CN105732690A - Rubber reinforcing agent, preparation method thereof, and preparation method of butadiene styrene rubber - Google Patents
Rubber reinforcing agent, preparation method thereof, and preparation method of butadiene styrene rubber Download PDFInfo
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Abstract
The invention provides a rubber reinforcing agent, a preparation method thereof, and a preparation method of butadiene styrene rubber. In the invention, firstly the rubber reinforcing agent having excellent reaction activity with butadiene styrene rubber latex is synthesized in a manner of mixing an aromatic compound containing an alkene unsaturated substituent and an organic siloxane monomer containing an alkene unsaturated substituent, adding an olefin metathesis catalyst and performing a normal-temperature reaction in a methylbenzene solvent with air and water isolated, and removing the methylbenzene solvent through a vacuum desolventizer to prepare the rubber reinforcing agent. The high-strength butadiene styrene rubber is prepared by feeding the rubber reinforcing agent and the butadiene styrene rubber latex into a polymerization kettle according to ratio with addition of an initiator, and performing a reaction for a certain time with reaction temperature controlled, and coagulating, washing and drying the product.
Description
Technical field
The preparation method that the present invention relates to a kind of rubber reinforcing filler and preparation method thereof and butadiene-styrene rubber, specifically a kind of employing olefin metathesis catalyst prepares butadiene-styrene rubber reinforcing agent, and butylbenzene reinforcing agent and styrene-butadiene latex are carried out glycerol polymerization, the preparation method preparing high intensity butadiene-styrene rubber.
Background technology
Butadiene-styrene rubber rubbery intensity is relatively low, generally only has 2.3-6.5MPa, and the reinforcing agent mainly by post-treatment process that improves of its intensity is improved, generally up to 21.5-24.5MPa.In recent years, the in-situ reinforcement technology of rubber, nano-powder process for modifying surface etc. be widely used.200910092836.8 the method that silicon in-situ hybridization graft modification is containing poly-conjugated-diolefin latex, organosiloxane is incorporated into the unsaturated rubber system containing double bond, by the reaction between unsaturated bond, organosiloxane is grafted in rubber backbone, after siloxanes hydrolysis, plays the effect of reinforcement.The method needs siloxanes and the unsaturated double-bond generation chemical reaction on rubber molecule, need in latex, to add initiator, improve the conditions such as reaction temperature, easily caused by the side reaction such as cross-linking reaction, breakdown of emulsion, most importantly siloxanes and latex are difficult to be formed homogeneous system, and graft reaction is difficult to carry out.201010114230.2 the preparation method that in-situ hybridization strengthens butadiene-acrylonitrile-isoprene copolymer, adopt the mode of multi-component copolymer to be introduced directly in polymer by VTES, reach the purpose of in-situ reinforcement.The method polymerizable monomer composition is complicated, and monomer reactivity ratio differs greatly, and polymerization process is difficult to control to.
Summary of the invention
It is an object of the present invention to provide a kind of rubber reinforcing filler and preparation method thereof, the preparation method that the present invention also provides for butadiene-styrene rubber simultaneously.
The present invention provides a kind of rubber reinforcing filler, shown in formula (1),
Wherein, R1、R3For the siloxy containing the alkoxyl of 1～12 carbon, the aryloxy group of 6～12 carbon or 3～12 carbon；R2It is and R1Identical group or the saturated segment containing 1～20 carbon, or containing the cyclic alkane of 1～8 carbon, aromatic hydrocarbon；R5It is the saturated substituent group of the straight chain of-H or C1-C20 or ring-type, R5It is connected to and phenyl ring arbitrarily replaces position.
