CN108659291A - A kind of hydrogenated nitrile rubber composition material and preparation method, application - Google Patents
A kind of hydrogenated nitrile rubber composition material and preparation method, application Download PDFInfo
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- CN108659291A CN108659291A CN201710209014.8A CN201710209014A CN108659291A CN 108659291 A CN108659291 A CN 108659291A CN 201710209014 A CN201710209014 A CN 201710209014A CN 108659291 A CN108659291 A CN 108659291A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/005—Hydrogenated nitrile rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
- B29B7/286—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control measuring properties of the mixture, e.g. temperature, density
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
- B29B7/728—Measuring data of the driving system, e.g. torque, speed, power, vibration
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of hydrogenated nitrile rubber composition material and preparation method, applications.Its raw material includes each component of following parts by weight:100 parts of hydrogenated nitrile-butadiene rubbers, 4~10 parts of zinc oxide, 0.5~2.5 part of stearic acid, 1~4 part of anti-aging agent, 20~30 parts of 26~30nm of grain size carbon blacks, 25~35 parts of 40~48nm of grain size carbon blacks, 5~15 parts of white carbons, 5~15 parts of polyester polyether plasticizers, 2~4 parts of vulcanizing agents, 1~3 part of assistant crosslinking agent;The acrylonitrile content of rubber is 41.3~43.1%, saturation degree >=99%, and Mooney viscosity is ML (1+4)@100 DEG C 60~70.More preferably, heat-resisting quantity, lower temperature resistance, oil resistivity are more excellent, and the service life is longer for material breaking strength, tearing strength, the Elastic extensibility, as automobile engine oil ruler casing oil sealing excellent material performance;Preparation method step is simple and convenient to operate, and is suitable for industrialized production.
Description
Technical field
Present invention relates particularly to a kind of hydrogenated nitrile rubber composition material and preparation method, applications.
Background technology
In automobile engine, oil rule is for checking lubrication hole engine oil storage capacity common control gage.Oil rule
It is made by super-elastic metal piece, oil rule pipe sleeve is connected (there are turn paths) with oil sump.Have between oil rule, its casing
One rubber seal (being sleeved on oil rule, hereinafter referred to as " oil rule casing oil sealing ") is used for canned motor lubricating system.
Oil rule casing oil sealing material must have excellent temperature-resistance characteristic (operating temperature -40~160 DEG C), excellent oil resistant characteristic.Oil
Ruler is frequently pulled and pushed when in use, has strict demand to sealing, extraction force, pullout forces, so generally also requiring dipstick oil sealing ruler
Very little precision high (the general requirement ± 0.1mm margins of tolerance), its material mechanical performance are excellent, and (high intensity, high anti-tear, high resiliency extend
Rate).Traditionally, oil rule casing oil sealing material uses acrylic rubber or hydrogen cyanide nitrile rubber.Acrylic rubber oil resistant,
High temperature resistant is good, but its mechanical strength is low, resistance to low temperature bad (- 25 DEG C of GENERAL TYPE acrylic rubber operating limit low temperature, spy
Different -35 DEG C of type acrylic rubber operating limit low temperature).Follow-on ethylene-acrylate rubber (trade mark of such as E.I.Du Pont Company
Vamac G, Vamac LS) high-low temperature resistant, mechanical characteristic have clear improvement, but its oil resistance has decline, especially resistance to low benzene
Amine point oil (such as IRM No.903 oil, ASTM No.3 oil) bad, resistance to polar solvent is bad.In addition, ethylene-acrylate rubber
It is kneaded and vulcanization machining control is more demanding, process parameter fluctuation easily causes vulcanization post-shrinkage ratio unstable, causes to use it
The oil rule oil sealing dimensional accuracy difficulty of making meets tolerance.Under normal circumstances, hydrogenated nitrile-butadiene rubber sulfur cross-linking system can
Meeting Long-term service temperature -40~125 DEG C, peroxide vulcanizing system vulcanization can meet Long-term service temperature -40~150 DEG C,
More elevated operating temperature is then difficult to meet.General hydrogenated nitrile-butadiene rubber (peroxide vulcanizing system) meets -40 DEG C of operating temperatures
Under the premise of, 160 DEG C of operating mode heat ageings, oil resistant difficulty meet index request of the depot to oil rule casing oil sealing material.It is above-mentioned these
The defect of material will all accelerate the decaying of oil rule casing oil sealing service life, keep its service life shorter.
Therefore, a kind of good temperature in use -40~160 DEG C, oil resistance, high intensity, high anti-tear and elastic prolong of meeting is developed
Malleability more preferably, the oil rule casing oil sealing material that sealing effect is more preferable, the service life is longer, meet vehicle lubricating system to machine oil
The various requirement of ruler casing oil sealing is this field technical problem urgently to be resolved hurrily.
Invention content
The present invention is practical, and the technical problem to be solved is that in order to overcome, oil rule casing oil sealing material is (such as in the prior art
Acrylic rubber) mechanical property is bad, resistance to low temperature is bad and the resistance to low aniline point of ethylene-acrylate rubber is oily (such as
IRM No.903 oil, ASTM No.3 oil) bad, resistance to polar oil is bad;And existing hydrogenated nitrile rubber composition material
In the defect that temperature end is heat-resisting, oil resistance is bad of -40~160 DEG C of operating temperature ranges, especially 160 DEG C, one kind is provided
Hydrogenated nitrile rubber composition material and preparation method, application.The hydrogenated nitrile rubber composition material breaking strength of the present invention,
More preferably, high temperature resistance is met the requirements for tearing strength, Elastic extensibility, and more preferably, oil resistivity is more excellent for resistance to low temperature, is used
Longer life expectancy, as automobile engine oil ruler casing oil sealing excellent material performance.In addition, the hydrogenated nitrile rubber composition material of the present invention
Preparation method for material step is simple and convenient to operate, and is suitable for industrialized production.
