CN104086686A - Styrene-acrylic emulsion with excellent freeze-thaw stability as well as preparation method and application thereof - Google Patents
Styrene-acrylic emulsion with excellent freeze-thaw stability as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of coatings, and discloses a styrene-acrylic emulsion with excellent freeze-thaw stability as well as a preparation method and an application thereof. The styrene-acrylic emulsion contains an anion-nonionic compound emulsifier of a specific type and content and a functional polymerization monomer, and also has a glass-transition temperature of a particle shell layer within a specific range. The styrene-acrylic emulsion is prepared by adopting a core-shell emulsion polymerization method, wherein the excellent freeze-thaw stability of the styrene-acrylic emulsion with is realized by controlling the usage amount and the adding mode of the functional polymerization monomer and controlling the core forming mode of emulsion particles. The styrene-acrylic emulsion has the excellent freeze-thaw stability, and a high-PVC (Poly Vinyl Chloride) interior wall coating product prepared by utilizing the styrene-acrylic emulsion also has the excellent freeze-thaw stability under the condition that no antifreeze agent is added.
Description
Technical field
The invention belongs to paint field, be specifically related to a kind of benzene emulsion with excellent freeze-thaw stability and preparation method thereof and application.
Background technology
Coating is and the closely-related finishing material of people's daily life, and interior wall coating is the important component part of coating, yet volatile organic compounds (VOC) in coating is the important environmental pollutant of a class, and HUMAN HEALTH has been formed to great threat.CNS GB18582-2008 < < indoor decorating and refurnishing materials---in interior wall coating, in limits of harmful substances > >, VOC is defined as to " under 101.3kPa standard pressure, any initial boiling point is less than or equal to the organic compound of 250 ℃ ".At present, zero VOC or low VOC interior wall coating have become the main flow coating products of American-European countries.Europe IAQ (indoor air quality) Joint Action Board has formulated new legislation, and regulation was from 1 day January in 2010, and the VOC content of decorative water zero diopter and non-flat paint will be reduced to the scope that is less than 30g/L and 40g/L respectively.China's interior wall coating market will progressively integrate with European & American Market, and zero/low VOC content, nontoxic health type green environmental friendly coatings are favored and praise highly by domestic consumers in general.
Polymer emulsion, as the chief component of coating, directly affects the over-all properties of coating.At numerous interior wall coating, with in polymer emulsion, benzene emulsion is widely used because of its inexpensive, good physical and chemical performance.Benzene emulsion (being cinnamic acrylic ester emulsion) is to be obtained through emulsion copolymerization by vinylbenzene and acrylate monomer.Benzene emulsion is in letex polymerization, to study more system, and there are one of ten large non-crosslinked type emulsions of essential industry using value the Ye Shi world today.
Benzene emulsion and coating thereof, take water as dispersion medium exists the poor shortcoming of freeze-thaw resistance because of it, in the transportation under low temperature environment and storage process, often because product freeze thawing cannot recover flowable state after condensing into piece, goes bad, and causes huge financial loss.At present, mainly to take to add antifreezing agent to solve the poor problem of freeze-thaw stability (seeing patent US20090186968A1, US6933415B2 and CN103205172A etc.), yet the antifreezing agent adding is generally high VOC solvent, this will certainly increase the VOC content of coating products.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide a kind of benzene emulsion with excellent freeze-thaw stability, not only VOC content is low, good combination property for the described benzene emulsion with excellent freeze-thaw stability, and has excellent freeze-thaw stability;
Another object of the present invention is to provide the above-mentioned preparation method with the benzene emulsion of excellent freeze-thaw stability, described preparation method has simple process, be easy to the feature controlled, polymerization system is stable, transformation efficiency is high;
A further object of the present invention is to provide the application of the benzene emulsion with excellent freeze-thaw stability.
