CN105732689B - The preparation method of rubber reinforcing filler and preparation method thereof and reinforcement nitrile rubber - Google Patents
The preparation method of rubber reinforcing filler and preparation method thereof and reinforcement nitrile rubber Download PDFInfo
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Abstract
The present invention provides a kind of rubber reinforcing filler and preparation method thereof, and provides the preparation method of a kind of acrylonitrile, butadiene and the high-strength nitrile butadiene rubber of nitrile rubber reinforcing agent ternary polymerization.The present invention, which first has to a kind of synthesis and acrylonitrile, butadiene, has the active nitrile rubber reinforcing agent of sound response, the organosiloxane monomer mixing of the nitrile-based compound and the substituent group of unsaturation containing alkene of the substituent group of unsaturation containing alkene, with toluene solvant, olefin metathesis catalyst is added, completely cut off air and water, after normal-temperature reaction, solvent is deviate from using vacuum desolvation agent device, nitrile rubber reinforcing agent is made.Acrylonitrile, butadiene and above-mentioned nitrile rubber reinforcing agent are put in proportion into polymeric kettle, emulsifier, soft water, initiator, controlling reaction temperature and reaction pressure is added, after reacting a period of time, through cohesion, washing, drying, obtains high-strength nitrile butadiene rubber product.
Description
Technical field
The present invention relates to a kind of rubber reinforcing fillers and preparation method thereof, and provide a kind of acrylonitrile, butadiene and butyronitrile rubber
The preparation method of the high-strength nitrile butadiene rubber of glue reinforcing agent ternary polymerization.
Background technology
Emulsion polymerization nitrile rubber green strength is relatively low, and generally only 5.5 ± 0.5MPa, the raising of intensity is mainly by rear
The reinforcing agent of process is improved, general up to 21.5-24.5MPa.Reinforcing agent mainly has carbon black, white carbon, nano-sized carbon
The inorganic particles such as sour calcium and montmorillonite, reinforcement mechanism are special by the abundant surface texture of inorganic particle or its nano adsorption
Property, make to form physical absorption or chemical bond between rubber macromolecule and reinforcing agent, and then form the net centered on inorganic particle
Luo Hua mechanisms are to play the role of to reinforcing rubber.Inorganic particle than more serious, will realize the mixing of itself and rubber from reuniting
Higher energy is needed, is generally required and is carried out prolonged kneading repeatedly on open mill or mixer and be kneaded.
In recent years, the in-situ reinforcement technology of rubber, the process for modifying surface etc. of nano-powder are widely used.
The method of 200910092836.8 silicon in-situ hybridization graft modification latex containing poly-conjugated-diolefin, organosiloxane is introduced into and is contained
Organosiloxane, is grafted in rubber backbone, silicon by the unsaturated rubber system for having double bond by the reaction between unsaturated bond
Play the role of reinforcement after the hydrolysis of oxygen alkane.This method needs siloxanes that chemistry occurs instead with the unsaturated double-bond on rubber molecule
It answers, needs that initiator is added into latex, improves the conditions such as reaction temperature, easily cause the side reactions such as cross-linking reaction, demulsification.
A kind of 201010114230.2 preparation methods of in-situ hybridization enhancing butadiene-acrylonitrile-isoprene copolymer, use are polynary
Vinyltriethoxysilane is introduced directly into polymer by the mode of copolymerization, achievees the purpose that in-situ reinforcement.This method is poly-
It is complicated to close monomer component, monomer reactivity ratio differs greatly, and polymerization process is difficult to control.
Invention content
It is an object of the present invention to provide a kind of rubber reinforcing fillers and preparation method thereof, and provide a kind of acrylonitrile, butadiene and
The preparation method of the high-strength nitrile butadiene rubber of nitrile rubber reinforcing agent ternary polymerization.
The present invention provides a kind of rubber reinforcing filler, by shown in formula (1),
Wherein, R1、R3For the alkoxy containing 1~12 carbon, the silica of the aryloxy group of 6~12 carbon or 3~12 carbon
Base；R2For with R1Identical group, or the saturation segment containing 1~20 carbon or 1~8 cyclic alkane, aromatic hydrocarbon.
