CN112500526A - Preparation method of large-particle-size styrene-butadiene latex - Google Patents
Preparation method of large-particle-size styrene-butadiene latex Download PDFInfo
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Abstract
The application belongs to the field of emulsion polymerization in high polymer materials, and relates to a preparation method of large-particle-size styrene-butadiene latex, which is characterized by comprising the following steps of: preparing small-particle-size styrene-butadiene latex with the particle size of 150-200 nm; slowly dripping an agglomerating agent into the small-particle-size butylbenzene latex, uniformly dispersing, and adjusting the pH value of a reaction system to 7-8; cooling to-15 to-25 ℃, keeping the temperature for a plurality of hours, heating to 30 to 40 ℃, uniformly dispersing, and filtering to obtain the large-particle-size styrene-butadiene latex with the particle size of 300 to 400 nm. The latex produced by the technology has the advantages of average particle size distribution of 300-400 nm, uniform particle size distribution, good fluidity, high stability and good purity.
Description
Technical Field
The invention belongs to the technical field of emulsion polymerization in high polymer materials, relates to latex used in the fields of latex foaming, adhesives, resin toughening and the like and a preparation method thereof, and particularly relates to a preparation method of large-particle-size styrene-butadiene latex.
Background
At present, the production method of the large-particle-size styrene-butadiene latex mainly comprises a one-step method and a two-step method. The one-step method directly adopts a low-temperature emulsion polymerization process, so that the small-particle size styrene-butadiene latex particles are gradually agglomerated in the polymerization reaction process to form the large-particle size styrene-butadiene latex. The two-step method is that firstly styrene-butadiene latex with certain particle size distribution is synthesized, and then physical agglomeration or chemical agglomeration is carried out on the latex to prepare the large-particle-size styrene-butadiene latex with certain particle size distribution.
When the large-particle-size styrene-butadiene latex is prepared by the one-step method, the polymerization temperature is low, the viscosity of a reaction system is high, the requirements on stirring rotating speed and other reaction equipment are high, the particle size of a product is easily influenced by the stirring rotating speed and the reaction temperature, so that the particle size distribution is generally wide, and the large-particle-size styrene-butadiene latex with narrow particle size distribution is difficult to prepare.
The two-step method is to prepare the large-particle size styrene-butadiene latex by agglomerating the latex with specific particle size distribution, and add a special chemical agglomerating agent into a latex system to quickly agglomerate latex particles or change the temperature of the latex system to prepare the large-particle size styrene-butadiene latex with uniform particle size distribution. The chemical agglomeration method has the characteristics of high agglomeration speed and good agglomeration effect, but the stability and the purity of the latex are reduced due to the addition of a large amount of the agglomerating agent, and the agglomeration effect of the latex is influenced by the addition amount, the concentration and the addition mode of the agglomerating agent. Compared with the chemical agglomeration process, the method of physical cooling, freezing and agglomeration is adopted, and other substances are not required to be added, so that the pure large-particle-size styrene-butadiene latex with uniform particle size distribution can be prepared. But the freezing temperature is lower, the freezing time is difficult to control, and the performance requirement on a temperature control system of the reaction equipment is higher.
Disclosure of Invention
The present application is directed to solving the above problems and providing a method for preparing a large-particle size styrene-butadiene latex.
In order to achieve the purpose, the invention adopts the following technical scheme:
the application creatively provides a preparation method of styrene-butadiene latex with large particle size, which comprises the following steps:
1) preparing small-particle-size styrene-butadiene latex with the average particle size of 150-200 nm; the preparation method of the small-particle-size styrene-butadiene latex comprises the following steps of,
A. preparing a water-phase pre-emulsion: preparing an aqueous phase pre-emulsion by using deionized water, an anionic emulsifier, an electrolyte, a pH buffer and a chelating agent for later use;
B. preparation of an oil phase dropwise addition phase: preparing an oil phase dropwise adding phase by using styrene and a molecular weight regulator for later use;
C. preparation of an initiator dropwise addition phase: preparing an initiator dropwise adding phase by using styrene and an initiator for later use;
D. and (3) segmented reaction:
a first stage of reaction, adding deionized water, a first part of water phase pre-emulsion, a first part of oil phase dropwise adding phase and a first part of butadiene in a vacuum state, emulsifying and dispersing for a plurality of hours, heating to 30-60 ℃, and dropwise adding a first part of initiator dropwise adding phase to react for a plurality of hours;
and in the second stage of reaction, continuously dropwise adding the residual water phase pre-emulsion, the residual oil phase dropwise adding phase, the residual butadiene and the residual initiator dropwise adding phase, keeping the temperature at 30-60 ℃ for reaction for several hours, reacting until the conversion rate reaches 80-90%, and adding a terminator to terminate the reaction to obtain the small-particle-size styrene-butadiene latex.
