Summary of the invention
The objective of the invention is to propose a kind of emulsion for re-dispersible emulsion powder and preparation method thereof, to overcome the defective of prior art.
The preparation method of emulsion for re-dispersible emulsion powder of the present invention may further comprise the steps:
Following umber is a weight part:
A) 0~100 part of vinyl ester, 0~100 part of (methyl) propenoate, 0~100 part of (methyl) vinylbenzene, 0.5~2 part of cationic monomer and 0~2 part of molecular weight regulator are mixed and made into mix monomer
B) 80~100 parts of mix monomers, 0.2~2 part of reactive emulsifier, 0.2~2 part of initiator and 35~100 parts of water are mixed, obtain mixed solution;
C) 0~20 part of mix monomer, 5~20 parts of modified polyvinyl alcohol emulsions, 0.1~2 part of reactive emulsifier, 0.1~2 part of initiator and 20~70 parts of water are mixed; 50 ℃~90 ℃ were reacted 10~40 minutes; The mixed solution that adds step b) then; Added in preferred 2~5 hours, and continued reaction 1~3 hour, collect emulsion for re-dispersible emulsion powder; Emulsion weight solid content is 40%~60%, and median size is 100nm~400nm, pH value 3~6;
Said modified polyvinyl alcohol is organic siloxane modified Z 150PH, and the alcoholysis degree of Z 150PH is 83~99 moles of %, and molecular weight is 500~5000g/mol;
Said organo-siloxane is selected from least a in vinyltrimethoxy silane, vinyl methoxyl group diethoxy silane, vinyltriethoxysilane or the vinyl oxyethyl group diisopropoxy silane;
The preparation method of modified polyvinyl alcohol emulsion comprises the steps:
With 40~80 weight account polyethylenes alcohol, 100~400 weight parts waters, 20~60 weight part organo-siloxanes and 0.5~2 part of molecular weight regulator mix, and 80~95 ℃ of reactions 0.5~3 hour, obtain the modified polyvinyl alcohol emulsion;
Said molecular weight regulator is at least a in ethyl thioglycolate, Thiovanic acid butyl ester, mercaptoethanol, 2 mercapto ethanol or the tert-dodecyl mercaptan;
Said initiator is selected from least a in Potassium Persulphate, Sodium Persulfate or the ammonium persulphate;
Said vinyl ester is selected from vinyl acetate, the tertiary ethylene carbonate of 1 to 10 carbon atom alkyl carboxylic acid; (1 to 10 carbon atom refers to alkyl carboxylic acid)
Preferred vinyl ester is vinyl-acetic ester, tertiary ethylene carbonate or TEB 3K;
Said (methyl) propenoate is selected from vinyl cyanide, methyl acrylate, ethyl propenoate, n-butyl acrylate, NSC 20949, ethyl acrylate, vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-2-hydroxypropyl acrylate, TEB 3K, Jia Jibingxisuanyizhi, n-BMA, methylacrylic acid-2-ethylhexyl, 2-hydroxyethyl methacrylate, methylacrylic acid-2-hydroxypropyl acrylate, acrylic or methacrylic acid C
8~C
16Alkyl ester;
Said reactive emulsifier is selected from least a in allyl polyethenoxy ether ammonium sulfate, allyl polyethenoxy ether, the vinyl Soxylat A 25-7;
Said cationic monomer is selected from least a in acrylyl oxy-ethyl-trimethyl salmiac, dimethyl diallyl ammonium chloride or the methylacryoyloxyethyl trimethyl ammonium chloride;
Emulsion for re-dispersible emulsion powder grafting small cations monomer of the present invention is a kind of both sexes emulsion, compares with ordinary emulsion to have better cohesiveness, water tolerance.
As everyone knows, add organic silicon emulsion or on the polymkeric substance long-chain, introduce siloxanyl monomers and can improve, but to the cohesive force raising seldom.And the present invention adopts organic-silicon-modified Z 150PH as protective colloid, unexpectedly, adds the water tolerance that this modified polyvinyl alcohol can not only improve emulsion, also increases significantly for the cohesiveness of emulsion.This possibly add small number of molecules amount regulator in modified polyvinyl alcohol makes modified polyethylene alcohol MWD is narrower and cause.Add a spot of cationic monomer among the present invention polymer chain is carried out grafting, make polymer emulsion be both sexes, unexpectedly, in mortar, add the cohesive force that this emulsion not only can increase substantially mortar, can obviously improve the water tolerance of mortar simultaneously.This maybe be because cement-based mortar be mainly anionic species; This emulsion is both sexes; Not only can improve with the bonding of cement based material and not reduce the matching with mortar simultaneously again, the cohesive force that so not only can improve mortar can improve the water tolerance of mortar simultaneously again.
