CN107674217A - A kind of core shell structure butylbenzene redispersable latex powder - Google Patents
A kind of core shell structure butylbenzene redispersable latex powder Download PDFInfo
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- CN107674217A CN107674217A CN201710952393.XA CN201710952393A CN107674217A CN 107674217 A CN107674217 A CN 107674217A CN 201710952393 A CN201710952393 A CN 201710952393A CN 107674217 A CN107674217 A CN 107674217A
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2313/00—Characterised by the use of rubbers containing carboxyl groups
- C08J2313/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
Abstract
The present invention relates to a kind of core shell structure butylbenzene redispersable latex powder, and it is the co-dried mixture of core shell structure styrene-butadiene latex and deflocculant, and the latex powder is prepared using following steps：(1) seed latex is prepared；(2) core shell structure styrene-butadiene latex is prepared；(3) redispersable latex powder is prepared.The present invention uses seeded emulsion polymerization technique, and the low monomer reaction of glass transition temperature is first added in preparation process and generates soft core, then add glass transition temperature height and continue to polymerize with polar functionalities monomer, obtain hard, good hydrophilic property shell, gained particle diameter distribution of latex is uniform, glass transition temperature is suitable, low viscous Gao Gu, the latex powder good fluidity of preparation, storage time is grown, redisperse is functional, suitable for the modification of cement mortar and concrete, it is also possible to makees powdery paints or other adhesive for building.
Description
Technical field
The present invention relates to a kind of redispersable latex powder, specifically, is related to one kind and is prepared by core shell structure styrene-butadiene latex
The redispersable latex powder formed.
Background technology
Redispersable latex powder, refer to the technique such as the water-based emulsion containing polymers compositions or solution be spray-dried
Dehydration efflorescence handles obtained polymer powder, can be dispersed in water again after adding water, generates stable aqueous phase redisperse liquid, and
With the performance worked as with original copolymer emulsion or solution.
Polymer is applied to cement mortar or concrete core shell structure, the caking property of mixing material is remarkably improved, resists
Intensity and deformability are rolled over, improves its durability and corrosion resistance.
The polymer for being generally used for cement mortar or concrete core shell structure is mixed in the form of polymer emulsion, its
Solid content is typically between 40%-70%.But the polymer packaging of emulsion or solution state, storage, the cost of transport are higher, also need
It is mould proof antifreeze.Redispersible latex powder is made into, in addition to solving the above problems, moreover it is possible to done with cement, aggregate etc.
It is mixed, the one-component product for being easy to apply at the construction field (site) is made, ensures the accurate of slurry composition proportioning.Thus Redispersable latex
Powder is commercially available commonly used in architectural chemistry product.
Recently as the increasingly strict of architectural chemistry conduct industry VOC emission requirement, redispersible polymer powder starts
Plastered applied to dry-mixed type dry powder paint, putty with the product such as tile bonding material, application field is increasingly extensive.
The preparation of Redispersible Polymeric Emulsion Powder is divided into matrix polymer solution or emulsion is prepared and taken off with solution or emulsion
Water dries two benches.The reversible of its film forming procedure is kept when the key of technology of preparing is dry.It is well known that polymer emulsion loses
Water can form continuous film when drying, and this is also that it can improve the basis of ordinary mortar application performance, and this process is usually not
Reversible.Redispersibility to recover polymer powder, it is necessary to before spray drying, protecting colloid is added into dispersion liquid,
It is set to be coated on emulsion particle surface so that particle surface still keeps glassy state under outlet temperature, prevents between polymer particle
Irreversible coalescence.Or appropriate core shell structure is carried out to polymer particle, increase the glass transition temperature on its top layer, reduce particle
Between irreversible coalescence tendency.
Since nineteen fifty-seven Germany Wa Ke company (Wacker-Chem ie Gm bh) first production goes out first generation vinyl acetate
Since type (PVAC) homopolymer latex powder, the production and application of redispersable latex powder have the history of nearly 60 years.At present should
There is polytype with wide redispersable latex powder, such as VAE (VAE) latex powder, ethene/chlorine
Ethene/vinyl laurate terpolymer latex powder, acrylate copolymer latex powder etc., wherein, ethylene-vinyl acetate is common
Polymers (EVA) latex powder is occupied an leading position because of its high performance-price ratio in global marketing.Additionally due to acrylic monomers is various
The unlimitedness of property and its polymer architecture, and the property such as the broad applicability of acrylate polymer emulsion and its good weatherability
Can, the redispersible acrylic polymer emulsion powder based on acrylate polymer emulsion has also obtained in-depth study, and it is applied
Also it is increasingly extensive.But whether which type of redispersable latex powder, the common drawback that presently, there are is them
Water resistance is poor, and its reason is essentially from two aspects:First, in order to ensure that it is good that polymer emulsion powder has during spray drying
Redispersibility energy, generally require to add a large amount of protecting colloids, such as polyvinyl alcohol (PVA), but protecting colloid is a kind of water-sensitive
The material of property, its addition can influence the water resistance of product；Second, it is past to prepare a kind of preferably Redispersible Polymeric Emulsion Powder
Toward to select suitable hydrophilic monomer to participate in copolymerization, because hydrophilic monomer can improve the redispersibility of polymer emulsion powder.