2) Slowly dripping an agglomerating agent into the small-particle-size butylbenzene latex, uniformly dispersing, and adjusting the pH value of a reaction system to 7-8;
3) cooling the reaction system in the step 2) to-15 to-25 ℃, keeping the temperature for a plurality of hours, heating to 30 to 40 ℃, uniformly dispersing, and filtering to obtain the large-particle-size styrene-butadiene latex with the average particle size of 300 to 400 nm.
In the preparation method of the styrene-butadiene latex with the large particle size, in the step A, the aqueous pre-emulsion is prepared by stirring and dispersing 60-110 parts by weight of deionized water, 1-5 parts by weight of an anionic emulsifier, 0.1-0.5 part by weight of an electrolyte, 0.1-0.5 part by weight of a pH buffer and 0.01-0.05 part by weight of a chelating agent for 1-2 hours.
In the preparation method of the styrene-butadiene latex with the large particle size, in the step B, the oil phase dropwise addition phase is prepared by stirring and dispersing 15-30 parts by weight of styrene and 0.3-0.8 part by weight of a molecular weight regulator for 1-2 hours.
In the preparation method of the styrene-butadiene latex with the large particle size, in the step C, the initiator dropwise adding phase is prepared by stirring and dispersing 5-10 parts by weight of styrene and 0.2-0.7 part by weight of initiator for 0.5-1 hour.
In the preparation method of the large-particle-size styrene-butadiene latex, in the step D, the total amount of butadiene in the sectional reaction is 50-70 parts by weight;
the first stage reaction specifically comprises the following steps: adding 60-110 parts by weight of deionized water, a first part of water phase pre-emulsion accounting for 20-30 wt% of the total amount of the water phase pre-emulsion, a first part of oil phase dropwise addition phase accounting for 10-30 wt% of the total amount of the oil phase dropwise addition phase and a first part of butadiene accounting for 10-30 wt% of the total amount of butadiene in a vacuum state, emulsifying and dispersing for 0.5-1 hour, then heating to 30-60 ℃, dropwise adding a first part of initiator dropwise addition phase accounting for 5-10 wt% of the total amount of the initiator dropwise addition phase, and reacting for 1-2 hours.
In the preparation method of the large-particle-size styrene-butadiene latex, in the step D, the second-stage reaction specifically comprises: and continuously dropwise adding the residual water phase pre-emulsion, the residual oil phase dropwise adding phase, the residual butadiene and the residual initiator dropwise adding phase, wherein the dropwise adding time is 3-5 hours, reacting at the temperature of 30-60 ℃ in a heat preservation manner until the conversion rate reaches 80-90%, and adding 0.1-0.5 part by weight of a terminator to terminate the reaction, thereby obtaining the small-particle-size styrene-butadiene latex.
In the preparation method of the large-particle-size styrene-butadiene latex, the anionic emulsifier is one or more of sodium oleate, potassium oleate, ammonium oleate, sodium fatty acid, sodium oleoyl sarcosinate, ammonium lauryl sulfate, sodium dodecyl benzene sulfonate, sodium lauroyl methylamine acetate, sodium alkylphenol polyoxyethylene ether sulfonate, potassium disproportionate abietate, sodium disproportionate abietate, potassium abietate, sodium abietate and castor oil sodium sulfate.
In the preparation method of the large-particle-size styrene-butadiene latex, the agglomerating agent is one or more of acetic acid, propionic acid, hydrochloric acid, octadecyl trimethyl ammonium chloride and polyamide, and the using amount of the agglomerating agent is 0.05-0.1 part by weight.
In the preparation method of the large-particle-size styrene-butadiene latex, the chelating agent comprises one or more of disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate, sodium gluconate, sodium pyrophosphate and sodium phosphate.
In the preparation method of the large-particle size styrene-butadiene latex, the molecular weight regulator comprises one or more of tert-dodecyl mercaptan, diisopropyl xanthogen disulfide, ethylene glycol dimethyl ether, isooctyl 3-mercaptopropionate, thioglycolate and alpha-methyl styrene linear dimer.
In the preparation method of the large-particle-size styrene-butadiene latex, the initiator comprises one or more of ammonium persulfate, diisopropyl peroxydicarbonate, potassium persulfate, sodium persulfate, tert-butyl hydroperoxide, diisopropylbenzene hydroperoxide, peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile, ammonium persulfate-ferrous sulfate and potassium persulfate-sodium bisulfite.
