CN106519118A - Preparing method of styrene-butadiene latex used for modified emulsified asphalt - Google Patents
Preparing method of styrene-butadiene latex used for modified emulsified asphalt Download PDFInfo
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- CN106519118A CN106519118A CN201611078997.8A CN201611078997A CN106519118A CN 106519118 A CN106519118 A CN 106519118A CN 201611078997 A CN201611078997 A CN 201611078997A CN 106519118 A CN106519118 A CN 106519118A
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/54—Aqueous solutions or dispersions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
The invention relates to a preparing method of styrene-butadiene latex used for modified emulsified asphalt. The preparing method comprises the steps of synthesizing butylbenzene colloidal particles with low-temperature performance through a low-temperature section reaction, controlling monomer distribution in low-temperature colloidal particles by controlling the proportion of low-temperature section styrene and butadiene, improving the compatibility of latex and asphalt, and guaranteeing the liquidity of the latex; a high-temperature section reaction, wherein low-temperature butylbenzene colloidal particles are adopted as nucleuses, a grafting reaction is carried out on the surfaces of the low-temperature colloidal particles, styrene-butadiene latex with a core-shell structure is synthesized, making the styrene-butadiene latex in the modified asphalt both have a certain low-temperature ductile property and a high-temperature resistant property. The two-section method reaction has the advantages of being fast in velocity, short in reaction time and high in conversion ratio and solid content.
Description
Technical field
The present invention relates to styrene-butadiene latex synthesis technical field, and in particular to a kind of system of modified emulsifying asphalt styrene-butadiene latex
Preparation Method.
Background technology
At present, one-step synthesis method styrene-butadiene latex is typically adopted, mainly has two methods of low temperature process and high temperature method, low temperature process is closed
Into styrene-butadiene latex, the response time is longer, generally 30 ~ 40h, conversion ratio control 70 ~ 80%, solid content 40 ~ 50%, due to butylbenzene
In rubber, gel content is relatively low, is applied to modified pitch its high-temperature behavior poor；High temperature method synthesizes styrene-butadiene latex, although solid content
It is higher, but its low temperature ductility in surname Colophonium is changed is bad.The High Solid Content SBR Latex method introduced in CN103159893A
Including：（1）High-temperature nuclei solid content is 50% styrene-butadiene latex；（2）Solid content is prepared for 60 ~ 65 by agglomeration centrifugation means
Styrene-butadiene latex.In polymerization（1）Middle conversion ratio reaches 98.5%, and its response time is longer, the styrene-butadiene latex gel content of synthesis compared with
Height, uses（2）It is higher to equipment requirements that agglomeration and centrifugal method improve solid content.Two step synthesis steps are cumbersome.
In consideration of it, a kind of preparation method of correctability butadiene-styrene latex of invention is imperative.
The content of the invention
To solve the problems referred to above of prior art, the present invention provides a kind of preparation side of modified emulsifying asphalt styrene-butadiene latex
Method.
A kind of preparation method of modified emulsifying asphalt styrene-butadiene latex, which comprises the following steps that shown：
The weight portion of wherein each reactant is as follows：Deionized water 60-100 parts；Monomer includes butadiene and styrene（Wherein
Butadiene 60-80 parts；Styrene 20-40 parts）；Emulsifying agent 4-7 parts, electrolyte 0.1-0.3 parts；Diffusant 0.1-0.5 parts；
Initiator includes thermal decomposition initiating and redox initiator, wherein thermal decomposition initiating 0-0.1 part, redox initiator
0.1-0.2 parts；Reducing agent 0.01-0.05 parts；Molecular weight regulator 0.1-0.5 parts；Free radical stabilizer 0.1-1 parts；Terminate
Agent 0.05-0.1 parts；Age resistor 0.1-0.15 parts.
