A kind of Redispersible Polymeric Emulsion Powder and preparation method
Technical field
The present invention relates to redispersable latex powder field, be specifically related to a kind of Redispersible Polymeric Emulsion Powder and preparation method.
Background technology
To 20 end of the centurys, shortage of resources and this two large problems of environmental pollution have become most important obstacle on society and national development road, relevant ministries and commissions of country have taken multinomial measure, propose move towards environmental protection, energy-conservation demand for development to the serious building trade of power consumption.Country promotes Introduced From Abroad Advanced Idea and modern technique, instructs building materials field to adopt based on the environmental protection be dry mixed, efficient building materials.With polymer emulsion, the inorganic coagulation material modifications such as cement are used widely, the water mixed in rear emulsion due to both can also finally solidify with cement generation hydration reaction immediately, so be in most cases the form adopting two-pack, at the construction field (site) each component is mixed in proportion, makes troubles to storage, transport, construction etc.The appearance of redispersable latex powder, changes above-mentioned phenomenon.Be developed rapidly as dry-mix, dry powder paint, tile binding material, waterproof paint, building heat-insulating mortar, flexible mortar, gravity flowing levelling mortar etc. are dry mixed building materials.Not only reduce the loss in process of construction and the harm in later stage, and save material, reduce cost, considerably reduce cement consumption, improve structural quality.
Redispersable latex powder is as the additive being dry mixed building materials key, and in recent years, at dry-mixed mortar, dry powder paint, buildings waterproof, ceramic tile is bonding is widely used.Along with redispersable latex powder is also more and more wider in the application of China, consumption increases gradually, and the redispersable latex powder range of product of current China is single, and quality product is poor, and therefore most redispersable latex powder is from abroad, and expensive.The domestic research to redispersable latex powder mainly concentrates on polymerization stage and drying stage, and to carry out modification more, but produce wayward, and technique is unstable, and cause production cost high, the performance of product does not reach requirement.Especially there is poor water retention property, poor water resistance and bonding strength and do not reach the defects such as requirement.
China Patent Publication No. CN100460427C discloses redispersable latex powder containing silane water-soluble polymers emulsion and preparation method, the method is by vinyl polyfunctional group organo-siloxane function monomer and alkyl methacrylate, hydroxy alkyl ester, alkyl acrylate and carboxylic acid cross-linking monomer obtain emulsion by letex polymerization, redispersable latex powder is obtained by drying, to some extent solve latex powder water tolerance, but carry out modification in the letex polymerization stage, cost is high, production technique is wayward, the polymerized emulsion obtained after drying, performance loss is serious, and the water-retentivity of unresolved latex powder and cementability.
China Patent Publication No. CN100482743C discloses and a kind ofly improves polymer powders redispersible Preparation Method And The Use in the water of water-fast adhesiveproperties, this synthetic resin powder is obtained by a kind of dispersion emulsion composition of drying, to some extent solve water tolerance and cementability, but after drying, performance receives serious loss.
Above-mentioned redispersable latex powder carries out modification in letex polymerization stage and drying stage, production technique is difficult to control, production cost is high, redispersable latex powder performance loss is serious after drying, therefore,, there is a certain distance in the problem that redispersable latex powder ubiquity is on the high side and water tolerance is poor at present compared with parent emulsion.
Summary of the invention
The present invention is directed to the defect of the heavy losses of the water-retentivity of redispersable latex powder obtained after emulsion drying at present, water tolerance and cementability, there is provided a kind of low cost Redispersible Polymeric Emulsion Powder by ethene rubber powder and amorphous starch graft copolymer, this Redispersible Polymeric Emulsion Powder has excellent water-retentivity, water tolerance and bonding strength.
Further aim of the present invention is to provide a kind of preparation method preparing Redispersible Polymeric Emulsion Powder under dry powder, and the method is by mechano-chemical reation, under dry powder condition, graft copolymerization occurs.
