CN107841010A - The preparation method of easy processing reinforced type butadiene-styrene rubber - Google Patents
The preparation method of easy processing reinforced type butadiene-styrene rubber Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
- C08L9/08—Latex
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08C19/00—Chemical modification of rubber
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
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Abstract
The invention provides the method for easy processing reinforced type butadiene-styrene rubber, butadiene-styrene rubber is dissolved in solvent is configured to solution first, adds olefin metathesis catalyst and coke preventing type rubber reinforcing filler, reacted glue are deviate from through solvent, obtain reinforced type softening agent；The softening agent is distributed into water body under emulsifying agent effect to be formed in emulsion, the emulsion mix with styrene-butadiene latex after through condensing, washing, drying, the reinforced type butadiene-styrene rubber product of obtained easy processing.The softening agent product can reduce by 0.2 2.5 units of basic glue Mooney/part, improve more than intensity 0.15MPa/ parts, the 15s/ parts of scorch-delaying time 1.
Description
Technical field
The present invention relates to a kind of preparation method of butadiene-styrene rubber, specifically a kind of butadiene-styrene rubber of the reinforced type of easy processing
Preparation method.
Background technology
SBR of emulsion polymerization crude rubber Mooney viscosity is generally 40-130ML1+4 100℃, elastomeric compound Mooney typically requires low
In 90ML1+4 100℃；Green strength is relatively low, typically only 5.5 ± 0.5MPa, the benefit of the raising of its intensity mainly by post-processing process
Strong agent is improved, general up to 21.5-24.5MPa.Reinforcing agent mainly has carbon black, white carbon, nano-calcium carbonate and covered de-
The inorganic particles such as soil, for inorganic particle from reuniting than more serious, to realize the mixing of itself and rubber needs higher energy, typically needs
Prolonged kneading repeatedly is carried out in mill or banbury and is kneaded.In mill or banburying process, it is typically necessary and adds
Enter a certain amount of softening agent.Typically kind can make sizing material have the lower-molecular substance of certain flexibility, and they can increase sizing material
Plasticity, mobility, adherence, in order to the technological operation such as die mould and shaping.And contribute to powdered compounding ingredient scattered and
Melting temperature is reduced, improves the machinability of rubber.
Most commonly used softening agent is petroleum line softener in rubber processing, and CN201410018005.7 provides a kind of moisture-resistant
Sliding RX and preparation technology, softening agent include the raw material of following parts by weight：Naphthenic oil：70-90 parts, alkenes compound tree
Fat：10-30 parts, alchlor：0.1-1.0 parts.Anti-slippery RX has had environment-friendly aromatic oil concurrently and environmentally friendly naphthenic oil is each
The advantages of item performance, there is good wet-sliding resistant performance, relatively low rolling resistance, good anti-wear performance.
CN201110345185.6 discloses a kind of RX and preparation method thereof, is made up of the raw material of following portions by weight：
10%-30% pitches, 90%-70% naphthenic oils；The RX of the asphalt modification, product is nontoxic, less than European Union's safety post
Standard, the blank of domestic production is filled up, greatlyd save the cost of domestic tyre production enterprise.This kind of softening agent of patent report
Actually physics plasticizer, mainly including aromatic naphtha, paraffin oil, naphthenic oil, heavy oil, paraffin, vaseline, pitch, oil tree
Fat etc., this kind of softening agent only have the effect for filling softening to rubber, without reinforcing effect, and easily sent out during product use
It is raw to separate out.
The Mooney scorch time of butadiene-styrene rubber can weigh the difficulty or ease that sizing material produces incipient scorch, and time of scorch is longer, then processes
Process is more not susceptible to the phenomenon of prevulcanization.Time of scorch can generally be determined by mooney's viscosimeter, be Mooney viscosity
Torque reaches the time needed for 10%, is represented with T10, and the T10 of butadiene-styrene rubber is 2-3min under standard testing formula.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of easy processing reinforced type butadiene-styrene rubber, concretely comprise the following steps：
1) reinforced type softening agent is prepared first, and butadiene-styrene rubber is dissolved in solvent and prepares 1%w-50%w, preferably 5%
W~15%w solution, in terms of 100 mass parts rubber, the alkene of 0.1-1.0 parts, preferably 0.1-0.3 parts is added into solution
Metathesis catalyst and 1-50 parts, preferably 10-30 parts coke preventing type rubber reinforcing filler, at 15-50 DEG C, preferably 20-30 DEG C every
Exhausted air and water, react 0.5-5 hours, preferably 1-2 hours, reacted glue is deviate from through solvent, and it is 3000- to obtain Mn
The reinforced type softening agent product of 100000 scopes；Described coke preventing type rubber reinforcing filler is to pass through alkene by antiscorching agent and reinforcing agent
Metathesis reaction is made, and described antiscorching agent is the nitroso compound, organic acid or thio Asia of the substituent of unsaturation containing alkene
Amide-type thing；Described reinforcing agent is the organic silane compound of the substituent of unsaturation containing alkene.