Object of the present invention is achieved through the following technical solutions:
A kind of benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, raw materials used component comprises polymerization main monomer, anionic-nonionic compound emulsifier, functional polymerization monomer, initiator, pH buffer reagent and water, and described polymerization main monomer is that alkyl acrylate mixes with cinnamic; Described anionic-nonionic compound emulsifier is to have a kind of in the compound of formula I～formula III general structure:
Described functional polymerization monomer is to have a kind of in the compound of formula IV～formula V general structure:
In formula I～formula V, R
1, R
2, R
3, R
4and R
5independently be selected from C
1～C
13straight-chain paraffin base, C
1～C
13the alkyl that contains branched structure or C
2～C
15hydroxyalkyl; M is 3 to 50 integer; N is 3 to 50 integer; O is 3 to 50 integer; X is sulfonate groups (-SO
3 -m
+), sulfate group (-SO
4 -m
+), carboxylate groups (-COO
-m
+) in a kind of; M
+for Na
+, K
+or NH
4 +;
Preferably, described anionic-nonionic compound emulsifier is the agent of non-APEO class environment protective emulsive, and its consumption is 0.5%～1% of polymerization main monomer total mass;
Preferably, the consumption of described functional polymerization monomer is 0.2%～1% of polymerization main monomer total mass;
The particle shell second-order transition temperature preferably, with the benzene emulsion of excellent freeze-thaw stability is 18～40 ℃;
Preferably, described alkyl acrylate is butyl acrylate or Isooctyl acrylate monomer;
Preferably, in described polymerization main monomer, alkyl acrylate and cinnamic mass ratio are (48～35): (52～65);
Preferably, described initiator is a kind of in Sodium Persulfate, ammonium persulphate or Potassium Persulphate; The consumption of described initiator is 0.4%～0.6% of polymerization main monomer total mass;
Preferably, described pH buffer reagent is NaHCO
3or NaHPO
4in a kind of; The consumption of described pH buffer reagent is 0.3%～0.6% of polymerization main monomer total mass.
The above-mentioned preparation method with the benzene emulsion of excellent freeze-thaw stability, comprises the steps:
(1) water of the initiator of pH buffer reagent, anionic-nonionic compound emulsifier, gross weight 20～40% and gross weight 60～80% is added in reactor, mix post-heating;
(2) question response actuator temperature is heated to 78～82 ℃, drips the polymerization main monomer of gross weight 8～15%, dropwises insulation 20～30min in 5～10min;
(3) then toward drip the polymerization main monomer of surplus in reactor simultaneously, the water of surplus and solution that initiator is prepared, polymerization main monomer residue until surplus starts to drip functional polymerization monomer at 1/2～1/3 o'clock, the all materials of this step dropwise in 3～4h, are then warming up to 85～90 ℃ of insulation reaction 0.5～1h;
(4) after step (3) reaction finishes, be cooled to 50～60 ℃, with ammoniacal liquor, regulate pH value to 7～9, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability.
The above-mentioned benzene emulsion with excellent freeze-thaw stability has the application in good freeze-thaw stability coating in preparation.
The emulsion paint that the described benzene emulsion with excellent freeze-thaw stability of take is prepared as raw material, by the raw material of following mass percent, modulate and form:
The present invention has following advantage and effect with respect to prior art:
(1) anionic-nonionic compound emulsifier of the present invention is non-APEO class emulsifying agent, biodegradable, environmental protection.
(2) the present invention adopts anionic-nonionic compound emulsifier, introduces functional polymerization monomer simultaneously, is bonded on polymer chain, plays the effect of internal emulsification, makes benzene emulsion have excellent polymerization stability and freeze-thaw stability simultaneously.
(3) benzene emulsion of the present invention, adopt core-shell emulsion polymerization method, the nucleation mode that makes the anionic-nonionic compound emulsifier Collaborative Control emulsion particle of itself and particular category by controlling the consumption of functional polymerization monomer and the mode that adds, promotes freeze-thaw stability jointly.
(4) the method for the invention simple process, be easy to control, polymerization process is stable, transformation efficiency is high.
