CN104086686B - A kind of benzene emulsion with excellent freeze-thaw stability and preparation method thereof and application - Google Patents
A kind of benzene emulsion with excellent freeze-thaw stability and preparation method thereof and application Download PDFInfo
- Publication number
- CN104086686B CN104086686B CN201410294831.4A CN201410294831A CN104086686B CN 104086686 B CN104086686 B CN 104086686B CN 201410294831 A CN201410294831 A CN 201410294831A CN 104086686 B CN104086686 B CN 104086686B
- Authority
- CN
- China
- Prior art keywords
- polymerization
- thaw stability
- benzene emulsion
- main monomer
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 *C(CC(O*)=O)C(O*)=N Chemical compound *C(CC(O*)=O)C(O*)=N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to paint field, disclose a kind of benzene emulsion with excellent freeze-thaw stability and preparation method thereof and application. The described benzene emulsion with excellent freeze-thaw stability includes anionic-nonionic compound emulsifier and the functional polymerization monomer of particular type and content, also has the particle shell glass transition temperature of particular range. Described benzene emulsion adopts core-shell emulsion polymerization legal system standby, by controlling the consumption and the nucleation mode that adds mode control emulsion particle of functional polymerization monomer, has the benzene emulsion of excellent freeze-thaw stability described in making. Described benzene emulsion has excellent freeze-thaw stability, and in the situation that not adding antifreeze, the high PVC interior wall coating product being made into also has good freeze-thaw stability.
Description
Technical field
The invention belongs to paint field, be specifically related to a kind of benzene emulsion with excellent freeze-thaw stability andPreparation method and application.
Background technology
Coating is and the closely-related ornament materials of people's daily life that interior wall coating is the important composition of coatingPart, but VOC (VOC) in coating is the important environmental contaminants of a class, rightHealth has formed great threat. CNS GB18582-2008 " indoor decorating materialMaterial---limits of harmful substances in interior wall coating " in VOC is defined as " under 101.3kPa normal pressure,Any initial boiling point is less than or equal to the organic compound of 250 DEG C ". At present, zero VOC or low VOC interior wall are coated withMaterial has become the main flow coating products of American-European countries. Europe IAQ Joint Action Board has formulatedNew legislation, regulation was from 1 day January in 2010, and the VOC of decorative water zero diopter and non-flat paint containsAmount will be reduced to the scope that is less than 30g/L and 40g/L respectively. China interior wall coating market will be progressively and America and EuropeMarket integrates with, and zero/low VOC content, nontoxic health type green environmental friendly coatings are by domestic vast consumptionPerson favors and praises highly.
Polymer emulsion, as the chief component of coating, directly affects the combination property of coating. NumerousInterior wall coating with in polymer emulsion, benzene emulsion obtains because of its inexpensive, good physical and chemical performanceApplication widely. Benzene emulsion (being cinnamic acrylic ester emulsion) is by styrene and acrylate monomerObtain through emulsion copolymerization. Benzene emulsion is in emulsion polymerisation, to study more system, and the Ye Shi world today has heavilyWant one of ten large non-crosslinked type emulsions of industrial application value.