2) obtained reinforced type softening agent product is added and mixed with emulsifying agent, water, softening agent emulsion is made in stirring；
3) styrene-butadiene latex and softening agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning：(1~50) is entered
Row mixing is made into mixing latex, optimum ratio 100：(10~30), in the case where reaction temperature is 10 DEG C~80 DEG C, add flocculating agent
Cohesion, scrubbed, centrifugal dehydration, drying, easy processing reinforced type butadiene-styrene rubber is made.
The specific preparation method of coke preventing type rubber reinforcing filler of the present invention includes：Antiscorching agent and reinforcing agent are with 1：(0.1~
5.0) mixed in molar ratio, the solution of 1%~30% mass concentration is configured to solvent, is added into solution and account for antiscorching agent and reinforcement
0.01~0.1% olefin metathesis catalyst of the amount of agent total material, completely cuts off air and water, after 0.5~8h of normal-temperature reaction, adopts
Solvent is deviate from vacuum desolvation agent device, coke preventing type rubber reinforcing filler is made.
Described antiscorching agent is the nitroso compound or organic acid or thio sub- amide-type of the substituent of unsaturation containing alkene
Thing, can be N- nitrosos two (vinyl benzene) amine, N- nitrosos-styryl-beta-naphthylamine, N- nitroso -2- acrylic -2,
4- dimethyl -1,2- EEDQ polymer, vinyl benzoic acid, vinyl salicylic acid, cyclobutenyl salicylic acid, vinyl neighbour's benzene
Dioctyl phthalate, N- vinyl cyclohexyls thiophthalimide or N- acrylic cyclohexylthiophthalimides etc.；
Solvent of the present invention is preferably the solvent that can dissolve butadiene-styrene rubber that alkene is free of in structure；Selected from hexane,
Hexamethylene, toluene, ethylbenzene etc..
For the organic silane compound of the substituent of unsaturation containing alkene, its structural formula is reinforcing agent of the present invention：
Wherein：
R4- unsaturated olefin aliphatic the segment containing 2~18 carbon, can be vinyl, acrylic, isopropenyl,
Isopentene group, 3- pentenyls, 6- octenyls, trimethyl-ethylene base, 1- heptenyls, methacryloxypropyl, metering system
Acyloxy, preferred vinyl；
R1、R3- the alkoxy containing 1~12 carbon, the aryloxy group of 6~12 carbon, the siloxy of 3~12 carbon can be with
Be methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, positive hexyloxy, n-pentyloxy, positive epoxide in heptan, different octyloxy,
Positive nonyl epoxide, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, trimethylsiloxy group, preferably methoxyl group, ethyoxyl；R1And R3
It is to hydrolyze alkoxy by the effect of heat and acid when butadiene-styrene rubber is processed to be set as the purpose containing alkoxy, so as in rubber
Formation-O-Si- spacial frameworks in colloid system, so as to play strengthening action to base rubber；If in organosilan only
One alkoxy, it then only forms dimer after hydrolyzing, it is impossible to forms-O-Si- spacial frameworks, does not have the work of reinforcement
With.
R2Can be and R1Identical group, the saturation segment containing 1~20 carbon is can also be, containing 3~8 carbon
Cycloalkyl or the aromatic radical containing 6~8 carbon；It is preferred that methyl, ethyl, methoxyl group, ethyoxyl.
Reinforcing agent of the present invention can be VTES, vinyl diethoxy-ethylsilane, second
Alkenyl trimethoxy silane, two amoxys of vinyl-hexyl silane, the n-butoxyethyl silane of isopropenyl two 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 (IIDichloro [o- isopropoxy benzylidene]
[double (2,4,6- the trimethylphenyls) -2- imidazolines subunits of 1,3-] close rutheniumUrged Deng the Grubbs series with identity function
Agent or other there is the metal carbene catalyst of olefin metathesis function, preferably
The present invention does not do particular determination to the species and dosage of used emulsifying agent and flocculating agent, and use is commonly used in the art
Auxiliary agent and dosage.Emulsifying agent can be the anion such as saturated or unsaturated fatty acid soaps, RA rosin acid as mentioned
Type emulsifying agent；Its dosage can be that 0.1~20 part, preferably 0.5~10 part is added in 100 parts of reinforced type softening agent products.
The present invention does not have particular/special requirement to the addition of described softening agent emulsion configuration process reclaimed water yet, as long as can make
Material forms emulsion state, and the addition of water is preferably 50~500 parts of water of addition in 100 parts of reinforced type softening agent products.
The present invention is not particularly limited to the temperature of described softening agent emulsion configuration process, as long as under agitation being capable of shape
It can be preferably 10-80 DEG C into emulsion, such as temperature.