But the presence of a large amount of water sensitivity monomers can reduce the water resistance after its film forming.Therefore, the redispersible of latex powder with it is water-fast
Property contradiction be Redispersible Polymeric Emulsion Powder research emphasis.
Redispersible Polymeric Emulsion Powder is possessed hydrophobic method two kinds:First, synthesis has hydrophobic structure
Polymer matrix emulsion, then it is dried and obtained Redispersible Polymeric Emulsion Powder is kept and its matrix polymer phase
As hydrophobicity；It is added to second, preparing a kind of redispersible hydrophobic additive in Redispersible Polymeric Emulsion Powder, shape
Into the redispersible powder of mixing with hydrophobic property.
Styrene-butadiene latex is copolymerized by two kinds of non-polar monomers and obtained, and molecular structure has preferable hydrophobicity.With its nucleocapsid knot
The cement-based material caking property of structure is good, bending strength is high, shrinkage, fracture property, water-reducing property, high abrasion resistance.Simultaneously
With preferable waterproof ability, deformation adaptability and durability.Compared with other birds of the same feather flock together compound cement core shell structure agent, its raw material
Cost is relatively low, is easy to mass automatic production, has preferable competitive advantage.The Redispersable latex made of styrene-butadiene latex
Powder equally has stronger competitiveness.
But due to easy containing the unsaturated construction unit that butadiene is flexible, polymer in the molecular structure of styrene-butadiene polymer
Cold flow properties are produced, during drying and storage, irreversible coalescence easily occurs for latex powder, influences to produce and uses.Therefore, city
The redispersable latex powder sold is seldom using styrene-butadiene latex as raw material.
To prevent the bonding between high-temperature drying procedures emulsion particle, emulsion particle can be designed as to stratum nucleare is softer, shell is harder
Core shell structure.Shell glass transition temperature (Tg) is higher, and glassy state is still kept under outlet temperature, can be used as separation layer.
Carboxylic hydrophilic monomer is added in styrene-butadiene emulsion polymerization process, on the one hand can improve the stabilization of copolymer emulsion
Property, while also improve the redispersibility energy of latex powder.When preparing redisperse rubber powder, typically need before spray drying to polymerization
In thing emulsion plus alkali, make carboxylic ions, improve stability of the carboxyl in spray drying and ensure the redispersibility energy of rubber powder.
But the emulsion containing carboxyl add in alkali and when thickening behavior be present, carboxyl-content is higher, and alkali thickening degree is bigger.To ensure
Rubber powder is easy to redisperse, prepares emulsion used in rubber powder and often contains a large amount of carboxyls, alkali thickening phenomenon is extremely serious.This to spray
The viscosity of preceding feed liquid is too high, it is necessary to it is diluted with water, in order to avoid block pumps road and drier.Though adding water to reduce viscosity, also drop simultaneously
The low solid content of feed liquid, adds water removal, accordingly adds energy consumption.Moisture also has influence on material as a kind of plasticizer simultaneously
The glass transition temperature (Tg) of liquid, usual Tg reduce with the increase of water content, directly affect effect of dusting.
To overcome the shortcomings of styrene-butadiene latex molecular structure, the redispersible butadiene-styrene latex with the market competitiveness is prepared
Powder, the dosage of the invention by reducing carboxylic monomer, and preferably other function monomers participate in copolymerization, using seeded emulsion polymerization
Method, first add the low monomer of glass transition temperature and participate in polymerisation, form soft core, then add the high monomer of glass transition temperature
Continue to polymerize with polar functionalities monomer, obtain hard, good hydrophilic property shell.Thereby is achieved high comprehensive performance be used for make
The core shell structure styrene-butadiene latex of standby redispersable latex powder.Using the latex as raw material, appropriate protecting colloid and interleaving agent are added i.e.
The excellent redispersable latex powder of availability.
CN1105696C and TW509714B is the relevant styrene-butadiene polymer base Redispersable latex of German Wa Ke companies application
Powder patent, it is used separately as Building Adhesive and based Wood Adhesives.The latex powder is present in one or more protective colloids
Under, styrene is carried out emulsifier-free emulsion polymerization with butadiene and obtain aqueous polymer dispersion, it is then spray-dried obtained.
Shortcoming is the protective colloid that the two is both needed to be added up to 30%, and aqueous dispersion viscosity is very high, and increasing amount is needed before spray drying
Water dilutes, and energy consumption for drying is high, low production efficiency.