（1）Configuration emulsifier solution：Whole emulsifying agents are taken by above-mentioned weight portion, is then gone to addition part in emulsifying agent
Ionized water, heats the solution to 70 DEG C and stirs one hour, all dissolves to emulsifying agent, obtains emulsifier solution, this step
In in rapid, the mass concentration of guarantee emulsifier solution is 25%-35%；
（2）To in polymeric kettle by weight disposably add mentioned emulsifier solution, electrolyte, reducing agent, molecular weight regulator,
Diffusant, free radical stabilizer and remaining deionized water；Then reactor is exhausted with nitrogen, empties 3 times, emptied
Finish, it is ensured that reactor is oxygen-free environment；Jing measuring tanks quickly add partial monosomy in reactor, control temperature of reaction kettle 5-15
DEG C, redox initiator initiation reaction is added, 3 ~ 6h is reacted, conversion ratio is controlled 50 ~ 70%, is then continuously added to remaining single
Body and thermal decomposition initiating, wherein monomer feed rates are 20 seconds/gram, continue anti-while raising temperature of reaction kettle and being 45 ~ 75 DEG C
Should, when conversion ratio reaches more than 90.0%, terminator stopped reaction is added, in the kettle vacuum that deaerates for -0.10Mpa, kettle temperature is
Under conditions of 50 DEG C, it is de-gassed to remove residual monomer, degassing time is 3 hours, obtains finished product after eventually passing filter.
Conversion ratio is that according to prior art, each is sampled detection in 1 hour to operator.
In above-mentioned preparation process, monomer used is butadiene and styrene, and two batches are added, low-temperature zone, by styrene：Fourth
The weight ratio of diene=1/3 ~ 5/6, adds the 50% ~ 80% of butadiene and styrene total weight parts, by adjust styrene and
The ratio of butadiene, monomer distribution in control low temperature micelle improve the compatibility of latex and Colophonium and ensure the mobility of latex；
High temperature section adds residual styrene and butadiene, monomer addition to feed for seriality, and charging rate is 20 seconds/gram, while improving
Reaction temperature is 45 ~ 75 DEG C, it is therefore an objective to which " starvation method " reacts, and monomer enters latex system, reacted on low temperature micelle surface rapidly,
Disconnecting branch, does not form certain gel, improves the softening point of modified pitch.
In above-mentioned preparation process, the initiator for being used is added at twice, and low-temperature zone adds 0.1 ~ 0.2 part of oxidoreduction to draw
Agent is sent out, high temperature section adds 0 ~ 0.1 part of heat decomposition type initiator, make to react faster in high temperature section, it is ensured that the conversion ratio of monomer.
Emulsifying agent of the present invention be oleate, linoleate, rosinate, laruate, soap etc. it is cloudy from
One or more anion emulsifier compounding use in sub- emulsifying agent, and the emulsifier solution mass concentration of its configuration is 25-
35%, the pH value of emulsifier solution is 8 ~ 11, it is ensured that the de-emulsification speed of modified emulsifying asphalt.
Described redox initiator is organic peroxide initiator, and hydrogen peroxide is different to Meng's alkane, hydrogen peroxide
Propyl benzene or cyclohexanone peroxide；
The electrolyte is potassium chloride, sodium bicarbonate；
Described redox initiator is organic peroxide initiator；
Described reducing agent is low price manganese, vanadium, the sulfate of ferrum or nitrate, manganese naphthenate, vanadium, iron salt or tertiary amines chemical combination
Thing；
Described diffusant is lignin sulfonate, one or more compounding use of naphthalene sulfonic acid-formaldehyde condensation product, it is ensured that
The good mobility of latex；
Described molecular weight regulator is the one kind or many in primary, secondary, tertiary mercaptan, mercaptan ester and the mercaptan ether of 9 ~ 14 carbon atoms
Plant compounding use, it is ensured that the molecular size of hot styrene rubber；
Ethoxylated fatty amines oxide of the described free radical stabilizer for 14 ~ 24 carbon, it is ensured that low temperature and pyroreaction
During free radical have higher activity；
Described thermal decomposition initiating is Ammonium persulfate., the aqueous solution of potassium peroxydisulfate, and its mass concentration is 2-5%；
Described terminator is Sodium Dimethyldithiocarbamate, sodium polysulphide, to prevent polymerized monomer auto-polymerization in production, storage, transport.
