CN108570168A - Nitrile rubber vulcanising composition and sulfurized nitrile rubber and the preparation method and application thereof - Google Patents
Nitrile rubber vulcanising composition and sulfurized nitrile rubber and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to vulcanized rubber fields, and in particular, to a kind of nitrile rubber vulcanising composition and sulfurized nitrile rubber and the preparation method and application thereof.The nitrile rubber vulcanising composition contains nitrile rubber base rubber, vulcanizing agent, vulcanization accelerator, reinforcing agent, plasticizer and activator, wherein, the plasticizer is one or more in aromatic dicarboxilic acid dialkyl ester and aliphatic dicarboxylic acid dialkyl ester, nitrile rubber base rubber relative to 100 parts by weight, the content of the reinforcing agent is 30 50 parts by weight, and the content of the plasticizer is 10 30 parts by weight.The composition of the present invention by the synergistic effect of wherein each active ingredient, can obtain with higher oil resistance, resistance to low temperature and be suitable for sealing rubber material sulfurized nitrile rubber.
Description
Technical field
The present invention relates to vulcanized rubber fields, and in particular, to a kind of nitrile rubber vulcanising composition and vulcanised nitrile rubber
Glue and the preparation method and application thereof.
Background technology
Rubber seal products are widely used in the fields such as automobile, machinery, electronics, oil and space flight and aviation, be prevent oil leak,
The indispensable critical elements such as gas leakage.With the rapid development of petroleum industry, modern petroleum exploitation from original land to
Ocean and desert area are goed deep into, and environment used in rubber seal products is increasingly severe；Simultaneously because the complication of oil ingredient, right
The oil resistivity of caulking gum product proposes new requirement.Rubber seal products performance, the quality of quality depend primarily on its
The common glue kind of matrix sizing material, oil-resistant seal material has：Fluorubber (FPM), acrylic rubber (ACM), silicon rubber (Q), fourth
Nitrile rubber (NBR) etc..
NBR is a kind of most general oil resistant rubber, is that one kind synthesizing rubber made of butadiene and acrylonitrile monemer copolymerization
Glue.Its maximum feature is exactly that oil resistivity (especially resistance to mineral oil, vegetable and animals oils, liquid fuel and solvent) is excellent, but its is resistance to
High-temperature behavior is medium, and cold resistance, anti-weather-aging property are poor.The study found that the oil resistivity of NBR and the close phase of acrylonitrile content
It closes, with the increase of acrylonitrile content, the oil resistivity of NBR significantly improves, but its cold tolerance is deteriorated.In recent years, people are to NBR
Blending and modification carried out a large amount of research, the property such as the high temperature resistant to improve NBR rubber is high and cold, resistance to weather, resistance to ozone aging
Can, so that NBR is used under more harsh environment.
Invention content
The purpose of the present invention is to provide can obtain with higher oil resistance, resistance to low temperature and be suitable for sealing
The nitrile rubber vulcanising composition of rubber material and sulfurized nitrile rubber and the preparation method and application thereof.
To achieve the goals above, the present invention provides a kind of nitrile rubber vulcanising composition, and the composition contains butyronitrile
Rubber-based adhesive, vulcanizing agent, vulcanization accelerator, reinforcing agent, plasticizer and activator, wherein the plasticizer is aromatic dicarboxilic acid
It is one or more in dialkyl ester and aliphatic dicarboxylic acid dialkyl ester, it is described relative to the nitrile rubber base rubber of 100 parts by weight
The content of reinforcing agent is 30-50 parts by weight, and the content of the plasticizer is 10-30 parts by weight.
The present invention also provides the sulfurized nitrile rubbers obtained by above-mentioned composition through being kneaded vulcanization.
The present invention also provides a kind of preparation method of sulfurized nitrile rubber, this method includes mixing above-mentioned conjunction object
Refining, and obtained rubber compound is vulcanized.
The present invention also provides sulfurized nitrile rubbers made from the above method.
