Preparation method of polymer latex for improving impermeability of cement-based concrete
Technical Field
The invention relates to a preparation method of polymer latex, in particular to a preparation method of polymer latex for improving impermeability of cement-based concrete, belonging to the technical field of building materials.
Background
The polymer latex modified concrete is a cement concrete containing organic polymer, which is formed by infiltrating polymer latex into the cement concrete in the stirring stage, curing and crosslinking after pouring, and the main components comprise cement, sand, stones, water and polymer latex, wherein common polymer latex comprises styrene-butadiene latex, acrylate emulsion, vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion and the like, and is mainly used for improving the impermeability of the concrete [ Xushixiqing, Wangbei, the strength and the chloride ion permeability resistance of the styrene-butadiene latex-doped concrete [ J ] academic report of building materials, 7(4):351 and 358 ].
In fact, the interpenetrating network structure is difficult to form in the mixing process of the polymer latex and the cement-based material in the emulsion state, the polymer is mostly dispersed in a cement mortar system in the form of nano-scale latex particles, and after subsequent cement hydration is cured, the polymer latex particles occupy the pores generated by hydration reaction, so that the purposes of water resistance and permeability resistance are realized [ Song in order to clear, preparation and characterization of the special styrene-butadiene latex for cement [ D ]. Zhejiang university, 2005 ]. Therefore, the interface between the polymer latex particles and the cement-based material in the prior art has the problem of poor compatibility, and the two materials have different responses to temperature and stress, so that the interface is easy to peel, and the peeled surface becomes a water seepage channel, so the polymer latex is adopted to improve the impermeability of cement-based concrete, and the effect is general.
Disclosure of Invention
The invention aims to solve the defects of the polymer latex in the prior art and provides a preparation method of the polymer latex for improving the impermeability of cement-based concrete, and the prepared polymer latex has excellent impermeability, heat resistance and aging resistance, is easy to resist permeability and self-repair after being damaged by stress and is suitable for improving the impermeability of cement-based concrete.
Technical scheme
The invention utilizes the rubber filling oil to disperse into emulsion under the action of the emulsifier, and forms the nano-scale microcapsule resin emulsion under the coating action of the polar resin grafting shell layer, so that when the subsequent resin emulsion is used for modifying the cement-based concrete material, the problem of interface stripping and water seepage of the ASA resin emulsion and the cement-based material is further improved from the source; once the two-phase interface is stripped, the permeation resistant agent seeps out from the inside and partially penetrates through the styrene and acrylonitrile shells, so that the stripped surface or cracks are actively filled, and the good fluidity of the resin chain segment is provided so that the resin chain segment can easily permeate to the cracks, thereby playing the roles of blocking holes and permeation resistance.
The specific scheme of the invention is as follows:
a preparation method of polymer latex for improving impermeability of cement-based concrete comprises the following steps:
(1) preparing an anti-permeability agent emulsion:
adding 100 parts of rubber filling oil, 5-15 parts of styrene, 1-3 parts of acrylonitrile, 0.5-5.5 parts of emulsifier, 0.06-1.8 parts of initiator and 150 parts of deionized water into a high-shear emulsifying machine for carrying out shearing and emulsifying reaction to obtain an anti-permeability agent emulsion;
(2) preparation of composite emulsion
Mixing the acrylic rubber emulsion and the anti-permeability agent emulsion obtained in the step (1) in a ratio of 1: (0.2-1.5) mixing the raw materials according to the dry basis mass ratio to obtain a composite emulsion;
(3) composite emulsion grafting
Adding a grafting monomer into the composite emulsion obtained in the step (2), wherein the grafting monomer accounts for 50-80% of the dry mass of the composite emulsion, the grafting monomer is a styrene monomer and an acrylonitrile monomer, and adding 0.2-2% of an emulsifier, 0.1-0.8% of a molecular weight regulator, 100-200% of deionized water and 0.3-0.8% of an initiator by taking the weight of the grafting monomer as 100% to carry out an emulsion grafting reaction, thereby obtaining the polymer latex product.
In the step (1), the rubber filling oil is one of high aromatic oil (the aromatic hydrocarbon content is more than 18%), naphthenic oil, paraffin oil or fatty oil.