(5) when benzene emulsion of the present invention is used for preparing high PVC (PVC value can up to 80～85%) interior wall coating, do not need to add antifreezing agent, gained coating products VOC content approaches zero, good combination property, and has good freeze-thaw stability.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: the functional polymerization monomer of 2g methacrylic acid (MAA) 0.2g (COPS-2), 0.75g anionic-nonionic compound emulsifier (KL-70), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (COPS-2) is the functional polymerization monomer that meets general structure IV, and concrete structure formula is:
Anionic-nonionic compound emulsifier (KL-70) is the anionic-nonionic compound emulsifier that meets general structure III, and concrete structure formula is:
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), the ammonium persulphate of gross weight 25% and the deionized water of gross weight 80% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 78 ℃, and the polymerization main monomer mixture of getting gross weight 10% starts to drip, and dropwises insulation 30min in 10min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/2 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 90 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 1.
Embodiment 2
A benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.6g (COPS-2), 0.75g anionic-nonionic compound emulsifier (KL-70), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (COPS-2) is and identical functional polymerization monomer described in embodiment 1;
Anionic-nonionic compound emulsifier (KL-70) is and identical anionic-nonionic compound emulsifier described in embodiment 1.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), the ammonium persulphate of gross weight 25% and the deionized water of gross weight 80% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 78 ℃, and the polymerization main monomer mixture of getting gross weight 10% starts to drip, and dropwises insulation 30min in 10min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/2 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 90 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 2.
Embodiment 3
A benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 1g (COPS-2), 0.75g anionic-nonionic compound emulsifier (KL-70), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (COPS-2) is and identical functional polymerization monomer described in embodiment 1;
Anionic-nonionic compound emulsifier (KL-70) is and identical anionic-nonionic compound emulsifier described in embodiment 1.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), the ammonium persulphate of gross weight 25% and the deionized water of gross weight 80% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 78 ℃, and the polymerization main monomer mixture of getting gross weight 10% starts to drip, and dropwises insulation 30min in 10min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/2 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 90 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 3.
Comparative example 1
A benzene emulsion, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), 0.75g anionic-nonionic compound emulsifier (KL-70), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, anionic-nonionic compound emulsifier (KL-70) is and identical anionic-nonionic compound emulsifier described in embodiment 1.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), the ammonium persulphate of gross weight 25% and the deionized water of gross weight 80% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 78 ℃, and the polymerization main monomer mixture of getting gross weight 10% starts to drip, and dropwises insulation 30min in 10min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared, all materials of this step dropwise in 3.5h, are then warming up to 90 ℃ of insulation reaction 1h simultaneously;
(4) after step (3) reaction finishes, be cooled to 50 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as comparative sample 1.
Embodiment 4
A benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.3g (COPS-2), 1g anionic-nonionic compound emulsifier (DNS-80), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (COPS-2) is and identical functional polymerization monomer described in embodiment 1;
Anionic-nonionic compound emulsifier (DNS-80) is the anionic-nonionic compound emulsifier that meets general structure II, and concrete structure formula is:
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (DNS-80), the ammonium persulphate of gross weight 40% and the deionized water of gross weight 60% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 82 ℃, and the polymerization main monomer mixture of getting gross weight 8% starts to drip, and dropwises insulation 20min in 5min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/2 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 85 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 60 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 4.
Embodiment 5
A benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.6g (COPS-2), 1g anionic-nonionic compound emulsifier (DNS-80), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (COPS-2) is and identical functional polymerization monomer described in embodiment 1;
Anionic-nonionic compound emulsifier (DNS-80) is and identical anionic-nonionic compound emulsifier described in embodiment 4.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (DNS-80), the ammonium persulphate of gross weight 40% and the deionized water of gross weight 60% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 82 ℃, and the polymerization main monomer mixture of getting gross weight 8% starts to drip, and dropwises insulation 20min in 5min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/2 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 85 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 60 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 5.
Embodiment 6
A benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 1g (COPS-2), 1g anionic-nonionic compound emulsifier (DNS-80), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (COPS-2) is and identical functional polymerization monomer described in embodiment 1;
Anionic-nonionic compound emulsifier (DNS-80) is and identical anionic-nonionic compound emulsifier described in embodiment 4.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (DNS-80), the ammonium persulphate of gross weight 40% and the deionized water of gross weight 60% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 82 ℃, and the polymerization main monomer mixture of getting gross weight 8% starts to drip, and dropwises insulation 20min in 5min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/2 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 85 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 60 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 6.