The present invention also provides above-mentioned sulfurized nitrile rubbers as the application in oil tank sealing material.
For the composition of the present invention by the synergistic effect of wherein each active ingredient, can obtain has higher oil resistivity
Can, resistance to low temperature and be suitable for sealing rubber material sulfurized nitrile rubber.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of nitrile rubber vulcanising composition, and the composition contains nitrile rubber base rubber, vulcanizing agent, sulphur
Change accelerating agent, reinforcing agent, plasticizer and activator, wherein the plasticizer is aromatic dicarboxilic acid dialkyl ester and fatty dicarboxyl
One or more in acid dialkyl ester, relative to the nitrile rubber base rubber of 100 parts by weight, the content of the reinforcing agent is 30-
The content of 50 parts by weight, the plasticizer is 10-30 parts by weight.
According to the present invention, although to can be obtained the present invention in above-mentioned amount ranges required for the reinforcing agent and plasticizer
Composition, but can be with the nitrile rubber for enhancing mechanical performance, oil resistance, resistance to low temperature in order to obtain, it is preferable that
Relative to the nitrile rubber base rubber of 100 parts by weight, the content of the reinforcing agent is 40-50 parts by weight, the content of the plasticizer
For 15-25 parts by weight.
According to the present invention, in a kind of preferred embodiment of the present invention, it is highly preferred that relative to 100 parts by weight
The content of nitrile rubber base rubber, the reinforcing agent is 45-50 parts by weight；The content of the plasticizer is 15-20 parts by weight, more excellent
It is selected as 15-18 parts by weight.
According to the present invention, in order to obtain the rubber for being suitable as sealing material, especially as large-scale crude oil
The rubber material of novel first and second sealing of storage tank, it is preferable that in the nitrile rubber base rubber, the structure list of acrylonitrile offer
The content of member is 20-40 weight %, and the content for the structural unit that butadiene provides is 60-80 weight %.It is highly preferred that the fourth
In nitrile rubber base rubber, the content for the structural unit that acrylonitrile provides is 25-35 weight %, and the structural unit that butadiene provides contains
Amount is 65-75 weight %.
According to the present invention, nitrile rubber base rubber of the invention preferably uses 100 DEG C of ML (1+4) for 40-80, particularly 50-
70 nitrile rubber is as base rubber.Thus, it is possible to so that the nitrile rubber base rubber and the others in the composition of the present invention
Active ingredient is preferably compatible, obtains the nitrile rubber of performance needed for the present invention.
According to the present invention, the compatibility of the plasticizer and nitrile rubber base rubber is good, can improve processing technology, is this
Under other active ingredients cooperation of the composition of invention, the elongation rate of tensile failure of gained NBR can be improved, reduce hardness and raising
NBR elastic propertys.Wherein, the aromatic dicarboxilic acid dialkyl ester can be the dialkyl group of the aromatic dicarboxilic acid of this field routine
Ester, preferably formula R2OOC-R1-COOR2Compound represented, wherein R1For the arlydene of C6-C15, two R2Each independently
Alkyl selected from C1-C10.Wherein, subunit, the naphthalene nucleus that the arylene group of C6-C15 can such as be formed for phenylene, biphenyl are formed
Subunit etc..The alkyl of C1-C10 for example can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tertiary fourth
Base, amyl, hexyl, heptyl, octyl, nonyl, decyl etc..It is highly preferred that the aromatic dicarboxilic acid dialkyl ester is O-phthalic
Dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dihexyl phthalate
With it is one or more in dioctyl phthalate.