The present invention solves above-mentioned technical problem by the following technical programs.
The present invention provides a kind of hydrogenated nitrile rubber composition material, feedstock composition includes following parts by weight
Each component:100 parts of hydrogenated nitrile-butadiene rubbers, 4~10 parts of activator A, 0.5~2.5 part of activator B, 1~4 part of anti-aging agent, 20~30
Part carbon black A, 25~35 parts of black Bs, 5~15 parts of white carbons, 5~15 parts of plasticizer, 2~4 parts of vulcanizing agents, 1~3 part help crosslinking
Agent;
Wherein, the acrylonitrile content of the hydrogenated nitrile-butadiene rubber is 41.3~43.1%, and the hydrogenated nitrile-butadiene rubber is satisfied
It is ML (1+4)@100 DEG C 60~70 with the Mooney viscosity of degree >=99%, the hydrogenated nitrile-butadiene rubber;The activator A is oxidation
Zinc, the activator B are stearic acid;The carbon black A is the carbon black of 26~30nm of grain size, the black B be grain size be 40~
The carbon black of 48nm;The plasticizer is polyester polyether plasticizer.
Preferably, the hydrogenated nitrile-butadiene rubber material compositions are grouped as by the group of following parts by weight:100 parts of hydrogen
Change nitrile rubber, 4~10 parts of activator A, 0.5~2.5 part of activator B, 1~4 part of anti-aging agent, 20~30 parts
The carbon black A, 25~35 parts of black Bs, 5~15 parts of precipitated silicas, 5~15 parts of the plasticizers, 2~4 parts
The vulcanizing agent, 1~3 part of assistant crosslinking agent.
In the present invention, as long as the hydrogenated nitrile-butadiene rubber can be this field it is conventional, meet above-mentioned acrylonitrile after mixing
The hydrogenated nitrile-butadiene rubber of content, saturation degree and Mooney viscosity range, preferably hydrogenated nitrile-butadiene rubber A and hydrogenated butyronitrile
The acrylonitrile content of the composition of rubber B, the hydrogenated nitrile-butadiene rubber A is 43.5 ± 1%, saturation degree >=99%, Mooney viscosity
For 100 DEG C 60~70 of ML (1+4)@;The acrylonitrile content of the hydrogenated nitrile-butadiene rubber B is 36 ± 1%, saturation degree >=99%, door
Buddhist nun's viscosity is ML (1+4)@100 DEG C 60~70.
Wherein, the dosage of the hydrogenated nitrile-butadiene rubber A is preferably 75~90 parts, is more preferably 80~85 parts, most preferably
It is 85 parts.The dosage of the hydrogenated nitrile-butadiene rubber B is preferably 10~25 parts, is more preferably 12~20 parts, is most preferably 15 parts.
The hydrogenated nitrile-butadiene rubber A is preferably the hydrogenated nitrile-butadiene rubber of model Therban*4307, model
It is one or more in the hydrogenated nitrile-butadiene rubber of Zetpol 1000L and the hydrogenated nitrile-butadiene rubber of model ZN43056.Wherein, institute
The hydrogenated nitrile-butadiene rubber for stating model Therban*4307 is the commercial product of Lang Sheng chemical companies of Germany.The model
The hydrogenated nitrile-butadiene rubber of Zetpol 1000L is the commercial product of Japanese Zeon Chemicals L. P..The hydrogen of the model ZN43056
Change the commercial product that nitrile rubber is Shanghai Zan Nan Science and Technology Ltd.s.
The hydrogenated nitrile-butadiene rubber B is preferably model Zetpol 2000L and/or model ZN35056 hydrogenated butyronitriles
Rubber.Wherein, the hydrogenated nitrile-butadiene rubber of the model Zetpol 2000L is the commercial product of Japanese Zeon Chemicals L. P..Institute
The hydrogenated nitrile-butadiene rubber for stating model ZN35056 is the commercial product of Shanghai Zan Nan Science and Technology Ltd.s.
100 DEG C of ML (1+4)@that the data of Mooney viscosity mentioned in the present invention are each meant.It can according to common sense in the field
Know, M indicates Mooney, and L expression greater trochanters, 1 indicates preheating 1 minute, and 4 indicate that experiment 4 minutes, 100 DEG C of@indicate that test temperature is
100℃.Mooney numerical value is bigger, indicates that viscosity is bigger, plasticity is lower.
In the present invention, the zinc oxide can be the indirect process zinc oxide of rubber processing routine.One embodiment of the invention
In, using zinc oxide (I types) top grade product that Anhui Province Hanshan County Jin Hua zinc oxide factory produces, generally have 99.7%
(w/w) purity.According to common sense in the field, the raw material of the indirect process zinc oxide be the metal zinc ingot obtained by smelting or
Cadmia.The dosage of the zinc oxide is preferably 2~5 parts, is more preferably 3 parts.