Benzene emulsion and coating thereof, because it exists the poor shortcoming of freeze-thaw resistance taking water as decentralized medium,After often condensing into piece because of product freeze thawing in transport under low temperature environment and storage process, cannot recover mobileState and going bad, causes huge economic loss. At present, be mainly to take to add antifreeze to solve freeze thawing steadyThe problem of qualitative difference (is shown in patent US20090186968A1, US6933415B2 and CN103205172ADeng), but the antifreeze adding is generally high VOC solvent, this will certainly increase the VOC of coating productsContent.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, it is excellent that primary and foremost purpose of the present invention is to provide one to haveThe benzene emulsion of different freeze-thaw stability, described in there is the not only VOC content of benzene emulsion of excellent freeze-thaw stabilityLow, good combination property, and there is excellent freeze-thaw stability;
Another object of the present invention is to provide the preparation side of the above-mentioned benzene emulsion with excellent freeze-thaw stabilityMethod, described preparation method has simple process, be easy to the feature controlled, polymerization system is stable, conversion ratio 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:
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component comprises polymerization main monomer, anionic-nonionic compound emulsifier, functional polymerizationMonomer, initator, pH buffer and water, described polymerization main monomer is alkyl acrylate and cinnamic mixedClose; Described anionic-nonionic compound emulsifier is the one having in the compound of formula I～formula III general structure:
Described functional polymerization monomer is the one having in the compound of formula IV～formula V general structure:
In formula I～formula V, R1、R2、R3、R4And R5Independently be selected from C1～C13Linear paraffin base, C1～C13The alkyl that contains branched structure or C2～C15Hydroxyalkyl; M is 3 to 50 integer; N is 3 to 50Integer; O is 3 to 50 integer; X is sulfonate groups (-SO3 -M+), sulfate group (-SO4 -M+)、Carboxylate groups (-COO-M+) in one; M+For Na+、K+Or NH4 +；
Preferably, described anionic-nonionic compound emulsifier is the agent of non-APEO class environment protective emulsive, and its consumption is0.5%～1% of polymerization main monomer gross mass;
Preferably, the consumption of described functional polymerization monomer is 0.2%～1% of polymerization main monomer gross mass;
Preferably, described in, there is the particle shell glass transition temperature of the benzene emulsion of excellent freeze-thaw stabilityIt is 18～40 DEG C;
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 initator is the one in sodium peroxydisulfate, ammonium persulfate or potassium peroxydisulfate; Described drawingThe consumption of sending out agent is 0.4%～0.6% of polymerization main monomer gross mass;
Preferably, described pH buffer is NaHCO3Or NaHPO4In one; The use of described pH bufferAmount is 0.3%～0.6% of polymerization main monomer gross mass.
The preparation method of the above-mentioned benzene emulsion with excellent freeze-thaw stability, comprises the steps:
(1) by initator and the gross weight of pH buffer, anionic-nonionic compound emulsifier, gross weight 20～40%The water of amount 60～80% adds in reactor, heating after mixing;
(2) question response actuator temperature is heated to 78～82 DEG C, drips the polymerization main monomer of gross weight 8～15%, inIn 5～10min, dropwise insulation 20～30min;
(3) then toward dripping the polymerization main monomer of surplus in reactor simultaneously, water and the initator of surplus joinedThe solution of system, starts to drip functional polymerization monomer, this step at 1/2～1/3 o'clock until the polymerization main monomer residue of surplusRapid all materials dropwise in 3～4h, are then warming up to 85～90 DEG C of insulation reaction 0.5～1h;
(4) after finishing, step (3) reaction is cooled to 50～60 DEG C, with ammoniacal liquor adjusting 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 in good freeze-thaw stability coating in preparationApplication.
An emulsion paint of preparing as raw material taking the described benzene emulsion with excellent freeze-thaw stability, by belowThe raw material modulation of mass percent forms:
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, can fall by biologySeparate environmental protection.
(2) the present invention adopts anionic-nonionic compound emulsifier, introduces functional polymerization monomer simultaneously, is bonded toOn polymer chain, play the effect of internal emulsification, make benzene emulsion there is excellent polymerization stability simultaneously and freezeMelt stability.
(3) benzene emulsion of the present invention, adopts core-shell emulsion polymerization method, by controlling functional polymerizationThe consumption of monomer and the mode that adds make the anionic-nonionic compound emulsifier Collaborative Control emulsion particle of itself and particular categoryNucleation mode, jointly promote freeze-thaw stability.
(4) the method for the invention simple process, be easy to control, polymerization process is stable, conversion ratio is high.