In the preparation method of the large-particle-size styrene-butadiene latex, the electrolyte comprises one or more of sodium chloride, potassium chloride, ammonium chloride, potassium sulfate, sodium sulfate, potassium nitrate, sodium nitrate, potassium phosphate and sodium bromide.
In the above preparation method of the large-particle size styrene-butadiene latex, the pH buffer comprises one or more of sodium bicarbonate, sodium sesquicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium dihydrogen phosphate, potassium dihydrogen phosphate and sodium hydrogen phthalate.
In the preparation method of the large-particle size styrene-butadiene latex, the terminating agent comprises one or more of diethylhydroxylamine, xanthic acid, sodium dimethyldithiocarbamate, hydroquinone, tert-butylcatechol and sodium nitrite.
Compared with the prior art, the invention has the advantages that:
the latex produced by the technology has the advantages of average particle size distribution of 300-400 nm, uniform particle size distribution, good fluidity, high stability and good purity.
The large-particle-size styrene-butadiene latex is prepared by combining chemistry and physics, the emulsion polymerization process is safe and easy to control, the dosage of a chemical agglomerating agent is small, the freezing agglomeration temperature is proper, the requirement on equipment is not high, the agglomeration effect is good, the film forming and film forming properties are excellent, and the method can be widely applied to the fields of latex foaming, adhesives, toughened resins, latex sponges and the like.
And step D, a sectional polymerization mode is adopted, so that the particle size distribution of the latex is uniform, and the physical property of the latex is further improved.
Detailed Description
Further illustrated by the following specific examples;
example one
A preparation method of large-particle-size styrene-butadiene latex comprises the following steps,
1) preparation of Small particle size styrene-butadiene latex
A. Preparing a water-phase pre-emulsion:
110kg of deionized water, 2.5kg of sodium fatty acid, 2.5kg of disproportionated rosin potassium, 0.35kg of potassium chloride, 0.15kg of sodium bicarbonate and 0.015kg of ethylene diamine tetraacetic acid tetrasodium salt are prepared into a water-phase pre-emulsion in a first proportioning tank with stirring sealed belts for later use.
B. Preparation of an oil phase dropwise addition phase:
an oil phase dropwise adding phase is prepared by adopting 25kg of styrene and 0.5kg of tert-dodecyl mercaptan in a second preparation tank with stirring in a sealing belt for later use.
C. Preparation of an initiator dropwise addition phase:
an initiator dropping phase is prepared by 10kg of styrene and 0.3kg of diisopropyl peroxydicarbonate in a third dosing tank with stirring by a sealing belt for standby.
D. The above 115.515kg of aqueous phase pre-emulsion, 25.5kg of oil phase dropwise addition phase, 10.3kg of initiator dropwise addition phase and 65kg of butadiene were used for the staged reaction:
and in the first stage of reaction, adding 60kg of deionized water into a clean and vacuumized 500kg polymerization reaction kettle, adding 23.5kg of first part of water phase pre-emulsion, 2.5kg of first part of oil phase dropwise addition phase and 6.5kg of first part of butadiene into the reaction kettle, stirring at a high speed, emulsifying and dispersing for 0.5 hour, heating the reaction system to 50-60 ℃, dropwise adding 0.6kg of first part of initiator dropwise addition phase, and reacting for 2 hours.
And in the second stage of reaction, continuously dropwise adding the residual 92.015kg of water-phase pre-emulsion, the residual 23kg of oil-phase dropwise adding phase, the residual 58.5kg of butadiene and the residual 9.7kg of initiator dropwise adding phase, finishing the dropwise adding, wherein the dropwise adding time is 4 hours, carrying out heat preservation reaction at 50-60 ℃, sampling and detecting every 2 hours, stopping the heat preservation reaction when the reaction is carried out until the conversion rate reaches 80-90%, discharging into a degassing kettle, and dropwise adding 0.1kg of diethylhydroxylamine to obtain the small-particle-size styrene-butadiene latex with the average particle size of 190 nm.
2) Slowly dripping 0.1kg of acetic acid into the small-particle-size styrene-butadiene latex in the degassing kettle, uniformly dispersing for 2 hours after the dripping is finished, and adjusting the pH value of a reaction system to 7-8.
3) And then cooling the materials in the degassing kettle to-15 to-25 ℃, preserving the heat for 0.5 hour, heating to 30 to 40 ℃, uniformly stirring and dispersing for 2 hours, discharging, filtering and packaging to obtain the large-particle-size styrene-butadiene latex with the average particle size of 370 nm.
