CN110183691A - Hydrogenated nitrile-butadiene rubber crosslinking agent masterbatch, hydrogenated nitrile rubber composition and hydrogenated nitrile-butadiene rubber are crosslinked formed products - Google Patents

Hydrogenated nitrile-butadiene rubber crosslinking agent masterbatch, hydrogenated nitrile rubber composition and hydrogenated nitrile-butadiene rubber are crosslinked formed products Download PDF

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CN110183691A
CN110183691A CN201910128280.7A CN201910128280A CN110183691A CN 110183691 A CN110183691 A CN 110183691A CN 201910128280 A CN201910128280 A CN 201910128280A CN 110183691 A CN110183691 A CN 110183691A
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hydrogenated nitrile
butadiene rubber
masterbatch
hnbr
carbon black
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川崎邦义
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Nok Corp
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Nok Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2315/00—Characterised by the use of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2415/00—Characterised by the use of rubber derivatives
    • 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
    • C08K2201/006—Additives being defined by their surface area
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a kind of hydrogenated nitrile-butadiene rubber organic peroxide masterbatch, and the content of organic peroxide is high, can eliminate in being kneaded operation hydrogenated nitrile-butadiene rubber and fall off the problems in such processing operation point from roller.Additionally, it is provided being crosslinked formed products using hydrogenated nitrile rubber composition made of the masterbatch and hydrogenated nitrile-butadiene rubber.The hydrogenated nitrile-butadiene rubber organic peroxide masterbatch is characterized in that, contain hydrogenated nitrile-butadiene rubber, 1, bis- (tert-butylperoxyiso-propyl) benzene of 3- and carbon black, the bonding acrylonitrile amount of the hydrogenated nitrile-butadiene rubber is less than 25 mass %, the content of the organic peroxide is 10~30 mass %, and the content of the carbon black is 10~30 mass %.In addition, the hydrogenated nitrile rubber composition and hydrogenated nitrile-butadiene rubber crosslinking formed products are using made of the masterbatch.