Present invention simultaneously provides a kind of rubber reinforcing filler preparation method, comprise the steps:
A. will the aromatic containing the unsaturated substituent group of alkene or alkynes shown in formula (2) and the organosiloxane monomer containing the unsaturated substituent group of alkene shown in formula (3) with 1:0.1～5.0 mixed in molar ratio,
Wherein, R1、R3For the siloxy containing the alkoxyl of 1～12 carbon, the aryloxy group of 6～12 carbon or 3～12 carbon；R2For with R1Identical group, or contain saturated segment or the cyclic alkane of 1～8 carbon, the aromatic hydrocarbon of 1～20 carbon；R4For the unsaturated olefin aliphatic segment containing 2～18 carbon；R5It is the saturated substituent group of the straight chain of-H or C1-C20 or ring-type, R5It is connected to and phenyl ring arbitrarily replaces position；R6It it is the saturated substituent group of the straight chain of-H or C1-C20 or ring-type；
B. the mixture toluene solvant that step A prepares is configured to the monomer solution of 1%～30% mass concentration；
C. add in the step B monomer solution prepared the amount accounting for monomeric substance 0.01～0.1% olefin metathesis catalyst, isolation air and water, after normal-temperature reaction 0.5～8h, adopt vacuum desolvation agent device to be deviate from by solvent, prepare rubber reinforcing filler.
The described aromatic containing the unsaturated substituent group of alkene or alkynes is styrene, propenylbenzene or methyl styrene.
Wherein, R1、R3For methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, hexyloxy, amoxy, positive heptan oxygen base, different octyloxy, positive ninth of the ten Heavenly Stems oxygen base, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group or trimethylsiloxy group.
Wherein, R2Selected from methyl, ethyl, methoxy or ethoxy
Wherein, R4For vinyl, acrylic, isopropenyl, isopentene group, 3-pentenyl, 6-octenyl, tetramethyl-ethylene base, 1-heptenyl, methacryloxypropyl or methacryloxy.
The described unsaturated substituent group containing alkene is VTES, vinyl diethoxy-ethylsilane, vinyltrimethoxy silane, vinyl two amoxys-hexyl silane or isopropenyl two n-butoxyethyl silane.
Described olefin metathesis catalyst is that dichloro (o-isopropoxy benzylidene) (tricyclohexyl phosphine) closes ruthenium (II)Or dichloro [o-isopropoxy benzylidene] [double; two (2,4,6-the trimethylphenyl)-2-imidazoline subunit of 1,3-] closes ruthenium
Described olefin metathesis catalyst isOr
The preparation method that the present invention also provides for a kind of butadiene-styrene rubber, comprise the following steps: by the styrene-butadiene latex that butt quality is 100 parts, the rubber reinforcing filler of 5～45 mass parts and the initiator of 0.01～0.1 mass parts join in polymeric kettle, controlling reaction temperature is 40～80 DEG C, reaction 3～10h, reacted emulsion, through condensing, wash, drying, obtains butadiene-styrene rubber product；
Described rubber reinforcing filler is above-mentioned rubber reinforcing filler.
Concrete, the present invention also can be stated as:
By styrene-butadiene latex (butt quality is 100 parts), the rubber reinforcing filler of 5～45 mass parts and the initiator of 0.01～0.1 mass parts join in polymeric kettle, controlling reaction temperature is 40～80 DEG C, reaction 3～10h, reacted emulsion, through condensing, wash, drying, obtains high intensity butadiene-styrene rubber product.
Rubber reinforcing filler of the present invention is represented by
Rubber reinforcing filler is by the aromatic containing the unsaturated substituent group of alkene or alkynesWith the organosiloxane monomer containing the unsaturated substituent group of alkene or alkynesPrepare through olefin metathesis reaction.
Concrete preparation method includes: the aromatic containing the unsaturated substituent group of alkene or alkynes and the organosiloxane monomer containing the unsaturated substituent group of alkene or alkynes are with 1 (0.1～5.0) mixed in molar ratio, the monomer solution of 1%～30% mass concentration it is configured to toluene solvant, in solution, addition accounts for the olefin metathesis catalyst of the 0.01～0.1% of the amount of monomeric substance, isolation air and water, after normal-temperature reaction 0.5～8h, adopt vacuum desolvation agent device to be deviate from by toluene solvant, prepare butadiene-styrene rubber reinforcing agent.
