CN106699968A - Method for preparing nanosilicon dioxide modified styrene-butadiene latex - Google Patents
Method for preparing nanosilicon dioxide modified styrene-butadiene latex Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a method for preparing nanosilicon dioxide modified styrene-butadiene latex. An emulsion polymerization mode of stepwise heating is adopted, styrene and butadiene monomers are added into a polyreactor at a time, meanwhile, nanosilicon dioxide with the surface modified with activated double bonds is added to serve as functional filler, a molecular weight modifier, an emulgator and an oxidizing agent are added in batches, and finally the styrene-butadiene latex with good mechanical stability, bonding strength and the like is obtained. The styrene-butadiene latex is good in heat resistance and wear resistance, and is mainly applied to road asphalt modification.
Description
Technical field
The present invention relates to the preparation of organic high molecular compound, more particularly to a kind of nano-silicon dioxide modified butadiene-styrene rubber
The preparation method of breast.
Background technology
Emulsion polymerization is one of four kinds of methods of production high polymer, and system is typically by monomer, medium (usually water), initiation
Agent and emulsifying agent are constituted.In styrene-butadiene emulsion polymerization system, monomer butadiene, styrene are insoluble in water, and emulsifying agent is generally used
Oil-in-water type anion surfactant such as alkyl sulfate, soap, rosin soap etc., when consumption, in CMC, (critical micell is dense
Degree) more than, system can form a large amount of micellas；Initiation system is typically gone back using water soluble persulfates such as potassium peroxydisulfate etc. or oxidation
Substance system such as hydrogen peroxide/iron sulfite.Additionally, also usually adding molecular weight regulator, such as tert-dodecyl mercaptan can be adjusted
Section molecular weight and the branched gel of reduction.
Styrene-butadiene latex is widely used in the every field such as papermaking, coating, weaving, building and asphalt.The oil of China
Pitch by resource and production technology due to being limited, and paraffin content is generally higher, and temperature sensitivity is big, and high temperature is also easy to produce rut, low
Warm easy to crack, poor durability, it is difficult to for High Grade Bitumen Pavement.Modifying road asphalt styrene-butadiene latex is using special synthesis
The obtained synthetic latex with rubber performance of technique, after being modified to domestic heavy duty road asphalt, can obviously improve original
There are high temperature resistant, the cryogenic property of pitch, improve pavement quality, extend the service life on road surface.Chinese patent
CN200910229283.6 discloses a kind of production method of styrene butadiene latex modified emulsified asphalt, but the technology has product stabilization
The shortcomings of property is poor, viscosity is big.
The content of the invention
It is an object of the invention to provide a kind of nano-silicon dioxide modified styrene-butadiene latex of surface modified active double bond
Preparation method, which overcome the weak point existing for the preparation method of prior art.
The technical solution adopted for the present invention to solve the technical problems is：A kind of nano-silicon dioxide modified styrene-butadiene latex
Preparation method, comprises the following steps：
1) raw material is provided, the raw material includes the component of following weight：
Wherein, the redox initiation system is made up of Oxidizing and Reducing Agents；
2) by the soft water of the raw material proportioning weight portion, monomer styrene, surface modified active double bond nanometer titanium dioxide
The molecular weight regulator of silicon, reducing agent, electrolyte and the weight portion 5%~10%, the weight portion 40%~60%
Oxidant, in the Compositional type emulsifying agent addition reactor of the weight portion 30%~40%, after vacuumizing, is passed through the weight portion
Monomer butadiene gas and be well mixed, the stage heat up by way of be progressively warming up to 35 DEG C~40 DEG C by 15 DEG C~20 DEG C
Reacted, molecular weight regulator, Compositional type emulsifying agent, the oxidation of residuals weight part are added when monomer conversion reaches 50%
Agent and the age resistor and terminator of the weight portion, continue to react 20~30h；
3) after reaction terminates, remaining divinylic monomer is removed using flash evaporation, obtains described nano-silicon dioxide modified
Styrene-butadiene latex.
Preferably, the raw material includes the component of following weight：
Preferably, stage heat up be with 15 DEG C~20 DEG C be initial temperature, be warming up to 25 DEG C~30 DEG C through 3~8min
And 8~15h times are incubated, then be warming up to 35 DEG C~40 DEG C through 3~8min times and be incubated.
Preferably, the Compositional type emulsifying agent is by sodium soap and rosin soap by weight 1:1~2 composition.
Preferably, in the redox initiation system, the oxidant is cumyl hydroperoxide, tert-butyl hydroperoxide
At least one in hydrogen, the reducing agent is at least one in ferrous sulfate, NaFeEDTA sodium salt.
Preferably, the raw material also includes the reducing agent that helps of 0.05~0.1 weight portion, described to help reducing agent in step 2) in
Together added in the reactor for iron ion is reduced into ferrous ion with the reducing agent.
Preferably, the surface modified active double bond nano silicon is by the nano silicon of 10~20 weight portions
It is added in the ethanol solution of 200~400 weight portions and 10~15min of ultrasonic disperse, adds the silane of 20~40 weight portions
Coupling agent 3- (isobutene acyl-oxygen) propyl trimethoxy silicane, continues 0.5~2h of ultrasonic disperse, through suction filtration, washing, vacuum drying
It is obtained.
Preferably, the molecular weight regulator is at least one in lauryl mercaptan, carbon tetrachloride.
Preferably, the age resistor is at least one in p-phenylenediamine, anti-aging agent RD；The terminator is nitrous acid
At least one in sodium, sodium polysulfide.
Preferably, the electrolyte is potassium phosphate.
Compared to prior art, the invention has the advantages that：
(1) using the nano silicon of surface modified active double bond as functional stuffing, its activity double key can join the present invention
With the copolymerization of styrene and butadiene, so as to realize the compatibility good with latex, by its modified styrene-butadiene latex
Material has excellent heat resistance, wearability, is conducive to the mixed combination properties of base-material such as raising and pitch.
(2) preparation method of the invention, during styrene and divinylic monomer disposably added into reactor, and Compositional type is newborn
Agent then by the way of being dividedly in some parts, can obviously reduce the floe content of gelling, so as to obtain solid content 33%~
40% or so, mechanical stability, adhesion strength and mobility etc. are compared with normal latex performance preferably styrene-butadiene latex.
(3) preparation method of the invention, oxidant is dividedly in some parts in reactor, and reducing agent is disposably added, and can be obtained
Obtain and preferably trigger effect so that nano-silicon dioxide modified styrene-butadiene latex application effect is preferable.
(4) preparation method of the invention, molecular weight regulator is dividedly in some parts in reactor, can significantly reduce the viscous of latex
Degree and structural gel content, are conducive to the mixing of later stage styrene-butadiene latex and road asphalt.
(5) preparation method of the invention is progressively warming up to reaction temperature by the way of the stage heats up, and is conducive to being fitted
In reaction speed, reduce styrene-butadiene latex polymerization system viscosity, while improve latex stability.
Following examples are described in further detail to the present invention；But a kind of nano-silicon dioxide modified butylbenzene of the invention
The preparation method of latex is not limited to embodiment.
Specific embodiment
Embodiment 1
10~20 parts of nano silicon is added in 300 parts of ethanol solution.After 10~15min of ultrasonic disperse,
20~40 parts silane coupler 3- (isobutene acyl-oxygen) propyl trimethoxy silicane is added, continues ultrasonic disperse 1h or so.Through
Suction filtration, washing, vacuum drying obtain the nano silicon of surface modified active double bond.
By sodium soap, (chemical formula is RCOONa (R=C11~17)) and rosin soap in mass ratio 1:1~2 is mixed to get again
Distribution type emulsifying agent.
There is provided by oxidants hydrogen peroxide isopropylbenzene, TBHP and reducing agent ferrous sulfate, NaFeEDTA sodium salt
The redox initiation system of composition.
By 200 parts of solvent soft water, 25 parts of styrene, 2 parts of the nano silicon of surface modified active double bond, oxidant
0.5 part, 0.8 part of reducing agent, help reducing agent rongalite 0.06 part, 0.1 part electrolyte potassium phosphate, molecular weight regulator dodecyl
2 parts of 0.01 part of mercaptan and Compositional type emulsifying agent are added in polymerization reaction kettle, are evacuated to -0.05MPa, are passed through gas butadiene
75 parts, reacted by three sections of heating modes, initial temperature is 22 DEG C, is warming up to 30 DEG C through 5min and is incubated the 10h times, then passes through
The 5min times are warming up to 40 DEG C and are incubated, and when measuring monomer conversion and reaching 50%, add molecular weight regulator dodecyl sulphur
0.09 part of alcohol, 0.5 part of oxidant, 3 parts of Compositional type emulsifying agent, age resistor p-phenylenediamine 0.05 and terminator natrium nitrosum 0.05
Part reaction time 24h.After polymerisation terminates, remaining divinylic monomer is removed using flash evaporation.Finally give mechanically stable
The nano-silicon dioxide modified styrene-butadiene latex of the better performances such as property, heat resistance and adhesive strength.
Embodiment 2
The preparation side of the nano silicon, Compositional type emulsifying agent and redox initiation system of surface modified active double bond
Method refer to embodiment 1.By 200 parts of solvent soft water, 35 parts of styrene, 4 parts of the nano silicon of surface modified active double bond,
0.2 part of oxidant, 0.3 part of reducing agent, help 0.08 part, 0.1 part electrolyte potassium phosphate of reducing agent rongalite and molecular-weight adjusting
0.1 part of agent carbon tetrachloride, 2 parts of Compositional type emulsifying agent are added in polymerization reaction kettle, after being evacuated to -0.05MPa, are passed through butadiene
65 parts, reacted by three sections of heating modes, initial temperature is 20 DEG C, is warming up to 28 DEG C through 5min and is incubated the 10h times, then passes through
The 5min times are warming up to 38 DEG C and are incubated, and when measuring monomer conversion and reaching 50%, add molecular weight regulator carbon tetrachloride 0.9
Part, 0.2 part of oxidant, 4 parts of Compositional type emulsifying agent, 0.05 part of age resistor p-phenylenediamine and 0.05 part of terminator natrium nitrosum, instead
24h between seasonable.After polymerisation terminates, remaining divinylic monomer is removed using flash evaporation.Finally give mechanical stability, resistance to
The nano-silicon dioxide modified styrene-butadiene latex of the better performances such as hot and adhesive strength.
Embodiment 3
The preparation side of the nano silicon, Compositional type emulsifying agent and redox initiation system of surface modified active double bond
Method refer to embodiment 1.By 200 parts of solvent soft water, 25 parts of styrene, 4 parts of the nano silicon of surface modified active double bond,
0.3 part of oxidant, 0.8 part of reducing agent, help 0.06 part, 0.3 part electrolyte potassium phosphate of reducing agent rongalite and molecular-weight adjusting
0.2 part of agent lauryl mercaptan, 2 parts of Compositional type emulsifying agent are added in polymerization reaction kettle, after being evacuated to -0.05MPa, are passed through fourth
75 parts of diene, is reacted by three sections of heating modes, and initial temperature is 20 DEG C, is warming up to 28 DEG C through 5min and is incubated 10h, then passes through
The 5min times are warming up to 38 DEG C and are incubated, and when measuring monomer conversion and reaching 50%, add molecular weight regulator dodecyl sulphur
1.8 parts of alcohol, 0.3 part of oxidant, 4 parts of Compositional type emulsifying agent, 0.05 part of age resistor p-phenylenediamine and terminator natrium nitrosum 0.05
Part, reaction time 30h.After polymerisation terminates, remaining divinylic monomer is removed using flash evaporation.Finally give mechanically stable
The nano-silicon dioxide modified styrene-butadiene latex of the better performances such as property, heat resistance and adhesive strength.
Embodiment 4
The preparation side of the nano silicon, Compositional type emulsifying agent and redox initiation system of surface modified active double bond
Method refer to embodiment 1.By 200 parts of solvent soft water, 30 parts of styrene, 6 parts of the nano silicon of surface modified active double bond,
0.3 part of oxidant, 0.6 part of reducing agent, help 0.06 part, 0.4 part electrolyte potassium phosphate of reducing agent rongalite and molecular-weight adjusting
0.1 part of agent lauryl mercaptan, 2 parts of Compositional type emulsifying agent are added in polymerization reaction kettle, after being evacuated to -0.05MPa, are passed through fourth
70 parts of diene, is reacted by three sections of heating modes, and initial temperature is 22 DEG C, is warming up to 30 DEG C through 5min and is incubated the 10h times,
40 DEG C are warming up to through the 5min times and be incubated, when measuring monomer conversion and reaching 50%, add molecular weight regulator dodecane again
0.05 part of 1.9 parts of base mercaptan, 0.2 part of oxidant, 4 parts of Compositional type emulsifying agent, 0.05 part of anti-aging agent RD and terminator sodium polysulfide,
Reaction time 30h or so.After polymerisation terminates, remaining divinylic monomer is removed using flash evaporation.Finally give mechanical steady
The nano-silicon dioxide modified styrene-butadiene latex of the better performances such as qualitative, heat resistance and adhesive strength.
Embodiment 5
The preparation side of the nano silicon, Compositional type emulsifying agent and redox initiation system of surface modified active double bond
Method refer to embodiment 1.By 200 parts of solvent soft water, 25 parts of styrene, 8 parts of the nano silicon of surface modified active double bond,
0.3 part of oxidant, 0.6 part of reducing agent, help 0.06 part, 0.6 part electrolyte potassium phosphate of reducing agent rongalite and molecular-weight adjusting
0.075 part of agent lauryl mercaptan, 2 parts of Compositional type emulsifying agent are added in polymerization reaction kettle, after being evacuated to -0.05MPa, are passed through
75 parts of butadiene, is reacted by three sections of heating modes, and initial temperature is 18 DEG C, is warming up to 26 DEG C through 5min and is incubated 12h, then
36 DEG C are warming up to through the 5min times and be incubated, when measuring monomer conversion and reaching 50%, add molecular weight regulator dodecyl
1.425 parts of mercaptan, 0.2 part of oxidant, 4 parts of Compositional type emulsifying agent, 0.05 part of age resistor p-phenylenediamine and terminator natrium nitrosum
0.05 part, reaction time 24h or so.After polymerisation terminates, remaining divinylic monomer is removed using flash evaporation.Finally give
The nano-silicon dioxide modified styrene-butadiene latex of the better performances such as mechanical stability, heat resistance and adhesive strength.
Above-described embodiment is only used for further illustrating a kind of preparation of nano-silicon dioxide modified styrene-butadiene latex of the invention
Method, but the invention is not limited in embodiment, it is every according to technical spirit of the invention above example is made it is any
Simple modification, equivalent variations and modification, each fall within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of preparation method of nano-silicon dioxide modified styrene-butadiene latex, it is characterised in that comprise the following steps：
1) raw material is provided, the raw material includes the component of following weight：
Wherein, the redox initiation system is made up of Oxidizing and Reducing Agents；
2) by the soft water of the raw material proportioning weight portion, monomer styrene, the nano silicon of surface modified active double bond, also
Former agent, the molecular weight regulator of electrolyte and the weight portion 5%~10%, the oxidation of the weight portion 40%~60%
Agent, in the Compositional type emulsifying agent addition reactor of the weight portion 30%~40%, after vacuumizing, is passed through the list of the weight portion
Body butadiene gas are simultaneously well mixed, and being progressively warming up to 35 DEG C~40 DEG C by 15 DEG C~20 DEG C by way of the stage heats up is carried out
Reaction, added when monomer conversion reaches 50% the molecular weight regulator of residuals weight part, Compositional type emulsifying agent, oxidant with
And the age resistor and terminator of the weight portion, continue to react 20~30h；
3) after reaction terminates, remaining divinylic monomer is removed using flash evaporation, obtains the nano-silicon dioxide modified butylbenzene
Latex.
2. the preparation method of nano-silicon dioxide modified styrene-butadiene latex according to claim 1, it is characterised in that：The original
Material includes the component of following weight：
3. the preparation method of nano-silicon dioxide modified styrene-butadiene latex according to claim 1, it is characterised in that：The rank
It with 15 DEG C~20 DEG C is initial temperature that Duan Shengwen is, is warming up to 25 DEG C~30 DEG C through 3~8min and is incubated 8~15h times, then passes through
3~8min times are warming up to 35 DEG C~40 DEG C and are incubated.
4. the preparation method of nano-silicon dioxide modified styrene-butadiene latex according to claim 1, it is characterised in that：It is described multiple
Distribution type emulsifying agent is by sodium soap and rosin soap by weight 1:1~2 composition.
5. the preparation method of nano-silicon dioxide modified styrene-butadiene latex according to claim 1, it is characterised in that：The oxygen
Change in reduction initiating system, the oxidant is at least one in cumyl hydroperoxide, TBHP, it is described to go back
Former agent is at least one in ferrous sulfate, NaFeEDTA sodium salt.
6. the preparation method of nano-silicon dioxide modified styrene-butadiene latex according to claim 5, it is characterised in that：The original
Material also helps reducing agent including 0.05~0.1 weight portion, described to help reducing agent in step 2) in together added with the reducing agent
For iron ion is reduced into ferrous ion in the reactor.
7. the preparation method of nano-silicon dioxide modified styrene-butadiene latex according to claim 1, it is characterised in that：The table
Face modification activities double bond nano silicon is to be added to 200~400 weight portions by the nano silicon of 10~20 weight portions
Ethanol solution in and 10~15min of ultrasonic disperse, add the silane coupler 3- (isobutene acyl-oxygen) of 20~40 weight portions
Propyl trimethoxy silicane, continues 0.5~2h of ultrasonic disperse, is obtained through suction filtration, washing, vacuum drying.
8. the preparation method of nano-silicon dioxide modified styrene-butadiene latex according to claim 1, it is characterised in that：Described point
Son amount conditioning agent is at least one in lauryl mercaptan, carbon tetrachloride.
9. the preparation method of nano-silicon dioxide modified styrene-butadiene latex according to claim 1, it is characterised in that：It is described anti-
Old agent is at least one in p-phenylenediamine, anti-aging agent RD；The terminator is at least in natrium nitrosum, sodium polysulfide
Kind.
10. the preparation method of nano-silicon dioxide modified styrene-butadiene latex according to claim 1, it is characterised in that：It is described
Electrolyte is potassium phosphate.
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| CN115043980A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing cold-resistant thermoplastic elastomer by emulsion polymerization method and prepared silicon-containing thermoplastic elastomer |
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| CN115043980A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing cold-resistant thermoplastic elastomer by emulsion polymerization method and prepared silicon-containing thermoplastic elastomer |
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