Wherein, the aliphatic dicarboxylic acid dialkyl ester can be the dialkyl ester of the aliphatic dicarboxylic acid of this field routine, excellent
It is selected as formula R4OOC-R3-COOR4Compound represented, R3For the alkylidene of C4-C12, two R4It is each independently selected from C1-C10
Alkyl；Wherein, the alkylidene of C4-C12 for example can by butyl, isobutyl group, sec-butyl, tertiary butyl, amyl, hexyl, heptyl,
The alkylidene that at least one of octyl, nonyl, decyl etc. are formed；The alkyl of C1-C10 is selected as described above.It is more excellent
Selection of land, the aliphatic dicarboxylic acid dialkyl ester are dibutyl adipate, dihexyl adipate, dioctyl adipate, suberic acid two
One in butyl ester, suberic acid dihexyl, suberic acid dioctyl ester, dibutyl sebacate, dihexyl sebacate and dioctyl sebacate
Kind is a variety of.
It is particularly preferred that the plasticizer is dibutyl phthalate, dihexyl phthalate, phthalic acid two
It is one or more in monooctyl ester, dioctyl adipate, suberic acid dioctyl ester and dioctyl sebacate.
According to the present invention, the reinforcing agent can be that this field is conventionally applied to the reinforcing agent in vulcanized rubber, it is preferable that
The reinforcing agent is carbon black, for example, carbon black N550.
According to the present invention, although the vulcanizing agent, vulcanization accelerator and activator may be used this field and prepare vulcanization fourth
The conventional amount used of nitrile rubber, but in order to enable the vulcanizing agent, vulcanization accelerator and activator can be with the reinforcement of the present invention
Agent and plasticizer coordinate well, and improve with the compatibility of nitrile rubber base rubber, then obtain required higher resistance to of the present invention
Oiliness energy, resistance to low temperature, good mechanical properties and be suitable for sealing rubber material nitrile rubber, preferable case
Under, relative to the nitrile rubber base rubber of 100 parts by weight, the content of the vulcanizing agent is 0.1-3 parts by weight, the vulcanization accelerator
Content be 1-8 parts by weight, the content of the activator is 2-10 parts by weight.It is highly preferred that the butyronitrile relative to 100 parts by weight
The content of rubber-based adhesive, the vulcanizing agent is 0.2-1 parts by weight；The content of the vulcanization accelerator is 2-5 parts by weight, more preferably
For 3-4 parts by weight；The content of the activator is 4-8 parts by weight, more preferably 5-7 parts by weight.
Wherein, the type of the vulcanizing agent can be the conventional selection of this field, such as can be selected from Sulfur, benzoyl peroxide
It is one or more in formyl, urethanes and 2,5- dimethyl -2,5- two (t-butylperoxy) hexane.
Wherein, the vulcanization accelerator can be it is existing it is various can shorten vulcanization time, reduce curing temperature, reduce
Vulcanizing agent dosage and improve rubber physical mechanical property substance, such as can be diphenylguanidine (diphenylguanidine), curing tetramethyl
Base thiuram (Vulcanization accelerator TMTD), 2- thiol benzothiazoles (captax), ethylene thiourea (accelerant N A-22), N- rings are
Base -2- benzothiazole sulfonamides (accelerant CZ), N tert butyl benzothiazole 2 sulfenamide (TBBS), 2,2 '-curing
Bisbenzothiazole (commercially available product such as altax), N- tertiary butyls-bis- (2-[4-morpholinodithio) sulfenamide (commercially available product such as accelerating agent
TBSI one or more) and in N- cyclohexyl -2-[4-morpholinodithio base sulfenamide (commercially available product such as accelerant C BBS).The present invention
It is preferred that using the combination of accelerant CZ and Vulcanization accelerator TMTD as the vulcanization accelerator, wherein the accelerant CZ and promotion
The weight ratio of agent TMTD such as can be 1：1-4, preferably 1：1.1-2.5 more preferably 1：1.1-1.5.
Wherein, the type of the vulcanizing activator can be this field conventional selection, preferably zinc oxide, magnesia and
It is one or more in stearic acid.Present invention preferably employs zinc oxide or magnesia with stearic composition as the vulcanization
Activator, wherein zinc oxide or magnesia and stearic weight ratio are preferably 3-6：1, more preferably 4-5：1.
