CN104356300A - Modified chitosan efficient retarding and water-reducing agent and preparation method and using method thereof - Google Patents
Modified chitosan efficient retarding and water-reducing agent and preparation method and using method thereof Download PDFInfo
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- CN104356300A CN104356300A CN201410566824.5A CN201410566824A CN104356300A CN 104356300 A CN104356300 A CN 104356300A CN 201410566824 A CN201410566824 A CN 201410566824A CN 104356300 A CN104356300 A CN 104356300A
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 65
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000000979 retarding effect Effects 0.000 title abstract 5
- 239000000178 monomer Substances 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 91
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000003999 initiator Substances 0.000 claims description 31
- 239000004568 cement Substances 0.000 claims description 19
- 238000013019 agitation Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000004567 concrete Substances 0.000 claims description 13
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004160 Ammonium persulphate Substances 0.000 claims description 9
- 239000004159 Potassium persulphate Substances 0.000 claims description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 9
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 235000019394 potassium persulphate Nutrition 0.000 claims description 9
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 8
- 239000003643 water by type Substances 0.000 claims description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 7
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 7
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 230000006196 deacetylation Effects 0.000 claims description 3
- 238000003381 deacetylation reaction Methods 0.000 claims description 3
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 3
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- DIKJULDDNQFCJG-UHFFFAOYSA-N sodium;prop-2-ene-1-sulfonic acid Chemical compound [Na+].OS(=O)(=O)CC=C DIKJULDDNQFCJG-UHFFFAOYSA-N 0.000 abstract 1
- 235000019263 trisodium citrate Nutrition 0.000 description 6
- 239000004576 sand Substances 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 230000003467 diminishing effect Effects 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Detergent Compositions (AREA)
Abstract
The invention discloses a modified chitosan efficient retarding and water-reducing agent and a preparation method and a using method thereof. Chitosan and itaconic anhydride react to prepare double-bond modified chitosan; the modified chitosan, acrylic monomer and sodium allysulfonate are subjected to copolymerization reaction; the product of polymerization reaction is compounded with a retarder to obtain the modified chitosan efficient retarding and water-reducing agent. The modified chitosan efficient retarding and water-reducing agent prepared by the preparation method provided by the invention has the characteristics of high water-reducing efficiency, high adaptability, long retarding time, capability of being used together with a polycarboxylate-type water-reducing agent, and the like.
Description
[technical field]
The present invention relates to the reinforcement of concrete water reducer field, efficient retardation water reducing agent of special and a kind of modified chitosan and preparation method thereof and using method.
[background technology]
Water reducer is a kind of important admixture that the production of modern concrete and construction process must use.The development experience of the water reducer ligno-sulfate based plasticizer of the first-generation, the naphthalene sulfonic salt of the s-generation and the polycarboxylate dehydragent of sulfamate water reducer and the third generation.China is main being most widely used with s-generation water reducer at present, and the poly carboxylic acid series water reducer of the third generation is also among popularization, and its consumption increases year by year.The naphthalene water reducer of the s-generation is when applying, and its solid volume is about 1% of cement weight, and water-reducing rate can reach 15% ~ 20%, and the slow setting time is 1 ~ 2 hour.The solid volume of the poly carboxylic acid series water reducer of the third generation is 0.2% of cement weight, and water-reducing rate is about 30%, and the slow setting time is 2 ~ 3 hours.The problem run in the application at third generation water reducer is at present that its adaptability is poor, more responsive to silt content in the kind of cement and sandstone, during cement for some brand, adaptability is good, then may poor effect when the cement for other brand, simultaneously when the silt content in sandstone is greater than 5%, the water-reducing rate of poly carboxylic acid series water reducer and concrete mobility are significantly declined, almost cannot use, the existence of these problems hampers poly carboxylic acid series water reducer Central China particularly the applying of the Northwest.Reason is that the general silt content of natural sand in the river course in these areas is higher.Poly carboxylic acid series water reducer becomes to sand silt content sensitive issue the focus studied in recent years.