A kind of Redispersible Polymeric Emulsion Powder of the present invention, is characterized in that parts by weight of raw materials is composed as follows:
Ethene rubber powder 45 ~ 55 parts,
Amorphous starch 35 ~ 45 parts,
Toughner 5 ~ 10 parts,
Ripening agent 1 ~ 4 part,
Crystallizing agent 3 ~ 5 parts,
Initiator 0.005 ~ 0.01 part,
Wherein, described ethene rubber powder is powdery, water-soluble rubber powder, the conventional at least one had in ethylene-vinyl acetate copolymerization rubber powder, vinyl acetate copolymerized rubber powder; Described amorphous starch is 100 ~ 200 object amorphous structure granular starchs, and degree of crystallinity≤5%, starch chain exists a large amount of living radical, and internal structure is loose, has good reactive behavior, preferred amorphous yam starch; Described toughner is acid amides and derivative thereof; Described ripening agent is at least one in sodium sulfate, zinc sulfate, ammonium sulfate, potassium alum; Described crystallizing agent is at least one in sodium methyl silicate, Starso, potassium silicate, has good water-soluble, perviousness, film-forming properties, cementability, can form free silicate in water; Described initiator is BPO peroxy initiator, can decomposite free radical at 75 ~ 100 DEG C, as the interfacial initiation agent of powder ethene rubber powder.
Acid amides described above and derivative thereof are at least one in urea, acrylamide, 2-acrylamide-2-methylpro panesulfonic acid.
The preparation method of a kind of Redispersible Polymeric Emulsion Powder provided by the invention, be by being prepared by graft copolymerization under dry powder condition, concrete preparation process is as follows:
1) 45 ~ 55 parts by weight of ethylene rubber powders, 35 ~ 45 weight part amorphous starch, 0.005 ~ 0.01 part of weight initiator are poured in ribbon mixer and mixed 3 ~ 5min, mix rear feeding rod mill, the rotating speed of rod mill controls at 150 ~ 250r/min, rod milling time controling is at 15 ~ 25min, ethene rubber powder active group under the Strong shear effect of rod mill is caused by initiator, forms backbone with the active group generation graft copolymerization of amorphous starch;
2) 5 ~ 10 weight part toughner, 1 ~ 4 weight part ripening agent are added in step 1), rod milling again, the rotating speed of rod mill controls at 100 ~ 200r/min, rod milling time controling is at 10 ~ 20min, under Mechanosensitive channels, amide group contained in toughner is ripened agent cross-linking curing, and with the activity hydroxy generation condensation reaction of amorphous starch, further formation backbone, significantly improves the bonding strength after film forming;
3) by step 2) the rod milling material that obtains puts into high mixer, namely obtains a kind of Redispersible Polymeric Emulsion Powder after mixing with 3 ~ 5 parts by weight Crystalline agent in high mixer.
By adopting amorphous starch, there is graft copolymerization with ethene rubber powder, adding ethene rubber powder backbone, its snappiness is increased in the present invention, water-retentivity improves under powdery condition; Toughner and the activity hydroxy generation condensation reaction being grafted to the amorphous starch on rubber powder of cross-linking curing, further formation backbone, the water-soluble good Redispersible Polymeric Emulsion Powder of a kind of backbone of final formation, has increased substantially water-retentivity, water tolerance and bonding strength.
The present invention have employed crystallizing agent further, when Redispersible Polymeric Emulsion Powder is applied in sand-cement slurry, putty, the calcium ion, the magnesium ion generation crystallization reaction that exist in silicate free in crystallizing agent and sand-cement slurry, putty, form fine and close structure, improve the film-forming properties of redispersable latex powder, cementability, water-repellancy.
Ribbon mixer described in above-mentioned preparation process, be made up of U-shaped container, double-deck ribbon agitating vane, the long body tube structure of U-shaped, ensure that the slight drag campaign in cylindrical shell of mixed material, under the effect of double-deck ribbon agitating vane, make material in flowing, form more eddy current, make mixing more even.
Rod mill described in above-mentioned preparation process is stirring-type rod mill, comprises cylindrical shell and stirring rod, and its technical characteristics is provided with 6 groups of rotatable stirring rod in cylindrical shell, and stirring rod is fixed on cylindrical shell two end axles end surface, and during rotation, stirring rod and cylinder face are ground.