In the present invention, the activator A further includes preferably magnesia.The magnesia can be that rubber processing is conventional
Activated magnesia, preferably model MA-150 magnesia.In one embodiment of the invention, using Japanese consonance company
Commercially available MA-150.The dosage of the magnesia can be that this field is conventional, and preferably 2~5 parts, be more preferably 4 parts.
In the present invention, the stearic acid can be rubber processing routinely using n-octadecane acid, preferably model
1801 200 type stearic acid.In one embodiment of the invention, using the commercially available model of Shijiazhuang Tai Xin Chemical Co., Ltd.s
1801 200 type stearic acid.The stearic dosage is preferably 0.5~2.5 part, is more preferably 1.5~2 parts, most preferably
It is 1.8 parts.
In the present invention, the anti-aging agent can be the conventional use of anti-aging agent of rubber materials, such as anti-aging agent RD, preferably 2,
2,4- trimethyl -1,2- dihyaroquinoline polymer.In one embodiment of this invention, described 2,2,4- trimethyls -1,2- bis-
Hydrogenated quinoline polymer is the commercial product of Research Institute of Nanjing Chemical Industry Group.
In the present invention, the dosage of the anti-aging agent is preferably 1.0~2.5 parts, is more preferably 1.8~2 parts.
In the present invention, the anti-aging agent further includes preferably the antioxidant MB of this field routine, preferably 2- sulfydryls benzene
And imidazoles.The dosage of the antioxidant MB can be that this field is conventional, and preferably 0.5~1.5 part, be more preferably 0.8~1 part.
In one embodiment of this invention, the 2-mercaptobenzimidazole is the commercial product of Research Institute of Nanjing Chemical Industry Group.
In the present invention, the carbon black A can be that this field routinely meets the carbon black that grain size is 26~30nm, preferably carbon black
N330.In one embodiment of the invention, using the carbon black N330 of Suzhou treasured companies market.In the present invention, the carbon black A's
Dosage is preferably 20~30 parts, is more preferably 25~28 parts.
In the present invention, the black B can be that this field routinely meets the carbon black that grain size is 40~48nm, preferably carbon black
N550.In one embodiment of the invention, using the carbon black N550 of Suzhou treasured companies market.In the present invention, the black B
Dosage is preferably 25~35 parts, is more preferably 26~32 parts, is most preferably 30 parts.
In the present invention, the white carbon is precipitated silica commonly used in the art.In one embodiment of the invention, use
Be De Gusai companies production the trade mark be VN3 white carbon.The dosage of the white carbon is preferably 10~12 parts.
In the present invention, the polyester polyether plasticizer can be polyester polyether plasticizer commonly used in the art.The present invention
It is the plasticizer of TP 759 using the trade mark of U.S.'s Hallstar companies markets in one embodiment.The use of the plasticizer
Preferably 8~12 parts of amount, is more preferably 10 parts.
In the present invention, the vulcanizing agent can be peroxide vulcanizing agent commonly used in the art, preferably peroxidating
Isopropylbenzene (abbreviation DCP).In one embodiment of the invention, using the commercial product vulcanizing agent of Dutch Akzo Nobel N.V.
DCP.The dosage of the vulcanizing agent is preferably 2.5~3.5 parts, is more preferably 3 parts.
In the present invention, the assistant crosslinking agent can be assistant crosslinking agent commonly used in the art, and preferably triallyl is different
Cyanurate (abbreviation TAIC).In one embodiment of the invention, using the commercial product TAIC of Shandong Bo Tao groups.It is described to help
The dosage of crosslinking agent is preferably 1.5~2.5 parts, is more preferably 2 parts.
Further include preferably sulphur in the feedstock composition of the hydrogenated nitrile rubber composition material in the present invention.Institute
State sulphur dosage can this field it is conventional, preferably 0.1~0.2 part, be more preferably 0.12~0.15 part, be most preferably 0.14
Part.In one embodiment of the invention, using the vulcanization of the model IS-60 of the auspicious Fine Chemical Co., Ltd's productions of Tai'an Gu Te
Agent.
Further include preferably poly- second two in the feedstock composition of the hydrogenated nitrile rubber composition material in the present invention
Alcohol and/or silane coupling agent.
Wherein, the polyethylene glycol can be polyethylene glycol commonly used in the art, preferably PEG4000, more preferably
For the commercially available product Macrogol 4000 of South Korea's Hunan petrochemical industry (top grade product).The dosage of the polyethylene glycol can be that this field is normal
Rule, preferably 1~3 part, be more preferably 2~2.5 parts, is most preferably 2.2 parts.
Wherein, the silane coupling agent is silane coupling agent commonly used in the art, preferably double-[γ-(three second
Oxygroup silicon) propyl] tetrasulfide.In one embodiment of this invention, double-[γ-(triethoxysilicane) propyl] four vulcanizes
Object is the silane coupling agent Si-69 of German Degussa Corporation's production.The dosage of the silane coupling agent is preferably 0.5~2.5
Part, it is more preferably 1.5~2 parts, is most preferably 1.8 parts.
In the present invention, the acrylonitrile content of the hydrogenated nitrile-butadiene rubber is preferably 41.3~43.1%, more preferably for
41.6~42.3%, it is most preferably 42%.
In the present invention, the hydrogenated nitrile-butadiene rubber saturation degree is preferably > 99%.