The invention has the beneficial effects as follows：Butylbenzene micelle with cryogenic property is synthesized by low-temperature zone, by control
Low-temperature zone styrene and butadiene ratios, monomer distribution in control low temperature micelle, improve the compatibility of latex and Colophonium and ensure
The mobility of latex；High temperature section is reacted, with low temperature butylbenzene micelle as core, in low temperature micelle Surface grafting reaction, synthesis nucleocapsid knot
The styrene-butadiene latex of structure, in modified pitch, enables which both have certain low temperature ductility, has resistance to elevated temperatures again.Two-stage method
Reaction is very fast with speed, and the response time is short, the characteristics of conversion ratio and high solid content.
Specific embodiment
Embodiment 1
Each substance weight part is as follows：
69 parts of deionized water；
Monomer be 70 parts of butadiene, 30 parts of styrene；
Emulsifying agent（Disproportionated rosin 3.6 parts of potassium of acid, 1.8 parts of sodium stearate）；
Electrolyte（0.3 part of potassium chloride）；
Diffusant（0.3 part of sodium metnylene bis-naphthalene sulfonate）；
Thermal decomposition initiating（Mass concentration is 0.1 part of 3% ammonium persulfate solution）；
Redox initiator（0.2 part of cumyl hydroperoxide）；
Reducing agent（0.04 part of ferrous sulfate）；
Molecular weight regulator（0.24 part of tert-dodecylmercaotan）；
Free radical stabilizer（1 part of oxidation hexadecylamine polyoxyethylene ether）；
Terminator（0.1 part of Sodium Dimethyldithiocarbamate）；
（1）Configuration emulsifier solution：Whole emulsifying agents are taken by above-mentioned weight portion（Wherein disproportionated rosin acid 3.6 parts of potassium, fatty acid
1.8 parts of sodium）, then 11.475 parts of deionized waters are added in emulsifying agent, heat the solution to 70 DEG C and stir one hour,
All dissolve to emulsifying agent, obtain emulsifier solution, the mass concentration of emulsifier solution is 32%；
（2）Emulsion agent is polymerized：Mentioned emulsifier solution, potassium chloride 0.3 part, sulfur are added in 2L polymeric kettles by weight disposably
Sour ferrous 0.04 part, 0.24 part of tert-dodecylmercaotan, 0.3 part of sodium metnylene bis-naphthalene sulfonate, oxidation hexadecylamine polyoxy second
1 part of alkene ether, and 57.525 parts of deionized water, are exhausted to reactor with nitrogen, are emptied 3 times, start stirring, by styrene：
The ratio of butadiene=3/7, wherein styrene and butadiene addition are monomer gross mass 60%, control temperature of reaction kettle and reach 5
DEG C when, add 0.2 part of cumyl hydroperoxide initiation reaction, react 5h, conversion ratio control is 60% or so；Then to reactor
In be continuously added to residual monomer and thermal decomposition initiating, wherein monomer feed rates are 20 seconds/gram, while raising the anti-of reactor
Answer temperature and continue reaction for 60 DEG C, when conversion ratio reaches more than 90.0%, add Sodium Dimethyldithiocarbamate stopped reaction, in degassing kettle vacuum
Spend for -0.10Mpa, under conditions of kettle temperature is 50 DEG C, be de-gassed to remove residual monomer, degassing time is 3 hours, most after Jing
Finished product is obtained after filtration.
The physical index of latex is：Conversion ratio 90.31%；Structural gel 45.35%.