Description

Hydrogenated nitrile-butadiene rubber crosslinking agent masterbatch, hydrogenated nitrile rubber composition and hydrogenation Nitrile rubber is crosslinked formed products
Technical field
The present invention relates to hydrogenated nitrile-butadiene rubber crosslinking agent masterbatch and use hydrogenated nitrile-butadiene rubber made of the masterbatch Composition and hydrogenated nitrile-butadiene rubber are crosslinked formed products.
Background technique
Hydrogenated nitrile-butadiene rubber is (hereinafter, sometimes referred to as " HNBR ".) it is to add hydrogen in nitrile rubber (NBR) and improve The rubber of heat resistance, weatherability is used as safe carrying material, various oil sealings, sealing element of automobile etc..
Bis- (tert-butylperoxyiso-propyl) benzene of 1,3- are primarily as synthetic rubber, the crosslinking agent or curing agent of synthetic resin The organic peroxide used.The organic peroxide has-O-O- key in the molecule, therefore heat point at a lower temperature Solution, or reacted with reducing substances, it is easy to generate free free radical.The free free radical generated causes in unsaturated double-bond The abstraction reaction of addition reaction or hydrogen etc., and make synthetic rubber etc. and crosslink or solidify.Bis- (the tert-butyl peroxy isopropyls of 1,3- Base) benzene is also used as the crosslinking agent of HNBR to use.
In the past, it was kneaded in (Japanese: promoting れ) process in crosslinking agent, that is, organic peroxide addition as HNBR, it will The organic peroxide of single-item is added mixing using roller, closed mixing machine etc..But mixing job requirements operator It is skilled, and taken a very long time to keep organic peroxide evenly dispersed, additionally, there are be kneaded in operation HNBR from roller fall off and (do not wind) as with roller operation manufacture on problem.
Therefore, in order to which the dispersibility for eliminating organic peroxide is involved in the problems, such as, using having containing organic peroxide Masterbatch.Some masterbatch with bis- (tert-butylperoxyiso-propyl) benzene of 1,3- for principal component are had existed on the market, it is known that Japan Oil Co Perbutyl P-40, Peroxymon F40 etc..These masterbatch generally use calcium carbonate, titanium dioxide Inactive inorganic filler is as diluent as silicon.
By using these masterbatch, the addition mixing time added when being kneaded into HNBR can be from previous 15 minutes Left and right shortens to 10 minutes or so.But HNBR does not change from the roller problem in such manufacture that falls off in being kneaded operation It is kind.
In addition, the diluent as masterbatch, exists and is not desired to the such expectation of the inorganic fillers such as cooperation calcium carbonate.Cause This, replaces inorganic filler using HNBR for the diluent of masterbatch, as a result distinguishes that 1,3- being difficult to improve in masterbatch is bis- The content of (tert-butylperoxyiso-propyl) benzene.That is, the ratio mixing dispersion 1 relative to HNBR with 10~50 mass % has been attempted, Bis- (tert-butylperoxyiso-propyl) benzene of 3-.But may not be high with the compatibility of HNBR, therefore the bis- (tert-butyl peroxy isopropyls of 1,3- Base) benzene from HNBR is easily separated (frosting bloom), it is difficult to the masterbatch of sheet material blank shape is made.
Disclose in patent document 1 by using and use HNBR and the polybutadiene oligomer of low molecular weight as diluent Bis- (tert-butylperoxyiso-propyl) benzene of 1,3- are the masterbatch of principal component.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2008-31334 bulletin
Summary of the invention
Problems to be solved by the invention
But the masterbatch of patent document 1 contains polybutadiene oligomer as ingredient, therefore cannot be made low without this The HNBR composition of polymers.
The present invention is completed in view of such situation.That is, problem of the present invention is that, a kind of HNBR organic peroxy is provided Compound masterbatch, the contents of 1,3- bis- (tert-butylperoxyiso-propyl) benzene is high, can eliminate in being kneaded operation HNBR from roller Fall off the problems in such processing operation point.Additionally, it is provided being handed over using HNBR composition made of the masterbatch and HNBR Join formed products.
The means used to solve the problem
The present inventor in order to solve the above problems, studies the composition of HNBR.Itself as a result, it has been found that, by by HNBR Bonding acrylonitrile amount (hereinafter, sometimes referred to as " bonding AN amount ".) it is set as range appropriate, it can be improved and the bis- (uncles of 1,3- Butylperoxyisopropyl) benzene compatibility.In addition, having also discovered suitable composition for the carbon black added as reinforcing agent.This Invention is based on such opinion so that completing.
That is, HNBR organic peroxide masterbatch of the invention contains HNBR, 1,3- bis- (tert-butylperoxyiso-propyls) The bonding AN amount of benzene and carbon black, the HNBR is less than 25 mass %, the content of bis- (tert-butylperoxyiso-propyl) benzene of 1,3- For 10~30 mass %, the content of the carbon black is 10~30 mass %.
In addition, the Mooney viscosity ML of HNBR of the invention with the preferred HNBR of organic peroxide masterbatch1+4(100 DEG C) are 30~100.
In addition, HNBR of the invention, in organic peroxide masterbatch, the preferred N2 adsorption specific surface area of carbon black is 20~80m2/ g, DBP uptake are 50~160cm3/100g。
In addition, HNBR composition of the invention be using above-mentioned HNBR made of organic peroxide masterbatch.
In addition, HNBR crosslinking formed products of the invention are will be made of the crosslinking forming of above-mentioned HNBR composition.
Invention effect
The content of bis- (tert-butylperoxyiso-propyl) benzene of 1,3- of HNBR of the invention organic peroxide masterbatch is high, HNBR can be eliminated in being kneaded operation to fall off the problems in such processing operation point from roller.