Flocculating agent of the present invention can be CaCl2、MgSO4、MgCl2、Al2(SO4)3、FeCl3、CuCl2、Ca
(HSO4)2Deng soluble metal salt and its mixture.Its dosage is preferably to add 1~25 mass parts in 100 parts of styrene-butadiene latexes to coagulate
Poly- agent, preferably 5~15 parts.
" part " being not specifically noted in the present invention each means mass parts.
The technical principle of foundation of the present invention is：
N ＞ m in formula
Above-mentioned chemical equation (1) is antiscorching agent and VTES as reinforcement using vinyl benzoic acid
Agent carries out olefin metathesis reaction and coke preventing type rubber reinforcing filler is made；Formula (2) is that butadiene-styrene rubber is made in olefin metathesis catalyst
Reduced with lower molecular weight, while the coke preventing type rubber reinforcing filler generated with formula (1) reacts and reinforcement base is introduced in side base
Group and anti-scorch group.
The softening agent is butadiene-styrene rubber and the product of coke preventing type rubber reinforcing filler agent metathesis reaction, is had with butadiene-styrene rubber
Similar composition, because its low molecule amount plays emollescence to rubber.Operation oil is used in usual rubber processing formula as softening
Agent, and the small molecule auxiliary agent such as reinforcing agent agent, antiscorching agent is added, the auxiliary agent is easily adsorbed onto surface by carbon black and lowers its effect effect
Fruit.Antiscorching agent, reinforcing agent and softening agent are chemically bonded by this programme, can effective reinforcement, and prevent the incipient scorch of rubber.
Easy processing reinforced type butadiene-styrene rubber prepared by the present invention, after tested, basic glue Mooney 0.2-2.5 units/part is reduced,
Improve more than intensity 0.15MPa/ parts, scorch-delaying time 1-15s/ parts.
Embodiment
Material auxiliary agent needed for present invention specific implementation is as described below：
(1) styrene butadiene rubber sbr 1500, SBR1712, technical grade, Lanzhou Petrochemical；
(2) VTES, vinyl ethyl diethoxy silane, vinyltrimethoxy silane, reagent
Level, Shanghai Hui Pu siloxanes Co., Ltd；
(3) olefin metathesis catalyst：Ruthenium carbone catalyst, 500mg/
Bottle, purity >=98%w, lark prestige Science and Technology Ltd.；
(4) hexane, hexamethylene, toluene, ethylbenzene, technical grade, Lanzhou Petrochemical；
(5) sodium soap, sodium abietate, aliphatic acid potassium, potassium rosinate, technical grade, Lanzhou Petrochemical；
(6)CaCl2、MgSO4、MgCl2、Al2(SO4)3, technical grade, Lanzhou Petrochemical；
(7) 2- vinyl benzoic acids, 3- vinylphthalic acids, SILVER REAGENT, Gansu Yin Cheng auxiliary agents company；
Softening agent emulsion is kneaded with styrene-butadiene latex liquid phase, test crude rubber Mooney viscosity, time of scorch and rubber mechanical property
Energy；Mooney viscosity of rubber and time of scorch are tested according to GB/T 1232.1-2000, and rubber mechanical property is according to GB/T 528-
2009 tests, RX molecular weight are tested using GPC.
Embodiment 1：
By antiscorching agent 2- vinyl benzoic acids and reinforcing agent VTES with 1.0：5.0 mixed in molar ratio,
The solution of 30% mass concentration is configured to hexane solvent, the amount for accounting for antiscorching agent and reinforcing agent total material is added into solution
0.1% olefin metathesis catalystCompletely cut off air and water, after normal-temperature reaction 8h, using vacuum desolvation
Agent device deviates from solvent, and anti-scorch rubber reinforcing filler 1-1 is made.
Styrene butadiene rubber sbr 1500 is dissolved in the solution that 1.5%w is prepared in hexane solvent, in terms of 100 mass parts rubber,
Add 0.13 part of olefin metathesis catalystWith 1.9 parts of coke preventing type rubber reinforcing filler 1-1,15.5
DEG C isolation air and water, reacts 0.53 hour, reacted glue is deviate from through solvent, obtains the reinforced type that Mn is 88000 and softens
Agent product；
By the obtained mass parts of reinforced type softening agent product 100 and 0.15 mass parts emulsifying agent sodium soap, 55 mass parts
Desalted water adds emulsifier, and it is 75 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the proportion by weight according to butt is 100：10 are carried out
Mixing is made into mixing latex, in the case where reaction temperature is 78 DEG C, adds 20 mass parts flocculating agent CaCl2Cohesion, scrubbed, centrifugation take off
Water, drying, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 48 by 52, and tensile strength brings up to 26.8MPa by 25.3MPa, time of scorch by
125s brings up to 189s.