The content of the invention
Deposited for the redispersable latex powder prepared in the prior art using butadiene and styrene by main monomers
Dispersion viscosity it is high, into the problem of powder is difficult, latex powder redisperse effect difference, the preferred polar co suitably of the present invention
Monomer, the dosage of carboxylic monomer is reduced, using the method for seeded emulsion polymerization, first add the low monomer of glass transition temperature and participate in
Polymerisation, form soft core, then add the high monomer of glass transition temperature and polar functionalities monomer continues to polymerize, obtain it is hard,
The shell of good hydrophilic property, thus obtained styrene-butadiene latex particle diameter distribution is uniform, solid content is high, viscosity is low, is easy to be spray dried to
Powder.Dried latex powder good fluidity, storage time length, redisperse is functional, suitable for cement mortar and concrete
It is modified, it is also possible to do powdery paints or other adhesive for building.
Technical scheme provided by the present invention is：A kind of core shell structure butylbenzene redispersable latex powder, it is core shell structure
The co-dried mixture of styrene-butadiene latex and deflocculant, the latex powder are prepared using following step：
(1) seed latex is prepared
Emulsifier solution and aqueous slkali are added into polymeric kettle, starts stirring, reactor is warming up to 85 DEG C, and initiator is added dropwise
Solution, styrene then being added, polymeric kettle temperature control is incubated 30 minutes after 84-86 DEG C, charging during charging,
35 DEG C are cooled to, with 300 mesh stainless (steel) wire filtering and dischargings, obtains seed latex；
(2) core shell structure styrene-butadiene latex is prepared
By itaconic acid deionized water dissolving, the itaconic acid aqueous solution is obtained；
Add deionized water in composite emulsifier fully to dissolve, then add acrylamide and acrylonitrile, obtain acrylamide/
Acrylonitrile/emulsifier solution；
Seed latex obtained by deionized water, EDTA, alkali and step (1) is added in polymeric kettle, removed free in kettle
Oxygen, stirring is opened, is warming up to 85 DEG C, styrene, butadiene and ammonium persulfate aqueous solution is then continuously added dropwise, is controlled during charging
In the range of 84-86 DEG C, butadiene, 1/2-2/3 styrene were added dropwise kettle temperature processed in 6 hours, then started dropwise addition third
Acrylamide/acrylonitrile/emulsifier solution and the itaconic acid aqueous solution, while continue to be added dropwise remaining styrene, time for adding 2h,
Charging finishes, and is incubated 2h, is cooled to 35 DEG C, with 300 mesh stainless (steel) wire filtering and dischargings, obtains core shell structure styrene-butadiene latex
(3) redispersable latex powder is prepared
Polyvinyl alcohol is added into core shell structure styrene-butadiene latex obtained by step (2), is spray-dried after well mixed, producing can
Redisperse latex powder.
Preferably, the polymerization formula of step (1) described seed latex is：The mass parts of styrene 100, composite emulsifier 5-8
Mass parts, ammonium persulfate 0.25-0.35 mass parts, the mass parts of potassium hydroxide 0.03, deionized water 220-230 mass parts.
Preferably, by percentage to the quality, the solid content of the seed latex is 30-32%, particle diameter 35-45nm, table
Face tension force is 35-40mN/m.
Preferably, the polymerization formula of step (2) the core shell structure styrene-butadiene latex is：Seed latex 1-3 mass parts, benzene second
Alkene 50-60 mass parts, butadiene 40-50 mass parts, itaconic acid 2-3 mass parts, acrylonitrile 3-5 mass parts, acrylamide 2-5 matter
Measure part, composite emulsifier 1.5-3 mass parts, ammonium persulfate 1-3 mass parts, potassium hydroxide 0.8-0.9 mass parts, EDTA
0.0005 mass parts, the mass parts of deionized water 100.
Preferably, by percentage to the quality, the solid content of the core shell structure styrene-butadiene latex is 50-52%, and particle diameter is
150-170nm, surface tension 47-56mN/m, viscosity 230-250mPas.
Preferably, the composite emulsifier is made up of anionic emulsifier and nonionic emulsifier, the quality of the two
Than for 1:2-2:1, anionic emulsifier is lauryl sodium sulfate, neopelex, dodecyl polyoxyethylene
Any one in ether sodium sulfate, nonionic emulsifier are OPEO, Arlacel-60 (letter
Any one in referred to as tween-60, similarly hereinafter).
Preferably, the degree of hydrolysis of step (3) described polyvinyl alcohol is 85%-95%, the Hoeppler viscosity of 4% aqueous solution
For 15-30mPas.
Preferably, in step (3), in terms of 100 mass parts core shell structure styrene-butadiene latexes, the addition of polyvinyl alcohol is
12-15 mass parts.
Specifically, in the above-mentioned technical solutions, the principal monomer butadiene in polymerization formula and matching somebody with somebody for styrene compare
The glass transition temperature of polymer has a great influence, and the minimum molding temperature of polymer emulsion (MFT) is with polymer glass temperature in just
It is related.Tg is too high, and the hardness of film is big, and polymer film forming is difficult under normal temperature, influences the core shell structure effect to cement mortar.Tg is too
It is low, irreversible bonding, fusion and caking can occur in spray process between polymer beads, it is big in spray dryer wall surface
Amount adhesion, can not be obtained very poor with excellent mobility, the latex powder of redispersible, the storage stability of latex powder.When
When phenylethylene/butadiene mass ratio is 55/45~45/55, the MFT of polymer is 15~20 DEG C, is easy to film forming under normal temperature, this matches somebody with somebody
Than for optimum ratio.