In the present invention, the Mooney viscosity of the hydrogenated butyronitrile is preferably 100 DEG C 61~69 of ML (1+4)@, is more preferably ML
(1+4)@100℃65。
The present invention also provides a kind of preparation methods of the hydrogenated nitrile rubber composition material comprising following step
Suddenly:
(1) hydrogenated nitrile-butadiene rubber is kneaded, obtains mixture A;
(2) by the mixture A, the activator A, the activator B, the anti-aging agent, the polyethylene glycol, described
Silane coupling agent, the precipitated silica are kneaded, and obtain mixture B;
(3) the mixture B and carbon black A is kneaded, obtains mixture C;
(4) after being kneaded the mixture C, the black B, the plasticizer, dumping, slice obtain rubber premixing glue;Its
In, when the dumping, the temperature of mixing is 125~155 DEG C;
(5) after the rubber premixing glue being plasticated, with the vulcanizing agent, assistant crosslinking agent mixing, dumping, slice, cold
But to room temperature.
In step (1)~(5), the condition and method of the mixing can be this field normal condition and method, preferably exist
It is carried out in mixer.
In step (1), the mixing time can be that this field is conventional, and preferably 40~60s is more preferably 52~58s,
Most preferably it is 54s.The temperature of the mixing can be that this field is conventional, and preferably 15~80 DEG C, be more preferably 61~69 DEG C, most
It is 64~67 DEG C goodly.
In step (2), time of the mixing can be that this field is conventional, preferably 20~40s, more preferably for 25~
35, it is most preferably 30s.The temperature of the mixing can be that this field is conventional, and preferably 15~80 DEG C, be more preferably 66~79
DEG C, it is most preferably 71~77 DEG C.
In step (3), time of the mixing can be that this field is conventional, preferably 50~70s, more preferably for 55~
65s is most preferably 60s.The temperature of the mixing can be that this field is conventional, preferably 15~129 DEG C, more preferably for 120~
125 DEG C, be most preferably 121~123 DEG C.
In step (4), according to common sense in the field it is found that the terminal of the mixing is the condition for meeting the dumping.
In step (4), the operation of the dumping and method can be this field normal condition and method, preferably in mixer
Middle progress.When the dumping, the temperature of mixing is preferably 145~153 DEG C, is more preferably 148~150 DEG C.
In step (4) and step (5), the condition and method of the slice can be this field normal condition and method, preferably
Ground carries out in open mill.The open mill can be open mill commonly used in the art, and the wheelspan of the open mill can be this
Field is conventional, and preferably 2~5mm is more preferably 3mm.
In step (5), before the rubber premixing glue is kneaded, preferably first stood.The standing is usually to be
The better static dissipation of guarantee sizing material, generally room temperature are parked.The time of the standing can be that this field is conventional, preferably
12 hours~3 months, be more preferably 1~7 day.
In step (5), the condition plasticated and method can be this field normal condition and method, preferably in mixer
Middle progress.The time plasticated can be that this field is conventional, and preferably 60~80s is more preferably 65~70s, most preferably for
68℃。
In step (5), according to common sense in the field it is found that the terminal of the mixing is the condition for meeting the dumping.
In step (5), time of the mixing can be that this field is conventional, preferably 90~150s, more preferably for 120~
138s.The temperature of the mixing can be that this field is conventional, and preferably 70~100 DEG C, be more preferably 80~100 DEG C, most preferably
It is 90~95 DEG C.
In step (5), the condition and method of the dumping can be the condition and method of this field routine, preferably in mixing
It is carried out in machine.The condition of the dumping is carried out in such a way that the condition to the condition of melting temperature or mixing time is monitored
It investigates;Refining can be crossed to avoid rubber in this way causes molecular weight too low or incipient scorch phenomenon, to influence rubber comprehensive performance.It is described
The condition of dumping, the temperature of the preferably described mixing reach 90~100 DEG C, more preferably the temperature for the mixing reach 93~
98 DEG C, be most preferably 95 DEG C.
In the present invention, usually, product contacts interleaving agent aqueous solution when the slice.The interleaving agent is that this field is normal
The aqueous solution of the interleaving agent of rule, generally zinc stearate or magnesium stearate, film impregnates dry after its aqueous solution after, store process
Agglomerating risk is bonded between film to substantially reduce.The temperature of the interleaving agent aqueous solution can be that this field is conventional, preferably 10~
40 DEG C or less.
In step (5), if the operation without " being cooled to room temperature ", the risk of incipient scorch is had.The room temperature is ability
Domain is conventional, and general environment temperature is 10~35 DEG C.
The present invention also provides a kind of hydrogenated nitrile rubber composition materials as automobile engine oil ruler casing oil sealing material
The application of material.
In the present invention, the automobile can be any type of automobile in this field.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention
Example.
The raw materials used in the present invention is commercially available.
The positive effect of the present invention is that:
1, preparation method is simple by the present invention;Hydrogenated nitrile rubber composition material produced by the present invention, height stretch
Intensity, it is high stretch elongation, high-tear strength, appropriate working temperature be -40~160 DEG C (short-period used can reach 180 DEG C, this
Place " short-term " refers to the uninterrupted duration no more than 2h), it is weather-proof ozone performance, resistance to low aniline point oil, fuel resistance energy, resistance to
Every synthesis such as machine oil performance is excellent.