Aromatic containing the unsaturated substituent group of alkene or alkynes of the present inventionR in structural formula5Can be the saturated substituent group of the straight chain of-H or C1-C20 or ring-type, R5May be coupled to phenyl ring arbitrarily replaces position；R6It can be the saturated substituent group of the straight chain of-H or C1-C20 or ring-type；Aromatic containing the unsaturated substituent group of alkene or alkynes can be the aromatic of the different carbon chain lengths such as styrene, propenylbenzene, methyl styrene and the unsaturated substituent group of alkene, it is preferable that styrene.
Its structural formula of organosiloxane monomer containing the unsaturated substituent group of alkene or alkynes is:
Wherein:
R4-unsaturated olefin aliphatic segment containing 2～18 carbon, it can be vinyl, acrylic, isopropenyl, isopentene group, 3-pentenyl, 6-octenyl, tetramethyl-ethylene base, 1-heptenyl, methacryloxypropyl, methacryloxy, it is preferable that vinyl；
R1、R3-alkoxyl containing 1～12 carbon, the aryloxy group of 6～12 carbon, the siloxy of 3～12 carbon, can be methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, hexyloxy, amoxy, positive heptan oxygen base, different octyloxy, positive ninth of the ten Heavenly Stems oxygen base, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group, trimethylsiloxy group, preferred methoxyl group, ethyoxyl；R1And R3It is set as that the purpose containing alkoxyl is to add at butadiene-styrene rubber to make alkoxyl be hydrolyzed by the effect of heat and acid man-hour, thus forming-O-Si-spacial framework in rubbery system, thus base rubber is played strengthening action；If only one of which alkoxyl in organosiloxane monomer, then only form dimer after its hydrolysis, it is impossible to form-O-Si-spacial framework, do not have the effect of reinforcement.
R2Can be and R1Identical group, it is also possible to be the saturated segment containing 1～20 carbon, the cyclic alkane of 1～8, aromatic hydrocarbon；Preferred methyl, ethyl, methoxyl group, ethyoxyl.
Organosiloxane monomer containing the unsaturated substituent group of alkene or alkynes of the present invention can be VTES, vinyl diethoxy-ethylsilane, vinyltrimethoxy silane, vinyl two amoxys-hexyl silane, isopropenyl two n-butoxyethyl silane etc..
Olefin metathesis catalyst of the present invention is a kind of Ru carbene complex catalyst, it is possible to be that dichloro (o-isopropoxy benzylidene) (tricyclohexyl phosphine) closes ruthenium (II)Dichloro [o-isopropoxy benzylidene] [double; two (2,4,6-the trimethylphenyl)-2-imidazoline subunit of 1,3-] closes rutheniumEtc. there is the Grubbs catalyst series of identity function or other have the metal carbene catalyst of olefin metathesis function, it is preferable thatOr
" part " of being not specifically noted in the present invention each means mass parts.
Counting with styrene-butadiene latex butt quality for 100 parts, the reinforcing agent amount of being preferably added to is 5～45 parts, and the initiator amount of being preferably added to is 0.01～0.1 part.
Initiator of the present invention can adopt benzoyl peroxide ((PhCO2)2), dicumyl peroxide, di-isopropylbenzene hydroperoxide or potassium peroxydisulfate etc..
The know-why of foundation of the present invention is:
Formula (1)
As shown in above-mentioned chemical equation (1), containing the aromatic of the unsaturated substituent group of alkene or alkynes and the organosiloxane monomer generation olefin metathesis reaction containing the unsaturated substituent group of alkene or alkynes in the present invention, make under the secondary catalyst action of solvent Grubbs with styrene and VTES at toluene, olefin metathesis reaction occurs under room temperature, and the benzene substituted ethylene ethyl triethoxy silicane alkane of generation is butadiene-styrene rubber reinforcing agent.
Butadiene-styrene rubber reinforcing agent issues lactogenesis liquid graft polymerization reaction with styrene-butadiene latex in agent effects such as peroxide draw and generates Reinforcing Styrene-butadiene Rubber product.
This butadiene-styrene rubber makes reinforcement group hydrolyze to form the spacial framework of (-Si-O-Si-) by heating or acid condition in application process, thus rubber mass plays the effect of reinforcement.Simultaneously need to it is emphasized that the phenyl ring of this butadiene-styrene rubber reinforcing agent or aromatic structure and double bond form big conjugated system, make double bond be prone to participate in polyreaction, and reinforcing agent be also easier to because of similar compatibility graft reaction in rubber.The enhancement mode butadiene-styrene rubber of the present invention is compared with common designations butadiene-styrene rubber, and hot strength can improve more than 30%.