The final glass transition temperature of polymer can use differential scanning calorimetry (DSC) to determine.Also FOX side shown in formula (1) can be used
The advance outline of formula calculates：
1/Tg=x1/Tg1+x2/Tg2+…xn/TgnFormula (1)
In formula (1), xnRepresent monomer n mass fraction, TgnIt is the glass transition temperature of monomer n homopolymer.
Performance of the water hydrocarbon than directly affecting product latex, determine the stability of polymerization process and the total solid substance of product latex
Content.The increase of system water, total solid substance are decreased obviously, and viscosity of latex is on a declining curve, but to surface tension and mechanical stability
Have no significant effect.
It is 80-90 DEG C according to the half-life period selective polymerization reaction temperature of initiator, reaction time 8-10h.
Using seeded emulsion polymerization technique, monomer is grafted on seed and grow up, reaction speed is steady with heat release, emulsion particle
Size is big, narrowly distributing.And the addition by adjusting seed can efficiently control the particle size of final products.
It is wide particle diameter distribution to be present in the styrene-butadiene latex prepared on a batch wise manner, and the problem of stability difference, and course of reaction heat release is bright
It is aobvious, it is difficult to control.By the way of continuous charging, latex particle size can be controlled well, reaction speed is steady with heat release, latex
Mechanical stability and chemical stability it is good.
Therefore, the present invention is synthesized for preparing redispersable latex powder using seeded emulsion polymerization and continuous charging mode
Core shell structure styrene-butadiene latex.
The specific synthesis technique of cross-linked core-shell structure styrene-butadiene latex is as follows：
1) seed latex is synthesized
The polymerization formula of seed emulsion is shown in Table 1.
The seed emulsion basic components of table 1
Operating procedure：
Initiator, emulsifying agent and alkali are distinguished into wiring solution-forming, first added into polymeric kettle the emulsifier solution that dissolve with
Aqueous slkali, stirring is started, reactor is warming up to 85 DEG C, start that initiator solution is added dropwise, start that styrene is added dropwise after 5 minutes,
Styrene is added dropwise with 1.5h, with l.7h ammonium persulfate is added dropwise, controlled polymerization temperature in 84- during dropwise addition
86 DEG C, after material is all added dropwise, 30 minutes are incubated, is cooled to 35 DEG C of dischargings.Filtered with 300 mesh stainless (steel) wires.
The property of seed latex is shown in Table 2.
The property of the seed latex of table 2
2) core shell structure styrene-butadiene latex is synthesized
The polymerization formula of core shell structure styrene-butadiene latex is shown in Table 3.
The core shell structure styrene-butadiene latex polymerization formula of table 3
Operating procedure：
Using the seeded emulsion polymerization technology of continuous charging.React and polymerize dress in the 10L stainless steels with automatic temperature control system
Put progress.First, itaconic acid is fully dissolved with deionized water.Acrylamide, acrylonitrile add appropriate the moon/nonionic emulsifier
For solution with together, initiator adds water fully to dissolve.Seed, each monomer are weighed by formula.
Deionized water, EDTA, alkali, seed are added in polymeric kettle.By vacuumizing the free oxygen in removal system, open
Stir and be warming up to 85 DEG C, then continuous dropwise addition styrene, butadiene emulsifier solution and ammonium persulfate aqueous solution, butadiene,
1/2-2/3 styrene was added dropwise in 6 hours.Strict temperature control is in the range of 84-86 DEG C during dropwise addition.Then open
Begin that acrylamide/acrylonitrile/emulsifier solution, the itaconic acid aqueous solution is added dropwise, continue that remaining styrene and initiator is added dropwise,
Time for adding is 2h.
Polymerisation can be implemented post-polymerization with known method after terminating and (be gathered after such as being triggered with oxidation reduction catalyst
Close reaction), remove residual monomer.Or it is reclaimed using distillation or steam stripped method.Then 35 DEG C are cooled to, is filtered with 300 mesh
Net filtration discharges.
The property of gained core shell structure styrene-butadiene latex is shown in Table 4.
The core shell structure styrene-butadiene latex fundamental property of table 4
The redispersable latex powder is prepared in the following manner：Above-mentioned polymer emulsion is added into deflocculant, glue
Body stabilizer is the derivative of polyvinyl alcohol, core shell structure starch, cellulose and its carboxymethyl, methyl, ethoxy and hydroxypropyl
In one or more.The poly- second that selective hydrolysis degree is 80%-95%, the Hoeppler viscosity of 4% aqueous solution is 15-30mPas
Enol class.The addition of polyvinyl alcohol is the 5%-25%, preferably 12%-15% of polymer.It can be also added before it is dried
His interleaving agent such as calcium carbonate, kaolin etc., dosage is generally 5% or so.For ease of operation, 0.2%- can be added into dispersion liquid
0.5% defoamer.