(5) benzene emulsion of the present invention is used for preparing high PVC (PVC value can up to 80～85%) interior wall and is coated withWhen material, do not need to add antifreeze, gained coating products VOC content approaches zero, good combination property, andThere is good freeze-thaw stability.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited toThis.
Embodiment 1
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component and consumption are as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: the functional polymerization monomer of 2g methacrylic acid (MAA) 0.2g (COPS-2), 0.75gAnionic-nonionic compound emulsifier (KL-70), 0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100gDeionized water;
Wherein, functional polymerization monomer (COPS-2) is the functional polymerization monomer that meets general structure IV,Concrete structure formula is:
Anionic-nonionic compound emulsifier (KL-70) is the anionic-nonionic compound emulsifier that meets general structure III,Concrete structure formula is:
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (KL-70), gross weight 25%The deionized water of ammonium and gross weight 80% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 78 DEG C, the polymerization main monomer mixture of getting gross weight 10% starts to drip, in 10min, dropwise,Insulation 30min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/2 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 90 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 DEG C, regulate pH value to 8 with ammoniacal liquor, cooling afterDescribed in obtaining, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 1.
Embodiment 2
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component and consumption are as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.6g (COPS-2), 0.75gAnionic-nonionic compound emulsifier (KL-70), 0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100gDeionized water;
Wherein, functional polymerization monomer (COPS-2) is and identical functional polymerization described in embodiment 1Monomer;
Anionic-nonionic compound emulsifier (KL-70) is compound with the identical anion-nonionic described in embodiment 1Emulsifying agent.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (KL-70), gross weight 25%The deionized water of ammonium and gross weight 80% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 78 DEG C, the polymerization main monomer mixture of getting gross weight 10% starts to drip, in 10min, dropwise,Insulation 30min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/2 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 90 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 DEG C, regulate pH value to 8 with ammoniacal liquor, cooling afterDescribed in obtaining, there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 2.
Embodiment 3
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component and consumption are as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 1g (COPS-2), 0.75gAnionic-nonionic compound emulsifier (KL-70), 0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100gDeionized water;
Wherein, functional polymerization monomer (COPS-2) is and identical functional polymerization described in embodiment 1Monomer;
Anionic-nonionic compound emulsifier (KL-70) is compound with the identical anion-nonionic described in embodiment 1Emulsifying agent.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (KL-70), gross weight 25%The deionized water of ammonium and gross weight 80% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 78 DEG C, the polymerization main monomer mixture of getting gross weight 10% starts to drip, in 10min, dropwise,Insulation 30min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/2 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 90 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 3.
Comparative example 1
A kind of benzene emulsion, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain raw materials used groupPoint and consumption as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), 0.75g anionic-nonionic compound emulsifier (KL-70),0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100g deionized water;
Wherein, anionic-nonionic compound emulsifier (KL-70) be with identical the moon-non-described in embodiment 1 fromSub-compound emulsifying agent.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (KL-70), gross weight 25%The deionized water of ammonium and gross weight 80% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 78 DEG C, the polymerization main monomer mixture of getting gross weight 10% starts to drip, in 10min, dropwise,Insulation 30min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslyWith the solution that ammonium persulfate is prepared, all materials of this step dropwise in 3.5h, are then warming up to 90 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as comparative sample 1.
Embodiment 4
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component and consumption are as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.3g (COPS-2), 1gAnionic-nonionic compound emulsifier (DNS-80), 0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100gDeionized water;
Wherein, functional polymerization monomer (COPS-2) is and identical functional polymerization described in embodiment 1Monomer;
Anionic-nonionic compound emulsifier (DNS-80) is the anion-nonionic composite emulsifying that meets general structure IIAgent, concrete structure formula is:
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (DNS-80), gross weight 40%The deionized water of ammonium and gross weight 60% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 82 DEG C, the polymerization main monomer mixture of getting gross weight 8% starts to drip, in 5min, dropwise,Insulation 20min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/2 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 85 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 60 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 4.