In the step (2), the acrylic ester rubber emulsion is one of methyl acrylate emulsion, ethyl acrylate emulsion or butyl acrylate emulsion.
Further, in the step (1), the temperature of the shearing emulsification reaction is 70-80 ℃, the rotation speed is 5000-.
Further, in the steps (1) and (3), the emulsifier is selected from any one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium saturated fatty acid, potassium dodecyl benzene sulfonate, potassium dodecyl sulfate and potassium saturated rosin acid.
Further, in the steps (1) and (3), the initiator is selected from any one of potassium persulfate, sodium persulfate or ammonium persulfate, and potassium persulfate is more preferable.
Further, in the step (2), the mixing temperature is 40-50 ℃, the rotation speed of the emulsifying machine during mixing is 800-1500rpm, and the mixing time is 30-60 min.
Further, in the step (3), the grafting monomer accounts for 55-65% of the dry basis weight of the composite emulsion. The proportion of the grafting monomer is too small, and the filler is easy to separate out in the post-treatment process; too much grafting monomer, incomplete release of filler during subsequent concrete preparation and poor water resistance.
Further, in the step (3), in the grafting monomer, the mass ratio of the styrene monomer to the acrylonitrile monomer is 3: 1.
further, in the step (3), the molecular weight regulator is tert-dodecyl mercaptan or dodecyl mercaptan.
Further, in the step (3), the temperature of the emulsion grafting reaction is 60-80 ℃, the stirring speed is 200-500rpm, and the time is 4-6 h.
A method for improving the impermeability of cement-based concrete comprises the following steps: the polymer latex prepared by the method is mixed with cement-based concrete in an addition amount of 5-25%, and then is cured.
The invention has the beneficial effects that: the invention blends the rubber filling oil emulsion and the polyacrylate emulsion, then grafts the styrene and the acrylonitrile to prepare the polymer latex, the polymer latex has better impermeability, is easy to be impervious and self-repaired after being damaged by stress, and can be used for improving the impermeability of cement-based concrete, the water absorption rate of the cement-based concrete doped with the polymer latex is lower than 2.5%, and the water absorption rate of the concrete is still lower than 5.5% after freeze-thaw test. The excellent impermeability of the oil-filled ASA resin emulsion is mainly reflected in the water-driving effect of hydrophobic filling oil, and after the filling oil is mixed into a concrete network along with the ASA resin emulsion, the filling oil with low molecular weight firstly expands into concrete cracks or pores under the stress state, and the tissue moisture permeates. Meanwhile, the diffusion of the filling oil can play a role in lubricating polymer molecular chain segments, and the migration and recombination of the chain segments can be realized through the infiltration effect of the low-molecular oil product when a polymer network fixed in cement concrete is damaged, so that self-repairing to a certain degree is realized. The damage and recovery of freeze-thaw cycling is also to some extent a water-repelling and self-healing effect that relies on the filling of low molecular components.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It is worth mentioning in the following examples:
(1) rubber extender oil: high aromatic oil and naphthenic oil are purchased from Xin corporation of petrochemical industry of Lanzhou; emulsifier: sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium saturated fatty acid, potassium dodecyl sulfonate, potassium dodecyl sulfate, commercially available, technical grade;
(2) acrylonitrile, styrene, tertiary dodecyl mercaptan, potassium persulfate, sodium persulfate, ammonium persulfate, deionized water, reagent grade, commercially available;
(3) other reagents not described were reagent grade and commercially available.
(4) The butyl acrylate emulsion is prepared by adopting an emulsion polymerization mode, and is a conventional preparation method in the field, and the preparation method specifically comprises the following steps: weighing 100g of butyl acrylate, 0.5g of emulsifier sodium dodecyl sulfate, 0.6g of initiator potassium persulfate and 150g of deionized water; reserving 30% of monomers and initiator, reserving 50% of emulsifier, adding the rest materials into the reactor under the stirring condition, and starting to heat; when the temperature is raised to 70 ℃, timing is started, after 1h, the reserved monomer and the initiator are dripped, and after dripping is finished within 4h, the residual emulsifier is replenished; heating to 75 deg.C, maintaining for 2h, cooling, and discharging.