2, the excellent combination property of hydrogenated nitrile rubber composition material of the invention, can meet Lubricant of Automobile Engine ruler
Oil sealing indices and road test requirement, have been successfully applied to the Lubricant of Automobile Engine ruler of certain type car of Fiat Auto factory
Casing oil sealing:
(1) Lubricant of Automobile Engine ruler oil sealing is mostly that the gum sleeve of the corrugated appearance in outside (is covered embedded in high resiliency gold
Belong on oil rule, has strict demand to sealing, extraction force, pullout forces, so generally requiring the oil rule casing oil sealing mechanics of materials
It has excellent performance (high intensity, high anti-tear, high resiliency elongation), it is desirable that oil rule oil sealing process of manufacture is easy to control, size
Stablize, high-precision height (the general requirement ± 0.1mm margins of tolerance).(2) index request of the depot to environmental test can be met:1. doing
Heat test (is placed) in 125 DEG C of * 168h hot-airs, and deformation, size variation (room temperature conditions correlation after test) is not allowed to be no more than
0.5%;2. hot test (is placed) in 135 DEG C of * 5h hot-airs, it is desirable that after experiment, do not allow deformation, size variation (after test
Room temperature condition compares) it is no more than 0.5%;3. (125 DEG C of * 168h, 35 ﹣ DEG C * 5h are a cycle, test 2 for high/low temperature cyclic test
Cycle), do not allow deformation, size variation (room temperature conditions correlation after test) to be no more than 0.5%.(3) depot can be met to hot water
The index request of soak test:80 DEG C of * 168h of hot-water dipping test do not allow deformation, size variation (room temperature condition pair after test
Than) it is no more than 0.5%;Water quality passes through certain automobile factory's entrucking road test without (4) are become cloudy, and sealing effect is excellent, and the road test service life reaches
Depot requires.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
Product specification selects.
Raw materials used source is as follows in the embodiment of the present invention, comparative example:
Trade mark Therban*4307 (acrylonitrile content 43%, the Mooney viscosity ML1+4 of German Lang Sheng chemical companies production
100 DEG C 60, hereinafter referred to as 4307);(acrylonitrile content 44%, Mooney are viscous by the trade mark Zetpol1000L of Nippon Zeon Co., Ltd.'s production
Spend 100 DEG C 70 of ML1+4@, hereinafter referred to as 1000L);The trade mark of Shanghai Zan Nan Science and Technology Ltd.s production is ZN43056 (acrylonitrile
Content 43%, 100 DEG C 65 of Mooney viscosity ML1+4@, hereinafter referred to as 43056).
Trade mark Zetpol 2000L (acrylonitrile content 36%, 100 DEG C of the Mooney viscosity ML1+4@of Nippon Zeon Co., Ltd.'s production
65, hereinafter referred to as 2000L);The trade mark of Shanghai Zan Nan Science and Technology Ltd.s production is ZN35056 (acrylonitrile content 36%, Mooney
100 DEG C 65 of viscosity ML1+4@, hereinafter referred to as 35056).
Activator:Zinc oxide is zinc oxide (I types) top grade product of Anhui Province Hanshan County Jin Hua zinc oxide factory production, general
Purity with 99.7% (w/w);Magnesia is the extra light calcined magnesia trade mark MA-150 of Japanese consonance company production;Stearic acid
For 200 type stearic acid of the model 1801 of Shijiazhuang Tai Xin Chemical Co., Ltd.s production.
Anti-aging agent:Anti-aging agent RD is the anti-aging agent RD of Research Institute of Nanjing Chemical Industry Group production;Antioxidant MB is studied for Nan Hua groups
The antioxidant MB of institute's production.
Polyethylene glycol is the trade mark Macrogol 4000 (top grade product, abbreviation PEG4000) of South Korea's Hunan petrochemical iy produced.
Silane coupling agent is the silane coupling agent Si-69 of German Degussa Corporation's production.
Carbon black A is the carbon black that the Suzhou Bao Hua companies production trade mark is N330.
Black B is the carbon black that the Suzhou Bao Hua companies production trade mark is N550.
White carbon is the white carbon that the trade mark of De Gusai companies production is VN3.
Plasticizer is the polyester polyether plasticizer that the trade mark of Hallstar companies of U.S. production is TP 759.
Vulcanizing agent is the vulcanizing agent DCP of Dutch Akzo Nobel N.V.'s production.
Assistant crosslinking agent:The production TAIC of Shandong Bo Tao groups;The model of the auspicious Fine Chemical Co., Ltd's productions of Tai'an Gu Te
For the insoluble sulfur of IS-60.
Acrylic rubber is that the trade mark of Japanese TOHPE companies production is the acrylic rubber of AR801, AR840.
Ethylene-acrylate rubber be DuPont Corporation production the trade mark be Vamac G, the ethylene-the third of Vamac GLE
Olefin(e) acid ester rubber.
Amine curing agents HMDC is the HMDC vulcanizing agents of E.I.Du Pont Company's production.
Accelerating agent di-o-tolylguanidine (abbreviation DOTG) is the DOTG accelerating agents of DuPont Corporation's production.
Trade mark Zetpol 1010L (acrylonitrile content 44%, 100 DEG C of the Mooney viscosity ML1+4@of Nippon Zeon Co., Ltd.'s production
85, saturation degree 96%, hereinafter referred to as 1010L), Zetpol 2010L (acrylonitrile content 36%, 100 DEG C of Mooney viscosity ML1+4@
58, saturation degree 96%, hereinafter referred to as 2010L).