Embodiment 5
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component and consumption are as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.6g (COPS-2), 1gAnionic-nonionic compound emulsifier (DNS-80), 0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100gDeionized water;
Wherein, functional polymerization monomer (COPS-2) is and identical functional polymerization described in embodiment 1Monomer;
Anionic-nonionic compound emulsifier (DNS-80) is multiple with the identical anion-nonionic described in embodiment 4Co-emulsifier.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (DNS-80), gross weight 40%The deionized water of ammonium and gross weight 60% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 82 DEG C, the polymerization main monomer mixture of getting gross weight 8% starts to drip, in 5min, dropwise,Insulation 20min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/2 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 85 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 60 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 5.
Embodiment 6
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component and consumption are as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 1g (COPS-2), 1g the moon-Nonionic compound emulsifier (DNS-80), 0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100g goesIonized water;
Wherein, functional polymerization monomer (COPS-2) is and identical functional polymerization described in embodiment 1Monomer;
Anionic-nonionic compound emulsifier (DNS-80) is multiple with the identical anion-nonionic described in embodiment 4Co-emulsifier.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (DNS-80), gross weight 40%The deionized water of ammonium and gross weight 60% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 82 DEG C, the polymerization main monomer mixture of getting gross weight 8% starts to drip, in 5min, dropwise,Insulation 20min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/2 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 85 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 60 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 6.
Comparative example 2
A kind of benzene emulsion, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain raw materials used groupPoint and consumption as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), 1g anionic-nonionic compound emulsifier (DNS-80),0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100g deionized water;
Wherein, anionic-nonionic compound emulsifier (DNS-80) is and identical the moon-non-described in embodiment 4Ion compound emulsifying agent.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (DNS-80), gross weight 40%The deionized water of ammonium and gross weight 60% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 82 DEG C, the polymerization main monomer mixture of getting gross weight 8% starts to drip, in 5min, dropwise,Insulation 20min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslyWith the solution that ammonium persulfate is prepared, all materials of this step dropwise in 3.5h, are then warming up to 85 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 60 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as comparative sample 2.
Embodiment 7
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component and consumption are as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.4g (KL-100-II), 0.6gAnionic-nonionic compound emulsifier (A-102), 0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100gDeionized water;
Wherein, functional polymerization monomer (KL-100-II) is the functional polymerization monomer that meets general structure V,Concrete structure formula is:
Anionic-nonionic compound emulsifier (A-102) is the anionic-nonionic compound emulsifier that meets general structure I,Concrete structure formula is:
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (KL-70), gross weight 20%The deionized water of ammonium and gross weight 70% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 80 DEG C, the polymerization main monomer mixture of getting gross weight 15% starts to drip, in 10min, dropwise,Insulation 20min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/3 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 90 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 7.
Embodiment 8
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component and consumption are as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.8g (KL-100-II), 0.6gAnionic-nonionic compound emulsifier (A-102), 0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100gDeionized water;
Wherein, functional polymerization monomer (KL-100-II) is and identical functional polyalkylene described in embodiment 7Close monomer;
Anionic-nonionic compound emulsifier (A-102) is compound with the identical anion-nonionic described in embodiment 7Emulsifying agent.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (KL-70), gross weight 20%The deionized water of ammonium and gross weight 70% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 80 DEG C, the polymerization main monomer mixture of getting gross weight 15% starts to drip, in 10min, dropwise,Insulation 20min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/3 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 90 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 8.
Embodiment 9
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component and consumption are as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 1g (KL-100-II), 1gAnionic-nonionic compound emulsifier (A-102), 0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100gDeionized water;
Wherein, functional polymerization monomer (KL-100-II) is and identical functional polyalkylene described in embodiment 7Close monomer;
Anionic-nonionic compound emulsifier (A-102) is compound with the identical anion-nonionic described in embodiment 7Emulsifying agent.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (KL-70), gross weight 20%The deionized water of ammonium and gross weight 70% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 80 DEG C, the polymerization main monomer mixture of getting gross weight 15% starts to drip, in 10min, dropwise,Insulation 20min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/3 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 90 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 9.