Redispersable latex powder of the present invention is a kind of product that can satisfy building concrete, building mortar with high-performance, environmental protection.This product uses in building concrete and mortar, can obviously improve workability, cohesive force and the water tolerance thereof of building concrete, mortar.
Embodiment
Embodiment 1
1) preparation of modified polyvinyl alcohol emulsion:
With the 40g Z 150PH (molecular weight: 500g/mol, alcoholysis degree: 83 moles of %), 100g deionized water, 60g vinyltrimethoxy silane, 0.5g ethyl thioglycolate mix, and is warming up to 80 ℃ of reactions 5 hours, reduces to 25 ℃, discharging, subsequent use.
2) emulsion for re-dispersible emulsion powder is synthetic:
A) 97.5g vinyl-acetic ester, 2g ethyl thioglycolate, the 0.633g acrylyl oxy-ethyl-trimethyl salmiac aqueous solution (Shanghai is extensively created scape and imported and exported the DAC.MC-80 of ltd, weight solid content 79%) are mixed, process mix monomer, subsequent use;
B) the 80g mix monomer is joined in the aqueous solution of being made up of 2g allyl polyethenoxy ether vitriol (RhodapexCL910 of Rhodia), 0.2g Potassium Persulphate and 100g deionized water, stirred 30 minutes, obtain mixed solution;
C) will remain mix monomer adds in the aqueous solution with 64.2g deionized water dissolving 20g modified polyvinyl alcohol A, 2g allyl polyethenoxy ether vitriol (the Rhodapex CL910 of Rhodia) and 2g Potassium Persulphate; Be warming up to 50 ℃; Reacted 40 minutes; Drip b then) mixed solution in the process, added in 5 hours, continue reaction 3 hours.Be cooled to 25 ℃.Filter through 100 eye mesh screens, obtain emulsion for re-dispersible emulsion powder, weight solid content: 40.1wt%, median size 100.5nm (using Malven particle diameter appearance to record) pH=3.18) (uses PHS-3C Accurate pH instrumentation to get).
Embodiment 2
1) preparation of modified polyvinyl alcohol emulsion:
With the 80g Z 150PH (molecular weight: 1000g/mol, alcoholysis degree: 99 moles of %), 400g deionized water, 20g vinyl methoxyl group diethoxy alkane, 1g mercaptoethanol mix, and is warming up to 95 ℃ of reactions 0.5 hour, reduces to 25 ℃, discharging, subsequent use.
2) emulsion for re-dispersible emulsion powder is synthetic:
A) 99.5g tertiary ethylene carbonate, the 0.77g dimethyl diallyl ammonium chloride aqueous solution (LYFM-205-65 of Shandong Lu Yue chemical industry ltd, weight solid content 65%) are subsequent use.
B) the 100g tertiary ethylene carbonate is joined in the aqueous solution of being made up of 0.2g allyl polyethenoxy ether vitriol (the Emulsogen APG2019 of Switzerland Clariant company), 2g Sodium Persulfate and 35g deionized water, stirred 30 minutes, obtain mixed solution, subsequent use.
C) in the aqueous solution of 10g modified polyvinyl alcohol B, 0.1g allyl polyethenoxy ether vitriol (EmulsogenAPG2019 of Switzerland Clariant company), 0.1g Sodium Persulfate and 26.33g deionized water; Be warming up to 90 ℃; Reacted 10 minutes; Drip b then) mixed solution in the process 2 hours, continue reaction 1 hour.Be cooled to 25 ℃.Filter through 100 eye mesh screens, obtain emulsion for re-dispersible emulsion powder, weight solid content: 58.9wt%, median size 389.2nm (using Malven particle diameter appearance to record) pH=5.63) (uses PHS-3C Accurate pH instrumentation to get).