Present invention simultaneously provides a kind of rubber reinforcing filler preparation methods, include the following steps：
A. the nitrile-based compound of the substituent group of unsaturation containing alkene and the insatiable hunger containing alkene shown in formula (3) shown in formula (2)
Organosiloxane monomer with substituent group is with 1：0.1~5.0 molar ratio mixes,
Wherein, R1、R3For the alkoxy containing 1~12 carbon, the silica of the aryloxy group of 6~12 carbon or 3~12 carbon
Base；R2For with R1Identical group, or the saturation segment containing 1~20 carbon or 1~8 cyclic alkane, aromatic hydrocarbon；R4
For the unsaturated olefin aliphatic segment containing 2~18 carbon；R5It is the straight chain of H or C1-C20 or cricoid saturation substituent group；
B., mixture made from step A is configured to the monomer solution of 1%~30% mass concentration with toluene solvant；
C. 0.01~0.1% olefin metathesis of the amount for accounting for monomeric substance is added into monomer solution made from step B
Catalyst, completely cuts off air and water, after 0.5~8h of normal-temperature reaction, deviates from solvent using vacuum desolvation agent device, rubber is made and mends
Strong agent.
Wherein, the nitrile-based compound of the substituent group of unsaturation containing eneyne is acrylonitrile, butene nitrile, hexene nitrile, hexamethylene
Alkene nitrile or laurylene nitrile.
The nitrile-based compound of the substituent group of unsaturation containing eneyne is acrylonitrile.
Wherein, R1、R3For methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, hexyloxy, amoxy, positive heptan
Oxygroup, different octyloxy, positive nonyl epoxide, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group or trimethyl silica
Base.
Wherein, R4For vinyl, acrylic, isopropenyl, isopentene group, 3- pentenyls, 6- octenyls, tetramethyl-ethylene
Base, 1- heptenyls, methacryloxypropyl or methacryloxy.
The substituent group of unsaturation containing alkene is vinyltriethoxysilane, vinyl diethoxy-ethylsilane, second
Two n-butoxyethyl silane of alkenyl trimethoxy silane, two amoxys of vinyl-hexyl silane or isopropenyl.
The olefin metathesis catalyst is that dichloro (o- isopropoxy benzylidene) (tricyclohexyl phosphine) closes ruthenium
(II) or dichloro [o- isopropoxy benzylidene] [bis- (2,4,6- the trimethylphenyls) -2- imidazolines subunits of 1,3-] closes
Ruthenium.
The olefin metathesis catalyst is
The present invention also provides a kind of preparation methods of reinforcement nitrile rubber, include the following steps：By acrylonitrile, butadiene with
Rubber reinforcing filler is 5~45 according to quality proportioning：95~50：1~45 is added polymeric kettle, sequentially adds emulsifier, water and initiation
Agent, controlling reaction temperature are 3~80 DEG C, and reaction pressure is 1.5~2.5MPa, react 5~15h, lotion after reaction through cohesion,
Washing, drying, obtain nitrile rubber product；
The rubber reinforcing filler is above-mentioned rubber reinforcing filler.
Wherein, it is in terms of 100 parts by acrylonitrile and butadiene monomer gross mass, emulsifier addition is 1~10 part.
Wherein, it is in terms of 100 parts by acrylonitrile and butadiene monomer gross mass, the addition of water is 150~200 parts.
Wherein, it is in terms of 100 parts by acrylonitrile and butadiene monomer gross mass, initiator addition is 0.01~0.1 part.
Specifically, the present invention can be also stated as：
By acrylonitrile, butadiene and rubber reinforcing filler according to quality proportioning for ((95~50) ︰ (1~45) are added 5~45) ︰
Polymeric kettle sequentially adds emulsifier, water and initiator, and controlling reaction temperature is 3~80 DEG C, and reaction pressure is 1.5~2.5MPa,
5~15h is reacted, the lotion after reaction obtains high-strength nitrile butadiene rubber product through cohesion, washing, drying.
Rubber reinforcing filler of the present invention is represented by
Rubber reinforcing filler is by the nitrile-based compound of the substituent group of unsaturation containing eneyneWith insatiable hunger containing eneyne
With the organosiloxane monomer of substituent groupMade from olefin metathesis reaction.