The raw materials and the auxiliary agents used in the examples are described in detail above, but are not limited thereto. In the following examples, the impermeability of the concrete is characterized by the water absorption, which is measured: weighing a resin concrete sample m1, immersing the resin concrete sample in water for 90min, taking out the resin concrete sample, wiping the surface water to dry, weighing m2 again, and enabling the water absorption rate to be (m2-m1)/m1 multiplied by 100%; the freeze-thaw experiments were performed with reference to the GB/T50082-2009 ordinary concrete long-term performance and durability test method.
Example 1
A preparation method of polymer latex for improving impermeability of cement-based concrete comprises the following steps:
(1) preparing an anti-permeability agent emulsion:
adding 100g of high aromatic oil, 5g of styrene, 1g of acrylonitrile, 0.5g of emulsifier sodium dodecyl sulfate, 0.06g of initiator potassium persulfate and 150g of deionized water into a high-shear emulsifying machine for carrying out a shearing emulsification reaction, wherein the temperature of the emulsification reaction is 70 ℃, the rotating speed is 5000rpm, and the time of the emulsification reaction is 30min, so as to obtain an anti-permeability agent emulsion;
(2) preparation of composite emulsion
Mixing butyl acrylate latex and the anti-permeability agent emulsion obtained in the step (1) in a ratio of 1: mixing according to a dry basis mass ratio of 0.2, controlling the temperature to be 40 ℃, controlling the rotating speed of an emulsifying machine to be 1500rpm, and mixing and emulsifying for 60min to obtain a composite emulsion;
(3) composite emulsion grafting
Adding a grafting monomer into the composite emulsion obtained in the step (2), calculating the mass of the grafting monomer according to the dry weight (600g) of the composite emulsion, wherein the grafting monomer accounts for 50 percent of the dry weight of the composite emulsion, namely 300g, adding 0.6g of emulsifier sodium dodecyl sulfate, 0.13g of molecular weight regulator tert-dodecyl mercaptan, 300g of deionized water and 0.9g of initiator potassium persulfate, and carrying out an emulsion grafting reaction (the temperature is 70 ℃, the stirring speed is 250rpm, and the time is 4 hours), thus obtaining the polymer latex product.
The polymer latex product prepared in the example is mixed with cement-based concrete by taking the dry basis as the addition amount of 15% of the cement mass, and the mixture is maintained to obtain the modified concrete, wherein the water absorption of the modified concrete is 1.1% according to the standard test, and the water absorption of the modified concrete is 3.5% after three freeze-thaw cycles.
Comparative example 1: without filling oil
Weighing 600g of butyl acrylate latex dry basis weight, wherein a grafting monomer accounts for 50% of the latex dry basis weight, weighing styrene and acrylonitrile monomers (the ratio of the styrene monomer to the acrylonitrile monomer is 3: 1) after calculation, namely 300g, adding 0.6g of emulsifier sodium dodecyl sulfate, 0.13g of molecular weight regulator tert-dodecyl mercaptan, 300g of deionized water, adding 0.9g of initiator potassium persulfate, controlling the reaction temperature and the stirring rotation speed (the temperature is 70 ℃, the stirring rotation speed is 250rpm, and the time is 4 hours), and obtaining the polymer latex after reaction.
The polymer latex obtained in the comparative example is mixed with cement-based concrete by taking the dry basis as the addition amount of 15% of the mass of the cement, the modified concrete is obtained after maintenance, the water absorption of the modified concrete is 7.1% according to the standard test, and the water absorption of the modified concrete is 17.5% after three freeze-thaw cycles.
Example 2
A preparation method of polymer latex for improving impermeability of cement-based concrete comprises the following steps:
(1) preparing an anti-permeability agent emulsion:
adding 100g of naphthenic oil, 15g of styrene, 3g of acrylonitrile, 5.5g of emulsifier sodium dodecyl benzene sulfonate, 0.6g of initiator ammonium persulfate and 150g of deionized water into a high-shear emulsifying machine for carrying out a shearing and emulsifying reaction, wherein the temperature of the emulsifying reaction is 80 ℃, the rotating speed is 15000rpm, and the emulsifying reaction time is 20min to obtain an anti-permeability agent emulsion;
(2) preparation of composite emulsion
Mixing butyl acrylate latex and the anti-permeability agent emulsion obtained in the step (1) in a ratio of 1: 1, mixing according to the dry basis mass ratio, controlling the temperature to be 50 ℃, controlling the rotation speed of an emulsifying machine to be 1200rpm, and mixing and emulsifying for 50min to obtain a composite emulsion;
(3) composite emulsion grafting
Adding a grafting monomer into the composite emulsion obtained in the step (2), calculating the mass of the grafting monomer according to the dry weight (200g) of the composite emulsion, wherein the grafting monomer accounts for 50 percent of the dry weight of the composite emulsion, namely 100g, adding 0.3g of emulsifier sodium dodecyl sulfate, 0.2g of molecular weight regulator tert-dodecyl mercaptan, 150g of deionized water and 0.6g of initiator potassium persulfate, and carrying out an emulsion grafting reaction (the temperature is 75 ℃, the stirring speed is 300rpm, and the time is 4 hours), thus obtaining the polymer latex product.