The feature that the present invention gives prominence to is:
1, under dry powder, under Mechanosensitive channels, there is graft copolymerization by ethene rubber powder and amorphous starch, toughner, condensation reaction forms a kind of Redispersible Polymeric Emulsion Powder with backbone, without the need to drying, water-retentivity, water tolerance and bonding strength are increased substantially;
2, the present invention is by adopting crystallizing agent, with free calcium ion, magnesium ion generation crystallization reaction when enabling redispersable latex powder be applied to sand-cement slurry, putty, form fine and close structure, improve the film-forming properties of redispersable latex powder, cementability, water-repellancy;
3, the present invention adopts natural polymer amorphous starch material, and raw material is easy to get, and cost is low, and product performance are excellent;
4, the present invention adopts totally-enclosed continuous cleaning type to produce, and technique is brief, product environmental protection, can be widely used in the building materials fields such as dry-mixed mortar, ceramic tile are bonding, putty paste, waterproofing slurry.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.
embodiment 1
1) 50 parts of ethylene-vinyl acetate copolymerization rubber powders, 40 parts of amorphous yam starchs, 0.005 part of BPO peroxy initiator are poured in ribbon mixer and mixed 4min, mix rear feeding rod mill, the rotating speed control 160r/min of rod mill, rod milling time 18min, ethene rubber powder active group under the Strong shear effect of rod mill is caused by initiator, forms backbone with the active group generation graft copolymerization of amorphous starch;
2) 5 parts of acrylamides, 1 part of sodium sulfate, 2 parts of zinc sulfate are added step 1), rod milling again, the rotating speed of rod mill controls at 110r/min, rod milling time controling is at 10min, under mechanical force, amide group contained in toughner is ripened agent cross-linking curing, and with the activity hydroxy generation condensation reaction of amorphous starch, form backbone further;
3) by step 2) the rod milling material that obtains puts into high mixer, namely obtains a kind of water-soluble good Redispersible Polymeric Emulsion Powder with 3 parts of Starsos in high mixer after mixing.
The Redispersible Polymeric Emulsion Powder obtained, for ceramic wall and floor bricks tackiness agent, has good bonding energy, water tolerance.Get the redispersable latex powder 7kg of gained, be that 50 ~ 100 object quartz sands mix with the general silicate cement of 400kg PO42.5,593kg fineness, be about 1:4 according to water cement ratio and stir modulation, establishing criteria JC/T547-2005 " ceramic wall and floor bricks tackiness agent " is for the bonding test of ceramic tile, and its performance reaches strong index.Concrete detected result is as follows:
Interventions Requested
|
Unit
|
Standard-required (strong C2)
|
The present embodiment test result
|
Stretch gluing former intensity |
Mpa |
≥1.0 |
4.5 |
Stretching adhesive strength after immersion |
Mpa |
≥1.0 |
4.4 |
Tensile strength after thermal ageing |
Mpa |
≥1.0 |
4.2 |
Stretching adhesive strength after freeze-thaw cycle |
Mpa |
≥1.0 |
4.1 |
embodiment 2
1) 50 parts of ethylene-vinyl acetate copolymerization rubber powders, 45 parts of amorphous yam starchs, 0.007 part of BPO peroxy initiator are poured in ribbon mixer and mixed 5min, rod mill is sent into after stirring, the rotating speed control 200r/min of rod mill, rod milling time 20min, ethene rubber powder active group under the Strong shear effect of rod mill is caused by initiator, forms backbone with the active group generation graft copolymerization of amorphous starch;
2) 5 parts of urea, 3 parts of acrylamides, 1 part of sodium sulfate, 1 part of zinc sulfate are added step 1), rod milling again, the rotating speed of rod mill controls at 150r/min, rod milling time controling is at 15min, under mechanical force, amide group contained in toughner is ripened agent cross-linking curing, and with the activity hydroxy generation condensation reaction of amorphous starch, form backbone further;
3) by step 2) the rod milling material that obtains puts into high mixer, namely obtains a kind of water-soluble good Redispersible Polymeric Emulsion Powder with 1 part of sodium methyl silicate, 2 parts of potassium silicates in high mixer after mixing.