Specifically preparation method includes：The nitrile-based compound of the substituent group of unsaturation containing alkene and the substituent group of unsaturation containing alkene it is organic
Siloxanyl monomers are mixed with 1 ︰ (0.1~5.0) molar ratio, and the monomer that 1%~30% mass concentration is configured to toluene solvant is molten
0.01~0.1% olefin metathesis catalyst of the amount for accounting for monomeric substance is added into solution for liquid, completely cuts off air and water, often
After 0.5~8h of temperature reaction, solvent is deviate from using vacuum desolvation agent device, nitrile rubber reinforcing agent is made.
R in the nitrile-based compound structural formula of the substituent group of unsaturation containing eneyne of the present invention5Can be-H or C1-C20
Straight chain or cricoid saturation substituent group；The nitrile-based compound of the substituent group of unsaturation containing eneyne can be acrylonitrile, butene nitrile, oneself
The nitrile-based compound of the different carbon chain lengths such as alkene nitrile, cyclohexene nitrile, laurylene nitrile and alkene unsaturation substituent group, preferably acrylonitrile.
Its structural formula of the organosiloxane monomer of the substituent group of unsaturation containing alkene is：
Wherein：
R4Unsaturated olefin aliphatic segment containing 2~18 carbon, can be vinyl, acrylic, isopropenyl,
Isopentene group, 3- pentenyls, 6- octenyls, tetramethyl-ethylene base, 1- heptenyls, methacryloxypropyl, metering system
Acyloxy, preferred vinyl；
R1、R3Alkoxy containing 1~12 carbon, the aryloxy group of 6~12 carbon, the siloxy of 3~12 carbon can be with
It is methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, hexyloxy, amoxy, positive oxygroup in heptan, different octyloxy, positive nonyl
Oxygroup, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group, trimethylsiloxy group, preferably methoxyl group, ethyoxyl；
R1And R3It is so that alkoxy is hydrolyzed by the effect of heat and acid when nitrile rubber is processed to be set as the purpose containing alkoxy, from
And formation-O-Si- the spacial frameworks in rubbery system, to play strengthening action to base rubber；If organic silica
Only there are one alkoxies in alkane monomer, then only form dimer after hydrolysis, cannot form-O-Si- spacial frameworks, rise
Less than the effect of reinforcement.
R2Can be and R1Identical group, can also be the saturation segment containing 1~20 carbon, 1~8 cyclic alkane,
Aromatic hydrocarbon；It is preferred that methyl, ethyl, methoxyl group, ethyoxyl.
The organosiloxane monomer of the substituent group of unsaturation containing alkene of the present invention can be vinyltriethoxysilane,
Vinyl diethoxy-ethylsilane, vinyltrimethoxysilane, two amoxys of vinyl-hexyl silane, isopropenyl two
N-butoxyethyl silane etc..
Olefin metathesis catalyst of the present invention is a kind of Ru carbene complex catalyst, can be that dichloro is (o-
Isopropoxy benzylidene) (tricyclohexyl phosphine) conjunction ruthenium (II)Dichloro [o- isopropoxy benzene methylene
Base] [bis- (2,4,6- the trimethylphenyls) -2- imidazolines subunits of 1,3-] conjunction rutheniumDeng with identity function
Grubbs catalyst series or other metal carbene catalysts with olefin metathesis function, preferably
" part " being not specifically noted in the present invention each means mass parts.
The emulsifier and initiator being added in the present invention are auxiliary agent generally in the art, be may be used commonly used in the art
Type；Its addition be also well known to those skilled in the art react according to butadiene and styrene monomer it is required normal
Dosage is advised, therefore, the present invention does not do particular determination.It is in terms of 100 parts by acrylonitrile and butadiene monomer gross mass, emulsifier is preferred
Addition is 1~10 part, and the initiator amount of being preferably added to is 0.01~0.1 part, and the amount of being preferably added to of water is 150~200 parts.
Emulsifier of the present invention may be used lauryl sodium sulfate, benzene sulfonic acid sodium salt, sodium soap, aliphatic acid potassium,
The anionic emulsifier such as sodium abietate, potassium oleate.
Benzoyl peroxide ((PhCO may be used in initiator of the present invention2)2), dicumyl peroxide, hydrogen peroxide
Diisopropylbenzene (DIPB) or potassium peroxydisulfate etc..