The polymer latex product prepared in the example is mixed with cement-based concrete by taking the dry basis as the addition amount of 25% of the cement mass, and the mixture is maintained to obtain the modified concrete, wherein the water absorption of the modified concrete is 1.6% according to the standard test, and the water absorption of the modified concrete is 4.5% after three freeze-thaw cycles.
Comparative example 2: direct blending of oil products
Weighing 100g of naphthenic oil and 150g of deionized water as filling oil, adding the filling oil and the deionized water into a high-shear emulsifying machine, controlling the temperature to be 80 ℃, adjusting the rotating speed to be 15000rpm, and carrying out shear emulsification reaction for 20min to obtain a filling oil emulsion; butyl acrylate latex and extender oil emulsion were mixed as 1: 1, mixing dry basis according to a mass ratio, controlling the temperature to be 50 ℃, controlling the rotation speed of an emulsifying machine to be 1200rpm, and mixing and emulsifying for 50min to obtain a composite emulsion; calculating the mass of a grafting monomer according to the dry basis weight (200g) of the composite emulsion, wherein the grafting monomer accounts for 50% of the dry glue weight of the composite emulsion, weighing 100g of styrene and acrylonitrile monomers (the ratio of the styrene monomer to the acrylonitrile monomer is 3: 1), adding 0.3g of emulsifier sodium dodecyl sulfate, 0.2g of molecular weight regulator tert-dodecyl mercaptan, 150g of deionized water, adding 0.6g of initiator potassium persulfate, controlling the reaction temperature and the stirring speed (the temperature is 75 ℃, the stirring speed is 300rpm, and the time is 4 hours), and obtaining polymer latex after reaction;
the polymer latex obtained in the comparative example is mixed with cement-based concrete by taking the dry basis as the addition amount of 25% of the mass of the cement, the modified concrete is obtained after maintenance, the water absorption of the modified concrete is 0.6% according to the standard test, and a large amount of grease seeps out from pores in a freeze-thaw cycle experiment.
Example 3
A preparation method of polymer latex for improving impermeability of cement-based concrete comprises the following steps:
(1) preparing an anti-permeability agent emulsion:
adding 100g of naphthenic oil, 10g of styrene, 3g of acrylonitrile, 4.5g of emulsifier sodium dodecyl benzene sulfonate, 1.6g of initiator ammonium persulfate and 150g of deionized water into a high-shear emulsifying machine for carrying out a shearing emulsification reaction, wherein the temperature of the emulsification reaction is 75 ℃, the rotating speed is 13000rpm, and the time of the emulsification reaction is 24min to obtain an anti-permeability agent emulsion;
(2) preparation of composite emulsion
Mixing butyl acrylate latex and the anti-permeability agent emulsion obtained in the step (1) in a ratio of 1: 1.2, mixing according to the dry basis mass ratio, controlling the temperature to be 45 ℃, controlling the rotation speed of an emulsifying machine to be 1100rpm, and mixing and emulsifying for 45min to obtain a composite emulsion;
(3) composite emulsion grafting
Adding a grafting monomer into the composite emulsion obtained in the step (2), calculating the mass of the grafting monomer according to the dry weight (180g) of the composite emulsion, wherein the grafting monomer accounts for 60% of the dry weight of the composite emulsion, namely 108g, adding 0.33g of emulsifier sodium dodecyl sulfate, 0.25g of molecular weight regulator tert-dodecyl mercaptan, 150g of deionized water and 0.69g of initiator potassium persulfate, and carrying out an emulsion grafting reaction (the temperature is 77 ℃, the stirring speed is 350rpm, and the time is 4 hours), thus obtaining the polymer latex product.