Comparative example 1：
Compared with Example 1, other conditions are identical, and difference is to be not added with coke preventing type reinforcing agent, are specially：By butylbenzene
Rubber SBR1500 is dissolved in the solution that 1.5%w is prepared in hexane solvent, in terms of 100 mass parts rubber, adds 0.13 part of alkene
Hydrocarbon metathesis catalystCompletely cut off air and water at 15.5 DEG C, react 0.53 hour, reacted glue
Liquid is deviate from through solvent, obtains the reinforced type softening agent product that Mn is 98000；
Obtained 100 parts of reinforced type softening agent product is added into breast with 0.15 part of emulsifying agent sodium soap, 55 parts of desalted waters
Change device, it is 75 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the proportion by weight according to butt is 100：10 are carried out
Mixing is made into mixing latex, in the case where reaction temperature is 78 DEG C, adds 20 mass parts flocculating agent CaCl2Cohesion, scrubbed, centrifugation take off
Water, drying, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 50 by 52, tensile strength 25.2MPa, does not improve, time of scorch is as short as
90s。
Embodiment 2：
By antiscorching agent 3- vinylphthalic acids and reinforcing agent vinyl diethoxymethylsilane with 1.0：0.1 mole
Than mixing, the solution of 1% mass concentration is configured to hexane solvent, is added into solution and accounts for antiscorching agent and reinforcing agent total material
0.01% olefin metathesis catalyst of amount, completely cuts off air and water, will using vacuum desolvation agent device after normal-temperature reaction 0.5h
Solvent is deviate from, and anti-scorch rubber reinforcing filler 2-1 is made.
Styrene butadiene rubber sbr 1500 is dissolved in the solution that 10%w is prepared in toluene solvant, in terms of 100 mass parts rubber, added
Enter 0.98 part of olefin metathesis catalystWith 48 parts of coke preventing type rubber reinforcing filler 2-1,48.9
DEG C isolation air and water, reacts 4.5 hours, reacted glue is deviate from through solvent, obtains the reinforced type softening agent that Mn is 3200
Product；
Obtained 100 parts of reinforced type softening agent product is added and emulsified with 19 parts of emulsifying agent sodium soaps, 490 parts of desalted waters
Device, it is 50 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the proportion by weight according to butt is 100：50 are carried out
Mixing is made into mixing latex, in the case where reaction temperature is 55 DEG C, adds 20 mass parts flocculating agent MgSO4Cohesion, scrubbed, centrifugation take off
Water, drying, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 32 by 52, and tensile strength brings up to 32.9MPa by 25.3MPa, time of scorch by
125s brings up to 143s.
Comparative example 2：
Compared with Example 2, other conditions are identical, and difference is to be not added with olefin metathesis catalyst, are specially：Will
Antiscorching agent 3- vinylphthalic acids and reinforcing agent vinyl diethoxymethylsilane are with 1.0：0.1 mixed in molar ratio, use
Hexane solvent is configured to the solution of 1% mass concentration, completely cuts off air and water, after normal-temperature reaction 0.5h, is filled using vacuum desolvation agent
Put and deviate from solvent, anti-scorch rubber reinforcing filler 2-2 is made.Styrene butadiene rubber sbr 1500 is dissolved in toluene solvant and prepares 10%w
Solution, in terms of 100 mass parts rubber, add 48 parts of coke preventing type rubber reinforcing filler 2-2, completely cut off air and water at 48.9 DEG C, instead
Answer 4.5 hours, reacted glue is deviate from through solvent, obtains the reinforced type softening agent product that Mn is 170000；
Obtained 100 parts of reinforced type softening agent product is added and emulsified with 19 parts of emulsifying agent sodium soaps, 490 parts of desalted waters
Device, it is 50 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the quality proportioning according to butt is 100：50 are mixed
Conjunction is made into mixing latex, in the case where reaction temperature is 55 DEG C, adds 20 mass parts flocculating agent MgSO4Cohesion, scrubbed, centrifugation take off
Water, drying, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity 52, do not reduce, tensile strength brings up to 26.5MPa, time of scorch by 25.3MPa
129s is brought up to by 125s.
Embodiment 3：
By antiscorching agent 3- vinylphthalic acids and reinforcing agent vinyltrimethoxy silane with 1.0：4.0 mol ratios are mixed
Close, the solution of 10% mass concentration is configured to hexane solvent, the amount for accounting for antiscorching agent and reinforcing agent total material is added into solution
0.09% olefin metathesis catalystCompletely cut off air and water, after normal-temperature reaction 4.5h, using vacuum desolvation
Agent device deviates from solvent, and anti-scorch rubber reinforcing filler 3-1 is made.