Embodiment 2
Each substance weight part is as follows：
69 parts of deionized water；
Monomer be 60 parts of butadiene, 40 parts of styrene；
Emulsifying agent（Disproportionated rosin 3.6 parts of potassium of acid, 1.8 parts of potassium oleate）；
Electrolyte（0.3 part of potassium chloride）；
Diffusant（0.3 part of sodium lignin sulfonate）；
Thermal decomposition initiating（Mass concentration is 3% 0.075 part of potassium persulfate solution）；
Redox initiator（Hydrogen peroxide is to 0.15 part of Meng's alkane）；
Reducing agent（0.03 part of ferrous sulfate）；
Molecular weight regulator（0.24 part of tert-dodecylmercaotan）；
Free radical stabilizer（1 part of oxidation octadecylamine polyoxyethylene ether）；
Terminator（0.1 part of sodium polysulphide）；
（1）Configuration emulsifier solution：Whole emulsifying agents are taken by above-mentioned weight portion（Wherein disproportionated rosin acid 3.6 parts of potassium, fatty acid
1.8 parts of sodium）, then 11.475 parts of deionized waters are added in emulsifying agent, heat the solution to 70 DEG C and stir one hour,
All dissolve to emulsifying agent, obtain emulsifier solution, the mass concentration of emulsifier solution is 32%；
（2）Emulsion agent is polymerized：Mentioned emulsifier solution, potassium chloride 0.3 part, sulfur are added in 2L polymeric kettles by weight disposably
Sour ferrous 0.03 part, 0.24 part of tert-dodecylmercaotan, 0.3 part of sodium lignin sulfonate, oxidation octadecylamine polyoxyethylene ether 1
57.525 parts of part and deionized water, are exhausted to reactor with nitrogen, are emptied 3 times, start stirring, by styrene：Butadiene
=4/6 ratio, adds the butadiene and styrene of monomer gross mass 60%, when control temperature of reaction kettle reaches 10 DEG C, adds
0.15 part of hydrogen peroxide reacts 4h to Meng's alkane initiation reaction, and conversion ratio is controlled 60% or so；Then it is continuously added to reactor
Residual styrene and butadiene and 0.075 part of mass concentration are 3% persulfate aqueous solution, monomer feed rates are 20 seconds/
Gram, continue reaction while rising high reaction temperature and being 65 DEG C, when conversion ratio reaches more than 90.0%, add Sodium Dimethyldithiocarbamate stopped reaction,
It is -0.10Mpa in degassing kettle vacuum, under conditions of kettle temperature is 50 DEG C, is de-gassed to remove residual monomer, degassing time is
3 hours, after eventually passing filter, obtain finished product.
The physical index of latex is：Conversion ratio 91.54%；Structural gel 52.43%.
Embodiment 3
Each substance weight part is as follows：
75.8 parts of deionized water；
Monomer be 65 parts of butadiene, 35 parts of styrene；
Emulsifying agent（Disproportionated rosin 2.5 parts of potassium of acid, 1 part of potassium stearate, 1.5 parts of potassium oleate）；
Electrolyte（0.25 part of sodium bicarbonate）；
Diffusant（0.15 part of sodium metnylene bis-naphthalene sulfonate, 0.1 part of sodium lignin sulfonate）；
Thermal decomposition initiating（0.1 part of Ammonium persulfate.）；
Redox initiator（0.15 part of cyclohexanone peroxide）；
Reducing agent（0.03 part of ferrous naphthenate）；
Molecular weight regulator（0.25 part of n- dodecyl mereaptan ether）；
Free radical stabilizer（0.8 part of oxidation octadecylamine polyoxyethylene ether）；
Terminator（0.1 part of Sodium Dimethyldithiocarbamate）；
（1）Configuration emulsifier solution：Whole emulsifying agents are taken by above-mentioned weight portion（Wherein disproportionated rosin acid 2.5 parts of potassium, Hard Fat
1 part of sour potassium, 1.5 parts of potassium oleate）, then 10.625 parts of deionized waters are added in emulsifying agent, heat the solution to 70 DEG C
And stir one hour, all dissolving to emulsifying agent, obtain emulsifier solution, the mass concentration of emulsifier solution is 32%；
（2）Emulsion agent is polymerized：Mentioned emulsifier solution, sodium bicarbonate 0.25 are added in 2L polymeric kettles by weight disposably