Example two
A preparation method of large-particle-size styrene-butadiene latex comprises the following steps,
1) preparation of Small particle size styrene-butadiene latex
A. Preparing a water-phase pre-emulsion:
80kg of deionized water, 2.5kg of potassium abietate, 0.45kg of potassium sulfate, 0.25kg of potassium bicarbonate and 0.05kg of disodium ethylene diamine tetraacetate are prepared into a water-phase pre-emulsion in a first proportioning tank with stirring by a sealing belt for later use.
B. Preparation of an oil phase dropwise addition phase:
15kg of styrene and 0.3kg of diisopropyl xanthogen disulfide are prepared into an oil phase dropwise adding phase for later use in a second dosing tank with stirring by a sealing belt.
C. Preparation of an initiator dropwise addition phase:
an initiator dropwise adding phase prepared from 5kg of styrene and 0.2kg of diisopropylbenzene hydroperoxide is used in a third preparation tank with stirring by a sealing belt for standby.
D. The above 83.25kg of aqueous phase pre-emulsion, 15.3kg of oil phase dropwise addition phase, 5.2kg of initiator dropwise addition phase and 50kg of butadiene were used for the staged reaction:
and in the first stage of reaction, adding 60kg of deionized water into a clean and vacuumized 500kg of polymerization reaction kettle, adding 24.8kg of first part of water phase pre-emulsion, 3kg of first part of oil phase dropwise addition phase and 6.5kg of first part of butadiene into the reaction kettle, stirring at a high speed, emulsifying and dispersing for 0.5 hour, heating the reaction system to 45-55 ℃, dropwise adding 0.37kg of first part of initiator dropwise addition phase, and reacting for 1.5 hours.
And in the second stage of reaction, continuously dropwise adding the residual 58.45kg of water-phase pre-emulsion, the residual 12.3kg of oil-phase dropwise addition phase, the residual 43.5kg of butadiene and the residual 4.83kg of initiator dropwise addition phase, completing the dropwise addition, wherein the dropwise addition time is 4 hours, carrying out heat preservation reaction at 50-55 ℃, sampling and detecting every 2 hours, stopping the heat preservation reaction when the conversion rate reaches 80-90% after the reaction, discharging to a degassing kettle, and dropwise adding 0.2kg of tert-butyl catechol to obtain the small-particle-size styrene-butadiene latex with the average particle size of 177 nm.
2) Slowly dripping 0.08kg of octadecyl trimethyl ammonium chloride into small-particle-size butadiene styrene latex in a degassing kettle, uniformly dispersing for 2 hours after finishing dripping, and adjusting the pH value of a reaction system to 7-8.
3) And then cooling the materials in the degassing kettle to-15 to-25 ℃, preserving the heat for 0.5 hour, heating to 30 to 40 ℃, uniformly stirring and dispersing for 2 hours, discharging, filtering and packaging to obtain the large-particle-size styrene-butadiene latex with the average particle size of 355 nm.
EXAMPLE III
A preparation method of large-particle-size styrene-butadiene latex comprises the following steps,
1) preparation of Small particle size styrene-butadiene latex
A. Preparing a water-phase pre-emulsion:
60kg of deionized water, 2kg of sodium dodecyl benzene sulfonate, 0.5kg of castor oil sodium sulfate, 0.4kg of potassium chloride, 0.4kg of sodium sesquicarbonate, 0.01kg of sodium pyrophosphate and 0.01kg of tetrasodium ethylene diamine tetraacetate are prepared into aqueous pre-emulsion for later use.
B. Preparation of an oil phase dropwise addition phase:
25kg of styrene and 0.6kg of ethylene glycol dimethyl ether are adopted to prepare an oil phase dropwise adding phase for later use.
C. Preparation of an initiator dropwise addition phase:
9kg of styrene and 0.65kg of azobisisoheptonitrile are adopted to prepare an initiator dropwise-adding phase for standby.
D. The above 63.32kg of aqueous phase pre-emulsion, 25.6kg of oil phase dropwise addition phase, 9.65kg of initiator dropwise addition phase and 60kg of butadiene were used for the staged reaction:
and in the first stage of reaction, adding 65kg of deionized water into a clean and vacuumized 500kg polymerization reaction kettle, adding 13kg of first part of water phase pre-emulsion, 2.8kg of first part of oil phase dropwise addition phase and 15kg of first part of butadiene into the reaction kettle, stirring at high speed, emulsifying and dispersing for 1 hour, heating the reaction system to 40-50 ℃, dropwise adding 1.9kg of first part of initiator dropwise addition phase, and reacting for 1.5 hours.