Comparative example 2
A benzene emulsion, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), 1g anionic-nonionic compound emulsifier (DNS-80), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, anionic-nonionic compound emulsifier (DNS-80) is and identical anionic-nonionic compound emulsifier described in embodiment 4.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (DNS-80), the ammonium persulphate of gross weight 40% and the deionized water of gross weight 60% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 82 ℃, and the polymerization main monomer mixture of getting gross weight 8% starts to drip, and dropwises insulation 20min in 5min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared, all materials of this step dropwise in 3.5h, are then warming up to 85 ℃ of insulation reaction 1h simultaneously;
(4) after step (3) reaction finishes, be cooled to 60 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as comparative sample 2.
Embodiment 7
A benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.4g (KL-100-II), 0.6g anionic-nonionic compound emulsifier (A-102), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (KL-100-II) is the functional polymerization monomer that meets general structure V, and concrete structure formula is:
Anionic-nonionic compound emulsifier (A-102) is the anionic-nonionic compound emulsifier that meets general structure I, and concrete structure formula is:
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), the ammonium persulphate of gross weight 20% and the deionized water of gross weight 70% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 80 ℃, and the polymerization main monomer mixture of getting gross weight 15% starts to drip, and dropwises insulation 20min in 10min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/3 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 90 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 7.
Embodiment 8
A benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.8g (KL-100-II), 0.6g anionic-nonionic compound emulsifier (A-102), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (KL-100-II) is and identical functional polymerization monomer described in embodiment 7;
Anionic-nonionic compound emulsifier (A-102) is and identical anionic-nonionic compound emulsifier described in embodiment 7.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), the ammonium persulphate of gross weight 20% and the deionized water of gross weight 70% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 80 ℃, and the polymerization main monomer mixture of getting gross weight 15% starts to drip, and dropwises insulation 20min in 10min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/3 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 90 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 8.
Embodiment 9
A benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 1g (KL-100-II), 1g anionic-nonionic compound emulsifier (A-102), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (KL-100-II) is and identical functional polymerization monomer described in embodiment 7;
Anionic-nonionic compound emulsifier (A-102) is and identical anionic-nonionic compound emulsifier described in embodiment 7.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), the ammonium persulphate of gross weight 20% and the deionized water of gross weight 70% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 80 ℃, and the polymerization main monomer mixture of getting gross weight 15% starts to drip, and dropwises insulation 20min in 10min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/3 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 90 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 9.
Comparative example 3
A benzene emulsion, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), 0.6g anionic-nonionic compound emulsifier (A-102), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, anionic-nonionic compound emulsifier (A-102) is and identical anionic-nonionic compound emulsifier described in embodiment 7.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), the ammonium persulphate of gross weight 25% and the deionized water of gross weight 75% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 80 ℃, and the polymerization main monomer mixture of getting gross weight 15% starts to drip, and dropwises insulation 20min in 10min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared, all materials of this step dropwise in 3.5h, are then warming up to 90 ℃ of insulation reaction 1h simultaneously;
(4) after step (3) reaction finishes, be cooled to 50 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as comparative sample 3.
Embodiment 10
A benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 52.5g vinylbenzene (St), 47.5g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.6g (COPS-2), 0.5g anionic-nonionic compound emulsifier (KL-70), 0.6g ammonium persulphate (APS), 0.6g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (COPS-2) is and functional polymerization monomer identical described in embodiment 1;
Anionic-nonionic compound emulsifier (KL-70) is and anionic-nonionic compound emulsifier identical described in embodiment 1;
Second-order transition temperature (Tg) is 18 ℃.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), the ammonium persulphate of gross weight 25% and the deionized water of gross weight 70% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 80 ℃, and the polymerization main monomer mixture of getting gross weight 10% starts to drip, and dropwises insulation 20min in 10min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/2 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 90 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 10; Second-order transition temperature is 18 ℃.