Comparative example 3
A kind of benzene emulsion, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain raw materials used groupPoint and consumption as follows:
Polymerization main monomer: 60g styrene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), 0.6g anionic-nonionic compound emulsifier (A-102),0.5g ammonium persulfate (APS), 0.4g sodium acid carbonate, 100g deionized water;
Wherein, anionic-nonionic compound emulsifier (A-102) be with identical the moon-non-described in embodiment 7 fromSub-compound emulsifying agent.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (KL-70), gross weight 25%The deionized water of ammonium and gross weight 75% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 80 DEG C, the polymerization main monomer mixture of getting gross weight 15% starts to drip, in 10min, dropwise,Insulation 20min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslyWith the solution that ammonium persulfate is prepared, all materials of this step dropwise in 3.5h, are then warming up to 90 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as comparative sample 3.
Embodiment 10
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component and consumption are as follows:
Polymerization main monomer: 52.5g styrene (St), 47.5g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.6g (COPS-2), 0.5gAnionic-nonionic compound emulsifier (KL-70), 0.6g ammonium persulfate (APS), 0.6g sodium acid carbonate, 100gDeionized water;
Wherein, functional polymerization monomer (COPS-2) is and functional polymerization list identical described in embodiment 1Body;
Anionic-nonionic compound emulsifier (KL-70) is and anion-nonionic Composite Milk identical described in embodiment 1Agent;
Glass transition temperature (Tg) is 18 DEG C.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (KL-70), gross weight 25%The deionized water of ammonium and gross weight 70% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 80 DEG C, the polymerization main monomer mixture of getting gross weight 10% starts to drip, in 10min, dropwise,Insulation 20min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/2 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 90 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 10; Glass transition temperature is 18 DEG C.
Embodiment 11
Have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerization methodPrepare and obtain, raw materials used component and consumption are as follows:
Polymerization main monomer: 65g styrene (St), 35g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.6g (COPS-2), 0.5gAnionic-nonionic compound emulsifier (KL-70), 0.6g ammonium persulfate (APS), 0.6g sodium acid carbonate, 100gDeionized water;
Wherein, functional polymerization monomer (COPS-2) is and functional polymerization list identical described in embodiment 1Body;
Anionic-nonionic compound emulsifier (KL-70) is and anion-nonionic Composite Milk identical described in embodiment 1Agent;
Glass transition temperature (Tg) is 40 DEG C.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (KL-70), gross weight 25%The deionized water of ammonium and gross weight 70% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 80 DEG C, the polymerization main monomer mixture of getting gross weight 10% starts to drip, in 10min, dropwise,Insulation 20min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/2 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 90 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as sample 11; Glass transition temperature is 40 DEG C.
Comparative example 4
A kind of benzene emulsion, described benzene emulsion adopts core-shell emulsion polymerization legal system standby and obtain raw materials used groupPoint and consumption as follows:
Polymerization main monomer: 50g styrene (St), 50g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization monomer of 0.6g (COPS-2), 0.5gAnionic-nonionic compound emulsifier (KL-70), 0.6g ammonium persulfate (APS), 0.6g sodium acid carbonate, 100gDeionized water;
Wherein, functional polymerization monomer (COPS-2) is and functional polymerization list identical described in embodiment 1Body;
Anionic-nonionic compound emulsifier (KL-70) is and anion-nonionic Composite Milk identical described in embodiment 1Agent;
Glass transition temperature (Tg) is 14 DEG C.