Detailed description of the invention
It is as described below that the present invention is embodied as required material auxiliary agent:
(1) containing the organosiloxane monomer of the unsaturated substituent group of alkene or alkynes: VTES, vinyl diethyl one Ethoxysilane, vinyl trimethoxy siloxanes, SILVER REAGENT, Shanghai Hui Pu siloxanes company limited；
(2) containing the aromatic of the unsaturated substituent group of alkene or alkynes: the aromatic of the different carbon chain lengths such as styrene, propenylbenzene, methyl styrene and the unsaturated substituent group of alkene, it is preferable that styrene.Technical grade, Lanzhou Petrochemical；
(3) olefin metathesis catalyst:WithRuthenium carbone catalyst, 500mg/ bottle, purity >=98%w, lark prestige Science and Technology Ltd.；
(4) styrene-butadiene latex SBR1500E, technical grade, Lanzhou Petrochemical；
(5) benzoyl peroxide ((PhCO2)2), dicumyl peroxide, di-isopropylbenzene hydroperoxide, potassium peroxydisulfate, technical grade, Lanzhou Petrochemical.
Reinforcing Styrene-butadiene Rubber Mechanics Performance Testing carries out according to GB/T528-2009.
Embodiment 1:
Styrene and VTES monomer, with 1:1 mixed in molar ratio, are configured to the monomer solution of 10% mass concentration with toluene solvant, add monomer 0.01%mol's in solutionCatalyst, isolation air and water, after 25 DEG C of reaction 2h, adopt vacuum desolvation agent device to be deviate from by toluene solvant, prepare butadiene-styrene rubber reinforcing agent.
By styrene-butadiene latex (butt quality is 100 parts), the above-mentioned rubber reinforcing filler of 5 mass parts and the potassium peroxydisulfate initiator of 0.01 mass parts join in polymeric kettle, controlling reaction temperature is 60 DEG C, reaction 3h, reacted emulsion, through condensing, wash, drying, obtains high intensity butadiene-styrene rubber product.After tested, compared with common butadiene-styrene rubber hot strength (18.6MPa), the enhancement mode butadiene-styrene rubber hot strength 25.3MPa of embodiment 1, improve 36.0%.
Comparative example 1:
This comparative example by butadiene-styrene rubber reinforcing agent directly and butadiene-styrene rubber mixing.Particularly as follows: styrene and VTES monomer are with 1:1 mixed in molar ratio, it is configured to the monomer solution of 10% mass concentration with toluene solvant, in solution, adds monomer 0.01%mol'sCatalyst, isolation air and water, after 25 DEG C of reaction 2h, adopt vacuum desolvation agent device to be deviate from by toluene solvant, prepare butadiene-styrene rubber reinforcing agent.
By direct to reinforcing agent and butadiene-styrene rubber mixing rear prepared sample, the addition of reinforcing agent is the 5% of butadiene-styrene rubber quality.After tested, compared with common butadiene-styrene rubber hot strength (18.6MPa), the enhancement mode butadiene-styrene rubber hot strength 20.8MPa of comparative example 1, only improves 11.8%.
Embodiment 2:
By styrene and vinyl diethoxymethylsilane monomer with 1:0.1 mixed in molar ratio, it is configured to the monomer solution of 30% mass concentration with toluene solvant, in solution, adds monomer 0.04%mol'sCatalyst, isolation air and water, after 25 DEG C of reaction 8h, adopt vacuum desolvation agent device to be deviate from by toluene solvant, prepare butadiene-styrene rubber reinforcing agent.
By styrene-butadiene latex (butt quality is 100 parts), the above-mentioned rubber reinforcing filler of 45 mass parts and the benzoyl peroxide initiator of 0.1 mass parts join in polymeric kettle, controlling reaction temperature is 40 DEG C, reaction 5h, reacted emulsion, through condensing, wash, drying, obtains high intensity butadiene-styrene rubber product.After tested, compared with common butadiene-styrene rubber hot strength (19.6MPa), the enhancement mode butadiene-styrene rubber hot strength 25.9MPa of embodiment 2, improve 32.1%.