Embodiment 3
1) preparation of modified polyvinyl alcohol emulsion:
With the 60g Z 150PH (molecular weight: 10000g/mol, alcoholysis degree: 88 moles of %), 300g deionized water, 40g vinyltriethoxysilane, 0.6g Thiovanic acid butyl ester mix, and is warming up to 90 ℃ of reactions 3 hours, reduces to 25 ℃, discharging, subsequent use.
2) emulsion for re-dispersible emulsion powder is synthetic:
A) with 50g TEB 3K, 47g n-butyl acrylate, the 2.56g methylacryoyloxyethyl trimethyl ammonium chloride aqueous solution (development area, the Yantai spark chemical industry DMC of ltd; Weight solid content 78%), the 1g mercaptoethanol is mixed and made into; Mix monomer, subsequent use.
B) the 90g mix monomer is joined in the aqueous solution by 1g allyl polyethenoxy ether (RhodasurfAAE-10 of Rhodia), 1g ammonium persulphate and 50g deionized water, stirred 30 minutes, subsequent use.
C) will remain mix monomer adds in the aqueous solution with 44g deionized water dissolving 20g modified polyvinyl alcohol, 1g allyl polyethenoxy ether vitriol (the Rhodapex CL910 of Rhodia) and 1g ammonium persulphate; Be warming up to 70 ℃; Reacted 20 minutes; Drip b then) mixed solution in the process 3 hours, continue reaction 2 hours.Be cooled to 25 ℃.Filter through 100 eye mesh screens, obtain emulsion for re-dispersible emulsion powder, solid content: 49.7wt%, median size 265nm (using Malven particle diameter appearance to record) pH=4.35) (uses PHS-3C Accurate pH instrumentation to get).
Embodiment 4
1) preparation of modified polyvinyl alcohol emulsion:
With 50g Z 150PH (molecular weight: 5000g/mol; 95 moles of %), 150g deionized water, 50g vinyl oxyethyl group diisopropoxy silane, 0.5g2-mercaptoethanol, 0.3g tert-dodecyl mercaptan mix, and is warming up to 85 ℃ of reactions 2 hours, reduces to 25 ℃ alcoholysis degree:; Discharging, subsequent use.
2) emulsion for re-dispersible emulsion powder is synthetic:
A) 80g vinylbenzene, 19g vinyl toluene, the 1.28g methylacryoyloxyethyl trimethyl ammonium chloride aqueous solution (development area, the Yantai spark chemical industry DMC of ltd, weight solid content 78%) are mixed and made into mix monomer, subsequent use.
B) the 85g mix monomer is joined in the aqueous solution of being made up of 0.5g vinyl Soxylat A 25-7 (EmulsogenR208 of Switzerland Clariant company), 1.5g ammonium persulphate and 40g deionized water, stirred 30 minutes.Subsequent use.
C) will remain mix monomer adds in the aqueous solution with 40.45g deionized water dissolving 18.75g modified polyvinyl alcohol, 1.5g vinyl Soxylat A 25-7 (the Emulsogen R208 of Switzerland Clariant company) and 0.5g Potassium Persulphate; Be warming up to 80 ℃; Reacted 15 minutes; Drip b then) mixed solution in the process, added in 4 hours, continue reaction 1.5 hours.Be cooled to 25 ℃.Filter through 100 eye mesh screens, obtain emulsion for re-dispersible emulsion powder, solid content: 54.95wt%, median size 323nm (using Malven particle diameter appearance to record) pH=4.53) (uses PHS-3C Accurate pH instrumentation to get).
Embodiment 5
1) preparation of modified polyvinyl alcohol emulsion:
With 70g Z 150PH (molecular weight: 2500g/mol; 92 moles of %), 200g deionized water, 10g vinyl oxyethyl group diisopropoxy silane, 20g vinyltriethoxysilane, 0.7g Thiovanic acid butyl ester mix alcoholysis degree:; Be warming up to 82 ℃ of reactions 3.5 hours; Reduce to 25 ℃, discharging, subsequent use.
2) the redispersable latex powder emulsion is synthetic:
A) with 50g vinyl-acetic ester, 30g ethyl acrylate, 17.5g vinylbenzene, the 1.92g methylacryoyloxyethyl trimethyl ammonium chloride aqueous solution (development area, the Yantai spark chemical industry DMC of ltd; Weight solid content 78%) and the 1g2-mercaptoethanol be mixed and made into mix monomer, subsequent use.
