten
Liquid 100g is added in autoclave, adds Wilkinson catalyst 0.04g, triphenylphosphine 0.12g.To reactor pump drainage nitrogen
Gas hydrogen is each three times, then is passed through hydrogen 4MPa, is heated to 110 DEG C, reacts 8h down in rotating speed 500r/min, obtain degree of hydrogenation 90%
Epoxidation hydrogenated nitrile-butadiene rubber solution above.
(3) nitrile rubber solution 100g is with there-necked flask, adding 6.52g propionic andydrides (C after taking hydrogenation6H10O3), 0.67g tetra-
Butyl ammonium chloride, pump drainage nitrogen three times, in nitrogen atmosphere, react 8h at 110 DEG C.Reacted mixed liquor is subjected to precipitating,
Washing, drying, obtains the hydrogenated nitrile-butadiene rubber of graft modification.
(4) hydrogenated nitrile-butadiene rubber 50g, stearic acid 0.5g, zinc oxide 2.5g, N220 carbon black 40g after graft modification, plasticising are taken
Agent dioctyl phthalate (DOP) 12.5g, sulphur 0.25g, DCP3g, Vulcanization accelerator TMTD 1.25g, CZ0.25g, in mill
Mixing obtains elastomeric compound, finally vulcanizes on 155 DEG C of vulcanizing press, and it is the extraordinary hydrogen for compressing cold resistance to obtain vulcanizate
Change nitrile rubber (HNBR).
Embodiment 2
By the 6.52g propionic andydrides (C in embodiment 16H10O3) it is replaced by 7.59g butyric anhydrides (C8H14O3), other conditions are not
Become, produce the hydrogenated nitrile-butadiene rubber of grafting butyl ester base.
Embodiment 3
By the 6.52g propionic andydrides (C in embodiment 16H10O3) it is replaced by 11.17g valeric anhydrides (C10H18O3), other conditions are not
Become, produce the hydrogenated nitrile-butadiene rubber of grafting pentyl ester base.
Embodiment 4
By the 6.52g propionic andydrides (C in embodiment 16H10O3) it is replaced by 12.86g acid anhydrides (C12H22O3), other conditions are not
Become, produce the hydrogenated nitrile-butadiene rubber for being grafted own ester group.
Embodiment 5
By the 6.52g propionic andydrides (C in embodiment 16H10O3) it is replaced by 17.45g heptanoic anhydrides (C14H26O3), other conditions are not
Become, produce the hydrogenated nitrile-butadiene rubber of grafting heptyl ester base.
Embodiment 6
By the 6.52g propionic andydrides (C in embodiment 16H10O3) it is replaced by 19.47g octanoic acids (C16H30O3), other conditions are not
Become, produce the hydrogenated nitrile-butadiene rubber of grafting monooctyl ester base.
Comparative example 1
(1) acrylonitrile content 19wt% nitrile rubbers are taken to be dissolved in dimethylbenzene, it is 5wt%'s to be configured to concentration of polymer solution
Nitrile rubber solution；
(2) take solution 100g to add in autoclave, add Wilkinson catalyst 0.04g, triphenylphosphine
0.12g.It is each to reactor pump drainage nitrogen hydrogen then to be passed through hydrogen 4MPa three times, be heated to 110 DEG C, in rotating speed 500r/min under
React 8h.Reacted mixed liquor is subjected to precipitating, washed, drying, obtains the hydrogenated nitrile-butadiene rubber of degree of hydrogenation more than 90%.
Experimental example 1
The performance test results of hydrogenated nitrile-butadiene rubber see the table below 1, table 2 made from embodiment 1-6 and comparative example 1.
The cryogenic property of the hydrogenated nitrile-butadiene rubber of the different ester group side bases of table 1
The extraordinary hydrogenated nitrile-butadiene rubber that the compression that it can be seen from the correction data of table 1 prepared by the present invention is resisted cold, compared to not
Modified hydrogenated nitrile-butadiene rubber, its cryogenic property improve a lot.The hydrogenated nitrile-butadiene rubber of monooctyl ester base is accessed, contrasts identical nitrile
The hydrogenated nitrile-butadiene rubber of base content, its Tg reduce by 11.4 DEG C, compress cold-resistant coefficient and reach 0.4, show excellent compression and resist cold
Performance.
The oil resistance of the hydrogenated nitrile-butadiene rubber of the different ester group side bases of table 2
Oil resistance is characterized to the hydrogenated nitrile-butadiene rubber for accessing different ester groups, is as a result listed in table 2.Soaked at 150 DEG C of temperature
48h is steeped, the rate of change of quality characterizes its oil resistance, the lower explanation oil resistant of mass change before and after measurement rubber immersion
Performance is better.It can be seen from the correction data of table 2 access monooctyl ester base hydrogenated nitrile-butadiene rubber mass change by
52.45% is reduced to 16.10%, and thus preparation method proposed by the present invention makes hydrogenated nitrile-butadiene rubber obtain excellent compression cold-resistant
Its oil resistance is significantly improved while performance.