Said mixture is spray-dried in traditional spray drying device, dryer export temperature control exists
It is 55-100 DEG C, optimal with 70-90 DEG C.
Beneficial effects of the present invention：
(1) when preparing the reemulsifiable latex powder of butylbenzene class, for prevent in high-temperature drying procedures between emulsion particle can not
It is inverse to bond, and done the best in the case where being adapted to the dispersion viscosity of spray drying and improve the solid content of latex, the preferably suitable pole of the present invention
Property comonomer, reduce the dosage of carboxylic monomer, using the method for seeded emulsion polymerization, first add the low list of glass transition temperature
Body participates in polymerisation, forms soft core, then adds the high monomer of glass transition temperature and polar functionalities monomer continues to polymerize, obtain
Hard, good hydrophilic property shell, thus obtained styrene-butadiene latex particle diameter distribution is uniform, solid content is high, viscosity is low, and it is dry to be easy to spraying
It is dry into powder, and production efficiency is high, solves dispersion viscosity before current butylbenzene class redispersable latex powder poor water resistance, spraying
High, the problems such as solid content is low and viscosity cumulative speed is big when cement mortar is modified, and cement composition setting rate is slow；
(2) degree of hydrolysis that polyvinyl alcohol is added in drying process is 85%-95%, the Hoeppler viscosity of 4% aqueous solution
For 15-30mPas, while the addition of polyvinyl alcohol is controlled, dried latex powder good fluidity, storage time length, redisperse
It is functional.
Embodiment
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
(1) preparation of seed latex：
Deionized water 4000g, lauryl sodium sulfate 35g, tween-60 emulsifying agent 65g, hydroxide are added in beaker
Potassium 0.6g, stirring and dissolving.It is another to take a beaker to add deionized water 400g, ammonium persulfate 5g, fully dissolving.Into 10L polymeric kettles
Emulsifying agent and aqueous alkali solution are added, starts stirring, while reactor is warming up to 85 DEG C, starts dropwise addition initiator solution, 5
Start that 2000g styrene is added dropwise after minute, styrene is added dropwise with 1.5h, with l.7h ammonium persulfate is added dropwise, drip
Polymerization temperature is controlled at 84-86 DEG C during adding, after material is all added dropwise, 30 minutes is incubated, is cooled to 35 DEG C and goes out
Material.Filtered with 300 mesh stainless (steel) wires, obtain seed latex.
(2) preparation of core shell structure latex：
Reaction is carried out on the 10L stainless steel polyplants with automatic temperature control system.First, 30g composite emulsifiers are weighed
(lauryl sodium sulfate 10g, tween-60 emulsifying agent 20g), add 400g deionized waters and fully dissolve.Take 200g emulsifying agents molten
Liquid, 60g acrylamides and 60g acrylonitrile pre-emulsifications are added, obtains acrylamide/acrylonitrile/emulsifier solution.By 40g itaconic acids
Fully dissolved with 500g deionized waters.40g ammonium persulfates are weighed, adds in 200g water and fully dissolves.Seed latex 20g is weighed,
Butadiene 800g, styrene 1200g.
900g deionized waters, 0.01gEDTA, 19g potassium hydroxide, 40g seed latex are added in polymeric kettle.It is true by taking out
Free oxygen in empty removal system, open and stir and be warming up to 85 DEG C, it is molten that styrene, butadiene, emulsifying agent is then continuously added dropwise
Liquid and ammonium persulfate aqueous solution, butadiene, 400g styrene, emulsifier solution were added dropwise in 6 hours, and process is added dropwise
Middle strict temperature control is in the range of 84-86 DEG C.Then start that acrylamide/acrylonitrile/emulsifier solution, itaconic acid water is added dropwise
Solution, continue that remaining 800g styrene, time for adding 2h is added dropwise.After whole material droppings terminate, 2h is incubated.
Polymerisation can be implemented post-polymerization with known method after terminating and (be gathered after such as being triggered with oxidation reduction catalyst
Close reaction), residual monomer is removed, or it is reclaimed using distillation or steam stripped method.
Gained latex is cooled to 35 DEG C of dischargings, is filtered with 300 mesh stainless (steel) wires, obtains core shell structure styrene-butadiene latex.
(3) preparation of redispersable latex powder
It is 80%-95% and 4% aqueous solution by the degree of hydrolysis that the addition of above-mentioned polymer emulsion accounts for polymer 12%
Hoeppler viscosity 1-30mPas polyvinyl alcohol.Then the kaolin for adding 5% cooks interleaving agent, adds 0.3% and disappears
Infusion, it is well mixed.