Suzhou Bao Hua companies produce the carbon black (61~100nm of grain size) that the trade mark is N774.
The Vulcanization accelerator TMTD of Hebi Uhoo Rubber Chemicals Co., Ltd.'s production.
Examples 1 to 5, comparative example 1~2
Table 1
"-" indicates that dosage is " 0 " in table 1.
Examples 1 to 5, the dosage of each raw material component of comparative example 1~2 are as shown in table 1.
Examples 1 to 5, by the raw material components of each embodiment in table 1 according to following preparation processes to get the production of each embodiment
Product (parameter of specific each step is as shown in table 2):
(1) in mixer, by hydrogenated nitrile-butadiene rubber A and hydrogenated nitrile-butadiene rubber B compounding rubbers, mixture A is obtained;
(2) in mixer, by mixture A, activator, magnesia, stearic acid, anti-aging agent, polyethylene glycol,
Si-69 mixings, white carbon, obtain mixture B;
(3) in mixer, mixture B and carbon black A is kneaded, mixture C is obtained;
(4) in mixer, mixture C, black B, plasticizer are kneaded, dumping is carried out in mixer, in open mill
Middle slice (being carried out in open mill, wheelspan 3mm), obtains rubber premixing glue;
(5) rubber premixing glue is stood, is generally placed at room temperature for;
(6) the rubber premixing glue after standing is plasticated in mixer, is then mixed with vulcanizing agent, assistant crosslinking agent, close
In mill be kneaded, in mixer dumping, slice (when slice product contact interleaving agent aqueous solution temperature at 40 DEG C or less), it is cold
But to room temperature (10~35 DEG C).
Table 2
Comparative example 1
Product made from this comparative example is acrylic rubber mixture.
Its production method can be made by this field routine two-stage mixing method, specific as follows:It is kneaded out premixing glue for the first time, in advance
Mixed glue is the sizing material without vulcanization accelerator;Second be added on the basis of premixing glue vulcanization accelerator be kneaded to obtain rubber it is mixed
Close object.
Comparative example 2
Product made from this comparative example is ethylene-acrylate rubber mixture, and vulcanizing agent is amine curing agents HMDC,
Accelerating agent is DOTG.
Its production method can be made by this field routine two-stage mixing method, specific as follows:It is kneaded out premixing glue (no for the first time
HMDC containing amine curing agents, accelerating agent DOTG), second be kneaded on the basis of premixing glue be added amine curing agents HMDC,
Accelerating agent is that DOTG is kneaded to get ethylene-acrylate rubber mixture.
Comparative example 3
Its production method is made for this field routine two-stage mixing method, specific as follows:For the first time premixing glue is kneaded out (to be free of
Vulcanizing agent DCP, assistant crosslinking agent TAIC, assistant crosslinking agent TMTD), second be kneaded on the basis of premixing glue be added vulcanizing agent DCP,
Assistant crosslinking agent TAIC, assistant crosslinking agent TMTD are kneaded to get hydrogenated nitrile-butadiene rubber rubber composition.
Effect example
Rubber material product in Examples 1 to 5, comparative example 1~2 is subjected to testing of materials, test result such as the following table 3 institute
Show:
Table 3
Remarks:Vulcanization test piece, examination button test institute are made according to this field conventional method (ASTM D3182, ASTM D3183)
3 data of table are obtained, conditions of vulcanization is 170 DEG C of * 10MPa*10min (three essential curing factors:Temperature, time, pressure), second of baking oven sulphur
Change condition is 180 DEG C of * 2h;Hardness test (shore A) executes standard ASTM D2240;It stretches strong, elongation at break and executes mark
Quasi- ASTM D412.
As shown in Table 3,1 gained acrylic rubber mixture of comparative example, tensile strength, elongation at break, tearing are strong
Depot's index request is all not achieved in degree, black brittleness characteristic, unqualified;2 gained ethylene-acrylate rubber of comparative example mixes
Object, depot's index request is not achieved in the No.903 of resistance to IRM oil properties, unqualified.3 gained hydrogenated nitrile-butadiene rubber of comparative example is mixed
Object is closed, tearing strength, 160 DEG C of * 72h hot air agings, 160 DEG C of agings of the * 72h No.903 of resistance to IRM oil products, 160 DEG C of * 72h are resistance to
Depot's index request is all not achieved in 5w-40 aeronautic ATEs, unqualified.
Examples 1 to 5,1~2 resulting materials of comparative example are made into car engine by this field regular injection sulfuration process
Machine oil rule casing oil sealing, conditions of vulcanization are 170 DEG C of * 10MPa*10min (three essential curing factors:Temperature, time, pressure), second
Secondary baking oven conditions of vulcanization is 180 DEG C of * 2h.Products obtained therefrom is subjected to simulated environmental test respectively, the results are shown in Table 4:
Table 4
Remarks:After 1 high/low temperature cyclic test of comparative example, (circular cross-section becomes slight ellipse to the deformation of oil rule casing oil sealing
Circle), this is related to acrylate vulcanized rubber elasticity, stiffening property relative mistake;After 2 high/low temperature cyclic test of comparative example, oil rule card
Set oil sealing size slightly becomes smaller, this and the unstable association of ethylene-acrylate vulcanized rubber shrinking percentage.