Experimental example 2
The product epoxidation HNBR of step 2 and implementation in hydrogenated nitrile-butadiene rubber (HNBR), embodiment 1 made from comparative example 1
The infrared absorption spectra of the epoxidation HNBR containing ester group is shown in Fig. 1 made from example 1, contrasts HNBR curves, and epoxidation HNBR exists
889cm-1There is epoxide group characteristic peak in place, illustrates successfully epoxide group is introduced into HNBR；Embodiment 1 is obtained containing ester group
Epoxidation HNBR, in 1735cm-1There is obvious carbonyl characteristic peak in place, in 1179cm-1There is the stretching vibration peak of ester group in place,
And 889cm-1Locate epoxy characteristic peak to weaken, it was demonstrated that be successfully grafted ester group in hydrogenated nitrile-butadiene rubber.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (13)
1. a kind of extraordinary hydrogenated nitrile-butadiene rubber for compressing cold resistance, it is characterised in that contain epoxide group, portion in its rubber backbone
The epoxide group is divided to be further connected with ester group side base；The epoxy content of the rubber is 1-45%, and the ester group side base is by C6-C24's
Acid anhydrides generates with the epoxide group ring-opening reaction.
2. extraordinary hydrogenated nitrile-butadiene rubber according to claim 1, it is characterised in that acrylonitrile in the hydrogenated nitrile-butadiene rubber
Content is 15-30wt%.
3. extraordinary hydrogenated nitrile-butadiene rubber according to claim 1, it is characterised in that acrylonitrile in the hydrogenated nitrile-butadiene rubber
Content is 19wt%.
4. according to the extraordinary hydrogenated nitrile-butadiene rubber described in claim any one of 1-3, it is characterised in that the epoxy content of the rubber
For 10-30%；And/or the ester group side base is generated by C10-C20 acid anhydrides with the epoxide group ring-opening reaction.
5. according to the extraordinary hydrogenated nitrile-butadiene rubber described in claim any one of 1-3, it is characterised in that the extraordinary hydrogenated butyronitrile
The glass transition temperature of rubber is -36.4 to -26.3 DEG C, and it is 0.22-0.4 to compress cold-resistant coefficient, and crystal region is not present.
6. a kind of preparation method for the extraordinary hydrogenated nitrile-butadiene rubber for compressing cold resistance, it is characterised in that the preparation method includes
Following steps：
Epoxidation reaction：Nitrile rubber is dissolved in organic solvent, nitrile rubber solution is made, sequentially add thereto acetic acid and
Hydrogen peroxide, epoxidation reaction is carried out, the Epoxy acrylonitrile-butadirubber rubber that epoxy content is 10~50% is made；
Hydrogenation：Obtained Epoxy acrylonitrile-butadirubber rubber is dissolved in organic solvent, Epoxy acrylonitrile-butadirubber rubber solution is made, to
Wilkinson catalyst and ligand triphenylphosphine are wherein added, carries out hydrogenation reaction, the epoxidation of degree of hydrogenation more than 90% is made
Hydrogenated nitrile-butadiene rubber；
Open loop graft reaction：Acid anhydrides and epoxide group ring opening catalyst are added into obtained epoxidation hydrogenated nitrile-butadiene rubber,
Heating response, reacted mixed liquor is subjected to precipitating, washed, drying, the hydrogenated nitrile-butadiene rubber containing ester group side base is made；Its
Described in acid anhydrides be C6-C24 acid anhydrides；The epoxide group open loop rate is 10%~90%；
Or the preparation method comprises the following steps：
Epoxidation reaction：Nitrile rubber is dissolved in organic solvent, nitrile rubber solution is made, sequentially add thereto acetic acid and
Hydrogen peroxide, epoxidation reaction is carried out, the Epoxy acrylonitrile-butadirubber rubber that epoxy content is 10~50% is made；
Open loop graft reaction：Acid anhydrides and epoxide group ring opening catalyst, heating are added into obtained Epoxy acrylonitrile-butadirubber rubber
Reaction, reacted mixed liquor is subjected to precipitating, washed, drying, the nitrile rubber containing ester group side base is made；Wherein described acid
Acid anhydride is C6-C24 acid anhydrides；The epoxide group open loop rate is 10%~90%；
Hydrogenation：The obtained nitrile rubber containing ester group side base is dissolved in organic solvent, is made containing ester group side base
Nitrile rubber solution, add Wilkinson catalyst and ligand triphenylphosphine thereto, carry out hydrogenation reaction, degree of hydrogenation is made
More than 90% hydrogenated nitrile-butadiene rubber containing ester group side base.