In a kind of preferred embodiment of the present invention, the vulcanizing agent is Sulfur, and the vulcanization accelerator is described
Accelerant CZ and Vulcanization accelerator TMTD, the vulcanizing activator zinc oxide and stearic acid.
In another preferred embodiment of the present invention, the vulcanizing agent is Sulfur, and the vulcanization accelerator is institute
State accelerant CZ and Vulcanization accelerator TMTD, the vulcanizing activator magnesia and stearic acid.
According to the present invention, the composition can also contain anti-aging agent, can further increase the composition warp in this way
The ageing-resistant performance and mechanical property of gained rubber after vulcanization.Wherein, the dosage of the anti-aging agent can be according to required rubber
Colloidality can be selected specifically, and for the rubber of required sealing material of the invention, especially Large Oil Tank is novel
For the rubber material of first and second sealing, relative to the nitrile rubber base rubber of 100 parts by weight, the dosage of the anti-aging agent is
1-5 parts by weight, preferably 1-3 parts by weight, more preferably 1.5-2.5 parts by weight.
The type of the anti-aging agent is known to those skilled in the art.For example, the anti-aging agent can be that amine is anti-old
Agent and/or quinoline type antioxidant.
The amines antioxidants can be selected from N- phenyl-α-aniline, N- phenyl-β-naphthylamines, N- phenyl-N '-cyclohexyl pair
Phenylenediamine, N- isopropyls-N '-diphenyl-para-phenylene diamine, N- (1,3- dimethylbutyls)-N '-diphenyl-para-phenylene diamines and N, N '-are bis-
It is one or more in (1,4- dimethyl amyl groups) p-phenylenediamine.
The quinoline type antioxidant can be selected from 2,2,4- trimethyl -1,2- dihyaroquinolines condensate, ethyoxyl -2 6-,
One kind or more in 2,4- trimethyl -1,2- dihyaroquinolines and 6- dodecyl -2,2,4- trimethyl -1,2- dihyaroquinolines
Kind.
It is particularly preferred that the anti-aging agent is 2,2,4- trimethyl -1,2- dihyaroquinoline condensates (anti-aging agent RD), 6-
Ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinolines (antioxidant A W), N- phenyl-α-aniline (antioxidant A), N- phenyl-β -
Naphthylamines (antioxidant D), N- phenyl-N '-cyclohexyl p-phenylenediamine (antioxidant 4010) and N- (1,3- dimethylbutyls)-N '-benzene
It is one or more in base p-phenylenediamine (antioxidant 4020).
Present invention preferably employs the combinations of anti-aging agent RD and antioxidant 4020 as the anti-aging agent, wherein anti-aging agent RD
Weight ratio with antioxidant 4020 is preferably 0.5-2：1, especially 1-2：1.
The present invention also provides the sulfurized nitrile rubbers obtained by above-mentioned composition through being kneaded vulcanization.As long as using the present invention
Composition carry out mixing vulcanization, you can obtain sulfurized nitrile rubber mentioned here.
The present invention also provides a kind of preparation method of sulfurized nitrile rubber, this method includes mixing above-mentioned composition
Refining, and obtained rubber compound is vulcanized.
The present invention is not particularly limited the mode of the mixing, can by each component in the composition simultaneously into
Row is kneaded, and first can also first be kneaded several components therein, be added followed by remaining ingredient and continue to be kneaded.According to this hair
The mode of a kind of bright preferred embodiment, the mixing includes by the nitrile rubber base rubber in the composition, vulcanizing agent, work
Agent and optional anti-aging agent are mixed, and then introduce reinforcing agent and plasticizer carries out one section of mixing, be then kneaded one section
Masterbatch and vulcanization accelerator carry out two-stage mixing.The ingredient for the rubber compound that such mixing mode enables to is more equal
One, subsequently there is after vulcanization better mechanical property and incompressible permanent deformation.