Styrene butadiene rubber sbr 1712 is dissolved in the solution that 25%w is prepared in cyclohexane solvent, in terms of 100 mass parts rubber,
Add 0.4 part of olefin metathesis catalystWith 25 parts of coke preventing type rubber reinforcing filler 3-1, completely cut off air at 25 DEG C
And water, react 2.5 hours, reacted glue is deviate from through solvent, obtains the reinforced type softening agent product that Mn is 58000；
Obtained 100 parts of reinforced type softening agent product is added and emulsified with 10 parts of emulsifying agent sodium abietates, 250 parts of desalted waters
Device, it is 40 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the proportion by weight according to butt is 100：25 are carried out
Mixing is made into mixing latex, in the case where reaction temperature is 55 DEG C, adds 20 mass parts flocculating agent MgSO4Cohesion, scrubbed, centrifugation take off
Water, drying, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 90 by 120, and tensile strength brings up to 27.5MPa, time of scorch by 26.3MPa
212s is brought up to by 125s.
Comparative example 3：
Compared with Example 3, other conditions are identical, difference be using aromatic naphtha be used as softening agent, specially：Will
100 parts of the aromatic naphtha softening agent adds emulsifier with 10 parts of sodium abietate emulsifying agents, 250 parts of desalted waters, and it is 40 DEG C to control temperature,
Stirring, is made softening agent emulsion；
Latex and softening agent emulsion are added into condensing field, the proportion by weight according to butt is 100：25, which carry out mixing, matches somebody with somebody
Into mixing latex, in the case where reaction temperature is 55 DEG C, 20 mass parts flocculating agent MgSO are added4Cohesion, scrubbed, centrifugal dehydration, do
It is dry, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 80 by 120, and tensile strength is reduced to 23.5MPa, time of scorch by 26.3MPa
For 130s.
Embodiment 4：
By antiscorching agent 2- vinyl benzoic acids and reinforcing agent vinyl two amoxys-hexyl silane with 1.0：3.0 mol ratio
Mixing, the solution of 15% mass concentration is configured to hexane solvent, is added into solution and account for antiscorching agent and reinforcing agent total material
0.029% olefin metathesis catalyst of amountCompletely cut off air and water, after normal-temperature reaction 4.8h, using vacuum
Desolventizing apparatus deviates from solvent, and anti-scorch rubber reinforcing filler 4-1 is made.
Styrene butadiene rubber sbr 1712 is dissolved in the solution that 45%w is prepared in ethyl benzene solvent, in terms of 100 mass parts rubber, added
Enter 0.5 part of olefin metathesis catalystWith 1.1 parts of coke preventing type rubber reinforcing filler 4-1, completely cut off air at 15 DEG C
And water, react 4.9 hours, reacted glue is deviate from through solvent, obtains the reinforced type softening agent product that Mn is 40000；
Obtained 100 parts of reinforced type softening agent product is added and emulsified with 18 parts of emulsifying agent potassium rosinates, 450 parts of desalted waters
Device, it is 60 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the proportion by weight according to butt is 100：40 are carried out
Mixing is made into mixing latex, in the case where reaction temperature is 30 DEG C, adds 15 mass parts flocculating agent Al2(SO4)3Cohesion, it is scrubbed, from
Heart dehydration, dry, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 55 by 120, and tensile strength brings up to 27.9MPa, time of scorch by 26.3MPa
194s is brought up to by 125s.
Comparative example 4：
Compared with Example 4, other conditions are identical, and difference is to use reinforcing agent vinyl amoxy-dihexyl
Silane, only containing a siloxanes, it is specially：By antiscorching agent 2- vinyl benzoic acids and reinforcing agent vinyl amoxy-two oneself
Base silane is with 1.0：3.0 mixed in molar ratio, the solution of 15% mass concentration is configured to hexane solvent, into solution add account for it is anti-
0.029% olefin metathesis catalyst of the amount of burnt agent and reinforcing agent total material, completely cut off air and water, normal-temperature reaction 4.8h
Afterwards, solvent is deviate from using vacuum desolvation agent device, anti-scorch rubber reinforcing filler 4-2 is made.
Styrene butadiene rubber sbr 1712 is dissolved in the solution that 45%w is prepared in ethyl benzene solvent, in terms of 100 mass parts rubber, added
Enter 0.5 part of olefin metathesis catalystWith 1.1 parts of coke preventing type rubber reinforcing filler 4-2, completely cut off air at 15 DEG C
And water, react 4.9 hours, reacted glue is deviate from through solvent, obtains the reinforced type softening agent product that Mn is 58000；
Obtained 100 parts of reinforced type softening agent product is added and emulsified with 18 parts of emulsifying agent potassium rosinates, 450 parts of desalted waters
Device, it is 60 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the proportion by weight according to butt is 100：40 are carried out
Mixing is made into mixing latex, in the case where reaction temperature is 30 DEG C, adds 15 mass parts flocculating agent Al2(SO4)3Cohesion, it is scrubbed, from
Heart dehydration, dry, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 78 by 120, and tensile strength brings up to 26.4MPa by 26.3MPa, without obvious
Change, time of scorch bring up to 196s by 125s.