Comparative example 2:
This comparative example replaces VTES and styrene to react with ethenylethoxy dimethylsilane.Particularly as follows: styrene and ethenylethoxy dimethylsilane monomer are with 1:0.1 mixed in molar ratio, it is configured to the monomer solution of 30% mass concentration with toluene solvant, in solution, adds monomer 0.04%mol'sCatalyst, isolation air and water, after 25 DEG C of reaction 8h, adopt vacuum desolvation agent device to be deviate from by toluene solvant, prepare butadiene-styrene rubber reinforcing agent.
By styrene-butadiene latex (butt quality is 100 parts), the above-mentioned rubber reinforcing filler of 45 mass parts and the benzoyl peroxide initiator of 0.1 mass parts join in polymeric kettle, controlling reaction temperature is 40 DEG C, reaction 5h, reacted emulsion, through condensing, wash, drying, obtains high intensity butadiene-styrene rubber product.After tested, compared with common butadiene-styrene rubber hot strength (17.9MPa), the enhancement mode butadiene-styrene rubber hot strength 18.4MPa of comparative example 2, intensity improves inconspicuous.
Embodiment 3:
By methyl styrene and vinyltrimethoxy silane monomer with 1:5 mixed in molar ratio, it is configured to the monomer solution of 1% mass concentration with toluene solvant, in solution, adds monomer 0.10%mol'sCatalyst, isolation air and water, after 25 DEG C of reaction 0.5h, adopt vacuum desolvation agent device to be deviate from by toluene solvant, prepare butadiene-styrene rubber reinforcing agent.
By styrene-butadiene latex (butt quality is 100 parts), the above-mentioned rubber reinforcing filler of 15 mass parts and the dicumyl peroxide initiator of 0.08 mass parts join in polymeric kettle, controlling reaction temperature is 65 DEG C, reaction 10h, reacted emulsion, through condensing, wash, drying, obtains high intensity butadiene-styrene rubber product.After tested, compared with common butadiene-styrene rubber hot strength (20.1MPa), the enhancement mode butadiene-styrene rubber hot strength 25.5MPa of embodiment 3, improve 26.8%.
Comparative example 3:
Compared with embodiment 3, other condition is identical, it is different in that employing butylene replaces styrene to react, particularly as follows: by butylene and vinyltrimethoxy silane monomer with 1:5 mixed in molar ratio, it is configured to the monomer solution of 1% mass concentration with toluene solvant, in solution, adds monomer 0.10%mol'sCatalyst, isolation air and water, after 25 DEG C of reaction 0.5h, adopt vacuum desolvation agent device to be deviate from by toluene solvant, prepare butadiene-styrene rubber reinforcing agent.
By styrene-butadiene latex (butt quality is 100 parts), the above-mentioned rubber reinforcing filler of 15 mass parts and the dicumyl peroxide initiator of 0.08 mass parts join in polymeric kettle, controlling reaction temperature is 65 DEG C, reaction 10h, after reacting, emulsion is through condensing, wash, drying, coacervation process finds a large amount of unreacted monomer, obtains a small amount of butadiene-styrene rubber product.After tested, compared with common butadiene-styrene rubber hot strength (17.9MPa), the enhancement mode butadiene-styrene rubber hot strength 18.5MPa of comparative example 3, it does not have significantly improve.
Embodiment 4:
By styrene and vinyl two amoxys-hexyl silane monomer with 1:1.9 mixed in molar ratio, it is configured to the monomer solution of 20% mass concentration with toluene solvant, in solution, adds monomer 0.03%mol'sCatalyst, isolation air and water, after 25 DEG C of reaction 4h, adopt vacuum desolvation agent device to be deviate from by toluene solvant, prepare butadiene-styrene rubber reinforcing agent.