B) the 95g mix monomer is joined in the aqueous solution of being made up of 1g allyl polyethenoxy ether vitriol (RhodapexCL910 of Rhodia), 1g allyl polyethenoxy ether (the Rhodasurf AAE-10 of Rhodia), 0.8g Sodium Persulfate and 61.8g deionized water, stirred 30 minutes.Subsequent use.
C) will remain mix monomer adds in the aqueous solution with 64g deionized water dissolving 12g modified polyvinyl alcohol E, 2g allyl polyethenoxy ether vitriol (the Rhodapex CL910 of Rhodia) and 0.7g Sodium Persulfate; Be warming up to 65 ℃; Reacted 25 minutes; Drip b then) mixed solution in the process, added in 3.5 hours, continue reaction 1.5 hours.Be cooled to 25 ℃.Filter through 100 eye mesh screens, obtain emulsion for re-dispersible emulsion powder, solid content: 45.00wt%, median size 138nm (using Malven particle diameter appearance to record) pH=3.68) (uses PHS-3C Accurate pH instrumentation to get).
Embodiment 6
1) preparation of modified polyvinyl alcohol emulsion:
With 65g Z 150PH (molecular weight: 7500g/mol; 85 moles of %), 300g deionized water, 25g vinyl oxyethyl group diisopropoxy silane, 10g vinyl methoxyl group diethoxy alkane, 2g ethyl thioglycolate mix alcoholysis degree:; Be warming up to 88 ℃ of reactions 2.5 hours; Reduce to 25 ℃, discharging, subsequent use.
2) the redispersable latex powder emulsion is synthetic:
A) with 70g vinyl-acetic ester, 25.3g methylacrylic acid-2-hydroxypropyl acrylate, 2.5g vinylformic acid, the 1.08g dimethyl diallyl ammonium chloride aqueous solution (LYFM-205-65 of Shandong Lu Yue chemical industry ltd; Weight solid content 65%) and 1.5g Thiovanic acid butyl ester be mixed and made into mix monomer, subsequent use.
B) the 88g mix monomer is joined in the aqueous solution of being made up of 0.6g allyl polyethenoxy ether vitriol (the Emulsogen APG2019 of Switzerland Clariant company), 0.4g vinyl Soxylat A 25-7 (EmulsogenR208 of Switzerland Clariant company), 1.2g ammonium persulphate and 61.5g deionized water, stirred 30 minutes.Subsequent use.
C) will remain mix monomer adds in the aqueous solution with 39.6g deionized water dissolving 24g modified polyvinyl alcohol F, 1.5g allyl polyethenoxy ether vitriol (the Rhodapex CL910 of Rhodia) and 0.6g Sodium Persulfate; Be warming up to 55 ℃; Reacted 22 minutes; Drip b then) mixed solution in the process, added in 2.5 hours, continue reaction 1.8 hours.Be cooled to 25 ℃.Filter through 100 eye mesh screens, obtain emulsion for re-dispersible emulsion powder, solid content: 47.98wt%, median size 229nm (using Malven particle diameter appearance to record) pH=3.88) (uses PHS-3C Accurate pH instrumentation to get).
Embodiment 7
1) preparation of modified polyvinyl alcohol emulsion:
With the 55g Z 150PH (molecular weight: 8000g/mol, alcoholysis degree: 90 moles of %), 350g deionized water, 45g vinyl oxyethyl group diisopropoxy silane, 1.5g mercaptoethanol mix, and is warming up to 92 ℃ of reactions 4 hours, reduces to 25 ℃, discharging, subsequent use.
2) the redispersable latex powder emulsion is synthetic:
A) with 60g vinylbenzene, 39.5g methylacrylic acid-2-ethylhexyl, the 1.08g dimethyl diallyl ammonium chloride aqueous solution (LYFM-205-65 of Shandong Lu Yue chemical industry ltd; Weight solid content 65%), the 0.64g methylacryoyloxyethyl trimethyl ammonium chloride aqueous solution (development area, the Yantai spark chemical industry DMC of ltd; Weight solid content 78%) and the 0.5g tert-dodecyl mercaptan be mixed and made into mix monomer, subsequent use.
B) the 88g mix monomer is joined in the aqueous solution of being made up of 1.2g allyl polyethenoxy ether vitriol (the Emulsogen APG2019 of Switzerland Clariant company), 1.8g Potassium Persulphate and 70g deionized water, stirred 30 minutes.Subsequent use.