Embodiment 5：
By antiscorching agent 2- vinyl benzoic acids and reinforcing agent vinyl ethyl diethoxy silane with 1.0：3.7 mol ratios are mixed
Close, the solution of 19% mass concentration is configured to hexane solvent, the amount for accounting for antiscorching agent and reinforcing agent total material is added into solution
0.05% olefin metathesis catalystCompletely cut off air and water, after normal-temperature reaction 7h, using vacuum
Desolventizing apparatus deviates from solvent, and anti-scorch rubber reinforcing filler 5-1 is made.
Styrene butadiene rubber sbr 1500 is dissolved in the solution that 37.5%w is prepared in hexane solvent, in terms of 100 mass parts rubber,
Add 0.18 part of olefin metathesis catalystWith 12 parts of coke preventing type rubber reinforcing filler 5-1,35 DEG C every
Exhausted air and water, react 4 hours, and reacted glue is deviate from through solvent, obtain the reinforced type softening agent product that Mn is 91000；
Obtained 100 parts of reinforced type softening agent product is added into breast with 0.5 part of emulsifying agent aliphatic acid potassium, 400 parts of desalted waters
Change device, it is 15 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the proportion by weight according to butt is 100：6.8 carry out
Mixing is made into mixing latex, in the case where reaction temperature is 12 DEG C, adds 1.5 mass parts flocculating agent Al2(SO4)3Cohesion, it is scrubbed, from
Heart dehydration, dry, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 45 by 52, and tensile strength brings up to 28.4MPa by 25.3MPa, time of scorch by
125s brings up to 174s.
Comparative example 5：
Compared with Example 5, other conditions are identical, and difference is to be kneaded work in liquid phase using reinforcing agent and antiscorching agent
Added in sequence, be specially：Styrene butadiene rubber sbr 1500 is dissolved in the solution that 37.5%w is prepared in hexane solvent, with 100 mass
Part rubber meter, add 0.18 part of olefin metathesis catalystCompletely cut off air and water, reaction 4 at 35 DEG C
Hour, reacted glue is deviate from through solvent, obtains the reinforced type softening agent product that Mn is 101000；
By obtained 100 parts and 12 parts rubber reinforcing filler vinyl ethyl diethoxy silanes of reinforced type softening agent product and
12 parts of antiscorching agent 2- vinyl benzoic acids and 0.5 part of emulsifying agent aliphatic acid potassium, 400 parts of desalted waters add emulsifier, control temperature
For 15 DEG C, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the proportion by weight according to butt is 100：6.8 carry out
Mixing is made into mixing latex, in the case where reaction temperature is 12 DEG C, adds 1.5 mass parts flocculating agent Al2(SO4)3Cohesion, it is scrubbed, from
Heart dehydration, dry, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 50 by 52, and tensile strength brings up to 25.8MPa by 25.3MPa, and intensity slightly carries
Height, time of scorch bring up to 134s by 125s.
Embodiment 6：
By antiscorching agent 2- vinyl benzoic acids and reinforcing agent vinyl ethyl diethoxy silane with 1.0：4.5 mol ratios are mixed
Close, the solution of 25% mass concentration is configured to hexane solvent, the amount for accounting for antiscorching agent and reinforcing agent total material is added into solution
0.06% olefin metathesis catalystCompletely cut off air and water, after normal-temperature reaction 4h, using vacuum
Desolventizing apparatus deviates from solvent, and anti-scorch rubber reinforcing filler 6-1 is made.
Styrene butadiene rubber sbr 1500 is dissolved in the solution that 20%w is prepared in cyclohexane solvent, in terms of 100 mass parts rubber,
Add 0.9 part of olefin metathesis catalystWith 38 parts of coke preventing type rubber reinforcing filler 6-1,28 DEG C every
Exhausted air and water, react 3.2 hours, and reacted glue is deviate from through solvent, obtain the reinforced type softening agent product that Mn is 6000；
Obtained 100 parts of reinforced type softening agent product is added into breast with 0.2 part of emulsifying agent aliphatic acid potassium, 443 parts of desalted waters
Change device, it is 78 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the proportion by weight according to butt is 100：1.3 carry out
Mixing is made into mixing latex, in the case where reaction temperature is 35 DEG C, adds 5.5 mass parts flocculating agent Al2(SO4)3Cohesion, it is scrubbed, from
Heart dehydration, dry, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 49.5 by 52, and tensile strength brings up to 25.9MPa, time of scorch by 25.3MPa
184s is brought up to by 125s.
Comparative example 6：
Compared with Example 6, other conditions are identical, and difference is to add simultaneously as softening agent using aromatic naphtha
Reinforcing agent and antiscorching agent, it is specially：By 100 parts of the aromatic naphtha softening agent and 0.2 part of emulsifying agent aliphatic acid potassium, 443 parts of desalted waters
Be 38 parts of rubber reinforcing filler vinyl ethyl diethoxy silanes and 1 part of antiscorching agent 2- vinyl benzene relative to aromatic hydrocarbons oil quality
Formic acid, emulsifier is added, it is 78 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion are added into condensing field, the proportion by weight according to butt is 100：1.3 are mixed
Mixing latex is made into, reaction temperature is 35 DEG C, adds the cohesion of 5.5 mass parts flocculating agents, scrubbed, centrifugal dehydration, drying, is made
The high intensity butadiene-styrene rubber of easy processing.