The preparation method of the described benzene emulsion with excellent freeze-thaw stability is as follows:
(1) by the persulfuric acid of sodium acid carbonate, anionic-nonionic compound emulsifier (KL-70), gross weight 25%The deionized water of ammonium and gross weight 70% adds in reactor, heating after mixing;
(2) polymerization main monomer and methacrylic acid are mixed to get to polymerization main monomer mixture, question response actuator temperatureBe heated to 80 DEG C, the polymerization main monomer mixture of getting gross weight 10% starts to drip, in 10min, dropwise,Insulation 20min;
(3) then in reactor, drip the polymerization main monomer mixture of surplus, the deionized water of surplus simultaneouslySolution with ammonium persulfate is prepared, remains at 1/2 o'clock until the polymerization main monomer mixture of surplus and starts to drip functionProperty polymerization single polymerization monomer (COPS-2), all materials of this step dropwise in 3.5h, are then warming up to 90 DEG CInsulation reaction 1h;
(4) after step (3) reaction finishes, be cooled to 50 DEG C, regulate pH value to 8 with ammoniacal liquor, must after coolingTo described in there is the benzene emulsion of excellent freeze-thaw stability, be designated as comparative sample 4; Glass transition temperature is14℃。
Performance test:
1, freeze-thaw stability test:
With reference to the freeze-thaw stability of GB/T20623-2006 test gained sample 1～11 and comparative sample 1～4.The household freezer that test sample is placed in to (10 ± 2) DEG C freezes to take out after 18h, then at (23 ± 2) DEG C barUnder part, placing 6h, is once complete freeze thawing circulation. Open container, fully stir test sample, if do not hadThere are lump, cohesion and segregation phenomenon, repeat freeze thawing circulation. 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, loose with Ma Erwen Nano-ZSZEN3600 type laserPenetrate 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, Brookfield company of the U.S.; Test-stripsPart: 3# rotor, 25 DEG C, 30rpm.
Emulsion paint viscosity test: adopt STM-III stormer viscosity meter, probe temperature: (23 ± 1) DEG C.
Test as stated above gained sample 1～11 and comparative sample 1～4 initial particle and viscosity, freeze at every turnMelt particle diameter and viscosity after circulation, result is as shown in table 1:
Table 1. sample freeze-thaw stability testing result
Note: "-" refers to that emulsion condenses into piece, and viscosity cannot record; 10+ still has good mobility after referring to emulsion freeze thawing circulation 10 times.
Can be found out by table 1 test result, not steady containing the freeze thawing of the comparative sample 1～4 of functional polymerization monomerQualitative all very poor, freeze thawing circulates after 1 to 2 time, the particle diameter of emulsion and viscosity generation great variety; And addAfter functional polymerization monomer, the freeze-thaw stability of emulsion be improved significantly, and functional polymerization monomer is poly-Close reaction and the later stage add the freeze-thaw stability that is more conducive to emulsion. This is because control after functional polymerization monomerPhase adds, and makes its skin that is distributed in latex particle, thereby can be compound with the anion-nonionic of described particular categoryEmulsifying agent produces synergy, controls the nucleation mode of emulsion particle, jointly promotes the freeze-thaw stability of emulsion.
Test result from comparative sample in table 14 with sample 2, sample 10, sample 11, only has TgWhen more than approximately 18 DEG C, the anionic-nonionic compound emulsifier of described ad hoc structure and functional polymerization monomer abilityPerformance acts synergistically, and jointly promotes 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 coatingTime, not needing to add any antifreeze, not only VOC content is low for gained coating products, good combination property, andAnd there is good freeze-thaw stability. Sample in embodiment 22 and commercially available benzene emulsion are pressed respectively to table 2Formula modulation high PVC interior wall coating, and according to GB/T9268-2008 is tested it at (10 ± 1) DEG CFreeze-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 |
| Coalescents | 0.9 |
| Defoamer | 0.2 |
| Ultramarine slurry | 0.02 |
| Thickener | 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 antifreeze, with the height of commercially available emulsion modulationPVC interiro wall latex paint freeze-thaw stability is very poor, and after freeze thawing circulation 1 time, KU viscosity changes greatly, and freeze thawing followsEncircle that to return above thick cohesion 2 times serious; And the high PVC interiro wall latex paint of modulating with gained benzene emulsion of the present invention,Have excellent freeze-thaw stability, the performance change such as the stormer viscosity after 5 freeze thawing circulations are less, and fullThe environmental requirement of low/zero VOC, more safer than conventional interiro wall latex paint enough.