In the case of, according to the invention it is preferred to, the condition of one section of mixing includes：Melting temperature is 80-130 DEG C, is kneaded
Time is 6-10min；The condition of the two-stage mixing includes：Melting temperature is 20-45 DEG C, mixing time 5-10min.This
Outside, be kneaded and two-stage mixing can carry out in existing various mixing facilities for described one section, for example, can in open mill or
It is carried out in person's mixer, such as one section of mixing carries out in mixer, the two-stage mixing carries out in open mill.
In the case of, according to the invention it is preferred to, the condition of the vulcanization includes：Temperature is 150-170 DEG C, pressure 10-
20MPa, time 5-12min.In the present invention, the pressure refers both to gauge pressure.
The present invention also provides the sulfurized nitrile rubbers made from the above method.
The present invention also provides above-mentioned sulfurized nitrile rubbers as the application in oil tank sealing material.
The sulfurized nitrile rubber for being suitable for oil tank sealing material of gained of the invention preferably has the following performance：
Tensile strength：12MPa or more, preferably 20-25MPa；
Elongation at break：500% or more, preferably 510-650%
Shao's A hardness：55-65；
Brittleness temperature：- 35 DEG C hereinafter, preferably -38 DEG C to -45 DEG C
Thermal aging property percentage (stretches change rate)：20% or less；
Oil resistant mass change：5% hereinafter, preferably 0.3-1%；
Compression set：10% hereinafter, preferably 5-6.5%；
Akron abrasion：1cm3Hereinafter, 0.11cm3Below.
The present invention will be described in detail by way of examples below.
In following embodiment：
100 DEG C of NBR2907, acrylonitrile content 29wt.%, ML (1+4) is 63, the production of Lanzhou Yuan Feng petrochemical industry Co., Ltd
Product；Carbon black N550 is Cabot Co., Ltd's product；Stearic acid is purchased from the polite Chemical Co., Ltd. in Hong Kong, trade mark SA1801；It is anti-old
Agent RD is purchased from Jiangsu Sheng'Ao Chemical Technology Co., Ltd；Antioxidant 4020 is purchased from Shanghai addition Chemical Co., Ltd.；Sulphur is purchased from
It is S-80 that Science and Technology Ltd.'s trade mark is contained in Guangzhou Jinchang.
Sulfurized nitrile rubber embodiment 1-7
The present embodiment is used to illustrate nitrile rubber of the invention and its vulcanising composition and preparation method and application.
It is formulated according to shown in nitrile rubber CB1-CB7 in table 1, is prepared by the following method sulfurized nitrile rubber：
First segment is kneaded：
In mixer, nitrile rubber base rubber is added, Sulfur is added after 1min, activator and anti-aging agent is added after 2min,
Reinforcing agent then is added and plasticizer carries out mixing 8min at 90 DEG C ± 3 DEG C, and controls dump temperature as 130 DEG C hereinafter, row
Glue obtains masterbatch.
Second segment is kneaded：
On chilling roller open mill, masterbatch and vulcanization accelerator is added, and it is to be carried out at 30 DEG C ± 3 DEG C to control melting temperature
It is kneaded 6min (3/4 cutter of left and right turns refining in the mixing process, thin 6 times logical), adjusts roll spacing bottom sheet.
Sulfurating stage：
On vulcanizing press, vulcanizes 8min at 155 DEG C, under pressure 10MPa, obtain sulfurized nitrile rubber.
Sulfurized nitrile rubber embodiment 8
The present embodiment is used to illustrate the nitrile rubber vulcanising composition and sulfurized nitrile rubber of the present invention.