[summary of the invention]
The object of the present invention is to provide efficient retardation water reducing agent of a kind of modified chitosan and preparation method thereof and using method, the efficient retardation water reducing agent of the modified chitosan prepared by the method diminishing efficiency is high.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for the efficient retardation water reducing agent of modified chitosan, comprises the following steps:
According to weight part by 15 ~ 20 parts of chitosans and 8 ~ 12 parts of furoate clothing acid anhydrides in drying, be heated to 70 ~ 80 DEG C in anhydrous reactor to be uniformly mixed, then be warmed up to 90 ~ 95 DEG C and continue insulation reaction 2 ~ 3 hours, 40 ~ 50 parts of deionized waters are under agitation added after being down to 40 ~ 50 DEG C, then being neutralized to pH value is 6.5 ~ 7.5, products therefrom solution keeps temperature to be 45 ~ 50 DEG C, under agitation drip 8 ~ 12 parts of mix monomers respectively, the initiator solution II of 2 ~ 4 parts initiator solution I and 1.5 ~ 3.5 part, time for adding is 1 ~ 1.5 hour, insulation reaction is continued 4 ~ 5 hours after reinforced, then 25 ~ 30 DEG C are cooled to, then being neutralized to pH value is 6.5 ~ 7.5, then 3 ~ 5 parts of retardant are added, stir and obtain the efficient retardation water reducing agent of modified chitosan.
Preferably, the deacetylation of described chitosan is greater than 85%, and viscosity is 350mPa.s ~ 250mPa.s, can be water-soluble.
Preferably, described mix monomer is mixed according to weight part 10:2:1:5 by vinylformic acid, methacrylic acid, third rare sodium sulfonate and water.
Preferably, described initiator solution I is dissolved in the water by ammonium persulphate, Potassium Persulphate or Sodium Persulfate and obtains, and wherein the mass ratio of ammonium persulphate, Potassium Persulphate, Sodium Persulfate and water is 1:10; Initiator solution II is dissolved in the water by sodium bisulfite, S-WAT or Sulfothiorine and obtains, and wherein the mass ratio of sodium bisulfite, S-WAT, Sulfothiorine and water is 1:10; The feed postition of initiator is that initiator solution I and initiator solution II drip respectively, does not mix before adding.
Preferably, described retardant is Trisodium Citrate, Sunmorl N 60S or tripoly phosphate sodium STPP.
Preferably, the time that chitosan and furoate clothing acid anhydride stir is 30 ~ 50 minutes.
Preferably, massfraction is adopted to be 40% sodium hydroxide solution adjust ph.
The using method of the efficient retardation water reducing agent of modified chitosan: when the add-on of the efficient retardation water reducing agent of this modified chitosan is 0.4% of cement weight, water-reducing rate is 27 ~ 30%, can be used in the concrete that sandstone silt content is less than 11%.
The using method of the efficient retardation water reducing agent of modified chitosan: during use, the modified chitosan water reducer accounting for cement weight 0.12% ~ 0.15% and the poly carboxylic acid series water reducer accounting for cement weight 0.12% ~ 0.16% is added in cement, water-reducing rate is 28% ~ 30%, can be used in the concrete that sandstone silt content is less than 9%.
Relative to prior art, the present invention has following beneficial effect: the present invention adopts chitosan and furoate clothing anhydride reactant to prepare the modified chitosan containing double bond, the retardant such as gained modified chitosan carries out Raolical polymerizable with acrylic monomer and allylsulfonate etc. again, last and Trisodium Citrate carry out composite modified chitosan colleges and universities water reducer of preparing; Water reducer diminishing efficiency prepared by the inventive method is high, when solid volume is 0.4% according to cement weight, water-reducing rate is 27 ~ 30%, and good to the adaptability of cement, the slow setting time is long, the independent slow setting time can reach 4 ~ 5 hours, can be used in the concrete that sandstone silt content is less than 11%.Simultaneously this product also can with poly carboxylic acid series water reducer with the use of, the easy bleeding existed when can improve polycarboxylate water-reducer, segregation and the defect to the sensitivity containing argillaceous sand stone, when the solid volume of poly carboxylic acid series water reducer is 0.12% ~ 0.16% according to cement weight, solid volume is 0.12% ~ 0.15% with the use of this product according to cement weight, water-reducing rate is 28% ~ 30%, concrete can be prevented in the phenomenon such as Mi Shui, segregation of mix construction process, be applicable to the concrete that sandstone silt content is less than 9%.
[embodiment]
The preparation method of the efficient retardation water reducing agent of a kind of modified chitosan of the present invention, comprises the following steps:
According to weight part by 15 ~ 20 parts of chitosans and 8 ~ 12 parts of furoate clothing acid anhydrides in drying, be heated to 70 ~ 80 DEG C in anhydrous reactor and be uniformly mixed 30 ~ 50 minutes, then be warmed up to 90 ~ 95 DEG C and continue insulation reaction 2 ~ 3 hours, 40 ~ 50 parts of deionized waters are under agitation slowly added after being down to 40 ~ 50 DEG C, be that to be neutralized to pH value be 6.5 ~ 7.5 to 40% sodium hydroxide solution with massfraction, products therefrom solution keeps temperature to be 45 ~ 50 DEG C, under agitation drip 8 ~ 12 parts of mix monomers respectively, the initiator solution II of 2 ~ 4 parts initiator solution I and 1.5 ~ 3.5 part, time for adding is 1 ~ 1.5 hour, insulation reaction is continued 4 ~ 5 hours after reinforced, then 25 ~ 30 DEG C are cooled to, be that to be neutralized to pH value be 6.5 ~ 7.5 to 40% sodium hydroxide solution with massfraction, then 3 ~ 5 parts of retardant are added, stir and obtain the efficient retardation water reducing agent of modified chitosan.
The deacetylation of above-mentioned chitosan is greater than 85%, and viscosity is 350mPa.s ~ 250mPa.s, water soluble.
Above-mentioned mix monomer of stating is mixed according to weight part 10:2:1:5 by vinylformic acid, methacrylic acid, third rare sodium sulfonate and water.
Above-mentioned initiator I is dissolved in 10 parts of water by 1 part of ammonium persulphate, 1 part of Potassium Persulphate or 1 part of Sodium Persulfate and obtains; Initiator II is dissolved in 10 parts of water by 1 part of sodium bisulfite, 1 part of S-WAT or 1 part of Sulfothiorine and obtains; The feed postition of initiator is that initiator I and initiator II drip respectively, must not mix before adding.
Above-mentioned retardant is Trisodium Citrate, Sunmorl N 60S or tripoly phosphate sodium STPP.
Embodiment 1
The preparation method of the efficient retardation water reducing agent of a kind of modified chitosan, comprise the following steps: according to weight part by 15 parts of chitosans and 12 parts of furoate clothing acid anhydrides in drying, be heated to 80 DEG C in anhydrous reactor and be uniformly mixed 30 minutes, then be warmed up to 90 DEG C and continue insulation reaction 2 hours, 40 parts of deionized waters are under agitation slowly added after being down to 40 DEG C, be that to be neutralized to pH value be 6.5 to 40% sodium hydroxide solution with massfraction, products therefrom solution keeps temperature to be 45 DEG C, under agitation drip 8 parts of mix monomers respectively, (ammonium persulphate is dissolved in the water and obtains 2 parts of initiator solution I, the mass ratio of ammonium persulphate and water is 1:10) and the initiator solution II of 3.5 parts (S-WAT is dissolved in the water and obtains, the mass ratio of S-WAT and water is 1:10), time for adding is 1 hour, insulation reaction is continued 4 hours after reinforced, then 25 DEG C are cooled to, be that to be neutralized to pH value be 6.5 to 40% sodium hydroxide solution with massfraction, then 5 parts of Trisodium Citrates are added as retardant, stir and obtain the efficient retardation water reducing agent of modified chitosan.
Embodiment 2
The preparation method of the efficient retardation water reducing agent of a kind of modified chitosan, comprise the following steps: according to weight part by 18 parts of chitosans and 8 parts of furoate clothing acid anhydrides in drying, be heated to 70 DEG C in anhydrous reactor and be uniformly mixed 50 minutes, then be warmed up to 95 DEG C and continue insulation reaction 3 hours, 50 parts of deionized waters are under agitation slowly added after being down to 40 DEG C, be that to be neutralized to pH value be 7.5 to 40% sodium hydroxide solution with massfraction, products therefrom solution keeps temperature to be 50 DEG C, under agitation drip 10 parts of mix monomers respectively, (Potassium Persulphate is dissolved in the water and obtains 2 parts of initiator solution I, the mass ratio of Potassium Persulphate and water is 1:10) and the initiator solution II of 2.5 parts (Sulfothiorine is dissolved in the water and obtains, the mass ratio of Sulfothiorine and water is 1:10), time for adding is 1 hour, insulation reaction is continued 4 hours after reinforced, then 30 DEG C are cooled to, be that to be neutralized to pH value be 7.5 to 40% sodium hydroxide solution with massfraction, then 4 parts of Trisodium Citrates are added as retardant, stir and obtain the efficient retardation water reducing agent of modified chitosan.
Embodiment 3
The preparation method of the efficient retardation water reducing agent of a kind of modified chitosan, comprise the following steps: according to weight part by 20 parts of chitosans and 10 parts of furoate clothing acid anhydrides in drying, be heated to 70 DEG C in anhydrous reactor and be uniformly mixed 50 minutes, then be warmed up to 95 DEG C and continue insulation reaction 2 hours, 50 parts of deionized waters are under agitation slowly added after being down to 40 DEG C, be that to be neutralized to pH value be 7.5 to 40% sodium hydroxide solution with massfraction, products therefrom solution keeps temperature to be 50 DEG C, under agitation drip 12 parts of mix monomers respectively, (Potassium Persulphate is dissolved in the water and obtains 2 parts of initiator solution I, the mass ratio of Potassium Persulphate and water is 1:10) and the initiator solution II of 1.5 parts (S-WAT is dissolved in the water and obtains, the mass ratio of S-WAT and water is 1:10), time for adding is 1.5 hours, insulation reaction is continued 5 hours after reinforced, then 25 DEG C are cooled to, be that to be neutralized to pH value be 7.5 to 40% sodium hydroxide solution with massfraction, then 3 parts of Sunmorl N 60Ss are added as retardant, stir and obtain the efficient retardation water reducing agent of modified chitosan.
Embodiment 4
The preparation method of the efficient retardation water reducing agent of a kind of modified chitosan, comprise the following steps: according to weight part by 16 parts of chitosans and 11 parts of furoate clothing acid anhydrides in drying, be heated to 80 DEG C in anhydrous reactor and be uniformly mixed 30 minutes, then be warmed up to 90 DEG C and continue insulation reaction 2 hours, 45 parts of deionized waters are under agitation slowly added after being down to 50 DEG C, be that to be neutralized to pH value be 7 to 40% sodium hydroxide solution with massfraction, products therefrom solution keeps temperature to be 50 DEG C, under agitation drip 10 parts of mix monomers respectively, (Sodium Persulfate is dissolved in the water and obtains 2 parts of initiator solution I, the mass ratio of Sodium Persulfate and water is 1:10) and the initiator solution II of 1.5 parts (sodium bisulfite is dissolved in the water and obtains, the mass ratio of sodium bisulfite and water is 1:10), time for adding is 1.5 hours, insulation reaction is continued 5 hours after reinforced, then 30 DEG C are cooled to, be that to be neutralized to pH value be 7.5 to 40% sodium hydroxide solution with massfraction, then 3 parts of tripoly phosphate sodium STPPs are added as retardant, stir and obtain the efficient retardation water reducing agent of modified chitosan.
Embodiment 5
The preparation method of the efficient retardation water reducing agent of a kind of modified chitosan, comprise the following steps: according to weight part by 15 parts of chitosans and 12 parts of furoate clothing acid anhydrides in drying, be heated to 70 DEG C in anhydrous reactor and be uniformly mixed 40 minutes, then be warmed up to 95 DEG C and continue insulation reaction 3 hours, 50 parts of deionized waters are under agitation slowly added after being down to 40 DEG C, be that to be neutralized to pH value be 7.5 to 40% sodium hydroxide solution with massfraction, products therefrom solution keeps temperature to be 50 DEG C, under agitation drip 12 parts of mix monomers respectively, (ammonium persulphate is dissolved in the water and obtains 2 parts of initiator solution I, the mass ratio of ammonium persulphate and water is 1:10) and the initiator solution II of 1.5 parts (sodium bisulfite is dissolved in the water and obtains, the mass ratio of sodium bisulfite and water is 1:10), time for adding is 1 hour, insulation reaction is continued 4 hours after reinforced, then 30 DEG C are cooled to, be that to be neutralized to pH value be 7.5 to 40% sodium hydroxide solution with massfraction, then 5 parts of Sunmorl N 60Ss are added as retardant, stir and obtain the efficient retardation water reducing agent of modified chitosan.
The present invention adopts chitosan and furoate clothing anhydride reactant to prepare the modified chitosan containing double bond, carry out Raolical polymerizable with acrylic monomer and allylsulfonate etc. again, the retardant such as products therefrom and Trisodium Citrate carries out compositely preparing modified chitosan colleges and universities water reducer; Water reducer diminishing efficiency prepared by the inventive method is high, when solid volume be cement weight is 0.4%, water-reducing rate is 27 ~ 30%, good to the adaptability of cement, is applicable to the concrete that sandstone silt content is less than 11%, the slow setting time is long, and the slow setting time can reach 5 hours.Simultaneously this product can with poly carboxylic acid series water reducer with the use of, the easy bleeding existed when can improve polycarboxylate water-reducer, segregation and the defect to the sensitivity containing argillaceous sand stone, when the solid volume of poly carboxylic acid series water reducer is 0.12% ~ 0.16% of cement weight, simultaneously according to solid volume, to be cement weight be 0.12% ~ 0.15% with the use of this product, concrete can be prevented in the phenomenon such as Mi Shui, segregation of mix construction process, water-reducing rate is 28% ~ 30%, is applicable to the concrete that sandstone silt content is less than 9%.
Claims (10)
1. a preparation method for the efficient retardation water reducing agent of modified chitosan, is characterized in that, comprise the following steps:
According to weight part by the chitosan of 15 ~ 20 parts and 8 ~ 12 parts of furoate clothing acid anhydrides in drying, be heated to 70 ~ 80 DEG C in anhydrous reactor to be uniformly mixed, then be warmed up to 90 ~ 95 DEG C and continue insulation reaction 2 ~ 3 hours, 40 ~ 50 parts of deionized waters are under agitation added after being down to 40 ~ 50 DEG C, then being neutralized to pH value is 6.5 ~ 7.5, products therefrom solution keeps temperature to be 45 ~ 50 DEG C, under agitation drip 8 ~ 12 parts of mix monomers respectively, the initiator solution II of 2 ~ 4 parts initiator solution I and 1.5 ~ 3.5 part, time for adding is 1 ~ 1.5 hour, insulation reaction is continued 4 ~ 5 hours after reinforced, then 25 ~ 30 DEG C are cooled to, then being neutralized to pH value is 6.5 ~ 7.5, then 3 ~ 5 parts of retardant are added, stir and obtain the efficient retardation water reducing agent of modified chitosan.
2. the preparation method of the efficient retardation water reducing agent of a kind of modified chitosan according to claim 1, is characterized in that: the deacetylation of described chitosan is greater than 85%, and viscosity is 350mPa.s ~ 250mPa.s, can be water-soluble.
3. the preparation method of the efficient retardation water reducing agent of a kind of modified chitosan according to claim 1, is characterized in that: described mix monomer is mixed according to weight part 10:2:1:5 by vinylformic acid, methacrylic acid, sodium allyl sulfonate and water.
4. the preparation method of the efficient retardation water reducing agent of a kind of modified chitosan according to claim 1, it is characterized in that: described initiator solution I is dissolved in the water by ammonium persulphate, Potassium Persulphate or Sodium Persulfate and obtains, and wherein the mass ratio of ammonium persulphate, Potassium Persulphate, Sodium Persulfate and water is 1:10; Initiator solution II is dissolved in the water by sodium bisulfite, S-WAT or Sulfothiorine and obtains, and wherein the mass ratio of sodium bisulfite, S-WAT, Sulfothiorine and water is 1:10; The feed postition of initiator is that initiator solution I and initiator solution II drip respectively, does not mix before adding.
5. the preparation method of the efficient retardation water reducing agent of a kind of modified chitosan according to claim 1, is characterized in that: described retardant is Trisodium Citrate, Sunmorl N 60S or tripoly phosphate sodium STPP.
6. the preparation method of the efficient retardation water reducing agent of a kind of modified chitosan according to claim 1, is characterized in that: the time that chitosan and furoate clothing acid anhydride stir is 30 ~ 50 minutes.
7. the preparation method of the efficient retardation water reducing agent of a kind of modified chitosan according to claim 1, is characterized in that: adopt massfraction to be 40% sodium hydroxide solution adjust ph.
8. the efficient retardation water reducing agent of the modified chitosan prepared by preparation method of the efficient retardation water reducing agent of a kind of modified chitosan according to any one of claim 1 to 7.
9. the using method of the efficient retardation water reducing agent of modified chitosan according to claim 8, it is characterized in that, be used in sandstone silt content when being less than in the concrete of 11%, when the solids loading content of the efficient retardation water reducing agent of this modified chitosan is 0.4% of cement weight, water-reducing rate is 27% ~ 30%, and the slow setting time reaches 4 ~ 5 hours.
10. the using method of the efficient retardation water reducing agent of modified chitosan according to claim 8, it is characterized in that, be used in sandstone silt content when being less than in the concrete of 9%, the modified chitosan water reducer that use solid volume is cement weight 0.12% ~ 0.15% and the poly carboxylic acid series water reducer of 0.12% ~ 0.16%, water-reducing rate is 28% ~ 30%, and the slow setting time is 4 ~ 5 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410566824.5A CN104356300B (en) | 2014-10-22 | 2014-10-22 | Efficient retardation water reducing agent of a kind of modification of chitosan and preparation method thereof and using method |
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|---|---|---|---|
| CN201410566824.5A CN104356300B (en) | 2014-10-22 | 2014-10-22 | Efficient retardation water reducing agent of a kind of modification of chitosan and preparation method thereof and using method |
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| CN105924030A (en) * | 2016-04-29 | 2016-09-07 | 华侨大学 | Ester polycarboxylate concrete additive containing chitosan, and preparation method thereof |
| CN105948563A (en) * | 2016-04-29 | 2016-09-21 | 华侨大学 | Ether type polycarboxylic acid concrete water reducer containing chitosan and preparation method thereof |
| CN105949403A (en) * | 2016-04-29 | 2016-09-21 | 华侨大学 | Chitosan containing ether type polycarboxylic acid concrete admixture and preparation method therefor |
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| CN112960961A (en) * | 2021-03-18 | 2021-06-15 | 湖北源特矿业科技有限公司 | Phosphorite mountain high-concentration full-tailing gravity-flow filling cementing material |
| CN114031735A (en) * | 2021-09-03 | 2022-02-11 | 科之杰新材料集团有限公司 | Graft modified concrete polycarboxylic acid slump retaining agent and preparation method thereof |
| CN114031735B (en) * | 2021-09-03 | 2023-08-29 | 科之杰新材料集团有限公司 | Graft modified concrete polycarboxylic acid slump retaining agent and preparation method thereof |
| CN113861353A (en) * | 2021-10-20 | 2021-12-31 | 陕西科之杰新材料有限公司 | Antibacterial slump retaining agent and preparation method thereof |
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