7. preparation method according to claim 6, it is characterised in that propylene in nitrile rubber described in step epoxidation reaction
Nitrile content is 15-30wt%.
8. preparation method according to claim 6, it is characterised in that propylene in nitrile rubber described in step epoxidation reaction
Nitrile content is 19wt%.
9. according to the preparation method described in claim any one of 6-8, it is characterised in that open loop described in step open loop graft reaction
Catalyst is one or both of N, accelerine, tetrabutylammonium chloride；And/or described in step open loop graft reaction
Acid anhydrides is C10-C20 acid anhydrides；And/or epoxide group open loop rate described in step open loop graft reaction is 40%~60%.
10. according to the preparation method described in claim any one of 6-8, it is characterised in that the organic solvent is toluene, chlorine
Benzene or dimethylbenzene.
11. preparation method according to claim 9, it is characterised in that the organic solvent is toluene, chlorobenzene or diformazan
Benzene.
12. preparation method according to claim 6, it is characterised in that comprise the following steps：
Epoxidation reaction：Nitrile rubber is dissolved in dimethylbenzene, the nitrile rubber solution that mass concentration is 3-15wt% is made, to
Acetic acid and hydrogen peroxide are wherein sequentially added, in 40~80 DEG C of 2~15h of epoxidation reaction, the ring that epoxy content is 10~50% is made
Aoxidize nitrile rubber；Acrylonitrile content is 15-30wt% in the nitrile rubber；The mol ratio of the acetic acid and hydrogen peroxide is
1.0：1.0~1.5；The molar ratio of carbon-carbon double bond and acetic acid is 1.0 in the nitrile rubber:0.5-1.5；
Hydrogenation：Obtained Epoxy acrylonitrile-butadirubber rubber is dissolved in dimethylbenzene, the epoxy that mass concentration is 2~12% is made
Change nitrile rubber solution, Wilkinson catalyst and ligand triphenylphosphine are added thereto, in 70~140 DEG C of temperature, hydrogen pressure
Under 1~5MPa of power, 3~15h of hydrogenation reaction, the epoxidation hydrogenated nitrile-butadiene rubber of obtained degree of hydrogenation more than 90%；The Weir gold
The mass ratio of gloomy catalyst and ligand triphenylphosphine is 1:1~1:8；
Open loop graft reaction：Acid anhydrides and epoxide group ring opening catalyst are added into obtained epoxidation hydrogenated nitrile-butadiene rubber,
Heating response under nitrogen atmosphere, reacted mixed liquor is subjected to precipitating, washed, drying, the hydrogenation containing ester group side base is made
Nitrile rubber；The mol ratio of the acid anhydrides and the epoxidation hydrogenated nitrile-butadiene rubber epoxide epoxy group group is 1.0~5.0:1；It is described
Ring opening catalyst is N, accelerine or tetrabutylammonium chloride；The ring opening catalyst and the epoxidation hydrogenated butyronitrile rubber
The mol ratio of glue epoxide epoxy group group is 5~20: 100；The epoxide group open loop rate is 40%~60%；The acid anhydrides is propionic acid
Acid anhydride, butyric anhydride, valeric anhydride, caproic anhydride, heptanoic anhydride or caprylic anhydride；The reaction temperature is 80-150 DEG C, reaction time 3-
10h。
13. the extraordinary hydrogenated nitrile-butadiene rubber of compression cold resistance prepared by any one of claim 6-12 methods described.
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| CN110183551B (en) * | 2019-07-02 | 2020-11-20 | 北京化工大学 | Bio-based oil-resistant eucommia ulmoides ester elastomer and preparation method thereof |
| CN113416268B (en) * | 2021-05-18 | 2022-08-30 | 北京化工大学 | Brominated hydrogenated nitrile rubber and preparation method and application thereof |
| CN114316399A (en) * | 2021-12-01 | 2022-04-12 | 杭州爱力智控技术有限公司 | Cold-resistant hydrogenated nitrile rubber |
| CN114015134A (en) * | 2021-12-01 | 2022-02-08 | 宁国市瑞普密封件有限公司 | High-temperature-resistant nitrile rubber material and preparation method thereof |
| CN114835928A (en) * | 2022-04-29 | 2022-08-02 | 贵州省材料产业技术研究院 | High cold-resistant hydrogenated nitrile rubber material and preparation method thereof |
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| CN102516558B (en) * | 2011-12-16 | 2013-12-04 | 山东大学 | Polysiloxane modified nitrile rubber, synthesis method and preparation of vulcanized rubber |
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