By styrene-butadiene latex (butt quality is 100 parts), the above-mentioned rubber reinforcing filler of 25 mass parts and the di-isopropylbenzene hydroperoxide initiator of 0.06 mass parts join in polymeric kettle, controlling reaction temperature is 75 DEG C, reaction 8h, reacted emulsion, through condensing, wash, drying, obtains high intensity butadiene-styrene rubber product.After tested, compared with common butadiene-styrene rubber hot strength (19.1MPa), the enhancement mode butadiene-styrene rubber hot strength 26.2MPa of embodiment 4, improve 37.1%.
Comparative example 4:
Compared with embodiment 4, other condition is identical, it is different in that employing ethyl methyl benzene replaces styrene to react, particularly as follows: ethyl methyl benzene and vinyl trimethoxy siloxanyl monomers are with 1:1.9 mixed in molar ratio, it is configured to the monomer solution of 20% mass concentration with toluene solvant, in solution, adds monomer 0.1%mol'sCatalyst, isolation air and water, after 25 DEG C of reaction 4h, adopt vacuum desolvation agent device to be deviate from by toluene solvant, prepare butadiene-styrene rubber reinforcing agent.
By styrene-butadiene latex (butt quality is 100 parts), the above-mentioned rubber reinforcing filler of 25 mass parts and the di-isopropylbenzene hydroperoxide initiator of 0.06 mass parts join in polymeric kettle, controlling reaction temperature is 75 DEG C, reaction 8h, reacted emulsion, through condensing, wash, drying, obtains high intensity butadiene-styrene rubber product.After tested, compared with straight styrene-butadiene rubber hot strength (18.2MPa), the butadiene-styrene rubber hot strength 18.9MPa of comparative example 4, intensity does not significantly improve.
Embodiment 5:
By methyl styrene and vinyltrimethoxy silane monomer with 1:4.5 mixed in molar ratio, it is configured to the monomer solution of 2% mass concentration with toluene solvant, in solution, adds monomer 0.075%mol'sCatalyst, isolation air and water, after normal-temperature reaction 7.5h, adopt vacuum desolvation agent device to be deviate from by solvent, prepare butadiene-styrene rubber reinforcing agent.
By styrene-butadiene latex (butt quality is 100 parts), 21.5 the benzoyl peroxide initiator of the above-mentioned rubber reinforcing filler of mass parts and 0.1 part joins in polymeric kettle, controlling reaction temperature is 65 DEG C, reaction 8h, reacted emulsion, through condensing, wash, drying, obtains high intensity butadiene-styrene rubber product.After tested, compared with common butadiene-styrene rubber hot strength (19.0MPa), the enhancement mode butadiene-styrene rubber hot strength 27.1MPa of embodiment 5, improve 42.6%.
Comparative example 5:
Compared with embodiment 5, other condition is identical, it is different in that employing benzoyl substitutes benzoyl peroxide benzoyl, particularly as follows: by methyl styrene and vinyltrimethoxy silane monomer with 1:4.5 mixed in molar ratio, it is configured to the monomer solution of 2% mass concentration with toluene solvant, in solution, adds monomer 0.075%mol'sCatalyst, isolation air and water, after normal-temperature reaction 7.5h, adopt vacuum desolvation agent device to be deviate from by solvent, prepare butadiene-styrene rubber reinforcing agent.
By styrene-butadiene latex (butt quality is 100 parts), 21.5 the benzoyl peroxide initiator of the above-mentioned rubber reinforcing filler of mass parts and 0.1 part joins in polymeric kettle, controlling reaction temperature is 65 DEG C, reaction 8h, after reacting, emulsion is through condensing, wash, drying, obtain butadiene-styrene rubber product, during cohesion, have unreacted monomer to precipitate out.After tested, compared with common butadiene-styrene rubber hot strength (19.0MPa), the enhancement mode butadiene-styrene rubber hot strength 18.1MPa of comparative example 5, it does not have improve.
Embodiment 6:
By styrene and isopropenyl two n-butoxyethyl silane monomer with 1:3.5 mixed in molar ratio, it is configured to the monomer solution of 25% mass concentration with toluene solvant, in solution, adds monomer 0.05%mol'sCatalyst, isolation air and water, after normal-temperature reaction 5h, adopt vacuum desolvation agent device to be deviate from by toluene solvant, prepare butadiene-styrene rubber reinforcing agent.