Embodiment 11
A benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 65g vinylbenzene (St), 35g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.6g (COPS-2), 0.5g anionic-nonionic compound emulsifier (KL-70), 0.6g ammonium persulphate (APS), 0.6g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (COPS-2) is and functional polymerization monomer identical described in embodiment 1;
Anionic-nonionic compound emulsifier (KL-70) is and anionic-nonionic compound emulsifier identical described in embodiment 1;
Second-order transition temperature (Tg) is 40 ℃.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), the ammonium persulphate of gross weight 25% and the deionized water of gross weight 70% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 80 ℃, and the polymerization main monomer mixture of getting gross weight 10% starts to drip, and dropwises insulation 20min in 10min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/2 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 90 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 11; Second-order transition temperature is 40 ℃.
Comparative example 4
A benzene emulsion, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, and raw materials used component and consumption are as follows:
Polymerization main monomer: 50g vinylbenzene (St), 50g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.6g (COPS-2), 0.5g anionic-nonionic compound emulsifier (KL-70), 0.6g ammonium persulphate (APS), 0.6g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization monomer (COPS-2) is and functional polymerization monomer identical described in embodiment 1;
Anionic-nonionic compound emulsifier (KL-70) is and anionic-nonionic compound emulsifier identical described in embodiment 1;
Second-order transition temperature (Tg) is 14 ℃.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), the ammonium persulphate of gross weight 25% and the deionized water of gross weight 70% are added in reactor, mix post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperature is heated to 80 ℃, and the polymerization main monomer mixture of getting gross weight 10% starts to drip, and dropwises insulation 20min in 10min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus and the solution that ammonium persulphate is prepared simultaneously, until the polymerization main monomer mixture of surplus, remain at 1/2 o'clock and start to drip functional polymerization monomer (COPS-2), the all materials of this step dropwise in 3.5h, are then warming up to 90 ℃ of insulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 ℃, with ammoniacal liquor, regulate pH value to 8, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability, be designated as comparative sample 4; Second-order transition temperature is 14 ℃.
Performance test:
1, freeze-thaw stability test:
Freeze-thaw stability with reference to GB/T20623-2006 test gained sample 1～11 and comparative sample 1～4.The refrigerated tank that test sample is placed in to (10 ± 2) ℃ freezes to take out after 18h, then under (23 ± 2) ℃ condition, places 6h, is once complete freeze-thaw cycle.Open container, fully stir test sample, if there is no lump, cohesion and separation phenomenon, repeat freeze-thaw cycle.Often pass through 1 time, freeze thawing exponent increase 1, result numeral, the freeze-thaw stability of the larger expression emulsion of numeral is better.
Particle diameter test: with reference to GB/T11175-2002, with Ma Erwen Nano-ZSZEN3600 type laser light scattering particle size analyzer determination test sample emulsion particle diameter, parallel testing is averaged for 3 times.
Emulsion viscosity test: adopt DV2 II+rotation viscosity apparatus, U.S. Brookfield company; Test condition: 3# rotor, 25 ℃, 30rpm.
Emulsion paint viscosity test: adopt STM-III stormer viscosity meter, probe temperature: (23 ± 1) ℃.
Test as stated above particle diameter and viscosity after the initial particle of gained sample 1～11 and comparative sample 1～4 and viscosity, each freeze-thaw cycle, result is as shown in table 1:
Table 1. sample freeze-thaw stability detected result
Note: "-" refers to that emulsion condenses into piece, and viscosity cannot record; 10+ still has good mobility after referring to emulsion freeze-thaw cycle 10 times.
By table 1 test result, can be found out, all not very poor containing the freeze-thaw stability of the comparative sample 1～4 of functional polymerization monomer, after freeze-thaw cycle 1 to 2 time, the particle diameter of emulsion and viscosity generation great variety; And add after functional polymerization monomer, the freeze-thaw stability of emulsion be improved significantly, and functional polymerization monomer adds the freeze-thaw stability that is more conducive to emulsion in polymerization reaction late stage.This is to add because control the functional polymerization monomer later stage, make it be distributed in the skin of latex particle, thereby can produce synergy with the anionic-nonionic compound emulsifier of described particular category, control the nucleation mode of emulsion particle, jointly promote the freeze-thaw stability of emulsion.