Said mixture is spray-dried in traditional spray drying device, dryer export temperature control is 70
℃。
Embodiment 2
1) preparation of seed latex：
Deionized water 4000g, neopelex 100g, OPEO 60g, hydrogen are added in beaker
Potassium oxide 0.6g, stirring and dissolving.It is another to take a beaker to add deionized water 600g, ammonium persulfate 7g, fully dissolving.It polymerize to 10L
Emulsifying agent and aqueous alkali solution are added in kettle, starts stirring, while reactor is warming up to 85 DEG C, it is molten to start dropwise addition initiator
Liquid, start that 2000g styrene is added dropwise after 5 minutes, styrene is added dropwise with 1.5h, with l.7h dripping ammonium persulfate
Finish, control polymerization temperature at 84-86 DEG C during dropwise addition, after material is all added dropwise, is incubated 30 minutes, is cooled to 35
DEG C discharging.Filtered with 300 mesh stainless (steel) wires.Obtain seed latex.
2) preparation of core shell structure latex：
Reaction is carried out on the 10L stainless steel polyplants with automatic temperature control system.First, 60g composite emulsifiers are weighed
(neopelex 40g, OPEO 20g), add 400g deionized waters and fully dissolve.200g is taken to emulsify
Agent solution, 40g acrylamides and 100g acrylonitrile pre-emulsifications are added, obtains acrylamide/acrylonitrile/emulsifier solution.By 60g clothing
Health acid is fully dissolved with 500g deionized waters.40g ammonium persulfates are weighed, adds in 200g water and fully dissolves.Weigh seed latex
60g, butadiene 1000g, styrene 1000g.
900g deionized waters, 0.01gEDTA, 19g potassium hydroxide, 40g seed latex are added in polymeric kettle.It is true by taking out
Free oxygen in empty removal system, open and stir and be warming up to 85 DEG C, styrene, butadiene, acrylamide is then continuously added dropwise
Emulsifier solution and ammonium persulfate aqueous solution, butadiene, 600g styrene, emulsifier solution were added dropwise in 6 hours,
Strict temperature control is in the range of 84-86 DEG C during dropwise addition.Then start be added dropwise acrylamide/acrylonitrile/emulsifier solution,
The itaconic acid aqueous solution, while continue that remaining 800g styrene, time for adding 2h is added dropwise.After whole material droppings terminate, protect
Warm 2h.
Polymerisation can be implemented post-polymerization with known method after terminating and (be gathered after such as being triggered with oxidation reduction catalyst
Close reaction), remove residual monomer.Or it is reclaimed using distillation or steam stripped method.
Gained latex is cooled to 35 DEG C of dischargings, is filtered with 300 mesh stainless (steel) wires, obtains crosslinking styrene-butadiene latex.
3) preparation of redispersable latex powder
It is 80%-95% and 4% aqueous solution by the degree of hydrolysis that the addition of above-mentioned polymer emulsion accounts for polymer 15%
Hoeppler viscosity 1-30mPas polyvinyl alcohol.Then the kaolin for adding 5% cooks interleaving agent, adds 0.3% and disappears
Infusion, it is well mixed.
Said mixture is spray-dried in traditional spray drying device, dryer export temperature control is 90
℃。
Embodiment 3
1) preparation of seed latex：
Deionized water 4000g, alkylpolyoxyethylene sodium sulphate 60g, tween-60 emulsifying agent are added in beaker
60g, potassium hydroxide 0.6g, stirring and dissolving.It is another to take a beaker to add deionized water 500g, ammonium persulfate 6g, fully dissolving.To
Emulsifying agent and aqueous alkali solution are added in 10L polymeric kettles, starts stirring, while reactor is warming up to 85 DEG C, starts to be added dropwise
Initiator solution, start that 2000g styrene is added dropwise after 5 minutes, styrene is added dropwise with 1.5h, with l.7h by ammonium persulfate
It is added dropwise, controls polymerization temperature at 84-86 DEG C during dropwise addition, after material is all added dropwise, is incubated 30 minutes, drop
Warm to 35 DEG C dischargings.Filtered with 300 mesh stainless (steel) wires.Obtain seed latex.
2) preparation of core shell structure latex：
Reaction is carried out on the 10L stainless steel polyplants with automatic temperature control system.First, 50g composite emulsifiers are weighed
(alkylpolyoxyethylene sodium sulphate 25g, tween-60 emulsifying agent 25g), add 400g deionized waters and fully dissolve.Take
200g emulsifier solutions, 100g acrylamides and 80g acrylonitrile pre-emulsifications are added, it is molten to obtain acrylamide/acrylonitrile/emulsifying agent
Liquid.50g itaconic acids are fully dissolved with 500g deionized waters.40g ammonium persulfates are weighed, adds in 200g water and fully dissolves.Claim
Take seed latex 20g, butadiene 900g, styrene 1100g.
900g deionized waters, 0.01gEDTA, 19g potassium hydroxide, 40g seed latex are added in polymeric kettle.It is true by taking out
Free oxygen in empty removal system, open and stir and be warming up to 85 DEG C, it is molten that styrene, butadiene, emulsifying agent is then continuously added dropwise
Liquid and ammonium persulfate aqueous solution, butadiene, 550g styrene, emulsifier solution were added dropwise in 6 hours, and process is added dropwise
Middle strict temperature control is in the range of 84-86 DEG C.Then start that acrylamide/acrylonitrile/emulsifier solution, itaconic acid water is added dropwise
Solution, continue that remaining 550g styrene, time for adding 2h is added dropwise.After whole material droppings terminate, 2h is incubated.