By styrene-butadiene latex (butt quality is 100 parts), the above-mentioned rubber reinforcing filler of 18.5 mass parts, the di-isopropylbenzene hydroperoxide initiator of 0.07 part, controlling reaction temperature is 60 DEG C, reacts 8h.After reacting, emulsion is through condensing, wash, drying, and obtains high intensity butadiene-styrene rubber product.After tested, compared with common butadiene-styrene rubber hot strength (20.5MPa), the enhancement mode butadiene-styrene rubber hot strength 25.7MPa of embodiment 6, improve 25.3%.
Comparative example 6:
Compared with embodiment 6, other condition is identical, air and water is not completely cut off when being different in that and carry out metathesis reaction, particularly as follows: by styrene and isopropenyl two n-butoxyethyl silane monomer with 1:3.5 mixed in molar ratio, it is configured to the monomer solution of 25% mass concentration with toluene solvant, in solution, adds monomer 0.05%mol'sCatalyst, isolation air and water, after normal-temperature reaction 5h, adopt vacuum desolvation agent device to be deviate from by toluene solvant, prepare butadiene-styrene rubber reinforcing agent.
By styrene-butadiene latex (butt quality is 100 parts), the above-mentioned rubber reinforcing filler of 18.5 mass parts, the di-isopropylbenzene hydroperoxide initiator of 0.07 part, controlling reaction temperature is 60 DEG C, reacts 8h.After reacting, emulsion is through condensing, wash, drying, and obtains high intensity butadiene-styrene rubber product, has unreacted monomer to precipitate out during cohesion.After tested, compared with common butadiene-styrene rubber hot strength (20.5MPa), the enhancement mode butadiene-styrene rubber hot strength 19.3MPa of comparative example 6, intensity does not improve.
Claims (10)
1. a rubber reinforcing filler, shown in formula (1),
Wherein, R1、R3For the siloxy containing the alkoxyl of 1～12 carbon, the aryloxy group of 6～12 carbon or 3～12 carbon；R2It is and R1Identical group or the saturated segment containing 1～20 carbon, or containing the cyclic alkane of 1～8 carbon, aromatic hydrocarbon；R5It is the saturated substituent group of the straight chain of-H or C1-C20 or ring-type, R5It is connected to and phenyl ring arbitrarily replaces position.
2. a rubber reinforcing filler preparation method, it is the preparation method of the rubber reinforcing filler described in claim 1, comprises the steps:
A. will the aromatic containing the unsaturated substituent group of alkene or alkynes shown in formula (2) and the organosiloxane monomer containing the unsaturated substituent group of alkene shown in formula (3) with 1:0.1～5.0 mixed in molar ratio,
Wherein, R1、R3For the siloxy containing the alkoxyl of 1～12 carbon, the aryloxy group of 6～12 carbon or 3～12 carbon；R2For with R1Identical group, or contain saturated segment or the cyclic alkane of 1～8 carbon, the aromatic hydrocarbon of 1～20 carbon；R4For the unsaturated olefin aliphatic segment containing 2～18 carbon；R5It is the saturated substituent group of the straight chain of-H or C1-C20 or ring-type, R5It is connected to and phenyl ring arbitrarily replaces position；R6It it is the saturated substituent group of the straight chain of-H or C1-C20 or ring-type；
B. the mixture toluene solvant that step A prepares is configured to the monomer solution of 1%～30% mass concentration；
C. add in the step B monomer solution prepared the amount accounting for monomeric substance 0.01～0.1% olefin metathesis catalyst, isolation air and water, after normal-temperature reaction 0.5～8h, adopt vacuum desolvation agent device to be deviate from by solvent, prepare rubber reinforcing filler.
3. rubber reinforcing filler preparation method as claimed in claim 2, it is characterised in that the described aromatic containing the unsaturated substituent group of alkene or alkynes is styrene, propenylbenzene or methyl styrene.