The technical principle of foundation of the present invention is：
As shown in above-mentioned chemical equation (1) and formula (2), the itrile group chemical combination of the substituent group of unsaturation containing alkene in the present invention
Olefin metathesis reaction occurs for the organosiloxane monomer of object and the substituent group of unsaturation containing alkene, with three ethoxy of acrylonitrile and vinyl
Olefin metathesis reaction reaction occurs in the case where chloroform makees solvent Grubbs bis- generations catalyst actions, under room temperature for base silane, generation
Itrile group vinyltriethoxysilane is nitrile rubber reinforcing agent.Nitrile rubber reinforcing agent is with acrylonitrile, butadiene in peroxidating
The effect of object initiator issues raw emulsion terpolymer reaction and generates reinforcement nitrile rubber product.
The nitrile rubber makes reinforcement group hydrolyze to form (- Si-O-Si-) by heating or acid condition in application process
Spacial framework, to playing the role of reinforcement to rubber mass.Simultaneously it is emphasized that the nitrile rubber reinforcing agent
Itrile group and double bond form big conjugated system, make double bond be easy to participate in the polymerisation of nitrile rubber, and reinforcing agent is in rubber
It is also more easily evenly dispersed because of similar compatibility in glue.The enhanced nitrile rubber and common designations nitrile rubber phase of the present invention
Than tensile strength can be improved 30% or more.
Specific implementation mode
Material auxiliary agent needed for present invention specific implementation is as described below：
(1) vinyltriethoxysilane, vinyl diethylethoxysilane, vinyl trimethoxy siloxanes, examination
Agent grade, Shanghai Hui Pu siloxanes Co., Ltd；
(2) acrylonitrile, butene nitrile, hexene nitrile, cyclohexene nitrile, laurylene nitrile, technical grade, Lanzhou Petrochemical；
(3) olefin metathesis catalyst：With ruthenium carbone catalyst, 500mg/ bottles, purity >=98%w, lark prestige science and technology has
Limit company；
(4) acrylonitrile monemer, divinylic monomer, technical grade, Lanzhou Petrochemical；
(5) lauryl sodium sulfate, benzene sulfonic acid sodium salt, sodium soap, aliphatic acid potassium, sodium abietate, potassium oleate, technical grade,
Lanzhou Petrochemical；
(6) benzoyl peroxide ((PhCO2)2), dicumyl peroxide, di-isopropylbenzene hydroperoxide, potassium peroxydisulfate, industry
Grade, Lanzhou Petrochemical.
The test of reinforcement Mechanical Properties of Rubber is carried out according to GB/T 528-2009.
Embodiment 1：
Acrylonitrile and vinyltriethoxysilane monomer are with 1:1 molar ratio mixes, and 10% matter is configured to toluene solvant
Monomer 0.05%mol is added into solution for the monomer solution for measuring concentrationCatalyst, isolation air and
Water after normal-temperature reaction 2h, is deviate from toluene solvant using vacuum desolvation agent device, and nitrile rubber reinforcing agent is made.
Acrylonitrile, butadiene and above-mentioned nitrile rubber reinforcing agent are put into according to the ratio that quality proportioning is 28/70/2 and gathered
Kettle is closed, the sodium soap emulsifier for accounting for 5 parts of monomer gross mass, 180 parts of soft water and 0.05 part of cumyl hydroperoxide is added
Initiator, controlling reaction temperature are 5 DEG C, reaction pressure 2.0MPa, react 8h.Will reaction after lotion through cohesion, washing, do
It is dry, obtain high-strength nitrile butadiene rubber product.After tested, compared with common butyronitrile Green tensile strength (18.6MPa), embodiment 1
Enhanced butyronitrile Green tensile strength 25.3MPa, improve 36.0%.
Comparative example 1：
Nitrile rubber reinforcing agent is directly kneaded with nitrile rubber by this comparative example.Specially：Three second of acrylonitrile and vinyl
Oxysilane monomer is with 1:1 molar ratio mixes, and the monomer solution of 10% mass concentration is configured to toluene solvant, adds into solution
Enter monomer 0.05%mol'sCatalyst, completely cuts off air and water, after normal-temperature reaction 2h, using vacuum desolvation
Agent device deviates from solvent, and nitrile rubber reinforcing agent is made.