And in the second stage of reaction, continuously dropwise adding the residual 50.32kg of water-phase pre-emulsion, the residual 22.8kg of oil-phase dropwise addition phase, the residual 45kg of butadiene and the residual 7.75kg of initiator dropwise addition phase, completing the dropwise addition, wherein the dropwise addition time is 3.5 hours, carrying out heat preservation reaction at 45-55 ℃, sampling and detecting every 1 hour, stopping the heat preservation reaction when the conversion rate reaches 80-90% after the reaction, discharging to a degassing kettle, and dropwise adding 0.1kg of xanthic acid to obtain the small-particle-size styrene-butadiene latex with the average particle size of 165 nm.
2) Slowly dripping 0.05kg of hydrochloric acid into the small-particle-size styrene-butadiene latex in the degassing kettle, uniformly dispersing for 2 hours after the dripping is finished, and adjusting the pH value of a reaction system to 7-8.
3) And then cooling the materials in the degassing kettle to-15 to-25 ℃, preserving the heat for 0.5 hour, heating to 30 to 40 ℃, uniformly stirring and dispersing for 2 hours, discharging, filtering and packaging to obtain the large-particle-size styrene-butadiene latex with the average particle size of 335 nm.
Example four
A preparation method of large-particle-size styrene-butadiene latex comprises the following steps,
1) preparation of Small particle size styrene-butadiene latex
A. Preparing a water-phase pre-emulsion:
110kg of deionized water, 3.5kg of sodium fatty acid, 1.5kg of disproportionated rosin potassium, 0.35kg of potassium chloride, 0.15kg of sodium bicarbonate and 0.015kg of ethylene diamine tetraacetic acid tetrasodium salt are prepared into a water-phase pre-emulsion in a first proportioning tank with stirring sealed belts for later use.
B. Preparation of an oil phase dropwise addition phase:
an oil phase dropwise adding phase is prepared by adopting 25kg of styrene and 0.6kg of tert-dodecyl mercaptan in a second preparation tank with stirring by a sealing belt for later use.
C. Preparation of an initiator dropwise addition phase:
an initiator dropping phase is prepared by adopting 15kg of styrene and 0.4kg of diisopropyl peroxydicarbonate in a third dosing tank with stirring by a sealing belt for standby.
E. The above 115.515kg of aqueous phase pre-emulsion, 25.6kg of oil phase dropwise addition phase, 15.4kg of initiator dropwise addition phase and 60kg of butadiene were used for the staged reaction:
and in the first stage of reaction, adding 60kg of deionized water into a clean and vacuumized 500kg of polymerization reaction kettle, adding 23.5kg of first part of water phase pre-emulsion, 2.5kg of first part of oil phase dropwise addition phase and 6.5kg of first part of butadiene into the reaction kettle, stirring at a high speed, emulsifying and dispersing for 0.5 hour, heating the reaction system to 50-55 ℃, dropwise adding 0.6kg of first part of initiator dropwise addition phase, and reacting for 2 hours.
And in the second stage of reaction, continuously dropwise adding the residual 92.015kg of water-phase pre-emulsion, the residual 23kg of oil-phase dropwise adding phase, the residual 58.5kg of butadiene and the residual 9.7kg of initiator dropwise adding phase, finishing the dropwise adding, wherein the dropwise adding time is 4 hours, carrying out heat preservation reaction at 50-55 ℃, sampling and detecting every 2 hours, stopping the heat preservation reaction when the reaction reaches 80-90% of conversion rate, discharging to a degassing kettle, and dropwise adding 0.1kg of diethylhydroxylamine to obtain the small-particle-size styrene-butadiene latex with the average particle size of 155 nm.
2) Slowly dripping 0.1kg of acetic acid into the small-particle-size styrene-butadiene latex in the degassing kettle, uniformly dispersing for 2 hours after the dripping is finished, and adjusting the pH value of a reaction system to 7-8.
3) And then cooling the materials in the degassing kettle to-15 to-25 ℃, preserving the heat for 0.5 hour, heating to 30 to 40 ℃, uniformly stirring and dispersing for 2 hours, discharging, filtering and packaging to obtain the large-particle-size styrene-butadiene latex with the average particle size of 320 nm.
EXAMPLE five
A preparation method of large-particle-size styrene-butadiene latex comprises the following steps,
1) preparation of Small particle size styrene-butadiene latex
A. Preparing a water-phase pre-emulsion:
110kg of deionized water, 1.5kg of sodium fatty acid, 3.5kg of disproportionated rosin potassium, 0.35kg of potassium chloride, 0.15kg of sodium bicarbonate and 0.015kg of ethylene diamine tetraacetic acid tetrasodium salt are prepared into a water-phase pre-emulsion in a first proportioning tank with stirring sealed belts for later use.
B. Preparation of an oil phase dropwise addition phase:
an oil phase dropwise adding phase is prepared by adopting 25kg of styrene and 0.6kg of tert-dodecyl mercaptan in a second preparation tank with stirring by a sealing belt for later use.
C. Preparation of an initiator dropwise addition phase:
an initiator dropping phase is prepared by adopting 15kg of styrene and 0.5kg of diisopropyl peroxydicarbonate in a third dosing tank with stirring by a sealing belt for standby.
D. The above 115.515kg of aqueous phase pre-emulsion, 25.6kg of oil phase dropwise addition phase, 15.4kg of initiator dropwise addition phase and 60kg of butadiene were used for the staged reaction:
and in the first stage of reaction, adding 60kg of deionized water into a clean and vacuumized 500kg of polymerization reaction kettle, adding 23.5kg of first part of water phase pre-emulsion, 2.5kg of first part of oil phase dropwise addition phase and 6.5kg of first part of butadiene into the reaction kettle, stirring at a high speed, emulsifying and dispersing for 0.5 hour, heating the reaction system to 45-50 ℃, dropwise adding 0.6kg of first part of initiator dropwise addition phase, and reacting for 2 hours.
And in the second stage of reaction, continuously dropwise adding the residual 92.015kg of water-phase pre-emulsion, the residual 23kg of oil-phase dropwise adding phase, the residual 58.5kg of butadiene and the residual 9.7kg of initiator dropwise adding phase, finishing the dropwise adding, wherein the dropwise adding time is 4 hours, carrying out heat preservation reaction at 50-55 ℃, sampling and detecting every 2 hours, stopping the heat preservation reaction when the reaction is carried out until the conversion rate reaches 80-90%, discharging to a degassing kettle, and dropwise adding 0.1kg of diethylhydroxylamine to obtain the small-particle-size styrene-butadiene latex with the average particle size of 183 nm.
2) Slowly dripping 0.1kg of acetic acid into the small-particle-size styrene-butadiene latex in the degassing kettle, uniformly dispersing for 2 hours after the dripping is finished, and adjusting the pH value of a reaction system to 7-8.
3) And then cooling the materials in the degassing kettle to-15 to-25 ℃, preserving the heat for 0.5 hour, heating to 30 to 40 ℃, uniformly stirring and dispersing for 2 hours, discharging, filtering and packaging to obtain the large-particle-size styrene-butadiene latex with the average particle size of 385 nm.
Comparative example 1
The formulation and procedure of this comparative example are substantially the same as those of example one, except that: and 3) not performing the step 3), slowly dripping 1kg of acetic acid into the small-particle-size styrene-butadiene latex in the degassing kettle in the step 2), uniformly dispersing for 5 hours after finishing dripping, adjusting the pH value of a reaction system to 7-8, discharging, filtering and packaging to directly prepare large-particle-size styrene-butadiene latex with the average particle size of 352 nm.
Comparative example No. two
The formulation and procedure of this comparative example was essentially the same as that of comparative example one, except that: in the step 2), 0.1kg of acetic acid is added into the small-particle-size styrene-butadiene latex in the degassing kettle at one time, the mixture is uniformly dispersed for 2 hours, and the pH value of the reaction system is adjusted to 7-8. And then carrying out the operation of the step 3).
The large-particle size styrene-butadiene latex obtained in the first to fifth examples was tested by the following standards or instruments:
total solid content: SH/T1154-92
Viscosity: SH/T1152-92
pH value: SH/T1150-92
Surface tension: SH/T1156-92
Mechanical stability: SH/T1151-92
Chemical stability (polymeric coacervate): SH/T1608-95
Average particle size: AUTOSIZER IIC particle size meter
Particle size dispersity: mastersizer 2000E
The test results are shown in table 1:
TABLE 1 summary of physical property test results of large particle size styrene-butadiene latex
The result shows that the large-particle-size styrene-butadiene latex prepared by the method has better fluidity, higher mechanical stability and higher purity, has uniform particle size and is beneficial to improving the product quality.
Application example
The application is divided into two steps: firstly, preparing high-solid-content styrene-butadiene latex by taking large-particle-size styrene-butadiene latex as basic latex; and secondly, preparing a styrene-butadiene latex sponge foamed product by using the styrene-butadiene latex with high solid content as a raw material.