After tested, Mooney viscosity is reduced to 49 by 52, and tensile strength does not improve, and time of scorch is brought up to by 125s
274s。
Embodiment 7：
By antiscorching agent 2- vinyl benzoic acids and reinforcing agent vinyl ethyl diethoxy silane with 1.0：4.5 mol ratios are mixed
Close, the solution of 25% mass concentration is configured to hexane solvent, the amount for accounting for antiscorching agent and reinforcing agent total material is added into solution
0.06% olefin metathesis catalystCompletely cut off air and water, after normal-temperature reaction 4h, using vacuum desolvation agent
Device deviates from solvent, and coke preventing type rubber reinforcing filler 7-1 is made.
Styrene butadiene rubber sbr 1500 is dissolved in the solution that 18%w is prepared in cyclohexane solvent, in terms of 100 mass parts rubber,
Add 0.95 part of olefin metathesis catalystIt is empty in 48 DEG C of isolations with 43 parts of coke preventing type rubber reinforcing filler 7-1
Gas and water, react 3.5 hours, reacted glue is deviate from through solvent, obtains the reinforced type softening agent product that Mn is 5500；
Obtained 100 parts of reinforced type softening agent product is added into breast with 0.29 part of emulsifying agent aliphatic acid potassium, 98 parts of desalted waters
Change device, it is 63 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the proportion by weight according to butt is 100：33 are carried out
Mixing is made into mixing latex, in the case where reaction temperature is 55 DEG C, adds 21 mass parts flocculating agent Ca (HSO4)2Cohesion, it is scrubbed, from
Heart dehydration, dry, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 39 by 52, and tensile strength brings up to 32.9MPa by 25.3MPa, time of scorch by
125s brings up to 194s.
Comparative example 7：
Compared with Example 7, other conditions are identical, and difference is urged first adding double decomposition in softening agent preparation process
Agent has been reacted and then added reinforcing agent and reacted a period of time again, adds antiscorching agent reaction a period of time, is specially：Will
Styrene butadiene rubber sbr 1500 is dissolved in the solution that 18%w is prepared in cyclohexane solvent, in terms of 100 mass parts rubber, adds 0.95 part
Olefin metathesis catalyst48 DEG C of isolation air and water reaction 2h, add 43 parts of rubber reinforcing filler vinyl
Ethyl diethoxy silane, completely cut off air and water at 48 DEG C, react 1.5 hours, add 10 parts of antiscorching agent 2- vinyl benzene first
Acid, completely cut off air and water at 48 DEG C, react 2 hours, reacted glue is deviate from through solvent, and it is soft to obtain the reinforced type that Mn is 7500
Agent product；
Obtained 100 parts of reinforced type softening agent product is added into breast with 0.29 part of emulsifying agent aliphatic acid potassium, 98 parts of desalted waters
Change device, it is 63 DEG C to control temperature, stirring, softening agent emulsion is made；
Latex and softening agent emulsion, stirring are added into condensing field, the proportion by weight according to butt is 100：33 are carried out
Mixing is made into mixing latex, in the case where reaction temperature is 55 DEG C, adds 21 mass parts flocculating agent Ca (HSO4)2Cohesion, it is scrubbed, from
Heart dehydration, dry, easy processing reinforced type butadiene-styrene rubber is made.
After tested, Mooney viscosity is reduced to 49 by 52, and tensile strength brings up to 27.9MPa by 25.3MPa, time of scorch by
125s brings up to 144s.
Claims (18)
1. a kind of preparation method of easy processing reinforced type butadiene-styrene rubber, is concretely comprised the following steps：
1) reinforced type softening agent is prepared first, and it is the molten of 1%w-50%w butadiene-styrene rubber to be dissolved in concentration is configured in solvent
Liquid, in terms of 100 mass parts rubber, 0.1-1.0 parts olefin metathesis catalyst and 1-50 part coke preventing type rubber are added into solution
Reinforcing agent, completely cut off air and water at 15-50 DEG C, react 0.5-5 hours, reacted glue is deviate from through solvent, obtains reinforced type
Softening agent product；Described coke preventing type rubber reinforcing filler is to be made by antiscorching agent and reinforcing agent by olefin metathesis reaction, institute
The antiscorching agent stated is the nitroso compound, organic acid or thio sub- amide-type thing of the substituent of unsaturation containing alkene；Described benefit
Strong agent is the organic silane compound of the substituent of unsaturation containing alkene.