C) will remain mix monomer adds in the aqueous solution with 55g deionized water dissolving 40.5g modified polyvinyl alcohol G, 0.8g allyl polyethenoxy ether vitriol (the Emulsogen APG2019 of Switzerland Clariant company) and 0.8g Sodium Persulfate; Be warming up to 55 ℃; Reacted 15 minutes; Drip b then) mixed solution in the process, added in 4 hours, continue reaction 1.2 hours.Be cooled to 25 ℃.Filter through 100 eye mesh screens, obtain emulsion for re-dispersible emulsion powder.Solid content: 41.85wt%, median size 287nm (using Malven particle diameter appearance to record) pH=4.20) (uses PHS-3C Accurate pH instrumentation to get).
Embodiment 8
1) preparation of modified polyvinyl alcohol emulsion:
With the 60g Z 150PH (molecular weight: 10000g/mol, alcoholysis degree: 88 moles of %), 300g deionized water, 40g vinyltriethoxysilane, 0.9g Thiovanic acid butyl ester mix, and is warming up to 90 ℃ of reactions 3 hours, reduces to 25 ℃, discharging, subsequent use.
2) the redispersable latex powder emulsion is synthetic:
A) 50g TEB 3K, 49.5g ethyl propenoate, the 0.633g acrylyl oxy-ethyl-trimethyl salmiac aqueous solution (Shanghai is extensively created scape and imported and exported the DAC.MC-80 of ltd, weight solid content 79%) are mixed and made into mix monomer, subsequent use.
B) the 90g mix monomer is joined in the aqueous solution of being made up of 1g allyl polyethenoxy ether (RhodasurfAAE-10 of Rhodia), 1g ammonium persulphate and 50g deionized water, stirred 30 minutes.Subsequent use.
C) will remain mix monomer adds in the aqueous solution with 44g deionized water dissolving 20g modified polyvinyl alcohol C, 1g allyl polyethenoxy ether vitriol (the Rhodapex CL910 of Rhodia) and 1g ammonium persulphate; Be warming up to 70 ℃; Reacted 20 minutes; Drip b then) mixed solution in the process, added in 3 hours, continue reaction 2 hours.Be cooled to 25 ℃.Filter through 100 eye mesh screens, obtain emulsion for re-dispersible emulsion powder, solid content: 49.5wt%, median size 259nm (using Malven particle diameter appearance to record) pH=4.28) (uses PHS-3C Accurate pH instrumentation to get).
Embodiment 9
Comparative Examples: the emulsion for re-dispersible emulsion powder of pressing the method preparation of CN200710046594.X
Embodiment 1~8 is used for following finishing mucilage compsn with the prepared emulsion for re-dispersible emulsion powder of Comparative Examples:
The finishing mucilage compsn:
300.0 parts by weight of cement 325
600.0 weight part silica sand (0.1-0.4mm)
40.0 weight part emulsion for re-dispersible emulsion powder (being converted into dry weight)
2.0 weight part ether of cellulose
0.8 weight part starch ethers
0.5 weight part fiber
150 weight part dicalcium powders
The every 1000g dry mixture of water 200g
The method of pressing JC/T 993-2006 detects tensile bond strength
Said sample maintenance 14 days (normal curing: temperature (23 ± 2) ℃, relative humidity 60%), curing in water 7 days (sample is immersed in the water, temperature (23 ± 2) ℃)
Finishing mucilage on the PS sheet material is measured
Sample |
Tensile bond strength, Mpa (normal curing 14 days) |
Tensile bond strength, Mpa (first normal curing 14 days, curing in water is 7 days again) |
Comparative Examples |
?0.15 |
?0.11 |
Embodiment 1 |
?0.18 |
?0.14 |
Embodiment 2 |
?0.19 |
?0.13 |
Embodiment 3 |
?0.20 |
?0.15 |
Embodiment 4 |
?0.19 |
?0.13 |
Embodiment 5 |
?0.18 |
?0.14 |
Embodiment 6 |
?0.19 |
?0.15 |
Embodiment 7 |
?0.21 |
?0.16 |
Embodiment 8 |
0.20 |
0.12 |
See from above-mentioned application experiment: use the finishing mucilage of the emulsion for re-dispersible emulsion powder preparation of embodiments of the invention 1~8 preparation to compare with Comparative Examples, tensile bond strength is good, water-tolerant.