Part, 0.03 part of ferrous naphthenate, 0.25 part of n- dodecyl mereaptan ether, 0.15 part of sodium metnylene bis-naphthalene sulfonate, sodium lignin sulfonate 0.1
Part, 0.8 part of oxidation octadecylamine polyoxyethylene ether, and 65.175 parts of deionized water, are exhausted to reactor with nitrogen,
Emptying 3 times, starts stirring, by styrene：The ratio of butadiene=35/65, adds the butadiene and benzene second of monomer gross mass 70%
Alkene, when control temperature of reaction kettle reaches 15 DEG C, adds 0.15 part of cyclohexanone peroxide initiation reaction, reacts 4h, conversion ratio control
70% or so；Then the persulfuric acid that residual styrene, butadiene and 0.1 part of mass concentration are 3% is continuously added to in reactor
Aqueous solutions of potassium, monomer feed rates are 20 seconds/gram, continue reaction while rising high reaction temperature and being 75 DEG C, when conversion ratio reaches
When more than 90.0%, Sodium Dimethyldithiocarbamate stopped reaction is added, be -0.10Mpa in degassing kettle vacuum, under conditions of kettle temperature is 50 DEG C, enter
To remove residual monomer, degassing time is 3 hours for row degassing, obtains finished product after eventually passing filter.
The physical index of latex is：Conversion ratio 93.43%；Structural gel 58.41%.
Embodiment 4
Each substance weight part is as follows：
57.8 parts of deionized water；
Butylbenzene be 70 parts of butadiene, 30 parts of styrene；
Emulsifying agent（Disproportionated rosin 1.6 parts of potassium of acid, 1.8 parts of potassium oleate, 2 parts of sodium laurate）；
Electrolyte（0.3 part of sodium bicarbonate）；
Diffusant（0.1 part of sodium metnylene bis-naphthalene sulfonate, 0.15 part of sodium lignin sulfonate）；
Thermal decomposition initiating（0.05 part of potassium peroxydisulfate）；
Redox initiator（Hydrogen peroxide is to 0.15 part of Meng's alkane）；
Reducing agent（0.04 part of ferrous naphthenate）；
Molecular weight regulator（0.15 part of n- dodecyl mereaptan ether, 0.1 part of tert-dodecyl mercaptan）；
Free radical stabilizer（0.8 part of oxidation hexadecylamine polyoxyethylene ether）；
Terminator（0.1 part of Sodium Dimethyldithiocarbamate）
（1）Configuration emulsifier solution：Whole emulsifying agents are taken by above-mentioned weight portion（Wherein disproportionated rosin acid 1.6 parts of potassium, Oleic acid
1.8 parts of potassium, 2 parts of sodium laurate）, then 11.475 parts of deionized waters are added in emulsifying agent, heat the solution to 70 DEG C
And stir one hour, all dissolving to emulsifying agent, obtain emulsifier solution, the mass concentration of emulsifier solution is 32%；
（2）Emulsion agent is polymerized：To in 2L polymeric kettles by weight disposably add mentioned emulsifier solution, 0.3 part of sodium bicarbonate,
0.04 part of ferrous naphthenate, 0.15 part of n- dodecyl mereaptan ether, 0.1 part of tert-dodecyl mercaptan, 0.1 part of sodium metnylene bis-naphthalene sulfonate, wood
0.15 part of quality sodium sulfonate, 0.8 part of oxidation hexadecylamine polyoxyethylene ether, and 16.325 parts of deionized water, with nitrogen to anti-
Answer kettle to be exhausted, empty 3 times, start stirring, by styrene：The ratio of butadiene=3/7, adds the fourth of monomer gross mass 50%
Diene and styrene, when control temperature of reaction kettle reaches 10 DEG C, add 0.15 part of hydrogen peroxide to Meng's alkane initiation reaction, reaction
5h, conversion ratio are controlled 70% or so；Then residual styrene, butadiene and 0.05 part of quality are continuously added to in reactor dense
The persulfate aqueous solution for 3% is spent, monomer feed rates are 20 seconds/gram, continues reaction while rising high reaction temperature and being 75 DEG C,
When conversion ratio reaches more than 90.0%, Sodium Dimethyldithiocarbamate stopped reaction is added, be -0.10Mpa in degassing kettle vacuum, kettle temperature is 50
Under conditions of DEG C, it is de-gassed to remove residual monomer, degassing time is 3 hours, obtains finished product after eventually passing filter.