Specific embodiment
Hereinafter, detailed description of embodiments of the present invention.But the scope of the present invention be not limited to it is described below Embodiment as concrete example.
The HNBR of present embodiment is with organic peroxide masterbatch (hereinafter, sometimes referred to as " masterbatch ".) contain Bis- (tert-butylperoxyiso-propyl) benzene of HNBR, 1,3- and carbon black.Hereinafter, being illustrated to each ingredient.
(HNBR)
HNBR is by that will be used as in main polymer chain possessed by the nitrile rubber of acrylonitrile-butadiene copolymer Unsaturated bond is hydrogenated, to improve the rubber of heat resistance, chemical resistance, weatherability etc..
As the standard of unsaturated bond amount remaining in the main polymer chain of HNBR, use iodine number (g/100g).If considering Heat resistance, then iodine number (g/100g) is preferably 20 hereinafter, more preferably 15 or less.On the other hand, by HNBR moderately Unsaturated bond is remained, peroxide crosslinking, special crosslinking (amine crosslinking etc.) are able to carry out, from heat resistance, mechanical strength, oil resistivity Deng raising from the perspective of preferably.
HNBR has the heat resistance close to acrylic rubber, has excellent chemical stability.In addition, mechanical strength, Abrasion resistence etc. is also excellent.Therefore, there is adaptability for the purposes of oil sealing, sealing element etc..
For the present inventor in order to improve HNBR and 1, the compatibility of bis- (tert-butylperoxyiso-propyl) benzene of 3- is conceived to HNBR's It is bonded AN amount.If the bonding AN quantitative change of HNBR is more, the in general polarity of HNBR is got higher, oil resistivity, the abrasion resistence of HNBR Deng raising.It but is being indefinite with the bonding AN amount being suitble in the relationship of bis- (tert-butylperoxyiso-propyl) benzene of 1,3-.Cause This, it is being studied as a result, it has been found that, if the bonding AN amount of HNBR be less than 25 mass %, even if it is bis- to contain 1,3- with high concentration (tert-butylperoxyiso-propyl) benzene, it is also difficult to separation (frosting) occur.
Speculating should be the result is that since the solubility parameter Sp value of bis- (tert-butylperoxyiso-propyl) benzene of 1,3- be bonded with low In the HNBR of AN amount close range.In addition, if the bonding AN amount of HNBR is less than 25 mass %, with the mixing facilities of HNBR Dirt in mixing channel also reduces.
From the viewpoint of mechanical strength, processability, the Mooney viscosity ML of HNBR1+4(100 DEG C) preferably 30~100, it is more excellent Select 30~80.Here, Mooney viscosity ML1+4(100 DEG C) are measured according to JIS K 6300-1:2013.
As HNBR, Zetpol (registered trademark), the Lanxess corporation of such as Nippon Zeon can be used Therban (registered trademark) etc..
(bis- (tert-butylperoxyiso-propyl) benzene of 1,3-)
Bis- (tert-butylperoxyiso-propyl) benzene of 1,3- are also known as bis- [1- (the t-butylperoxy) -1- methyl second of 1,3- Base] benzene organic peroxide.It is the powder of white, is the compound of CAS number 25155-25-3.
(carbon black)
In masterbatch, carbon black is added as reinforcing agent.As reinforcing agent, there are also silica (hard charcoals other than carbon black It is black), magnesium carbonate, clay etc., but preferred carbon black.By selecting carbon black appropriate, it can further improve processing workability.
As carbon black, preferably N2 adsorption specific surface area is 20~80m2The carbon black of/g, more preferable 30~50m2The carbon black of/g. If the N2 adsorption specific surface area of carbon black is less than above-mentioned numberical range, the dispersion of carbon black is become inadequate, blank hardening, roller processing Property reduce.On the other hand, if the N2 adsorption specific surface area of carbon black is greater than above-mentioned numberical range, the green strength of blank is reduced, Roller processability reduces.The N2 adsorption specific surface area of carbon black can be measured according to JIS K 6217:1997.
In addition, preferably DBP (dibutyl phthalate) uptake is 50~160cm as carbon black3The carbon black of/100g, More preferably 100~150cm3The carbon black of/100g.DBP uptake becomes the index of the voidage between the aggregation of carbon black.If charcoal Black DBP uptake is in above-mentioned numberical range, then roller processability becomes good.The DBP uptake of carbon black can be according to JIS K 6217:1997 is measured.
(masterbatch)
The content of bis- (tert-butylperoxyiso-propyl) benzene of 1,3- in masterbatch is 10~30 mass %, preferably 20~30 matter Measure %.In addition, the content of the carbon black in masterbatch is 10~30 mass %, preferably 20~30 mass %.In masterbatch, 1,3- is bis- Ingredient other than (tert-butylperoxyiso-propyl) benzene and carbon black is substantially HNBR.Such masterbatch just contains 1,3- with high concentration Bis- (tert-butylperoxyiso-propyl) benzene.If the content of bis- (tert-butylperoxyiso-propyl) benzene of 1,3- and carbon black is in above-mentioned numberical range Interior, then mixing, roller excellent in workability can eliminate in being kneaded operation HNBR and fall off asking in such processing operation from roller Topic point.
Versatility is required for masterbatch, therefore as in addition to bis- (tert-butylperoxyiso-propyl) benzene of HNBR, 1,3- and charcoal Ingredient other than black can cooperate the additives such as processing aid.These additives are properly added as needed.
(manufacturing method of masterbatch)
Kneading device used in manufacture as masterbatch, in order to block the influence of atmosphere, it is preferable to use closed as far as possible The kneading device of formula.Kneading device can be intermittent, or continous way.As batch-type mixer device, there is pressurization to pinch Conjunction machine, Banbury, open roller etc..As continous way kneading device, have single screw extrusion machine, double screw extruder, Feeding extruder (Feeder-Ruder) etc..