According to formula：NBR2907 is 100 parts by weight, and magnesia is 5 parts by weight, and carbon black N550 is 50 parts by weight, adjacent benzene two
Formic acid dihexyl is 20 parts by weight, and benzoyl peroxide is 0.7 parts by weight, and the dosage of anti-aging agent RD is 1.5 parts by weight, anti-aging agent
4020 dosage is 1 parts by weight, and accelerant CZ is 1 parts by weight, and Vulcanization accelerator TMTD is 2 parts by weight；It is prepared by the following method sulphur
Change nitrile rubber CB8：
First segment is kneaded：
In mixer, nitrile rubber base rubber is added, benzoyl peroxide is added after 2min, be added after 5min activator and
Anti-aging agent is then added reinforcing agent and plasticizer carries out mixing 10min at 85 DEG C ± 3 DEG C, and it is 120 DEG C to control dump temperature
Hereinafter, dumping obtains masterbatch.
Second segment is kneaded：
On chilling roller open mill, masterbatch and vulcanization accelerator is added, and it is to be carried out at 25 DEG C ± 3 DEG C to control melting temperature
It is kneaded 5min (3/4 cutter of left and right turns refining in the mixing process, thin 6 times logical), adjusts roll spacing bottom sheet.
Sulfurating stage：
On vulcanizing press, vulcanizes 10min at 160 DEG C, under pressure 12MPa, obtain sulfurized nitrile rubber.
Sulfurized nitrile rubber embodiment 9
The present embodiment is used to illustrate the nitrile rubber vulcanising composition and sulfurized nitrile rubber of the present invention.
According to the method described in sulfurized nitrile rubber embodiment 8, the difference is that, adjacent benzene two is replaced using dioctyl adipate
Formic acid dihexyl, to which sulfurized nitrile rubber CB9 be made.
Sulfurized nitrile rubber embodiment 10
The present embodiment is used to illustrate the nitrile rubber vulcanising composition and sulfurized nitrile rubber of the present invention.
According to the method described in sulfurized nitrile rubber embodiment 8, the difference is that, it is added without anti-aging agent, and use 3 parts by weight
Diphenylguanidine replace accelerant CZ and Vulcanization accelerator TMTD, to which sulfurized nitrile rubber CB10 be made.
Comparative example 1-5
According to method shown in embodiment 1, the difference is that, it is prepared according to being formulated shown in nitrile rubber DB1-DB5 in table 1
Sulfurized nitrile rubber.
Table 1
Note：DOP is dioctyl phthalate.
Test case 1
Following test is carried out to the nitrile rubber CB1-CB10 and DB1-DB5 with gained in upper table 1, as a result such as table 2 and 3
It is shown：
Mooney viscosity (100 DEG C of ML (1+4))：Mooney viscosity uses the Mooney viscosity of the model SMV-300 of Shimadzu Corporation
Meter is measured according to the method for GB/T1232.1-2000, and test temperature is 100 DEG C, and preheating time is 1 minute, rotation time
It is 4 minutes.
Vulcanization characteristics is tested：It is measured without rotor vulcameter (High Speed Rail Testing Instruments Co., Ltd) using GT-M2000A,
Wherein, 155 DEG C of curing temperature, vibration angle ± 1 °, vibration frequency 1.66Hz, air pressure 0.46MPa, sample volume 5cm3；Ts1 tables
Show that time of scorch, Tc90 indicate vulcanization time.
Tensile property tests (mechanical performance)：Tensile strength, elongation at break, 100% stress at definite elongation are (hereinafter referred to as
100% stress), 300% stress at definite elongation (hereinafter referred to as 300% stress) and Compression Set according to GB/T528-1998 into
Row test.
Shao Er A type hardness testers：Shao Er A type hardness testers are measured according to method specified in GB/T23651-2009.
Akron abrasion：Akron abrasion by GBT/1689-1998 provide specified in method be measured.
Oil resistant mass change (hereinafter referred to as oil resistant change rate) refers to using 3# standard oils, it is ensured that sample is completely soaked
In experimental liquid, soaking temperature is room temperature (23 ± 2 DEG C), and soaking time is 72 hours, weighs sample under air at room temperature
Quality W1, sample is taken out after reaching the stipulated time, wipes specimen surface remaining liq with filter paper, and park 30min in air,
Weigh quality W of the sample in air at room temperature after impregnating2, calculate the mass change of sample.