Examples 1 to 5,1~2 resulting materials of comparative example are made into car engine by this field regular injection sulfuration process
Machine oil rule casing oil sealing, conditions of vulcanization are 170 DEG C of * 10MPa*10min (three essential curing factors:Temperature, time, pressure), second
Secondary baking oven conditions of vulcanization is 180 DEG C of * 2h.Products obtained therefrom is subjected to hot-water dipping test respectively, the results are shown in Table 5:
Table 5
Examples 1 to 5,1~2 resulting materials of comparative example are made into car engine by this field regular injection sulfuration process
Machine oil rule casing oil sealing, conditions of vulcanization are 170 DEG C of * 10MPa*10min (three essential curing factors:Temperature, time, pressure), second
Secondary baking oven conditions of vulcanization is 180 DEG C of * 2h.Products obtained therefrom is supplied to client's entrucking road test, the results are shown in Table 6.
Table 6
Remarks:After the product road test of comparative example 1, there are 1mm deep torn grains in the deformation of oil rule casing oil sealing, its surface, because
Its material mechanical performance difference causes durability damage;There are 1mm depths in oil rule casing oil sealing surface after the product road test of comparative example 2
Crackle, the durability damage caused by the oil property of the resistance to aniline point of its material is poor.After the product road test of comparative example 3, machine
There are 1mm deep torn grains in dipstick casing oil sealing surface, because its material is poor in limit hot environment (160 DEG C) heatproof, oil resistance
Caused durability damage.
Claims (10)
1. a kind of hydrogenated nitrile rubber composition material, which is characterized in that its feedstock composition includes each of following parts by weight
Component:100 parts of hydrogenated nitrile-butadiene rubbers, 4~10 parts of activator A, 0.5~2.5 part of activator B, 1~4 part of anti-aging agent, 20~30 parts
Carbon black A, 25~35 parts of black Bs, 5~15 parts of white carbons, 5~15 parts of plasticizer, 2~4 parts of vulcanizing agents, 1~3 part of assistant crosslinking agent;
Wherein, the acrylonitrile content of the hydrogenated nitrile-butadiene rubber is 41.3~43.1%, the saturation degree of the hydrogenated nitrile-butadiene rubber
>=99%, the Mooney viscosity of the hydrogenated nitrile-butadiene rubber is ML 1+4,100@DEG C 60~70;The activator A is zinc oxide, institute
It is stearic acid to state activator B;The carbon black A is the carbon black of 26~30nm of grain size, and the black B is the charcoal that grain size is 40~48nm
It is black;The plasticizer is polyester polyether plasticizer.
2. hydrogenated nitrile rubber composition material as described in claim 1, which is characterized in that the hydrogenated nitrile-butadiene rubber material
Composition is grouped as by the group of following parts by weight:100 parts of hydrogenated nitrile-butadiene rubbers, 4~10 parts of activator A, 0.5~
2.5 parts of activator B, 1~4 part of anti-aging agent, 20~30 parts of carbon black A, 25~35 parts of black Bs, 5~15 parts
The precipitated silica, 5~15 parts of the plasticizers, 2~4 parts of vulcanizing agents, 1~3 part of assistant crosslinking agent.
3. hydrogenated nitrile rubber composition material as claimed in claim 1 or 2, which is characterized in that the hydrogenated nitrile-butadiene rubber
For the composition of hydrogenated nitrile-butadiene rubber A and hydrogenated nitrile-butadiene rubber B, the acrylonitrile content of the hydrogenated nitrile-butadiene rubber A is 43.5 ±
1%, saturation degree >=99%, Mooney viscosity is ML 1+4,100@DEG C 60~70;The acrylonitrile content of the hydrogenated nitrile-butadiene rubber B
It is 36 ± 1%, saturation degree >=99%, Mooney viscosity is ML 1+4,100@DEG C 60~70;
Wherein, the hydrogenated nitrile-butadiene rubber A is preferably the hydrogenated nitrile-butadiene rubber of model Therban*4307, model
It is one or more in the hydrogenated nitrile-butadiene rubber of Zetpol 1000L and the hydrogenated nitrile-butadiene rubber of model ZN43056;The hydrogen
Change nitrile rubber B and is preferably model Zetpol 2000L and/or model ZN35056 hydrogenated nitrile-butadiene rubbers;
The activator A further includes magnesia;The magnesia is preferably model MA-150 magnesia;
The stearic acid is 200 type stearic acid of model 1801;
The anti-aging agent is 2,2,4- trimethyl -1,2- dihyaroquinoline polymer;
The anti-aging agent further includes antioxidant MB, and the antioxidant MB is preferably 2-mercaptobenzimidazole;
The carbon black A is carbon black N330;
The black B is carbon black N550;
The white carbon is the white carbon of VN3;
The polyester polyether plasticizer is the plasticizer of trade mark TP 759;
The vulcanizing agent is dicumyl peroxide;
And/or the assistant crosslinking agent is Triallyl isocyanurate.