Sample is made after reinforcing agent and nitrile rubber are directly kneaded, the addition of reinforcing agent is the 5 of nitrile rubber quality
Part.After tested, compared with common butyronitrile Green tensile strength (18.6MPa), the enhanced butyronitrile Green tensile strength of comparative example 1
20.8MPa only improves 11.8%.
Embodiment 2：
By butene nitrile and vinyl diethoxymethylsilane monomer with 1:0.1 molar ratio mixes, and is configured with toluene solvant
At the monomer solution of 30% mass concentration, it is added monomer 0.1%mol's into solutionCatalyst completely cuts off air
And water, after normal-temperature reaction 8h, solvent is deviate from using vacuum desolvation agent device, nitrile rubber reinforcing agent is made.
Butene nitrile, butadiene and above-mentioned nitrile rubber reinforcing agent are put into according to the ratio that quality proportioning is 15/70/15 and gathered
Kettle is closed, the potassium rosinate emulsifier of 10 parts of monomer mass, 200 parts of soft water, 0.01 part of potassium peroxydisulfate initiator, control is added
Reaction temperature is 80 DEG C, reaction pressure 2.5Mpa, reacts 8h.Lotion obtains high-strength through cohesion, washing, drying after reacting
Spend nitrile rubber product.After tested, compared with common butyronitrile Green tensile strength (19.6MPa), the enhanced butyronitrile of embodiment 2
Green tensile strength 25.9MPa, improves 32.1%.
Comparative example 2：
This comparative example replaces vinyltriethoxysilane to be carried out instead with acrylonitrile with vinyl oxethyl dimethylsilane
It answers, an ethyoxyl can not be crosslinked reinforcement.Specially：Butene nitrile and vinyl oxethyl dimethylsilane monomer are with 1:0.1 rubs
You are configured to the monomer solution of 30% mass concentration with toluene solvant than mixing, are added monomer 0.1%mol's into solutionCatalyst, completely cuts off air and water, after normal-temperature reaction 8h, deviates from solvent using vacuum desolvation agent device, is made
Nitrile rubber reinforcing agent.
Butene nitrile, butadiene and above-mentioned nitrile rubber reinforcing agent are put into according to the ratio that quality proportioning is 15/70/15 and gathered
Kettle is closed, the potassium rosinate emulsifier of 10 parts of monomer mass, 200 parts of soft water, 0.01% part of potassium peroxydisulfate initiator, control is added
Reaction temperature processed is 80 DEG C, reaction pressure 2.5Mpa, reacts 8h.Lotion obtains height through cohesion, washing, drying after reacting
Intensity nitrile rubber product.After tested, compared with common butyronitrile Green tensile strength (17.9MPa), the enhanced fourth of comparative example 2
Nitrile Green tensile strength 18.4MPa, intensity improve unobvious.
Embodiment 3：
By acrylonitrile and vinyltrimethoxysilane monomer with 1:5 molar ratios mix, and 1% matter is configured to toluene solvant
The monomer solution for measuring concentration is added monomer 0.10%mol's into solutionCatalyst completely cuts off air and water,
After normal-temperature reaction 0.5h, toluene solvant is deviate from using vacuum desolvation agent device, nitrile rubber reinforcing agent is made.
Acrylonitrile, butadiene and above-mentioned nitrile rubber reinforcing agent are put into according to the ratio that quality proportioning is 5/50/45 and gathered
Kettle is closed, the potassium rosinate emulsifier of 3 parts of monomer mass, 190 parts of soft water is added, 0.07 part of di-isopropylbenzene hydroperoxide causes
Agent, controlling reaction temperature are 6 DEG C, reaction pressure 2.5Mpa, react 8h.Lotion is obtained through cohesion, washing, drying after reacting
To high-strength nitrile butadiene rubber product.After tested, compared with common butyronitrile Green tensile strength (20.1MPa), the enhancing of embodiment 3
Type butyronitrile Green tensile strength 25.5MPa, improves 26.8%.