Polymerisation can be implemented post-polymerization with known method after terminating and (be gathered after such as being triggered with oxidation reduction catalyst
Close reaction), remove residual monomer.Or it is reclaimed using distillation or steam stripped method.
Gained latex is cooled to 35 DEG C of dischargings, is filtered with 300 mesh stainless (steel) wires, obtains core shell structure styrene-butadiene latex.
3) preparation of redispersable latex powder
It is 80%-95% and 4% aqueous solution by the degree of hydrolysis that the addition of above-mentioned polymer emulsion accounts for polymer 13%
Hoeppler viscosity 1-30mPas polyvinyl alcohol.Then the kaolin for adding 5% cooks interleaving agent, adds 0.3% and disappears
Infusion, it is well mixed.
Said mixture is spray-dried in traditional spray drying device, dryer export temperature control is 80
℃。
Redispersable latex powder dispersiveness and fluidity determining：
(1) rubber powder redisperse performance measurement：
50g latex powders are taken to add in 50ml water, fully wetting, it is 0.5% to be then diluted with water to solids content, and stirring is equal
It is even.Above-mentioned solution 100ml is taken, is poured into a graduated test tube, the precipitate height of solid is measured after 1h and 24h.
(2) rubber powder anti-caking performance determines：
Latex powder is poured into one has in the iron pipe of threaded cap, and applies load with metal formpiston.After applying load, at 50 DEG C
Drying box in by the pipe store 16h, after being cooled to room temperature, powder is taken out from pipe, crushes the powder to determine its resistive connection
Block.The height of anticaking capacity is divided into following level Four：
1- anticaking capacities are splendid
2- anticaking capacities are good
3- anticaking capacities can
4- can not crush without anticaking capacity, powder, or be no longer able to flow freely after crushing.
Latex powder obtained by Example 1-3 simultaneously, determines its redispersibility energy and anticaking capacity, as a result as follows：
Latex powder dispersiveness and anticaking capacity test result obtained by the embodiment 1-3 of table 5
Redispersable latex powder Mechanics Performance Testing：
Certain commercially available Portland cement of 200 parts by weight, 600 parts by weight yellow ground are added in blender, 0.4 parts by weight disappear
Infusion, 10,20,30,40 parts by weight latex powders are weighed respectively, it is dry-mixed that water is uniformly slowly added under stirring, control mortar jumping table stream
Dynamic degree is 150 ± 5mm.Shaping and maintenance are pressed《Polymer cement mortar》(JT/T984-2005) method is carried out.And in standard
Maintenance is stripped after 1 day in curing box, natural curing 28 days again after then being conserved 7 days in water.Mechanical strength, tension adhesion strength are pressed
《Polymer-modified cement mortar testing regulations》(DL/T5126-2001) tested.It the results are shown in Table 6.
The mechanical experimental results of the core shell structure butadiene-styrene latex powder cement mortar of table 6
Claims (8)
1. a kind of core shell structure butylbenzene redispersable latex powder, it is the co-dried of core shell structure styrene-butadiene latex and deflocculant
Mixture, it is characterised in that the latex powder is prepared using following step：
(1) seed latex is prepared
Compound emulsion agent solution and aqueous slkali are added into polymeric kettle, starts stirring, reactor is warming up to 85 DEG C, and initiator is added dropwise
Solution, styrene then being added, polymeric kettle temperature control is incubated 30 minutes after 84-86 DEG C, charging during charging,
35 DEG C are cooled to, with 300 mesh stainless (steel) wire filtering and dischargings, obtains seed latex；
(2) core shell structure styrene-butadiene latex is prepared
By itaconic acid deionized water dissolving, the itaconic acid aqueous solution is obtained；
Deionized water is added in composite emulsifier fully to dissolve, and is then added acrylamide and acrylonitrile, is obtained acrylamide/propylene
Nitrile/emulsifier solution；
Seed latex obtained by deionized water, EDTA, alkali and step (1) is added in polymeric kettle, the free oxygen in kettle is removed, opens
Stirring is opened, is warming up to 85 DEG C, styrene, butadiene and ammonium persulfate aqueous solution is then continuously added dropwise, kettle is controlled during charging
In the range of 84-86 DEG C, butadiene, the styrene of 1/2-2/3 mass were added dropwise temperature in 6 hours, then started dropwise addition third
Acrylamide/acrylonitrile/emulsifier solution and the itaconic acid aqueous solution, while continue to be added dropwise remaining styrene, time for adding 2h,
Charging finishes, and is incubated 2h, is cooled to 35 DEG C, with 300 mesh stainless (steel) wire filtering and dischargings, obtains core shell structure styrene-butadiene latex；
(3) redispersable latex powder is prepared
Polyvinyl alcohol is added into core shell structure styrene-butadiene latex obtained by step (2), is spray-dried after well mixed, produce to divide again
Dissipate latex powder.