Firstly, the large-particle size styrene-butadiene latex prepared in the first, second, third, fourth and fifth examples and the first and second comparative examples is taken as the base latex, and the following formula is added in parts by weight:
large particle size styrene-butadiene latex base latex: 100 portions of
Antioxidant: 0.1 to 0.2 portion
A stabilizer: 0.1 to 0.5 portion
pH regulator: 0.01 to 0.1 portion
Defoaming agent: 0.01 to 0.1 portion
Adding large-particle-size styrene-butadiene latex into a degassing kettle, gradually heating to 50-80 ℃, adding an antioxidant, uniformly mixing and reacting for 0.5-1 hour, then gradually vacuumizing the degassing kettle to remove water, vacuumizing to-0.01 MPa to-0.06 MPa, vacuumizing for 3-8 hours, timely and properly adding an antifoaming agent according to the foam condition in the degassing kettle, adding a proper amount of a stabilizing agent when the solid content of the styrene-butadiene latex is calculated to be 60-65% according to the amount of the vacuumizing water removal, uniformly dispersing for 0.5-1 hour, then adding a proper amount of a pH regulator, uniformly dispersing and reacting for 0.5-1 hour, adjusting the pH value of the latex to be 6-9, then cooling to 30-40 ℃, discharging, filtering and packaging to obtain the high-solid-content styrene-butadiene latex with the solid content of 60-65%, the viscosity of 400-800 cps and the pH of 6-9.
The physical properties of the prepared high-solid content styrene-butadiene latex are shown in Table 2:
TABLE 2 physical Properties of high solid content styrene-butadiene latex
The result shows that the high-solid-content styrene-butadiene latex prepared by the method has better fluidity, stability and purity.
And taking the prepared high-solid-content styrene-butadiene latex as raw material latex, and feeding according to the following formula in parts by mass:
high solid content styrene-butadiene latex: 100 portions of
Foaming agent: 0.1 to 0.5 portion
A stabilizer: 0.01 to 0.2 portion
pH regulator: 0.01 to 0.05 portion
Sulfur dispersion: 1 to 5 portions of
Diluent agent: 1 to 10 parts of
Filling: 1 to 50 parts of
Gelling agent: 0.1 to 1 portion
Under a proper stirring speed, sequentially adding high-solid-content styrene-butadiene latex, a foaming agent, a stabilizer, a pH regulator, a sulfur dispersion, a diluent and a filler into a foaming machine, fully stirring and uniformly dispersing at 20-50 ℃, then starting foaming at a proper stirring speed, adding a gelling agent when indexes such as foaming volume, foam fineness and the like meet requirements, uniformly dispersing at a proper stirring speed, injecting a foaming material into a clean mold, placing at 40-120 ℃, and vulcanizing for 0.5-2 hours.
The physical properties of the prepared high-solid-content styrene-butadiene latex foamed sponge product are as shown in Table 3, wherein the test standard adopted by the tearing strength is GB/T10808-2006, and the test standard adopted by the compression permanent deformation is GB/T6669-2008:
TABLE 3 physical Properties of high solid content styrene-butadiene latex foamed sponge products
The result shows that the styrene butadiene latex sponge foamed product prepared by the method has proper pore diameter and excellent strength and elasticity, and can be widely used for manufacturing sofas and seats.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Although the terms anionic emulsifier, electrolyte, pH buffer, chelating agent, molecular weight regulator, initiator, terminating agent, agglomerating agent, etc. are used more herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention and they are to be interpreted as any additional limitation which is not in accordance with the spirit of the present invention.
Claims (10)
1. A preparation method of large-particle-size styrene-butadiene latex is characterized by comprising the following steps of:
1) preparing small-particle-size styrene-butadiene latex with the particle size of 150-200 nm;
2) slowly dripping an agglomerating agent into the small-particle-size butylbenzene latex, uniformly dispersing, and adjusting the pH value of a reaction system to 7-8;
3) cooling to-15 to-25 ℃, keeping the temperature for a plurality of hours, heating to 30 to 40 ℃, uniformly dispersing, and filtering to obtain the large-particle-size styrene-butadiene latex with the particle size of 300 to 400 nm.
2. The method for preparing styrene-butadiene latex with large particle size according to claim 1, wherein the method for preparing styrene-butadiene latex with small particle size comprises the following steps:
A. preparing a water-phase pre-emulsion: preparing an aqueous phase pre-emulsion by using deionized water, an anionic emulsifier, an electrolyte, a pH buffer and a chelating agent for later use;
B. preparation of an oil phase dropwise addition phase: preparing an oil phase dropwise adding phase by using styrene and a molecular weight regulator for later use;
C. preparation of an initiator dropwise addition phase: preparing an initiator dropwise adding phase by using styrene and an initiator for later use;
D. and (3) segmented reaction:
a first stage of reaction, adding deionized water, a first part of water phase pre-emulsion, a first part of oil phase dropwise adding phase and a first part of butadiene in a vacuum state, emulsifying and dispersing for a plurality of hours, heating to 30-60 ℃, and dropwise adding a first part of initiator dropwise adding phase to react for a plurality of hours;
and in the second stage of reaction, continuously dropwise adding the residual water phase pre-emulsion, the residual oil phase dropwise adding phase, the residual butadiene and the residual initiator dropwise adding phase, keeping the temperature at 30-60 ℃ for reaction for several hours, reacting until the conversion rate reaches 80-90%, and adding a terminator to terminate the reaction to obtain the small-particle-size styrene-butadiene latex.