Comparative example 3：
Compared with Example 3, other conditions are identical, the difference is that it is anti-to carry out double decomposition using butenes instead of propylene nitrile
It answers, specially：By butylene and vinyltrimethoxysilane monomer with 1:5 molar ratios mix, and 1% matter is configured to toluene solvant
The monomer solution for measuring concentration is added monomer 0.10%mol's into solutionCatalyst completely cuts off air and water,
After normal-temperature reaction 0.5h, toluene solvant is deviate from using vacuum desolvation agent device, nitrile rubber reinforcing agent is made.
Acrylonitrile, butadiene and above-mentioned nitrile rubber reinforcing agent are put into according to the ratio that quality proportioning is 5/50/45 and gathered
Kettle is closed, the potassium rosinate emulsifier of 3 parts of monomer mass, 190 parts of soft water is added, 0.07 part of di-isopropylbenzene hydroperoxide causes
Agent, controlling reaction temperature are 6 DEG C, reaction pressure 2.5Mpa, react 8h.Lotion is coagulated through cohesion, washing, drying after reacting
A large amount of unreacted reinforcement monomers are found in collecting process, obtain a small amount of nitrile rubber product.After tested, it is drawn with common butyronitrile raw rubber
It stretches intensity (17.9MPa) to compare, the enhanced butyronitrile Green tensile strength 18.5MPa of comparative example 3 is not significantly improved.
Embodiment 4：
By two amoxys of acrylonitrile and vinyl-hexyl silane monomer with 1:1.9 molar ratios mix, and are configured with toluene solvant
At the monomer solution of 20% mass concentration, it is added monomer 0.03%mol's into solutionCatalyst, isolation are empty
Gas and water after normal-temperature reaction 4h, are deviate from solvent using vacuum desolvation agent device, and nitrile rubber reinforcing agent is made.
Acrylonitrile, butadiene and above-mentioned nitrile rubber reinforcing agent are put into polymerization according to the ratio that quality proportioning is 8/90/2
The sodium soap emulsifier of 1 part of monomer mass, 150 parts of soft water, 0.01 part of benzoyl peroxide initiator, control is added in kettle
Reaction temperature processed is 3 DEG C, reaction pressure 1.5Mpa, reacts 15h.Lotion obtains height through cohesion, washing, drying after reacting
Intensity nitrile rubber product.After tested, compared with common butyronitrile Green tensile strength (19.1MPa), the enhanced fourth of embodiment 4
Nitrile Green tensile strength 26.2MPa, improves 37.1%.
Comparative example 4：
Compared with Example 4, other conditions are identical, the difference is that replacing acrylonitrile to carry out subdivision using itrile group propane
Solution reaction, specially：Itrile group propane and vinyl trimethoxy siloxanyl monomers are with 1:1.9 molar ratios mix, and use toluene solvant
It is configured to the monomer solution of 20% mass concentration, is added monomer 0.1%mol's into solutionCatalyst, isolation
Air and water after normal-temperature reaction 4h, are deviate from solvent using vacuum desolvation agent device, and nitrile rubber reinforcing agent is made.
Reinforcing agent is calculated into addition with 15% part of nitrile rubber quality, sample is made after being directly kneaded with nitrile rubber
Product.After tested, compared with common nitrile rubber tensile strength (18.2MPa), the nitrile rubber tensile strength 18.9MPa of comparative example 4, by force
Degree does not significantly improve.
Embodiment 5：
By hexene nitrile and vinyltrimethoxysilane monomer with 1:4.5 molar ratios mix, and 2% is configured to toluene solvant
The monomer solution of mass concentration is added monomer 0.07%mol's into solutionCatalyst completely cuts off air and water,
After normal-temperature reaction 8h, solvent is deviate from using vacuum desolvation agent device, nitrile rubber reinforcing agent is made.
Acrylonitrile, butadiene and above-mentioned nitrile rubber reinforcing agent are put into according to the ratio that quality proportioning is 8.5/90/1.5
Polymeric kettle, is added the sodium soap emulsifier of 10 parts of monomer mass, 150 parts of soft water, and 0.1 part of benzoyl peroxide causes
Agent, controlling reaction temperature are 10 DEG C, reaction pressure 1.5Mpa, react 15h.Will after reaction lotion through cohesion, washing, drying,
Obtain high-strength nitrile butadiene rubber product.After tested, compared with common butyronitrile Green tensile strength (19.0MPa), the increasing of embodiment 5
Strong type butyronitrile Green tensile strength 27.1MPa, improves 42.6%.