Each ingredient can be kneaded 10 minutes or so to prepare by using above-mentioned kneading device by masterbatch.It is specific next It says, carries out in the following way: after HNBR polymer is plasticated, the bis- (tert-butyl peroxy isopropyls of 1,3- will be pre-mixed in advance Base) benzene and carbon black etc. 2~3 investments of mixture point, and be kneaded 10 minutes or so.
Obtained masterbatch by be measured with the organic peroxide amount considerable proportion needed for being crosslinked, and with HNBR and other ingredients mix and carry out melting mixing etc., obtain so as to the form as HNBR composition.In turn, may be used Thus to make by the way that obtained HNBR composition is carried out crosslinking forming using the molding condition that is crosslinked of the HNBR usually carried out At being cross-linked into shape product.
In the past, it when bis- (tert-butylperoxyiso-propyl) the benzene additions of 1,3- of powder are kneaded into HNBR by low melting point, deposits It is fallen off such problems from roller roller operation is very long, drug disperses that operating environment is caused to deteriorate, there are also HNBR.By using this The masterbatch of embodiment does not need the skilled of operator, can substantially shorten the activity duration.In turn, in being kneaded operation HNBR is eliminated from the roller such problems that falls off, and operating environment is improved, it can be ensured that safety work.
Embodiment
Hereinafter, by embodiment and comparative example, the present invention will be described, but these embodiments do not limit the present invention.
(masterbatch raw material)
HNBR: Nippon Zeon Zetpol 2000L, 3110,4310
HNBR:Lanxess corporation Therban AT LT2004VP
The bonding AN amount and Mooney viscosity of each HNBR is shown in table 1.
Bis- (tert-butylperoxyiso-propyl) benzene of 1,3-: Kayaku Akzo corporation Perkadox 14
Carbon black: Tokai Carbon corporation carbon black, SRF-HS (SEAST SVH), SRF (SEAST S), FEF (SEAST SO)、MAF(SEAST 116)
The N2 adsorption specific surface area and DBP uptake of each carbon black are shown in table 2.
Silica: Tosoh Silica corporation precipitated silica, Nipsil ER
[table 1]
[table 2]
(manufacture of masterbatch composition)
As the kneading machine of masterbatch manufacture, using kneader, (Nihon Spindle manufacturing company adding pressure type 3l is pinched Conjunction machine).
It is formed with what table 3 was recorded, after HNBR polymer is plasticated, being pre-mixed 1,3- in advance, bis- (t-butyl peroxy is different Propyl) benzene and reinforcing agent 3 investments of mixture point, with revolving speed 30rpm mixing 10 minutes.
Using obtained each masterbatch composition, the evaluation of the following terms purpose is carried out, the results are shown in table 3.
(kneader mixing)
Situation when for mixing based on kneader and after being kneaded, is evaluated from the viewpoint of following.
Zero: without special problem, mixing is good
△: electric power torque is low, is kneaded insufficient
×: mixing does not work, or cannot be kneaded, and especially becomes sand shape without with the shape of blank when kneader is discharged When formula concentrates in together, be × among worst state
(roller processability)
Each masterbatch composition is kneaded using 12 inch open formula rollers, is processed according to benchmark evaluation roller below Property.Here, arch camber refers to, the blank being rolled on roller floats from roller surface, and knife cannot be introduced into, without can be carried out showing for slice operation As.
Zero: processability is good
△: slightly arch camber (being difficult to wind)
×: arch camber is serious (cannot wind)
(the easy severing of blank)
Using each masterbatch composition, the sheet material blank of 5mm thickness is prepared.The sheet material blank of preparation is let cool 24 at room temperature After hour, with scissors severing.
Zero: being capable of easily severing
△: slightly hard but being capable of severing
×: it is difficult to severing firmly
[table 3]
By the evaluation result of table 3 it is found that the masterbatch composition of Examples 1 to 2 kneader mixing, roller processability and It is with good performance in the easy severing of blank.The bonding AN amount of the HNBR of the masterbatch composition of comparative example 1 is 25 mass %, Therefore mixing when kneader is kneaded becomes inadequate, and when being kneaded a little arch camber occurs for roller, in kneader mixing, roller processability With it is slightly worse in the easy severing of blank.The bonding AN amount of the HNBR of the masterbatch composition of comparative example 2 is 36 mass %, therefore is mediated Machine becomes spongy when being discharged, and is not wound up on roller, without can be carried out performance evaluation thereafter.The masterbatch of comparative example 3 combines For object since the content of carbon black is more, the bonding AN amount of HNBR is big, therefore becomes spongy when kneader discharge, and all properties are all poor.
The type of the carbon black of the masterbatch composition of comparative example 4~6 is different, but the content of carbon black is more, is kneaded in kneader It is poor in property, roller processability and certain performances of the easy severing of blank.Although the masterbatch composition of comparative example 7 uses silica As reinforcing agent, but blank viscosity becomes very high, and when being kneaded arch camber occurs for roller, also poor in the easy severing of blank.
The masterbatch composition of comparative example 8 is poor in roller processability since the content of carbon black is more.The mother of comparative example 9 For refining glue composition since the content of crosslinking agent is more, kneader becomes sand shape without concentrating on one in the form of blank when being discharged It rises, not can be carried out performance evaluation thereafter.