Brittleness temperature refer to sample at low temperature impact fracture when temperature, the cold resistance of sample can be weighed, be according to
What the method for GB/T 15256-94 measured.
Vulcanizate thermal-oxidative aging property refers to the vulcanizate physical mechanical before and after aging under certain aging temperature and time
The variation of performance is measured according to the method for GB/T3512-2001 samples, wherein tensile strength change rate (following table
Be shown as stretching change rate) refer to tensile strength before and after thermo-oxidative ageing change rate, firmness change refers to the front and back vulcanization of thermo-oxidative ageing
The hardness number of glue changes.
Table 2
Table 3
| CB8 | CB9 | CB10 | |
| ML(1+4)100℃ | 56 | 56 | 55 |
| Ts1, min | 1.62 | 1.58 | 1.71 |
| Tc90, min | 4.58 | 4.76 | 4.93 |
| Tensile strength, MPa | 19.5 | 18.9 | 19.1 |
| Elongation at break, % | 510 | 505 | 502 |
| 100% stress, MPa | 1.95 | 1.87 | 1.91 |
| 300% stress, MPa | 8.9 | 8.8 | 7.9 |
| Compression set, % | 7.09 | 7.13 | 6.90 |
| Shore hardness | 63 | 60 | 61 |
| Akron abrasion, cm3 | 0.15 | 0.12 | 0.17 |
| Oil resistant change rate, % | 0.42 | 0.41 | 0.48 |
| Brittleness temperature, DEG C | -40 | -38 | -37 |
| Firmness change | 56 | 56 | 55 |
By table 2 and 3 as can be seen that by using the present invention butyl rubber vulcanising composition, can obtain with compared with
High oil resistance, resistance to low temperature and be suitable for sealing rubber material nitrile rubber.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (12)
1. a kind of nitrile rubber vulcanising composition, which is characterized in that the composition contains nitrile rubber base rubber, vulcanizing agent, sulphur
Change accelerating agent, reinforcing agent, plasticizer and activator, wherein the plasticizer is aromatic dicarboxilic acid dialkyl ester and fatty dicarboxyl
One or more in acid dialkyl ester, relative to the nitrile rubber base rubber of 100 parts by weight, the content of the reinforcing agent is 30-
The content of 50 parts by weight, the plasticizer is 10-30 parts by weight.
2. composition according to claim 1, wherein relative to the nitrile rubber base rubber of 100 parts by weight, the reinforcing agent
Content be 40-50 parts by weight；The content of the plasticizer is 15-25 parts by weight, preferably 15-18 parts by weight；
Preferably, the reinforcing agent is carbon black.
3. composition according to claim 1 or 2, wherein the aromatic dicarboxilic acid dialkyl ester is formula R2OOC-R1-
COOR2Compound represented, wherein R1For the arlydene of C6-C15, two R2It is each independently selected from the alkyl of C1-C10；More
Preferably, the aromatic dicarboxilic acid dialkyl ester is repefral, diethyl phthalate, phthalic acid two
It is one or more in propyl ester, dibutyl phthalate, dihexyl phthalate and dioctyl phthalate；
The aliphatic dicarboxylic acid dialkyl ester is formula R4OOC-R3-COOR4Compound represented, R3For the alkylidene of C4-C12, two
A R4It is each independently selected from the alkyl of C1-C10；It is highly preferred that the aliphatic dicarboxylic acid dialkyl ester be dibutyl adipate,
Dihexyl adipate, dioctyl adipate, suberic acid dibutyl ester, suberic acid dihexyl, suberic acid dioctyl ester, two fourth of decanedioic acid
It is one or more in ester, dihexyl sebacate and dioctyl sebacate；
Preferably, the plasticizer be dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, oneself
It is one or more in adipate, suberic acid dioctyl ester and dioctyl sebacate.