Comparative example 5：
Compared with Example 5, other conditions are identical, the difference is that benzoyl peroxide benzoyl is substituted using benzoyl,
Specially：By hexene nitrile and vinyltrimethoxysilane monomer with 1:4.5 molar ratios mix, and 2% is configured to toluene solvant
The monomer solution of mass concentration is added monomer 0.07%mol's into solutionCatalyst completely cuts off air and water,
After normal-temperature reaction 8h, solvent is deviate from using vacuum desolvation agent device, nitrile rubber reinforcing agent is made.
Acrylonitrile, butadiene and above-mentioned nitrile rubber reinforcing agent are put into according to the ratio that quality proportioning is 8.5/90/1.5
The sodium soap emulsifier of 10 parts of monomer mass, 150 parts of soft water, 0.1 part of benzoyl initiator, control is added in polymeric kettle
Reaction temperature is 10 DEG C, reaction pressure 1.5Mpa, reacts 15h.Polymerisation does not cause, and cannot obtain nitrile rubber production
Product.
Embodiment 6：
By laurylene nitrile and two n-butoxyethyl silane monomer of isopropenyl with 1:3.5 molar ratios mix, molten with toluene
Agent is configured to the monomer solution of 25% mass concentration, is added monomer 0.05%mol's into solutionCatalyst,
Completely cut off air and water, after normal-temperature reaction 5h, toluene solvant is deviate from using vacuum desolvation agent device, nitrile rubber reinforcement is made
Agent.
Acrylonitrile, butadiene and above-mentioned nitrile rubber reinforcing agent are put into according to the ratio that quality proportioning is 5/50/45 and gathered
Kettle is closed, the potassium rosinate emulsifier of 5 parts of monomer mass, 190 parts of soft water is added, 0.07 part of di-isopropylbenzene hydroperoxide causes
Agent, controlling reaction temperature are 7 DEG C, reaction pressure 2.0Mpa, react 8h.Lotion is obtained through cohesion, washing, drying after reacting
To high-strength nitrile butadiene rubber product.After tested, compared with common butyronitrile Green tensile strength (20.5MPa), the enhancing of embodiment 6
Type butyronitrile Green tensile strength 25.7MPa, improves 25.3%.
Comparative example 6：
Compared with Example 6, other conditions are identical, the difference is that carry out metathesis reaction when do not completely cut off air and
Water, specially：By laurylene nitrile and two n-butoxyethyl silane monomer of isopropenyl with 1:3.5 molar ratios mix, and use toluene
Solvent is configured to the monomer solution of 25% mass concentration, and monomer 0.05%mol is added into solutionCatalysis
Agent under open condition, after normal-temperature reaction 5h, is deviate from toluene solvant using vacuum desolvation agent device, and nitrile rubber reinforcement is made
Agent.
Acrylonitrile, butadiene and above-mentioned nitrile rubber reinforcing agent are put into according to the ratio that quality proportioning is 5/50/45 and gathered
Kettle is closed, the potassium rosinate emulsifier of 5 parts of monomer mass, 190 parts of soft water is added, 0.07 part of di-isopropylbenzene hydroperoxide causes
Agent, controlling reaction temperature are 7 DEG C, reaction pressure 2.0Mpa, react 8h.Lotion is obtained through cohesion, washing, drying after reacting
To high-strength nitrile butadiene rubber product.After tested, compared with common butyronitrile Green tensile strength (20.5MPa), the enhancing of comparative example 6
Type butyronitrile Green tensile strength 19.3MPa, intensity do not improve.
Claims (13)
1. a kind of rubber reinforcing filler, by shown in formula (1),
Wherein, R1、R3For the alkoxy containing 1~12 carbon；R2For the saturation segment containing 1~20 carbon.