Claims (5)

1. a kind of hydrogenated nitrile-butadiene rubber organic peroxide masterbatch, which is characterized in that
Containing bis- (tert-butylperoxyiso-propyl) benzene of hydrogenated nitrile-butadiene rubber, 1,3- and carbon black,
The bonding acrylonitrile amount of the hydrogenated nitrile-butadiene rubber is less than 25 mass %,
The content of bis- (tert-butylperoxyiso-propyl) benzene of 1,3- is 10~30 mass %,
The content of the carbon black is 10~30 mass %.
2. hydrogenated nitrile-butadiene rubber according to claim 1 organic peroxide masterbatch, wherein
Mooney viscosity ML of the hydrogenated nitrile-butadiene rubber at 100 DEG C1+4It is 30~100.
3. according to claim 1 or hydrogenated nitrile-butadiene rubber as claimed in claim 2 organic peroxide masterbatch, feature exist In,
The N2 adsorption specific surface area of the carbon black is 20~80m2/ g, DBP uptake are 50~160cm3/100g。
4. a kind of hydrogenated nitrile rubber composition,
It is using hydrogenated nitrile-butadiene rubber described in any one of claims 1 to 33 made of organic peroxide masterbatch.
5. a kind of hydrogenated nitrile-butadiene rubber is crosslinked formed products,
It is will be made of hydrogenated nitrile rubber composition as claimed in claim 4 crosslinking forming.
CN201910128280.7A 2018-02-22 2019-02-21 Hydrogenated nitrile-butadiene rubber crosslinking agent masterbatch, hydrogenated nitrile rubber composition and hydrogenated nitrile-butadiene rubber are crosslinked formed products Pending CN110183691A (en)

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JP2018029421A JP7064901B2 (en) 2018-02-22 2018-02-22 Crosslinking agent for hydrided nitrile rubber Master batch, hydrided nitrile rubber composition and hydrided nitrile rubber crosslinked molded product

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CN112500588B (en) * 2020-12-08 2021-07-27 南京工业大学 Method for preparing high-fluidity carbon black master batch by peroxide in-situ degradation of polypropylene

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CN107108977A (en) * 2014-12-18 2017-08-29 Nok株式会社 Hydrogenated nitrile rubber composition and power drive system oil sealing

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Application publication date: 20190830