The redispersable latex powder obtained, for exterior coating, has good water tolerance, film-forming properties, cementability.According to GB/T9755-2001 " exterior wall coating material of synthetic resin emulsion " requirement, it is as follows to test its specific targets:
Project
|
Standard-required
|
Originally example test result is executed
|
Application property |
Brush accessible |
Brush accessible |
Appearance of film |
Normally |
Normally |
Low-temperature stability |
Never degenerate |
Never degenerate |
Time of drying (surface drying)/h |
≤2 |
1.0 |
Water tolerance |
96 hours without exception |
240 hours without exception |
Alkali resistance (48h) |
Without exception |
Without exception |
Artificial ageing resistance |
600h is non-foaming, do not peel off, flawless |
1000h is non-foaming, do not peel off, flawless |
embodiment 3
1) 25 parts of ethylene-vinyl acetate copolymerization rubber powders, 25 parts of vinyl acetate copolymerized rubber powders, 40 parts of amorphous yam starchs, 0.008 part of BPO peroxy initiator are poured in ribbon mixer and mixed 4min, mix rear feeding rod mill, the rotating speed control 160r/min of rod mill, rod milling time 18min, ethene rubber powder active group under the Strong shear effect of rod mill is caused by initiator, forms backbone with the active group generation graft copolymerization of amorphous starch;
2) 2 parts of urea, 3 parts of 2-acrylamide-2-methylpro panesulfonic acids, 2 parts of sodium sulfate, 1 part of ammonium sulfate are added step 1), rod milling again, the rotating speed of rod mill controls at 180r/min, rod milling time controling is at 13min, under mechanical force, amide group contained in toughner is ripened agent cross-linking curing, and with the activity hydroxy generation condensation reaction of amorphous starch, form backbone;
3) by step 2) the rod milling material that obtains puts into high mixer, namely obtains a kind of water-soluble good Redispersible Polymeric Emulsion Powder with 2 parts of sodium methyl silicates, 3 parts of potassium silicates after high mixer mixes.
The Redispersible Polymeric Emulsion Powder obtained significantly can promote water-retentivity, workability, the plasticity of mortar, and 1% addition water-reducing rate is more than 25%, and its fundamental property detected result is as follows:
Interventions Requested
|
Unit
|
The present embodiment test result
|
Outward appearance |
-- |
White can free flowing powder |
Solid content |
% |
98.5 |
PH value |
|
6-8 |
Minimum film-forming temperature |
℃ |
-5 |
embodiment 4
1) 22 parts of ethylene-vinyl acetate copolymerization rubber powders, 23 parts of vinyl acetate copolymerized rubber powders, 45 parts of amorphous yam starchs, 0.01 part of BPO peroxy initiator are poured in ribbon mixer and mixed 4min, mix rear feeding rod mill, the rotating speed control 190r/min of rod mill, rod milling time 20min, ethene rubber powder active group under the Strong shear effect of rod mill is caused by initiator, forms backbone with the active group generation graft copolymerization of amorphous starch;
2) 3 parts of acrylamides, 2 parts of 2-acrylamide-2-methylpro panesulfonic acids, 1 part of sodium sulfate, 1 part of ammonium sulfate are added step 1), rod milling again, the rotating speed of rod mill controls at 130r/min, rod milling time controling is at 17min, under mechanical force, amide group contained in toughner is ripened agent cross-linking curing, and with the activity hydroxy generation condensation reaction of amorphous starch, form backbone further;
3) by step 2) the rod milling material that obtains puts into high mixer, namely obtains a kind of water-soluble good Redispersible Polymeric Emulsion Powder with 2 parts of sodium methyl silicates, 2 parts of potassium silicates in high mixer after mixing.
The redispersable latex powder obtained, for interior wall coating, has excellent over-all properties.According to the interior wall primer requirement of GB/T9756-2009 " resin latex dope ", test its specific targets as following table:
Project |
Standard-required |
Originally example test result is executed |
Application property |
Brush accessible |
Brush accessible |
Appearance of film |
Normally |
Normally |
Low-temperature stability (3 circulations) |
Never degenerate |
Never degenerate |
Time of drying (surface drying)/h |
≤2 |
1.1 |
Alkali burnout resistance (48h) |
Without exception |
Without exception |
Alkali resistance (24h) |
Without exception |
Without exception |