4. hydrogenated nitrile rubber composition material as claimed in claim 3, which is characterized in that the hydrogenated nitrile-butadiene rubber A's
Dosage is 75~90 parts, and preferably 80~85 parts, be more preferably 85 parts;
The dosage of the hydrogenated nitrile-butadiene rubber B is 10~25 parts, and preferably 12~20 parts, be more preferably 15 parts;
The dosage of the magnesia is 2~5 parts, preferably 4 parts;
The dosage of the zinc oxide is 2~5 parts, preferably 3 parts;
The stearic dosage is 0.5~2.5 part, and preferably 1.5~2 parts, be more preferably 1.8 parts;
The dosage of the anti-aging agent is 1.0~2.5 parts, preferably 1.8~2 parts;
The dosage of the antioxidant MB is 0.5~1.5 part, preferably 0.8~1 part;
The dosage of the carbon black A is 20~30 parts, preferably 25~28 parts;
The dosage of the black B is 25~35 parts, and preferably 26~32 parts, be more preferably 30 parts;
The dosage of the white carbon is 10~12 parts;
The dosage of the plasticizer is 8~12 parts, preferably 10 parts;
The dosage of the vulcanizing agent is 2.5~3.5 parts, preferably 3 parts;
And/or the dosage of the assistant crosslinking agent is 1.5~2.5 parts, preferably 2 parts.
5. hydrogenated nitrile rubber composition material as described in claim 1, which is characterized in that the hydrogenated nitrile-butadiene rubber combination
Further include sulphur in the feedstock composition of object material;The dosage of the sulphur is preferably 0.1~0.2 part, is more preferably 0.12
~0.15 part, be most preferably 0.14 part;
Further include that polyethylene glycol and/or silane are even and/or in the feedstock composition of the hydrogenated nitrile rubber composition material
Join agent;
Wherein, the polyethylene glycol is preferably PEG4000;The dosage of the polyethylene glycol is preferably 1~3 part, more preferably
It is 2~2.5 parts, is most preferably 2.2 parts;The silane coupling agent preferably double-[γ-(triethoxysilicane) propyl] four vulcanizes
Object;The dosage of the silane coupling agent is preferably 0.5~2.5 part, is more preferably 1.5~2 parts, is most preferably 1.8 parts.
6. hydrogenated nitrile rubber composition material as described in claim 1, which is characterized in that the third of the hydrogenated nitrile-butadiene rubber
Alkene nitrile content is 41.3~43.1%, preferably 41.6~42.3%, is more preferably 42%;
The hydrogenated nitrile-butadiene rubber saturation degree is > 99%;
And/or the Mooney viscosity of the hydrogenated butyronitrile is ML 1+4,100@DEG C 61~69, preferably ML 1+4,100@DEG C
65。
7. a kind of preparation method of the hydrogenated nitrile rubber composition material as described in any one of claim 1~6, feature exist
In comprising following steps:
(1) hydrogenated nitrile-butadiene rubber is kneaded, obtains mixture A;
(2) by the mixture A, the activator A, the activator B, the anti-aging agent, the polyethylene glycol, the silane
Coupling agent, the precipitated silica are kneaded, and obtain mixture B;
(3) the mixture B and carbon black A is kneaded, obtains mixture C;
(4) after being kneaded the mixture C, the black B, the plasticizer, dumping, slice obtain rubber premixing glue;Wherein,
When the dumping, the temperature of mixing is 125~155 DEG C;
(5) after the rubber premixing glue being plasticated, with the vulcanizing agent, assistant crosslinking agent mixing, dumping, slice, be cooled to
Room temperature.
8. preparation method as claimed in claim 7, which is characterized in that in step (1)~(5), the mixing is in mixer
It carries out;
In step (1), the mixing time is 40~60s, preferably 52~58s, is more preferably 54s;
In step (1), the temperature of the mixing is 15~80 DEG C, and preferably 61~69 DEG C, be more preferably 64~67 DEG C;
In step (2), time of the mixing is 20~40s, preferably 25~35, it is more preferably 30s;
In step (2), the temperature of the mixing is 15~80 DEG C, and preferably 66~79 DEG C, be more preferably 71~77 DEG C;
In step (3), the time of the mixing is 50~70s, preferably 55~65s, is more preferably 60s;
In step (3), the temperature of the mixing is 15~129 DEG C, and preferably 120~125 DEG C, be more preferably 121~123
℃;
In step (4), the dumping carries out in mixer;When the dumping, the temperature of mixing is 145~153 DEG C, preferably
It is 148~150 DEG C;
And/or in step (4) and step (5), the slice carries out in open mill;The wheelspan of the open mill is 2~5mm,
Preferably 3mm.
9. preparation method as claimed in claim 7, which is characterized in that in step (5), the rubber premixing glue is kneaded
Before, first stood;The time of the standing is 12 hours~3 months, preferably 1~7 day;
In step (5), described plasticate carries out in mixer;
In step (5), the time plasticated is 60~80s, preferably 65~70s, is more preferably 68 DEG C;
In step (5), the time of the mixing is 90~150s, preferably 120~138s;
In step (5), the temperature of the mixing is 70~100 DEG C, and preferably 80~100 DEG C, be more preferably 90~95 DEG C;
In step (5), the dumping carries out in mixer;The condition of the dumping be the temperature of the mixing reach 90~
100 DEG C, the temperature of the preferably described mixing reaches 93~98 DEG C, and the more preferably temperature for the mixing is reached for 95 DEG C;
And/or in step (5), product contacts interleaving agent aqueous solution when the slice;The temperature of the interleaving agent aqueous solution is 10
~40 DEG C or less.
10. one kind hydrogenated nitrile rubber composition material as described in any one of claim 1~6 is oily as automobile engine oil ruler casing
The application of closure material.
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