The polymer latex product prepared in the example is mixed with cement-based concrete by taking the dry basis as the addition amount of 20% of the cement mass, and the modified concrete is obtained after maintenance, wherein the water absorption of the modified concrete is 1.4% according to the standard test, and the water absorption of the modified concrete is 4.1% after three freeze-thaw cycles.
Comparative example 3: the filling oil emulsion is added in the concrete preparation process
Weighing 100g of filling oil naphthenic oil and 150g of deionized water, adding the filling oil naphthenic oil and the deionized water into a high-shear emulsifying machine, controlling the temperature to be 75 ℃, adjusting the rotating speed to be 13000rpm, and carrying out shear emulsion reaction for 24min to obtain a filling oil emulsion; the mass of a grafting monomer is calculated according to the dry basis weight (180g) of the composite emulsion, the grafting monomer accounts for 60% of the dry basis weight of the composite emulsion, the calculated weight is styrene and acrylonitrile monomers (the ratio of the styrene monomer to the acrylonitrile monomer is 3: 1), the mass is 108g, 0.33g of emulsifier sodium dodecyl sulfate, 0.25g of molecular weight regulator tert-dodecyl mercaptan, 150g of deionized water and 0.69g of initiator potassium persulfate are added, the reaction temperature and the stirring speed (the temperature is 77 ℃, the stirring speed is 350rpm, and the time is 4 hours) are controlled, and the ASA resin emulsion is obtained after reaction.
The total amount (dry basis ratio is 1: 1.2) of the ASA resin emulsion and the filling oil emulsion is calculated as the addition amount of 20 percent of the cement mass, the ASA resin emulsion and the filling oil emulsion are mixed with cement-based concrete, modified concrete is obtained after curing, and a large amount of filling oil seeps out in the mixing, stirring and curing processes.
Example 4:
a preparation method of polymer latex for improving impermeability of cement-based concrete comprises the following steps:
(1) preparing an anti-permeability agent emulsion:
adding 100g of high aromatic oil, 14g of styrene, 2g of acrylonitrile, 4.6g of sodium dodecyl benzene sulfonate as an emulsifier, 1.7g of sodium persulfate as an initiator and 150g of deionized water into a high-shear emulsifying machine for carrying out a shearing emulsification reaction, wherein the temperature of the emulsification reaction is 71 ℃, the rotating speed is 11000rpm, and the time of the emulsification reaction is 28min, so as to obtain an anti-permeability agent emulsion;
(2) preparation of composite emulsion
Mixing butyl acrylate latex and the anti-permeability agent emulsion obtained in the step (1) in a ratio of 1: 1.5, controlling the temperature to be 44 ℃, controlling the rotation speed of an emulsifying machine to be 1190rpm, and carrying out mixing and emulsification for 43min to obtain a composite emulsion;
(3) composite emulsion grafting
Adding a grafting monomer into the composite emulsion obtained in the step (2), calculating the mass of the grafting monomer according to the dry weight (160g) of the composite emulsion, wherein the grafting monomer accounts for 60% of the dry weight of the composite emulsion, namely 96g, adding 1.8g of emulsifier sodium dodecyl sulfate, 0.7g of molecular weight regulator tert-dodecyl mercaptan, 150g of deionized water and 0.62g of initiator sodium persulfate, and carrying out an emulsion grafting reaction (the temperature is 80 ℃, the stirring speed is 200rpm, and the time is 4 hours), thus obtaining the polymer latex product.
The polymer latex product prepared in the example is mixed with cement-based concrete by taking the dry basis as the addition amount of 10% of the cement mass, and the modified concrete is obtained after maintenance, wherein the water absorption of the modified concrete is 2.4% according to the standard test, and the water absorption of the modified concrete is 6.1% after three freeze-thaw cycles.
Comparative example 4: direct blending of impervious emulsions
Weighing 100g of filling oil high aromatic oil, 14g of styrene, 2g of acrylonitrile, 4.6g of emulsifier sodium dodecyl benzene sulfonate, 1.7g of initiator sodium persulfate and 150g of deionized water, adding into a high shear emulsifying machine, controlling the temperature to be 71 ℃, adjusting the rotating speed to be 11000rpm, and carrying out shear emulsion reaction for 28min to obtain the anti-permeability agent emulsion.