Above-described embodiment is preferably embodiment of the present invention, but embodiments of the present invention are not subject to above-mentioned enforcementThe restriction of example, other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, replacesGeneration, combination, simplification, all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (7)
1. have a benzene emulsion for excellent freeze-thaw stability, described benzene emulsion adopts core-shell emulsion polymerizationLegal system is standby and obtain, and raw materials used component comprises polymerization main monomer, anionic-nonionic compound emulsifier, functional polyalkyleneClose monomer, initator, pH buffer and water, described polymerization main monomer is alkyl acrylate and cinnamicMix; It is characterized in that:
Described anionic-nonionic compound emulsifier is the one having in the compound of formula I～formula III general structure:
Described functional polymerization monomer is the one having in the compound of formula IV～formula V general structure:
In formula I～formula V, R1、R2、R3、R4And R5Independently be selected from C1～C13Linear paraffin base, C1～C13The alkyl that contains branched structure or C2～C15Hydroxyalkyl; M is 3 to 50 integer; nIt is 3 to 50 integer; O is 3 to 50 integer; X is sulfonate groups, sulfate group, carboxylateOne in group; M+For Na+、K+Or NH4 +；
The particle shell glass transition temperature of the described benzene emulsion with excellent freeze-thaw stability is18～40℃。
2. a kind of benzene emulsion with excellent freeze-thaw stability according to claim 1, its featureBe: the consumption of described anionic-nonionic compound emulsifier is 0.5%～1% of polymerization main monomer gross mass.
3. a kind of benzene emulsion with excellent freeze-thaw stability according to claim 1, its featureBe: the consumption of described functional polymerization monomer is 0.2%～1% of polymerization main monomer gross mass.
4. a kind of benzene emulsion with excellent freeze-thaw stability according to claim 1, its feature existsIn: 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 initator is the one in sodium peroxydisulfate, ammonium persulfate or potassium peroxydisulfate;
The consumption of described initator is 0.4%～0.6% of polymerization main monomer gross mass;
Described pH buffer is NaHCO3Or NaHPO4In one;
The consumption of described pH buffer is 0.3%～0.6% of polymerization main monomer gross mass.
5. one kind according to the benzene emulsion with excellent freeze-thaw stability described in claim 1～4 any onePreparation method, is characterized in that comprising the steps:
(1) by initator and the gross weight of pH buffer, anionic-nonionic compound emulsifier, gross weight 20～40%The water of amount 60～80% adds in reactor, heating after mixing;
(2) question response actuator temperature is heated to 78～82 DEG C, drips the polymerization main monomer of gross weight 8～15%, inIn 5～10min, dropwise insulation 20～30min;
(3) then toward dripping the polymerization main monomer of surplus in reactor simultaneously, water and the initator of surplus joinedThe solution of system, starts to drip functional polymerization monomer, this step at 1/2～1/3 o'clock until the polymerization main monomer residue of surplusRapid all materials dropwise in 3～4h, are then warming up to 85～90 DEG C of insulation reaction 0.5～1h;
(4) after finishing, step (3) reaction is cooled to 50～60 DEG C, with ammoniacal liquor adjusting pH value to 7～9,Described in obtaining after cooling, there is the benzene emulsion of excellent freeze-thaw stability.
6. one kind exists according to the benzene emulsion with excellent freeze-thaw stability described in claim 1～4 any onePreparation has the application in good freeze-thaw stability coating.