The physical index of latex is：Conversion ratio 94.76%；Structural gel 59.78%.
Embodiment 5
Each substance weight part is as follows：
57.8 parts of deionized water；
Butylbenzene be 70 parts of butadiene, 30 parts of styrene；
Emulsifying agent（Disproportionated rosin 2.5 parts of potassium of acid, 1 part of potassium stearate, 1.5 parts of potassium oleate）；
Electrolyte（0.3 part of potassium chloride）；
Diffusant（0.4 part of sodium metnylene bis-naphthalene sulfonate）；
Thermal decomposition initiating（Mass concentration is 0.1 part of 3% ammonium persulfate solution）；
Redox initiator（Hydrogen peroxide is to 0.15 part of Meng's alkane）；
Reducing agent（0.03 part of ferrous naphthenate）；
Molecular weight regulator（0.25 part of n- dodecyl mereaptan ether）；
Free radical stabilizer（1 part of oxidation octadecylamine polyoxyethylene ether）；
Terminator（0.1 part of Sodium Dimethyldithiocarbamate）
（1）Configuration emulsifier solution：Whole emulsifying agents are taken by above-mentioned weight portion（Wherein（Disproportionated rosin 2.5 parts of potassium of acid, Hard Fat
1 part of sour potassium, 1.5 parts of potassium oleate）, then 10.625 parts of deionized waters are added in emulsifying agent, heat the solution to 70 DEG C
And stir one hour, all dissolving to emulsifying agent, obtain emulsifier solution, the mass concentration of emulsifier solution is 32%；
（2）Emulsion agent is polymerized：Mentioned emulsifier solution, potassium chloride 0.3 part, ring are added in 2L polymeric kettles by weight disposably
0.03 part of alkanoic acid ferrous iron, 0.25 part of n- dodecyl mereaptan ether, 0.4 part of sodium metnylene bis-naphthalene sulfonate, oxidation octadecylamine polyoxy second
1 part of alkene ether, and 47.175 parts of deionized water, are exhausted to reactor with nitrogen, are emptied 3 times, start stirring, by styrene：
The ratio of butadiene=3/7, adds the butadiene and styrene of monomer gross mass 80%, when control temperature of reaction kettle reaches 15 DEG C,
0.15 part of hydrogen peroxide is added to Meng's alkane initiation reaction, 6h is reacted, conversion ratio is controlled 75% or so；Then connect in reactor
The continuous ammonium persulfate aqueous solution for adding residual styrene, butadiene and 0.1 part 3%, monomer feed rates are 20 seconds/gram, while rising
High reaction temperature is 45 DEG C and continues reaction, when conversion ratio reaches more than 90.0%, addition Sodium Dimethyldithiocarbamate stopped reaction, in degassing kettle
Vacuum is -0.10Mpa, under conditions of kettle temperature is 50 DEG C, is de-gassed to remove residual monomer, and degassing time is 3 hours.Most
Afterwards after filtering into finished product.
The physical index of latex is：Conversion ratio 92.55%；Structural gel 49.98%.
To butylbenzene styrene butadiene latex modified emulsified asphalt performance test in the various embodiments described above, wherein performance test methods are adopted
Prior art, which comprises the following steps that：The above-mentioned styrene-butadiene latex product for synthesizing is added into 5 parts of quaternaries cation emulsifyings
Agent, adjusts pH to 5-6 with HCl after stirring, and anion styrene-butadiene latex is transformed into cation styrene-butadiene latex.Then by 3 parts
During latex after transition adds the soap lye prepared by cationic emulsifier, acid adjustment adds 70# matrix pitch systems under mulser
For into modified emulsifying asphalt.The basic index of matrix pitch used by of the invention is 47 DEG C of softening point, 10 DEG C of ductilities 100cm, 25 DEG C
Needle penetration 7mm, its concrete outcome are as follows：
| Numbering | Solid content | Softening point | 10 DEG C of ductilities |
| Embodiment 1 | 55.02% | 53.1℃ | >150cm |
| Embodiment 2 | 55.77% | 54.9℃ | >150cm |
| Embodiment 3 | 56.78% | 56.4 ℃ | >150cm |
| Embodiment 4 | 61.59% | 55.8℃ | >150cm |
| Embodiment 5 | 60.15% | 54.6℃ | >150cm |
Can be obtained according to the above results：The solid content of the latex prepared using the present invention brings up to more than 55% by 40%, improves substrate
The softening point of Colophonium brings up to 55 DEG C or so by 47, more than mixing and stirring with emulsified asphalt BCR standards（53℃）Require, the present invention is made
The 5 of Colophonium DEG C of ductilities can be brought up to more than 150cm by standby latex, considerably beyond standard（20cm）Require, with reaction rate
Comparatively fast, the response time is short, the characteristics of conversion ratio and high solid content.
Claims (10)
1. a kind of preparation method of modified emulsifying asphalt styrene-butadiene latex, it is characterised in that：Shown in comprising the following steps that：
Configuration emulsifier solution：Whole emulsifying agents are taken by above-mentioned weight portion, then portions of de-ionized water are added in emulsifying agent,
Heat the solution to 70 DEG C and stir one hour, all dissolve to emulsifying agent, obtain emulsifier solution；
（2）To in polymeric kettle by weight disposably add mentioned emulsifier solution, electrolyte, reducing agent, molecular weight regulator,
Diffusant, free radical stabilizer and remaining deionized water；Then reactor is exhausted with nitrogen, empties 3 times, emptied
Finish, it is ensured that reactor is oxygen-free environment；Jing measuring tanks quickly add partial monosomy in reactor, control temperature of reaction kettle 5-15
DEG C, redox initiator initiation reaction is added, 3 ~ 6h is reacted, conversion ratio is controlled 50 ~ 70%, is then continuously added to remaining single
Body and thermal decomposition initiating, wherein monomer feed rates are 20 seconds/gram, continue anti-while raising temperature of reaction kettle and being 45 ~ 75 DEG C
Should, when conversion ratio reaches more than 90.0%, terminator stopped reaction is added, in the kettle vacuum that deaerates for -0.10Mpa, kettle temperature is
Under conditions of 50 DEG C, it is de-gassed to remove residual monomer, degassing time is 3 hours, obtains finished product after eventually passing filter.
2. the weight portion of wherein each reactant is deionized water 60-100 parts；Monomer includes butadiene and styrene（Wherein fourth two
Alkene 60-80 parts；Styrene 20-40 parts）；Emulsifying agent 4-7 parts, electrolyte 0.1-0.3 parts；Diffusant 0.1-0.5 parts；Cause
Agent includes thermal decomposition initiating and redox initiator, wherein thermal decomposition initiating 0-0.1 part, redox initiator
0.1-0.2 parts；Reducing agent 0.01-0.05 parts；Molecular weight regulator 0.1-0.5 parts；Free radical stabilizer 0.1-1 parts；Terminate
Agent 0.05-0.1 parts.
3. the preparation method of modified emulsifying asphalt styrene-butadiene latex according to claim 1, it is characterised in that：Monomer used
For butadiene and styrene, low-temperature zone, by styrene：The weight ratio of butadiene=1/3 ~ 5/6, adds butadiene and benzene second
The 50% ~ 80% of alkene total weight parts；High temperature section adds residual styrene and butadiene, monomer addition to feed for seriality, charging speed
Spend for 20 seconds/gram.
4. the preparation method of modified emulsifying asphalt styrene-butadiene latex according to claim 3, it is characterised in that：Described breast
Agent is oleate, linoleate, rosinate, laruate, one or more anion emulsifier compounding in soap
Use, and its mass concentration is 25-35%, the pH value of emulsifier solution is 8 ~ 11.
5. the preparation method of modified emulsifying asphalt styrene-butadiene latex according to claim 3, it is characterised in that：Described oxygen
It is organic peroxide initiator to change reduction initiator, and hydrogen peroxide is to Meng's alkane, cumyl hydroperoxide or peroxidating hexamethylene
Ketone；
The preparation method of modified emulsifying asphalt styrene-butadiene latex according to claim 4, it is characterised in that：The electrolyte
For potassium chloride, sodium bicarbonate.
6. the preparation method of the modified emulsifying asphalt styrene-butadiene latex according to claim 1 or 4, it is characterised in that：It is described
Redox initiator be organic peroxide initiator；Described thermal decomposition initiating is Ammonium persulfate., potassium peroxydisulfate
Aqueous solution, and its mass concentration be 2-5%.
7. the preparation method of modified emulsifying asphalt styrene-butadiene latex according to claim 6, it is characterised in that：Described goes back
Former agent is low price manganese, vanadium, the sulfate of ferrum or nitrate, manganese naphthenate, vanadium, iron salt or tertiary amine compounds；Described expansion
Powder be lignin sulfonate, one or more of naphthalene sulfonic acid-formaldehyde condensation product.
8. the preparation method of modified emulsifying asphalt styrene-butadiene latex according to claim 7, it is characterised in that：Described divides
Son amount regulator is one or more in primary, secondary, tertiary mercaptan, mercaptan ester and the mercaptan ether of 9 ~ 14 carbon atoms.
9. the preparation method of modified emulsifying asphalt styrene-butadiene latex according to claim 8, it is characterised in that：It is described from
By the ethoxylated fatty amines oxide that based stabilizer is 14 ~ 24 carbon.
10. the preparation method of modified emulsifying asphalt styrene-butadiene latex according to claim 9, it is characterised in that：Described
Terminator is Sodium Dimethyldithiocarbamate, sodium polysulphide.
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| CN108285513A (en) * | 2018-02-09 | 2018-07-17 | 黄河三角洲京博化工研究院有限公司 | A kind of styrene-butadiene latex and preparation method thereof |
| CN111320792A (en) * | 2020-04-14 | 2020-06-23 | 山东京博中聚新材料有限公司 | Modified latex for road emulsified asphalt, preparation method of modified latex and road emulsified asphalt |
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| CN111804253A (en) * | 2020-07-14 | 2020-10-23 | 山东京博中聚新材料有限公司 | Recycling process of styrene-butadiene latex reaction kettle washing water |
| CN113512148A (en) * | 2021-08-04 | 2021-10-19 | 福建亮晶晶新材料有限公司 | Preparation method of special styrene-butadiene latex for road asphalt modification |
| CN116496510A (en) * | 2023-05-29 | 2023-07-28 | 山东京博中聚新材料有限公司 | Trimodal high-solid polymer emulsion and preparation method thereof |
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| CN111804253A (en) * | 2020-07-14 | 2020-10-23 | 山东京博中聚新材料有限公司 | Recycling process of styrene-butadiene latex reaction kettle washing water |
| CN113512148A (en) * | 2021-08-04 | 2021-10-19 | 福建亮晶晶新材料有限公司 | Preparation method of special styrene-butadiene latex for road asphalt modification |
| CN116496510A (en) * | 2023-05-29 | 2023-07-28 | 山东京博中聚新材料有限公司 | Trimodal high-solid polymer emulsion and preparation method thereof |
| CN116496510B (en) * | 2023-05-29 | 2024-03-29 | 山东京博中聚新材料有限公司 | Trimodal high-solid polymer emulsion and preparation method thereof |
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