Calculating the mass of a grafting monomer according to the dry weight (160g) of butyl acrylate latex, wherein the grafting monomer accounts for 60% of the dry weight of the composite emulsion, weighing styrene and acrylonitrile monomers (the ratio of the styrene monomer to the acrylonitrile monomer is 3: 1) after calculation, adding 1.8g of emulsifier sodium dodecyl sulfate, 0.7g of molecular weight regulator tert-dodecyl mercaptan, 150g of deionized water, adding 0.62g of initiator sodium persulfate, controlling the reaction temperature and the stirring speed (the temperature is 80 ℃, the stirring speed is 200rpm, and the time is 4 hours), and obtaining the ASA resin emulsion after reaction.
The dry basis amount of the ASA resin emulsion and the anti-permeability agent emulsion (dry basis ratio is 1: 1.5) is calculated to be 10% of the mass of the cement, the ASA resin emulsion and the anti-permeability agent emulsion are mixed with cement-based concrete, the modified concrete is obtained after curing, the water absorption of the ASA resin emulsion modified concrete is 1.4% according to standard tests, and filling oil seeps out in freeze-thaw experiments.
Example 5
A preparation method of polymer latex for improving impermeability of cement-based concrete comprises the following steps:
(1) preparing an anti-permeability agent emulsion:
adding 100g of high aromatic oil, 5g of styrene, 3g of acrylonitrile, 3.6g of potassium dodecylbenzene sulfonate emulsifier, 1.4g of sodium persulfate as an initiator and 150g of deionized water into a high-shear emulsifying machine for carrying out a shearing emulsification reaction, wherein the temperature of the emulsification reaction is 70 ℃, the rotating speed is 8000rpm, and the time of the emulsification reaction is 20min, so as to obtain an anti-permeability agent emulsion;
(2) preparation of composite emulsion
Mixing butyl acrylate latex and the anti-permeability agent emulsion obtained in the step (1) in a ratio of 1: 1, controlling the temperature to be 40 ℃, controlling the rotation speed of an emulsifying machine to be 1250rpm, and mixing and emulsifying for 55min to obtain a composite emulsion;
(3) composite emulsion grafting
Adding a grafting monomer into the composite emulsion obtained in the step (2), calculating the mass of the grafting monomer according to the dry weight (200g) of the composite emulsion, wherein the grafting monomer accounts for 60 percent of the dry weight of the composite emulsion, namely 120g, adding 2g of sodium dodecyl sulfate serving as an emulsifier, 0.6g of tert-dodecyl mercaptan serving as a molecular weight regulator, 240g of deionized water and 0.6g of sodium persulfate serving as an initiator, and carrying out an emulsion grafting reaction (the temperature is 71 ℃, the stirring speed is 450rpm, and the time is 4 hours), thus obtaining the polymer latex product.
The polymer latex product prepared in the example is mixed with cement-based concrete by taking the dry basis as the addition amount of 15% of the cement mass, and the modified concrete is obtained after maintenance, wherein the water absorption of the modified concrete is 1.9% according to the standard test, and the water absorption of the modified concrete is 5.1% after three freeze-thaw cycles.
Comparative example 5: without addition of molecular weight regulators
Weighing 100g of filling oil high aromatic oil, 5g of styrene, 3g of acrylonitrile, 3.6g of emulsifier potassium dodecyl benzene sulfonate, 1.4g of initiator sodium persulfate and 150g of deionized water, adding into a high shear emulsifying machine, controlling the temperature to be 70 ℃, adjusting the rotating speed to be 8000rpm, and carrying out shear emulsion reaction for 20min to obtain an anti-permeability agent emulsion; butyl acrylate latex and the anti-permeability agent emulsion were mixed in a ratio of 1: 1, mixing according to a dry basis mass ratio, controlling the temperature to be 40 ℃, controlling the rotation speed of an emulsifying machine to be 1250rpm, and mixing and emulsifying for 55min to obtain a composite emulsion; calculating the mass of a grafting monomer according to the dry basis weight (200g) of the composite emulsion, wherein the grafting monomer accounts for 60% of the dry glue weight of the composite emulsion, weighing styrene and acrylonitrile monomers (the ratio of the styrene monomer to the acrylonitrile monomer is 3: 1) after calculation, adding 2g of sodium dodecyl sulfate serving as an emulsifier, 0g of tert-dodecyl mercaptan serving as a molecular weight regulator, 240g of deionized water, adding 0.6g of sodium persulfate serving as an initiator, controlling the reaction temperature and the stirring speed (the temperature is 71 ℃, the stirring speed is 450rpm, and the time is 4 hours), and reacting to obtain the polymer latex.