3. The method of claim 2, wherein the large-particle size styrene-butadiene latex comprises: in the step A, the aqueous phase pre-emulsion is prepared by stirring and dispersing 60-110 parts by weight of deionized water, 1-5 parts by weight of an anionic emulsifier, 0.1-0.5 part by weight of an electrolyte, 0.1-0.5 part by weight of a pH buffering agent and 0.01-0.05 part by weight of a chelating agent for 1-2 hours;
in the step B, the oil phase dropwise adding phase is prepared by stirring and dispersing 15-30 parts by weight of styrene and 0.3-0.8 part by weight of molecular weight regulator for 1-2 hours;
in the step C, the initiator dropwise adding phase is prepared by stirring and dispersing 5-10 parts by weight of styrene and 0.2-0.7 part by weight of initiator for 0.5-1 h.
4. The method for preparing styrene-butadiene latex with large particle size according to claim 3, wherein the amount of butadiene is 50 to 70 parts by weight;
in the step D, the first stage reaction specifically comprises the following steps: adding 60-110 parts by weight of deionized water, a first part of water phase pre-emulsion accounting for 20-30 wt% of the total amount of the water phase pre-emulsion, a first part of oil phase dropwise addition phase accounting for 10-30 wt% of the total amount of the oil phase dropwise addition phase and a first part of butadiene accounting for 10-30 wt% of the total amount of butadiene in a vacuum state, emulsifying and dispersing for 0.5-1 hour, then heating to 30-60 ℃, dropwise adding a first part of initiator dropwise addition phase accounting for 5-10 wt% of the total amount of the initiator dropwise addition phase, and reacting for 1-2 hours.
5. The method for preparing styrene-butadiene latex with large particle size according to claim 4, wherein in the step D, the second stage reaction comprises the following specific steps: and continuously dropwise adding the residual water phase pre-emulsion, the residual oil phase dropwise adding phase, the residual butadiene and the residual initiator dropwise adding phase, wherein the dropwise adding time is 3-5 hours, reacting at the temperature of 30-60 ℃ in a heat preservation manner until the conversion rate reaches 80-90%, and adding 0.1-0.5 part by weight of a terminator to terminate the reaction, thereby obtaining the small-particle-size styrene-butadiene latex.
6. The method of claim 2, wherein the large-particle size styrene-butadiene latex comprises: the anionic emulsifier is one or more of sodium oleate, potassium oleate, ammonium oleate, sodium fatty acid, sodium oleoyl sarcosine, ammonium lauryl sulfate, sodium dodecyl benzene sulfonate, sodium lauroyl methylamine acetate, sodium alkylphenol polyoxyethylene ether sulfonate, disproportionated potassium rosinate, disproportionated sodium rosinate, potassium rosinate, sodium rosinate and castor oil sodium sulfate.
7. The method of claim 3, wherein the large-particle size styrene-butadiene latex comprises: the agglomerating agent is one or more of acetic acid, propionic acid, hydrochloric acid, octadecyl trimethyl ammonium chloride and polyamide, and the using amount of the agglomerating agent is 0.05-0.1 part by weight.
8. The method of claim 2, wherein the large-particle size styrene-butadiene latex comprises: the chelating agent comprises one or more of disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate, sodium gluconate, sodium pyrophosphate and sodium phosphate.
9. The method of claim 2, wherein the large-particle size styrene-butadiene latex comprises: the molecular weight regulator comprises one or more of tert-dodecyl mercaptan, diisopropyl xanthogen disulfide, ethylene glycol dimethyl ether, isooctyl 3-mercaptopropionate, thioglycolate and alpha-methyl styrene linear dimer.
10. The method of claim 2, wherein the large-particle size styrene-butadiene latex comprises: the initiator comprises one or more of ammonium persulfate, diisopropyl peroxydicarbonate, potassium persulfate, sodium persulfate, tert-butyl hydroperoxide, diisopropylbenzene hydroperoxide, peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile, ammonium persulfate-ferrous sulfate and potassium persulfate-sodium bisulfite.
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