4. according to the composition described in any one of claim 1-3, wherein in the nitrile rubber base rubber, acrylonitrile carries
The content of the structural unit of confession is 20-40 weight %, and the content for the structural unit that butadiene provides is 60-80 weight %；
Preferably, in the nitrile rubber base rubber, the content for the structural unit that acrylonitrile provides is 25-35 weight %, butadiene
The content of the structural unit of offer is 65-75 weight %；
Preferably, 100 DEG C of the ML (1+4) of the nitrile rubber base rubber is 40-80, preferably 50-70.
5. according to the composition described in any one of claim 1-3, wherein the nitrile rubber base relative to 100 parts by weight
The content of glue, the vulcanizing agent is 0.1-3 parts by weight, and the content of the vulcanization accelerator is 1-8 parts by weight, the activator
Content is 2-10 parts by weight；Preferably, the content of the vulcanizing agent is 0.2-1 parts by weight；The content of the vulcanization accelerator is
2-5 parts by weight, more preferably 3-4 parts by weight；The content of the activator is 4-8 parts by weight, more preferably 5-7 parts by weight；
Preferably, the vulcanizing agent is sulphur, benzoyl peroxide, urethanes and 2, (the tertiary fourth of 5- dimethyl -2,5- bis-
Base peroxy) it is one or more in hexane；
Preferably, the vulcanization accelerator is diphenylguanidine, tetramethylthiuram disulfide, 2- thiol benzothiazoles, ethylidene
Thiocarbamide, N- cyclohexyl -2- benzothiazole sulfonamides, N tert butyl benzothiazole 2 sulfenamide, 2,2 '-diphenyl disulfides
And one in thiazole, N- tertiary butyls-bis- (2-[4-morpholinodithio) sulfenamide and N- cyclohexyl -2-[4-morpholinodithio base sulfenamide
Kind is a variety of；
Preferably, the activator is one or more in zinc oxide, magnesia and stearic acid, more preferably zinc oxide or oxygen
Change magnesium and stearic composition；Still more preferably zinc oxide or magnesia and stearic weight ratio are 3-6：1, more preferably
For 4-5：1.
6. according to the composition described in any one of claim 1-5, wherein the composition also contains anti-aging agent, relatively
In the nitrile rubber base rubber of 100 parts by weight, the dosage of the anti-aging agent is 1-5 parts by weight, preferably 1-3 parts by weight, more preferably
For 1.5-2.5 parts by weight.
7. the sulfurized nitrile rubber that a kind of composition by described in any one of claim 1-6 is obtained through being kneaded vulcanization.
8. a kind of preparation method of sulfurized nitrile rubber, this method includes by the combination described in any one of claim 1-6
Object is kneaded, and obtained rubber compound is vulcanized.
9. according to the method described in claim 8, wherein, the mode of the mixing includes by the nitrile rubber in the composition
Base rubber, vulcanizing agent, activator and optional anti-aging agent are mixed, and then introduce reinforcing agent and plasticizer carries out one section of mixing,
Then the masterbatch and vulcanization accelerator one section being kneaded carry out two-stage mixing；
Preferably, the condition of one section of mixing includes：Melting temperature is 80-130 DEG C, mixing time 6-10min；Described two
Section be kneaded condition include：Melting temperature is 20-45 DEG C, mixing time 5-10min.
10. method according to claim 8 or claim 9, wherein the condition of the vulcanization includes：Temperature is 150-170 DEG C, pressure
Power is 10-20MPa, time 5-12min.
11. the sulfurized nitrile rubber made from the method described in any one of claim 8-10.
12. the sulfurized nitrile rubber described in claim 7 or 11 is as the application in oil tank sealing material.
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| CN113402791A (en) * | 2020-03-17 | 2021-09-17 | 中国石油化工股份有限公司 | Nitrile rubber-based vulcanized composition, vulcanized rubber, and preparation method and application thereof |
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