2. a kind of rubber reinforcing filler preparation method, is the preparation method of rubber reinforcing filler described in claim 1, including as follows
Step：
A. the nitrile-based compound of the substituent group of unsaturation containing alkene shown in formula (2) and the unsaturation containing alkene shown in formula (3) are taken
The organosiloxane monomer of Dai Ji is with 1：0.1~5.0 molar ratio mixes,
Wherein, R1、R3For the alkoxy containing 1~12 carbon；R2For the saturation segment containing 1~20 carbon；R4To contain 2~8
The unsaturated olefin aliphatic segment of a carbon；R5It is the straight chain saturation substituent group of H or C1-C20；
B., mixture made from step A is configured to the monomer solution of 1%~30% mass concentration with toluene solvant；
C. 0.01~0.1% olefin metathesis catalysis for the amount for accounting for monomeric substance is added into monomer solution made from step B
Agent, completely cuts off air and water, after 0.5~8h of normal-temperature reaction, deviates from solvent using vacuum desolvation agent device, reinforcing rubber is made
Agent.
3. rubber reinforcing filler preparation method as claimed in claim 2, which is characterized in that the substituent group of unsaturation containing alkene
Nitrile-based compound is acrylonitrile, butene nitrile, hexene nitrile or laurylene nitrile.
4. rubber reinforcing filler preparation method as claimed in claim 3, which is characterized in that the substituent group of unsaturation containing alkene
Nitrile-based compound is acrylonitrile.
5. rubber reinforcing filler preparation method as claimed in claim 2, which is characterized in that R1、R3For methoxyl group, ethyoxyl, the third oxygen
Base, isopropoxy, n-butoxy, hexyloxy, amoxy, positive oxygroup in heptan, different octyloxy, positive nonyl epoxide.
6. rubber reinforcing filler preparation method as claimed in claim 2, which is characterized in that R4For vinyl, acrylic, isopropyl alkene
Base, isopentene group, 3- pentenyls, 6- octenyls, 1- heptenyls.
7. rubber reinforcing filler preparation method as claimed in claim 2, which is characterized in that the substituent group of unsaturation containing alkene
Organosiloxane monomer is vinyltriethoxysilane, vinyl diethoxy-ethylsilane, vinyl trimethoxy silicon
Two n-butoxyethyl silane of alkane, two amoxys of vinyl-hexyl silane or isopropenyl.
8. rubber reinforcing filler preparation method as claimed in claim 2, which is characterized in that the olefin metathesis catalyst is
Dichloro (o- isopropoxy benzylidene) (tricyclohexyl phosphine) closes ruthenium (II) or dichloro [o- isopropoxy benzene methylene
Base] [bis- (2,4,6- the trimethylphenyls) -2- imidazolines subunits of 1,3-] conjunction ruthenium.
9. rubber reinforcing filler preparation method as claimed in claim 2, which is characterized in that the olefin metathesis catalyst is
10. a kind of preparation method of reinforcement nitrile rubber, which is characterized in that include the following steps：By acrylonitrile, butadiene and rubber
Glue reinforcing agent is 5~45 according to quality proportioning：95~50：1~45 is added polymeric kettle, sequentially adds emulsifier, water and initiator,
Controlling reaction temperature is 3~80 DEG C, and reaction pressure is 1.5~2.5MPa, reacts 5~15h, the lotion after reaction is through agglomerating, washing
It washs, dry, obtain nitrile rubber product；
The rubber reinforcing filler is rubber reinforcing filler described in claim 1.
11. the preparation method of reinforcement nitrile rubber as claimed in claim 10, which is characterized in that with acrylonitrile and butadiene list
Body gross mass is 100 parts of meters, and emulsifier addition is 1~10 part.
12. the preparation method of reinforcement nitrile rubber as claimed in claim 10, which is characterized in that with acrylonitrile and butadiene list
Body gross mass is 100 parts of meters, and the addition of water is 150~200 parts.
13. the preparation method of reinforcement nitrile rubber as claimed in claim 10, which is characterized in that with acrylonitrile and butadiene list
Body gross mass is 100 parts of meters, and initiator addition is 0.01~0.1 part.
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| CN102167780A (en) * | 2010-02-25 | 2011-08-31 | 中国石油天然气股份有限公司 | Preparation method of in-situ hybrid reinforced butadiene-acrylonitrile-isoprene copolymer |
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| CN102167780A (en) * | 2010-02-25 | 2011-08-31 | 中国石油天然气股份有限公司 | Preparation method of in-situ hybrid reinforced butadiene-acrylonitrile-isoprene copolymer |
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