Known with the test result of sample 2, sample 10, sample 11 by comparative sample in table 14, only having Tg is approximately 18 ℃ when above, the anionic-nonionic compound emulsifier of described ad hoc structure and functional polymerization monomer competence exertion act synergistically, and jointly promote the freeze-thaw stability of emulsion; Otherwise this synergy will be suppressed, the freeze-thaw stability of emulsion is poor.
Gained benzene emulsion of the present invention has excellent freeze-thaw stability, when it is applied to high PVC interior wall coating, does not need to add any antifreezing agent, and not only VOC content is low for gained coating products, good combination property, and has good freeze-thaw stability.Sample in embodiment 22 and commercially available benzene emulsion press respectively to table 2 formula and modulate high PVC interior wall coating, and according to GB/T9268-2008, at (10 ± 1) ℃, test its freeze-thaw stability, test result is as table 3.
Table 2 high PVC interiro wall latex paint basic recipe
| Material name | Mass percent/% |
| Water | 36.67 |
| Wetting dispersing agent | 0.5 |
| Film coalescence aid | 0.9 |
| Defoamer | 0.2 |
| Ultramarine slurry | 0.02 |
| Thickening material | 0.47 |
| Ammoniacal liquor | 0.04 |
| Titanium dioxide | 2 |
| Kaolin | 10 |
| Talcum powder | 9 |
| Coarse whiting | 30 |
| Mould inhibitor | 0.2 |
| The commercially available benzene emulsion of samples of latex 2/ | 10 |
| Add up to | 100 |
Table 3 high PVC emulsion paint freeze thawing test result
From the test result of table 3, in the situation that not adding antifreezing agent, very poor with the high PVC interiro wall latex paint freeze-thaw stability of commercially available emulsion modulation, after freeze-thaw cycle 1 time, KU viscosity changes greatly, and it is serious that freeze-thaw cycle returns thick cohesion 2 times above; And the high PVC interiro wall latex paint of modulating with gained benzene emulsion of the present invention has excellent freeze-thaw stability, the performance variation such as stormer viscosity after 5 freeze-thaw cycle are less, and meet the environmental requirement of low/zero VOC, more safer than conventional interiro wall latex paint.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1. a benzene emulsion with excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain, raw materials used component comprises polymerization main monomer, anionic-nonionic compound emulsifier, functional polymerization monomer, initiator, pH buffer reagent and water, and described polymerization main monomer is that alkyl acrylate mixes with cinnamic; It is characterized in that:
Described anionic-nonionic compound emulsifier is to have a kind of in the compound of formula I～formula III general structure:
Described functional polymerization monomer is to have a kind of in the compound of formula IV～formula V general structure:
In formula I～formula V, R
1, R
2, R
3, R
4and R
5independently be selected from C
1～C
13straight-chain paraffin base, C
1～C
13the alkyl that contains branched structure or C
2～C
15hydroxyalkyl; M is 3 to 50 integer; N is 3 to 50 integer; O is 3 to 50 integer; X is a kind of in sulfonate groups, sulfate group, carboxylate groups; M
+for Na
+, K
+or NH
4 +.
2. a kind of benzene emulsion with excellent freeze-thaw stability according to claim 1, is characterized in that: the consumption of described anionic-nonionic compound emulsifier is 0.5%～1% of polymerization main monomer total mass.
3. a kind of benzene emulsion with excellent freeze-thaw stability according to claim 1, is characterized in that: the consumption of described functional polymerization monomer is 0.2%～1% of polymerization main monomer total mass.
4. a kind of benzene emulsion with excellent freeze-thaw stability according to claim 1, is characterized in that: described in there is the benzene emulsion of excellent freeze-thaw stability particle shell second-order transition temperature be 18～40 ℃.