2) obtained reinforced type softening agent product is added and mixed with emulsifying agent, water, softening agent emulsion is made in stirring；
3) styrene-butadiene latex and softening agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning：(1~50) is mixed
Conjunction is made into mixing latex, in the case where reaction temperature is 10 DEG C~80 DEG C, adds flocculating agent and condenses, scrubbed, centrifugal dehydration, drying,
Easy processing reinforced type butadiene-styrene rubber is made.
2. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that described butylbenzene rubber
Glue is dissolved in the solution for being configured to that concentration is 5%w~15%w in solvent.
3. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that in described reinforcement
In type softening agent preparation process, in terms of 100 mass parts rubber, 0.1-0.3 part olefin metathesis catalysts are added.
4. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that in described reinforcement
In type softening agent preparation process, in terms of 100 mass parts rubber, 10-30 part rubber reinforcing fillers are added.
5. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that described solvent is
The solvent that can dissolve butadiene-styrene rubber of alkene is free of in structure.
6. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that described solvent choosing
From hexane, hexamethylene, toluene or ethylbenzene.
7. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that described coke preventing type
The preparation method of rubber reinforcing filler is：By antiscorching agent and reinforcing agent with 1：(0.1~5.0) mixed in molar ratio, is configured to solvent
The solution of 1%~30% mass concentration, the 0.01~0.1% of the amount for accounting for antiscorching agent and reinforcing agent total material is added into solution
Olefin metathesis catalyst, completely cuts off air and water, after 0.5~8h of normal-temperature reaction, is deviate from solvent using vacuum desolvation agent device,
Coke preventing type rubber reinforcing filler is made.
8. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 7, it is characterised in that described antiscorching agent
Selected from N- nitrosos two (vinyl benzene) amine, N- nitrosos-styryl-beta-naphthylamine, N- nitroso -2- acrylic -2,4- two
Methyl isophthalic acid, 2- EEDQ polymer, vinyl benzoic acid, vinyl salicylic acid, cyclobutenyl salicylic acid, vinyl O-phthalic
Acid, N- vinyl cyclohexyls thiophthalimide or N- acrylic cyclohexylthiophthalimides.
9. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that described reinforcing agent
Structural formula is：Wherein：R4For the unsaturated olefin aliphatic segment containing 2~18 carbon；R1、R3For containing 1~
The siloxy of the alkoxy of 12 carbon, the aryloxy group of 6~12 carbon or 3~12 carbon；R2For with R1Identical group, Huo Zhewei
Saturation segment containing 1~20 carbon, the cycloalkyl containing 3~8 carbon or the aromatic radical containing 6~8 carbon.
10. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 9, it is characterised in that described reinforcing agent
R described in structural formula4Selected from vinyl, acrylic, isopropenyl, isopentene group, 3- pentenyls, 6- octenyls, trimethyl second
Alkenyl, 1- heptenyls, methacryloxypropyl or methacryloxy.
11. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 9, it is characterised in that described reinforcing agent
R described in structural formula1、R3Selected from methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, positive hexyloxy, n-pentyloxy,
Positive epoxide in heptan, different octyloxy, positive nonyl epoxide, phenoxy group, chlorophenoxy, allyloxy, benzyloxy or trimethylsiloxy group.
12. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 9, it is characterised in that described reinforcing agent
R described in structural formula2Selected from methyl, ethyl, methoxy or ethoxy.
13. the preparation method of the easy processing reinforced type butadiene-styrene rubber as described in claim 1 or 9, it is characterised in that described benefit
Strong agent is selected from VTES, vinyl diethoxy-ethylsilane, vinyltrimethoxy silane, vinyl
Two amoxys-hexyl silane or the n-butoxyethyl silane of isopropenyl two.
14. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that described alkene is answered
Decomposition catalyst is the metal carbene class catalyst with olefin metathesis function.
15. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that described alkene is answered
Decomposition catalyst is selected from dichloro (o- isopropoxy benzylidene) (tricyclohexyl phosphine) and closes rutheniumTwo
Chlorine [o- isopropoxy benzylidene] [double (2,4,6- the trimethylphenyls) -2- imidazolines subunits of 1,3-] closes ruthenium
16. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that described emulsifying agent
Selected from saturated or unsaturated fatty acid soaps or RA rosin acid, dosage be add 0.1 in 100 parts of reinforced type softening agent products~
20 parts.
17. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that described flocculating agent
Selected from CaCl2、MgSO4、MgCl2、Al2(SO4)3、FeCl3、CuCl2Or Ca (HSO4)2In one kind or its mixture, its dosage
To add 1~25 part in 100 parts of styrene-butadiene latexes.
18. the preparation method of easy processing reinforced type butadiene-styrene rubber as claimed in claim 1, it is characterised in that the 3) butylbenzene in step
The butt proportioning of latex and softening agent emulsion is 100：10~30.
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| WO2022181545A1 (en) * | 2021-02-24 | 2022-09-01 | 株式会社カネカ | Manufacturing method for polymer comprising hydrolyzable silyl group, and polymer, curable composition, and cured product |
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