A kind of 2. core shell structure butylbenzene redispersable latex powder according to claim 1, it is characterised in that step (1) institute
The polymerization formula for stating seed latex is：The mass parts of styrene 100, composite emulsifier 5-8 mass parts, ammonium persulfate 0.25-0.35
Mass parts, the mass parts of potassium hydroxide 0.03, deionized water 220-230 mass parts.
3. a kind of core shell structure butylbenzene redispersable latex powder according to claim 2, it is characterised in that with quality percentage
Than meter, the solid content of the seed latex is 30-32%, particle diameter 35-45nm, surface tension 35-40mN/m.
A kind of 4. core shell structure butylbenzene redispersable latex powder according to claim 1, it is characterised in that step (2) institute
The polymerization formula for stating core shell structure styrene-butadiene latex is：Seed latex 1-3 mass parts, styrene 50-60 mass parts, butadiene 40-
50 mass parts, itaconic acid 2-3 mass parts, acrylonitrile 3-5 mass parts, acrylamide 2-5 mass parts, composite emulsifier 1.5-3 matter
Measure part, ammonium persulfate 1-3 mass parts, potassium hydroxide 0.8-0.9 mass parts, the mass parts of EDTA 0.0005, the matter of deionized water 100
Measure part.
A kind of 5. core shell structure butylbenzene redispersable latex powder according to claim 1, it is characterised in that the compounding breast
Agent is made up of anionic emulsifier and nonionic emulsifier, and the mass ratio of the two is 1:2-2:1, anionic emulsifier
For any one in lauryl sodium sulfate, neopelex, alkylpolyoxyethylene sodium sulphate, nonionic
Type emulsifying agent is any one in OPEO, Arlacel-60.
6. a kind of core shell structure butylbenzene redispersable latex powder according to claim 5, it is characterised in that with quality percentage
Than meter, the solid content of the core shell structure styrene-butadiene latex is 50-52%, particle diameter 150-170nm, surface tension 47-56mN/
M, viscosity 230-250mPas.
A kind of 7. core shell structure butylbenzene redispersable latex powder according to claim 1, it is characterised in that step (3) institute
The degree of hydrolysis for stating polyvinyl alcohol is 85%-95%, and the Hoeppler viscosity of 4% aqueous solution is 15-30mPas.
8. a kind of core shell structure butylbenzene redispersable latex powder according to claim 1, it is characterised in that in step (3)
In, in terms of 100 mass parts core shell structure styrene-butadiene latexes, the addition of polyvinyl alcohol is 12-15 mass parts.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359050A (en) * | 2018-03-02 | 2018-08-03 | 上海三瑞高分子材料股份有限公司 | A kind of preparation method of the modified butadiene-styrene latex of nucleocapsid |
| CN110483674A (en) * | 2019-07-18 | 2019-11-22 | 广东腾龙化工科技有限公司 | A kind of Paper Coating butadiene-styrene copolymer latex and its preparation method and application |
| CN115073646A (en) * | 2022-08-09 | 2022-09-20 | 山东亿科化学有限责任公司 | High-solid-content styrene-butadiene latex and preparation method thereof |
| CN115260374A (en) * | 2022-09-14 | 2022-11-01 | 广东巴德富新材料有限公司 | High-water-resistance styrene-butadiene latex and rigid waterproof mortar coating applying same |
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2017
- 2017-10-13 CN CN201710952393.XA patent/CN107674217A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359050A (en) * | 2018-03-02 | 2018-08-03 | 上海三瑞高分子材料股份有限公司 | A kind of preparation method of the modified butadiene-styrene latex of nucleocapsid |
| CN108359050B (en) * | 2018-03-02 | 2020-06-09 | 瑞固新能(上海)材料科技有限公司 | Preparation method of modified styrene-butadiene latex with core-shell structure |
| CN110483674A (en) * | 2019-07-18 | 2019-11-22 | 广东腾龙化工科技有限公司 | A kind of Paper Coating butadiene-styrene copolymer latex and its preparation method and application |
| CN115073646A (en) * | 2022-08-09 | 2022-09-20 | 山东亿科化学有限责任公司 | High-solid-content styrene-butadiene latex and preparation method thereof |
| CN115073646B (en) * | 2022-08-09 | 2023-06-23 | 山东亿科化学有限责任公司 | High-solid-content styrene-butadiene latex and preparation method thereof |
| CN115260374A (en) * | 2022-09-14 | 2022-11-01 | 广东巴德富新材料有限公司 | High-water-resistance styrene-butadiene latex and rigid waterproof mortar coating applying same |
| CN115260374B (en) * | 2022-09-14 | 2023-11-03 | 广东巴德富新材料有限公司 | High-water-resistance styrene-butadiene latex and rigid waterproof mortar coating using same |
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