5. a kind of benzene emulsion with excellent freeze-thaw stability according to claim 1, is characterized in that: described alkyl acrylate is butyl acrylate or Isooctyl acrylate monomer;
In described polymerization main monomer, alkyl acrylate and cinnamic mass ratio are (48～35): (52～65);
Described initiator is a kind of in Sodium Persulfate, ammonium persulphate or Potassium Persulphate;
The consumption of described initiator is 0.4%～0.6% of polymerization main monomer total mass;
Described pH buffer reagent is NaHCO
3or NaHPO
4in a kind of;
The consumption of described pH buffer reagent is 0.3%～0.6% of polymerization main monomer total mass.
6. according to a preparation method for the benzene emulsion with excellent freeze-thaw stability described in claim 1～5 any one, it is characterized in that comprising the steps:
(1) water of the initiator of pH buffer reagent, anionic-nonionic compound emulsifier, gross weight 20～40% and gross weight 60～80% is added in reactor, mix post-heating;
(2) question response actuator temperature is heated to 78～82 ℃, drips the polymerization main monomer of gross weight 8～15%, dropwises insulation 20～30min in 5～10min;
(3) then toward drip the polymerization main monomer of surplus in reactor simultaneously, the water of surplus and solution that initiator is prepared, polymerization main monomer residue until surplus starts to drip functional polymerization monomer at 1/2～1/3 o'clock, the all materials of this step dropwise in 3～4h, are then warming up to 85～90 ℃ of insulation reaction 0.5～1h;
(4) after step (3) reaction finishes, be cooled to 50～60 ℃, with ammoniacal liquor, regulate pH value to 7～9, described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability.
7. one kind has the application in good freeze-thaw stability coating according to the benzene emulsion with excellent freeze-thaw stability described in claim 1～5 any one in preparation.
8. the emulsion paint that the benzene emulsion with excellent freeze-thaw stability of take described in claim 1～5 any one is prepared as raw material, is characterized in that: the raw material modulation by following mass percent forms:
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038429A (en) * | 2015-08-20 | 2015-11-11 | 华南理工大学 | Inner wall latex paint with excellent freeze thawing stability and preparation method of inner wall latex paint |
| CN105254800A (en) * | 2015-11-05 | 2016-01-20 | 浩力森涂料（上海）有限公司 | Acrylate emulsion used for water-based metallic paint and preparation method thereof |
| CN111675790A (en) * | 2020-06-04 | 2020-09-18 | 山东凯威尔新材料有限公司 | Freeze-thaw resistant polymer emulsion and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702437A (en) * | 2012-06-29 | 2012-10-03 | 上海东升新材料有限公司 | Styrene-acrylic emulsion as well as preparation method and application thereof |
| CN102827320A (en) * | 2012-09-17 | 2012-12-19 | 上海富臣化工有限公司 | Styrene acrylic emulsion for interior wall coating material, and preparation method thereof |
-
2014
- 2014-06-26 CN CN201410294831.4A patent/CN104086686B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702437A (en) * | 2012-06-29 | 2012-10-03 | 上海东升新材料有限公司 | Styrene-acrylic emulsion as well as preparation method and application thereof |
| CN102827320A (en) * | 2012-09-17 | 2012-12-19 | 上海富臣化工有限公司 | Styrene acrylic emulsion for interior wall coating material, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈立军等: "超低VOC内墙涂料用核壳结构苯丙乳液的制备研究", 《新型建筑材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038429A (en) * | 2015-08-20 | 2015-11-11 | 华南理工大学 | Inner wall latex paint with excellent freeze thawing stability and preparation method of inner wall latex paint |
| CN105254800A (en) * | 2015-11-05 | 2016-01-20 | 浩力森涂料（上海）有限公司 | Acrylate emulsion used for water-based metallic paint and preparation method thereof |
| CN105254800B (en) * | 2015-11-05 | 2017-11-24 | 浩力森涂料（上海）有限公司 | Aqueous metallic paint acrylic acid ester emulsion and preparation method thereof |
| CN111675790A (en) * | 2020-06-04 | 2020-09-18 | 山东凯威尔新材料有限公司 | Freeze-thaw resistant polymer emulsion and preparation method thereof |
| CN111675790B (en) * | 2020-06-04 | 2022-08-02 | 山东凯威尔新材料有限公司 | Freeze-thaw resistant polymer emulsion and preparation method thereof |
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