4. rubber reinforcing filler preparation method as claimed in claim 2, it is characterised in that R1、R3For methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, hexyloxy, amoxy, positive heptan oxygen base, different octyloxy, positive ninth of the ten Heavenly Stems oxygen base, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group or trimethylsiloxy group.
5. rubber reinforcing filler preparation method as claimed in claim 2, it is characterised in that R2Selected from methyl, ethyl, methoxy or ethoxy.
6. rubber reinforcing filler preparation method as claimed in claim 2, it is characterised in that R4For vinyl, acrylic, isopropenyl, isopentene group, 3-pentenyl, 6-octenyl, tetramethyl-ethylene base, 1-heptenyl, methacryloxypropyl or methacryloxy.
7. rubber reinforcing filler preparation method as claimed in claim 2, it is characterized in that, the described unsaturated substituent group containing alkene is VTES, vinyl diethoxy-ethylsilane, vinyltrimethoxy silane, vinyl two amoxys-hexyl silane or isopropenyl two n-butoxyethyl silane.
8. rubber reinforcing filler preparation method as claimed in claim 2, it is characterised in that described olefin metathesis catalyst is that dichloro (o-isopropoxy benzylidene) (tricyclohexyl phosphine) closes ruthenium (II)Or dichloro [o-isopropoxy benzylidene] [double; two (2,4,6-the trimethylphenyl)-2-imidazoline subunit of 1,3-] closes ruthenium
9. rubber reinforcing filler preparation method as claimed in claim 2, it is characterised in that described olefin metathesis catalyst is
10. the preparation method of a butadiene-styrene rubber, it is characterized in that, comprise the following steps: by the styrene-butadiene latex that butt quality is 100 parts, the rubber reinforcing filler of 5～45 mass parts and the initiator of 0.01～0.1 mass parts join in polymeric kettle, controlling reaction temperature is 40～80 DEG C, reaction 3～10h, reacted emulsion, through condensing, wash, drying, obtains butadiene-styrene rubber product；
Described rubber reinforcing filler is the rubber reinforcing filler described in claim 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107841005A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | A kind of reinforced type nitrile rubber of easy processing and preparation method thereof |
| CN107840902A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | A kind of preparation method of nitrile rubber reinforced type plasticizer |
| CN107841008A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | A kind of easy processing reinforced type butadiene-styrene rubber and preparation method thereof |
| CN107840903A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | A kind of preparation method of butadiene-styrene rubber reinforced type softening agent |
| CN107841010A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | The preparation method of easy processing reinforced type butadiene-styrene rubber |
| CN107841007A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | The preparation method of easy processing reinforced type nitrile rubber |
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| CN103159866A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method of reinforced powdered rubber |
| CN104650291A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Method of preparing reinforced butadiene styrene rubber with olefin metathesis catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107841005A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | A kind of reinforced type nitrile rubber of easy processing and preparation method thereof |
| CN107840902A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | A kind of preparation method of nitrile rubber reinforced type plasticizer |
| CN107841008A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | A kind of easy processing reinforced type butadiene-styrene rubber and preparation method thereof |
| CN107840903A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | A kind of preparation method of butadiene-styrene rubber reinforced type softening agent |
| CN107841010A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | The preparation method of easy processing reinforced type butadiene-styrene rubber |
| CN107841007A (en) * | 2016-09-20 | 2018-03-27 | 中国石油天然气股份有限公司 | The preparation method of easy processing reinforced type nitrile rubber |
| CN107840903B (en) * | 2016-09-20 | 2020-08-07 | 中国石油天然气股份有限公司 | Preparation method of reinforced softener for styrene butadiene rubber |
| CN107841008B (en) * | 2016-09-20 | 2020-08-07 | 中国石油天然气股份有限公司 | Easily-processed reinforced styrene butadiene rubber and preparation method thereof |
| CN107841010B (en) * | 2016-09-20 | 2020-09-04 | 中国石油天然气股份有限公司 | Preparation method of easy-to-process reinforced styrene butadiene rubber |
| CN107840902B (en) * | 2016-09-20 | 2020-09-04 | 中国石油天然气股份有限公司 | Preparation method of reinforcing plasticizer for nitrile rubber |
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