7. one kind taking the benzene emulsion with excellent freeze-thaw stability described in claim 1～4 any one as formerThe emulsion paint of material preparation, is characterized in that: the raw material modulation by following mass percent forms:
The described benzene emulsion 10% with excellent freeze-thaw stability.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410294831.4A CN104086686B (en) | 2014-06-26 | 2014-06-26 | A kind of benzene emulsion with excellent freeze-thaw stability and preparation method thereof and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410294831.4A CN104086686B (en) | 2014-06-26 | 2014-06-26 | A kind of benzene emulsion with excellent freeze-thaw stability and preparation method thereof and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104086686A CN104086686A (en) | 2014-10-08 |
| CN104086686B true CN104086686B (en) | 2016-05-18 |
Family
ID=51634466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410294831.4A Active CN104086686B (en) | 2014-06-26 | 2014-06-26 | A kind of benzene emulsion with excellent freeze-thaw stability and preparation method thereof and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104086686B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038429B (en) * | 2015-08-20 | 2018-05-15 | 华南理工大学 | A kind of internal wall emulsion coating with excellent freeze-thaw stability 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 |
| 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 |
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 |
|---|
| 超低VOC内墙涂料用核壳结构苯丙乳液的制备研究;陈立军等;《新型建筑材料》;20070331(第3期);第57-63页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104086686A (en) | 2014-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101481437B (en) | Preparation of high closeness polyacrylacid ester dispersion | |
| CN101974277B (en) | White waterborne wood base coat for medium density fiberboard and preparation technology thereof | |
| CN102134296B (en) | Fluosilicic modification water-soluble acrylic resin dispersion and uses thereof | |
| CN103059681B (en) | Water-based quick-drying external crosslinking functional paint and preparation method thereof | |
| CN103709885B (en) | A kind of aqueous environments friendly acid modified alcoholic wood lacquer | |
| CN102675521B (en) | Water-soluble macromolecular sand fixing agent and preparation method | |
| CN104371607B (en) | High-solid-content and low-viscosity acrylate emulsion stick and preparation method | |
| CN102134294B (en) | High-covering-power styrene-acrylate emulsion, synthesis method thereof and use thereof in aqueous printing ink | |
| CN104086686B (en) | A kind of benzene emulsion with excellent freeze-thaw stability and preparation method thereof and application | |
| CN101891859A (en) | Elastic styrene acrylic emulsion for polymer cement waterproof coating and preparation method thereof | |
| CN106565897A (en) | Outer wall elastic emulsion with lotus effect and preparing method of outer wall elastic emulsion | |
| CN101270247B (en) | Water-proof emulsion for coal pile in the open air | |
| CN105085771A (en) | Waterborne acrylic resin and preparation method therefor | |
| CN109439123A (en) | A kind of aqueous damping coating acrylic emulsion and preparation method thereof and a kind of aqueous damping coating | |
| CN102399344B (en) | Self-thickening pure acrylic latex used in art paints, and preparation method thereof | |
| CN101368053A (en) | Watersoluble pure acrylic emulsion for construction and method of producing the same | |
| CN103553426A (en) | Preparation method of polymer and cement composite waterproof coating | |
| CN101353391B (en) | Silicone-acrylate emulsion and production process thereof | |
| CN107418351B (en) | A kind of one-component water solubility release-free electrochemical aluminum paint and preparation method thereof | |
| CN102492100A (en) | Water-dispersed fluorine-containing hydroxyl acrylic-epoxy ester heterozygous body resin and coating thereof | |
| CN103951794A (en) | Low-foam polycarboxylate dispersant and its preparation method | |
| CN106433352A (en) | High-speed railway vehicle damping coating for spraying inner layer and preparation method of high-speed railway vehicle damping coating | |
| CN103011674A (en) | Polyether amine modified polycarboxylate-type concrete slump retaining agent and preparation method thereof | |
| CN102732075B (en) | Wood putty and preparation method thereof | |
| CN103145929B (en) | Peat/polyethyleneglycol-grafted composite phase-change energy storage material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |