CN104387529A - Cationic polyacrylamide emulsion and synthesis method thereof - Google Patents
Cationic polyacrylamide emulsion and synthesis method thereof Download PDFInfo
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- CN104387529A CN104387529A CN201410662829.8A CN201410662829A CN104387529A CN 104387529 A CN104387529 A CN 104387529A CN 201410662829 A CN201410662829 A CN 201410662829A CN 104387529 A CN104387529 A CN 104387529A
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- monomer
- polyacrylamide emulsion
- initiator
- stablizer
- cation polyacrylamide
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- 239000000839 emulsion Substances 0.000 title claims abstract description 35
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 28
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title abstract 4
- 238000004945 emulsification Methods 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 238000007599 discharging Methods 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 33
- 150000001768 cations Chemical class 0.000 claims description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004160 Ammonium persulphate Substances 0.000 claims description 10
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 10
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000010189 synthetic method Methods 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- -1 acrylyl Chemical group 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000033116 oxidation-reduction process Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 2
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 2
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 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 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- JPFBCOVYODWLJO-UHFFFAOYSA-N [NH4+].S([O-])(O)=O.[K] Chemical compound [NH4+].S([O-])(O)=O.[K] JPFBCOVYODWLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical group [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 2
- AJURYMCOXVKKFB-UHFFFAOYSA-M trimethyl(3-prop-2-enoyloxypropyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCOC(=O)C=C AJURYMCOXVKKFB-UHFFFAOYSA-M 0.000 claims description 2
- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 239000003112 inhibitor Substances 0.000 abstract 2
- 239000003381 stabilizer Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 241000237502 Ostreidae Species 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 235000020636 oyster Nutrition 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000004908 Emulsion polymer Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000012688 inverse emulsion polymerization Methods 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001370 static light scattering Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a cationic polyacrylamide emulsion and a synthesis method thereof. The cationic polyacrylamide emulsion is characterized by comprising the following components in percentage by mass: 8-25 wt% of sum of nonionic monomer and cationic monomer, 10-35 wt% of inorganic salt, 0.5-5 wt% of stabilizer, initiator accounting for 0.001-0.08 wt% of the monomers, polymerization inhibitor accounting for 0.001-0.01 wt% of the monomers, and the balance of water. The synthesis method comprises the following steps: adding the nonionic monomer, cationic monomer, inorganic salt and stabilizer into a container, uniformly dissolving in water, and regulating the temperature of the solution to 25-60 DEG C; and introducing nitrogen, adding the initiator after 30 minutes, stirring for 2-24 hours in a closed state, adding the polymerization inhibitor, continuing stirring for 30 minutes, cooling to room temperature, and discharging to obtain the cationic polyacrylamide emulsion product. The synthesis method is suitable for synthesizing various cationic polyacrylamide emulsions with high yield and favorable flowability, and is simple, green and environment-friendly; and the cationic polyacrylamide emulsion has the characteristics of high stability, high water solubility and low cost.
Description
Technical field:
The present invention relates to a kind of cation polyacrylamide emulsion and synthetic method thereof, belong to water-soluble high-molecular material synthesis technical field.
Background technology:
Polyacrylamide water-soluble high-molecular material, owing to having the performances such as good water-soluble, tackifying, is widely used in multiple industrial circle.Wherein, cationic polyacrylamide has the material charge adsorption effect with anionic charge due to the cationic groups that its molecule contains, and is more suitable for the toughener etc. being used as the coating agent in drilling fluid, the flocculation agent in sewage disposal, sludge dehydrating agent, paper.
In the synthetic method of cationic polyacrylamide, aqueous solution polymerization method is widely used, but the product needed of this method synthesis obtains powder product after the operation such as granulation, drying, and energy consumption is large, and during powder product use, dissolution rate is slow, needs to stir for a long time.Inverse emulsion polymerization and conversed phase micro emulsion copolymerization method are the newer synthetic methods adopted, and these methods not only can synthesize the product of high molecular, and can solve the slower problem of product dissolution rate.But, inverse emulsion polymerization and conversed phase micro emulsion copolymerization method are when preparing polyacrylamide amine product, need a large amount of organic solvents and tensio-active agent, this not only adds synthesis cost, and in use can cause secondary pollution and the performance affecting product performance.
Summary of the invention:
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of cation polyacrylamide emulsion and synthetic method thereof, be suitable for synthesizing that various productive rate is high, the cation polyacrylamide emulsion of good fluidity, have that synthetic method is simple, good stability, water-soluble strong, environmental protection and the low feature of cost.
The present invention realizes above-mentioned purpose by following technical solution.
A kind of cation polyacrylamide emulsion provided by the present invention, wherein the mass percent of each component is:
Non-ionic monomer and cation mono weight sum account for 8-25wt%, and wherein, cationic monomer accounts for the 3-45wt% of monomer total mass;
Inorganic salt account for 10-35wt%;
Stablizer accounts for 0.5-5wt%;
Initiator accounts for the 0.001-0.08wt% of monomer total mass;
Stopper accounts for the 0.001-0.01wt% of monomer total mass;
Surplus is water;
The synthetic method of a kind of cation polyacrylamide emulsion provided by the present invention, comprises the steps:
(1), by non-ionic monomer, cationic monomer, inorganic salt and stablizer join in proportion in container, after even by water dissolution, regulate its solution temperature to 25 ~ 60 DEG C; Logical nitrogen protection is carried out to solution, after 30 minutes, adds initiator in proportion, continue to stir, carry out polyreaction;
(2) maintain the temperature at 25 ~ 60 DEG C after adding initiator, in the solution, close stirring and add stopper in proportion after 2 ~ 24 hours, continue stirring after 30 minutes, be cooled to room temperature, discharging, obtain cation polyacrylamide emulsion product.
Described non-ionic monomer is the one in acrylamide, Methacrylamide, N methacrylamide, N,N-DMAA, vinylbenzene, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate and NVP;
Described cationic monomer is the one in acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acryloxypropyl trimethyl ammonium chloride, methacryloxypropyl trimethyl ammonium chloride and N, N-dimethyl diallyl ammonium chloride;
Described inorganic salt are the one that the positively charged ion of potassium, sodium, lithium and ammonium and the negatively charged ion of sulfate radical, inferior sulfate radical, halogen ion, phosphate radical and nitrate radical form in salt;
Described stopper is the one in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, Sodium dimethyldithiocarbamate 40min, p-ten.-butylcatechol, 2-Tert. Butyl Hydroquinone and 2,5 di tert butyl hydroquinone;
Described initiator is the one in oxidation system, oxidation-reduction trigger system and azo-bis-isobutyrate hydrochloride;
Wherein: oxidation system is the one in Potassium Persulphate and ammonium persulphate;
Oxidation-reduction trigger system is made up of with sodium bisulfite or ammonium bisulfite Potassium Persulphate or ammonium persulphate;
Described stablizer has following chemical structural formula (I):
Wherein: R
1, R
3and R
5be respectively H, CH
3and CH
2cH
3in one, R
1, R
3and R
5can be the same or different;
R
2for NH
2, NHCH
3with N (CH
3)
2in one;
R
4for 2-Pyrrolidone base;
R
6for NH or NCH
3;
O, p and m be respectively 1 or be greater than 1 integer, x be greater than 1 integer, the product of x and (o+p+m) is between 4000-11000;
The described synthetic method with the stablizer of chemical structural formula (I), comprises the steps:
(1) monomer mixture (is made up of the one in acrylamide, Methacrylamide and N methacrylamide and NVP, wherein, NVP accounts for the 3-10wt% of monomer total mass) be dissolved in the water, be mixed with the aqueous solution that concentration is 4-8wt%, regulate its aqueous temperature to 25 ~ 60 DEG C, when logical nitrogen protection, add the initiator ammonium persulfate of monomer mixture quality 0.1-0.12wt%, react and can obtain the aqueous solutions of polymers that the polymerization degree is 4000-11000 after 2-3 hour;
(2) at 40-70 DEG C, paraformaldehyde and S-WAT is added again in aqueous solutions of polymers, both quality and be the 10-20wt% of monomer mixture, wherein: the mol ratio of paraformaldehyde and S-WAT is 1:1.5-1:4, react after 2-10 hour, obtain the stablizer aqueous solution of structural formula (I).
The present invention has following beneficial effect compared with prior art:
(1) reaction solution preparation is easy, and temperature of reaction is low, the selectivity of temperature of reaction and workable, at room temperature, is added water by all materials and stirs, can realize " one kettle way " reinforced.
(2) environmental protection, synthesis cost is low, adopts water as solvent, avoids the environmental pollution adopting organic solvent or tensio-active agent to cause.
(3) good emulsion stability, good fluidity, the stablizer of employing can make emulsion intercalation method reach more than 100 days, is convenient to store and transport, easy to use.
(4) by force water-soluble, effective content is high, and in emulsion, monomer content can reach 25wt%, to realize in water slightly stirring and solubilized.
(5) universality, the product emulsion of synthesis can be used as the toughener etc. of the coating agent in drilling fluid, the flocculation agent in sewage disposal, sludge dehydrating agent, paper.
Embodiment:
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1:
This example is used for the synthesis of the stablizer aqueous solution of structural formula (I).
Monomer mixture (acrylamide 95wt% and NVP 5wt%) is mixed with the aqueous solution that concentration is 5wt%, be warming up to 60 DEG C, when logical nitrogen protection, add the ammonium persulphate of acrylamide quality 0.1wt%, react the aqueous solution that can obtain polyacrylamide after 2 hours;
The temperature of polyacrylamide solution is controlled at 50 DEG C, add paraformaldehyde and the sodium bisulfite (both mol ratios are 1:1.06) of monomer mixture quality 10wt%, react after 5 hours, namely obtain the stablizer aqueous solution of structural formula I.
Embodiment 2:
Under room temperature, with temperature regulating device, whipping appts, nitrogen passes into mouth, in the round-bottomed flask of reflux condensing tube, add 70g water respectively, 36g acrylamide, 34g ammonium sulfate, 20g ammonium chloride, 5g acrylyl oxy-ethyl-trimethyl salmiac, 4g N, the stablizer aqueous solution of preparation in the N-dimethyl diallyl ammonium chloride aqueous solution (concentration 65wt%) and 40g embodiment 1, after stirring, logical nitrogen, be warming up to 35 DEG C, continue stirring after 30 minutes, add the ammonium persulphate of 1wt% and the aqueous solution 2.5mL of sodium bisulfite (mass ratio 1:1), continue stirring after 15 hours, add the Resorcinol aqueous solution 0.4mL of 1wt%, be reduced to room temperature, collect, obtain oyster white, the emulsion of good fluidity, stability is greater than 110 days.
Embodiment 3:
Under room temperature, with temperature regulating device, whipping appts, nitrogen passes into mouth, in the round-bottomed flask of reflux condensing tube, add 50g water respectively, 24g acrylamide, 6g N methacrylamide, 24g ammonium sulfate, 18g ammonium nitrate, 4.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 3g N, the stablizer aqueous solution of preparation in the N-dimethyl diallyl ammonium chloride aqueous solution (concentration 65wt%) and 35g embodiment 1, after stirring, logical nitrogen, be warming up to 35 DEG C, after 30 minutes, add the ammonium persulphate of 1wt% and the aqueous solution 1.8mL of sodium bisulfite (mass ratio 1:1), continue stirring after 16 hours, add the Resorcinol aqueous solution 0.3mL of 1wt%, be reduced to room temperature, collect, obtain oyster white, the emulsion of good fluidity, stability is greater than 140 days.
Embodiment 4:
Material and dosage thereof are identical with embodiment 3, and temperature of reaction is 50 DEG C, adds the persulfate aqueous solution 1.8mL of 1wt%, react after 10 hours, add the Resorcinol aqueous solution 0.3mL of 1wt%, after being down to room temperature, collect, obtain product emulsion, stability is greater than 125 days.
Embodiment 5:
Material and dosage thereof are identical with embodiment 3, and temperature of reaction is 30 DEG C, add the ammonium persulphate of 1wt% and the azo-bis-isobutyrate hydrochloride aqueous solution 0.5mL of sodium bisulfite (mass ratio 1:1) solution 1mL and 1wt%, react after 18 hours, add the Resorcinol aqueous solution 0.3mL of 1wt%, after being down to room temperature, collect, obtain product emulsion, stability is greater than 135 days.
Embodiment 6:
Under room temperature, with temperature regulating device, whipping appts, nitrogen passes into mouth, in the round-bottomed flask of reflux condensing tube, add 90g water respectively, 18g N, N-DMAA, 24g N methacrylamide, 60g ammonium sulfate, 14g N, the stablizer aqueous solution of preparation in the N-dimethyl diallyl ammonium chloride aqueous solution (concentration 65wt%) and 45g embodiment 1, after stirring, logical nitrogen, be warming up to 40 DEG C, after 30 minutes, add the ammonium persulphate of 1wt% and the aqueous solution 2.2mL of sodium bisulfite (mass ratio 1:1), continue stirring after 16 hours, add the Resorcinol aqueous solution 0.4mL of 1wt%, be down to room temperature, collect, obtain oyster white, the emulsion of good fluidity, stability is greater than 130 days.
Embodiment 7:
Under room temperature, with temperature regulating device, whipping appts, nitrogen passes into mouth, in the round-bottomed flask of reflux condensing tube, add 80g water respectively, 40g N, N-DMAA, 2g NVP, 60g ammonium sulfate, 14g N, the stablizer aqueous solution of preparation in the N-dimethyl diallyl ammonium chloride aqueous solution (concentration 65wt%) and 50g embodiment 1, after stirring, logical nitrogen, be warming up to 40 DEG C, after 30 minutes, add the ammonium persulphate of 1wt% and the aqueous solution 2mL of sodium bisulfite (mass ratio 1:1), after continuing to stir 15h, add the Resorcinol aqueous solution 0.4mL of 1wt%, be down to room temperature, collect, obtain oyster white, the emulsion of good fluidity, stability is greater than 135 days.
Embodiment 8-13:
This embodiment 8-13 measures the emulsion of synthesizing in embodiment 2-7 is water-soluble.
The amount of the emulsion of synthesizing in embodiment 2-7 by 2wt% be added to the water, slightly stirring or stirring are no more than 10min, can disperse, show the well water-soluble of all emulsions in water.
Embodiment 14-19:
This embodiment 14-19 measures the emulsion polymer weight-average molecular weight of synthesizing in embodiment 2-7.
Adopt static light scattering method to measure emulsion polymer weight-average molecular weight in embodiment 2-7 and be all greater than 4,200,000, wherein, the weight-average molecular weight of embodiment 3 and embodiment 5 is greater than 7,500,000 and be greater than 8,300,000 respectively.
Claims (8)
1. a cation polyacrylamide emulsion, is characterized in that the mass percent of wherein each component is:
Non-ionic monomer and cation mono weight sum account for 8-25wt%, and wherein, cationic monomer accounts for the 3-45wt% of monomer total mass;
Inorganic salt account for 10-35wt%;
Stablizer accounts for 0.5-5wt%;
Initiator accounts for the 0.001-0.08wt% of monomer total mass;
Stopper accounts for the 0.001-0.01wt% of monomer total mass;
Surplus is water.
2. the synthetic method of a kind of cation polyacrylamide emulsion as claimed in claim 1, is characterized in that comprising the steps:
(1), by non-ionic monomer, cationic monomer, inorganic salt and stablizer join in proportion in container, after even by water dissolution, regulate its solution temperature to 25 ~ 60 DEG C; Logical nitrogen protection is carried out to solution, after 30 minutes, adds initiator in proportion, continue to stir, carry out polyreaction;
(2) maintain the temperature at 25 ~ 60 DEG C after adding initiator, in the solution, close stirring and add stopper in proportion after 2 ~ 24 hours, continue stirring after 30 minutes, be cooled to room temperature, discharging, obtain cation polyacrylamide emulsion product.
3. a kind of cation polyacrylamide emulsion according to claim 1, it is characterized in that described non-ionic monomer is the one in acrylamide, Methacrylamide, N methacrylamide, N,N-DMAA, vinylbenzene, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate and NVP.
4. a kind of cation polyacrylamide emulsion according to claim 3, it is characterized in that described cationic monomer is the one in acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acryloxypropyl trimethyl ammonium chloride, methacryloxypropyl trimethyl ammonium chloride and N, N-dimethyl diallyl ammonium chloride.
5. a kind of cation polyacrylamide emulsion according to claim 4, is characterized in that described inorganic salt are the one that the positively charged ion of potassium, sodium, lithium and ammonium and the negatively charged ion of sulfate radical, inferior sulfate radical, halogen ion, phosphate radical and nitrate radical form in salt.
6. a kind of cation polyacrylamide emulsion according to claim 5, it is characterized in that described stopper is the one in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, Sodium dimethyldithiocarbamate 40min, p-ten.-butylcatechol, 2-Tert. Butyl Hydroquinone and 2,5 di tert butyl hydroquinone.
7. a kind of cation polyacrylamide emulsion according to claim 6, is characterized in that described initiator is the one in oxidation system, oxidation-reduction trigger system and azo-bis-isobutyrate hydrochloride;
Wherein: oxidation system is the one in Potassium Persulphate and ammonium persulphate; Oxidation-reduction trigger system is made up of with sodium bisulfite or ammonium bisulfite Potassium Persulphate or ammonium persulphate.
8. a kind of cation polyacrylamide emulsion according to claim 7, is characterized in that described stablizer has following chemical structural formula (I):
Wherein: R
1, R
3and R
5be respectively H, CH
3and CH
2cH
3in one, R
1, R
3and R
5can be the same or different;
R
2for NH
2, NHCH
3with N (CH
3)
2in one;
R
4for 2-Pyrrolidone base;
R
6for NH or NCH
3;
O, p and m be respectively 1 or be greater than 1 integer, x be greater than 1 integer, the product of x and (o+p+m) is between 4000-11000;
The described synthetic method with the stablizer of chemical structural formula (I), comprises the steps:
(1) monomer mixture (is made up of the one in acrylamide, Methacrylamide and N methacrylamide and NVP, wherein, NVP accounts for the 3-10wt% of monomer total mass) be dissolved in the water, be mixed with the aqueous solution that concentration is 4-8wt%, regulate its aqueous temperature to 25 ~ 60 DEG C, when logical nitrogen protection, add the initiator ammonium persulfate of monomer mixture quality 0.1-0.12wt%, react and can obtain the aqueous solutions of polymers that the polymerization degree is 4000-11000 after 2-3 hour;
(2) at 40-70 DEG C, paraformaldehyde and S-WAT is added again in aqueous solutions of polymers, both quality and be the 10-20wt% of monomer mixture, wherein: the mol ratio of paraformaldehyde and S-WAT is 1:1.5-1:4, react after 2-10 hour, obtain the stablizer aqueous solution of structural formula (I).
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| CN108914630A (en) * | 2018-05-07 | 2018-11-30 | 东莞德永佳纺织制衣有限公司 | A kind of salt-free dyeing technique of cotton fabric |
| CN109575185A (en) * | 2018-12-25 | 2019-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation of fluorided-modified hydrophobicity amphoteric organic polymer coargulator and product and application |
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| CN114015300A (en) * | 2021-10-25 | 2022-02-08 | 华麟海(海南)新材料科技有限公司 | Concrete protective coating capable of sterilizing and adsorbing sulfate ions and preparation method thereof |
| CN114015300B (en) * | 2021-10-25 | 2023-10-13 | 华麟海(海南)新材料科技有限公司 | Concrete protective coating capable of sterilizing and adsorbing sulfate ions and preparation method thereof |
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