The polymer latex obtained in the comparative example is mixed with cement-based concrete by taking the dry basis as the addition amount of 15% of the cement mass, the modified concrete is obtained after maintenance, the water absorption of the ASA resin emulsion modified concrete is 2.2% according to the standard test, the filling oil is sealed, and the water absorption is 8.1% after three freeze-thaw cycles.
Example 6
A preparation method of polymer latex for improving impermeability of cement-based concrete comprises the following steps:
(1) preparing an anti-permeability agent emulsion:
adding 100g of high aromatic oil, 7g of styrene, 1g of acrylonitrile, 2.6g of potassium dodecylbenzene sulfonate emulsifier, 1.2g of sodium persulfate initiator and 150g of deionized water into a high-shear emulsifying machine for carrying out a shearing emulsification reaction, wherein the temperature of the emulsification reaction is 75 ℃, the rotating speed is 8500rpm, and the time of the emulsification reaction is 25min, so as to obtain an anti-permeability agent emulsion;
(2) preparation of composite emulsion
Mixing butyl acrylate latex and the anti-permeability agent emulsion obtained in the step (1) in a ratio of 1: mixing according to a dry basis mass ratio of 0.3, controlling the temperature to be 43 ℃, controlling the rotation speed of an emulsifying machine to be 1450rpm, and mixing and emulsifying for 57min to obtain a composite emulsion;
(3) composite emulsion grafting
Adding a grafting monomer into the composite emulsion obtained in the step (2), calculating the mass of the grafting monomer according to the dry weight (430g) of the composite emulsion, wherein the grafting monomer accounts for 50% of the dry weight of the composite emulsion, namely 215g, adding 4g of sodium dodecyl sulfate serving as an emulsifier, 1.6g of dodecyl mercaptan serving as a molecular weight regulator, 250g of deionized water and 1.6g of sodium persulfate serving as an initiator, and carrying out an emulsion grafting reaction (the temperature is 76 ℃, the stirring speed is 500rpm, and the time is 4 hours), thus obtaining the polymer latex product.
The polymer latex product prepared in the example is mixed with cement-based concrete by taking the dry basis as the addition amount of 22% of the cement mass, and the modified concrete is obtained after maintenance, wherein the water absorption of the modified concrete is 1.7% according to the standard test, and the water absorption of the modified concrete is 3.9% after three freeze-thaw cycles.
Comparative example 6: without grafting, directly blending with SAN emulsion
Weighing 100g of filling oil high aromatic oil, 7g of styrene, 1g of acrylonitrile, 2.6g of emulsifier potassium dodecyl benzene sulfonate, 1.2g of initiator sodium persulfate and 150g of deionized water, adding into a high shear emulsifying machine, controlling the temperature to be 75 ℃, adjusting the rotating speed to be 8500rpm, and carrying out shear emulsion reaction for 25min to obtain an anti-permeability agent emulsion; butyl acrylate latex and the anti-permeability agent emulsion were mixed in a ratio of 1: mixing at dry basis weight ratio of 0.3, controlling temperature at 43 deg.C, rotating speed of emulsifying machine at 1450rpm, and mixing and emulsifying for 57min to obtain composite emulsion; the amount of the graft-blended SAN emulsion was 215g calculated as the amount of the composite emulsion on a dry basis (430g), and a polymer latex was obtained after mixing.
The polymer latex obtained in the comparative example is mixed with cement-based concrete by taking the dry basis as the addition amount of 22% of the mass of the cement, the modified concrete is obtained after maintenance, the water absorption of the ASA resin emulsion modified concrete is 4.7% according to the standard test, and filling oil is separated out in the freeze-thaw experiment process.