CN102585089A - Cationic polyacrylamide polymer, method for preparing same and application thereof - Google Patents
Cationic polyacrylamide polymer, method for preparing same and application thereof Download PDFInfo
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- CN102585089A CN102585089A CN201110002565XA CN201110002565A CN102585089A CN 102585089 A CN102585089 A CN 102585089A CN 201110002565X A CN201110002565X A CN 201110002565XA CN 201110002565 A CN201110002565 A CN 201110002565A CN 102585089 A CN102585089 A CN 102585089A
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Abstract
The invention discloses a method for preparing cationic polyacrylamide polymer, which is characterized by comprising the following steps: in the water, acrylamide monomer, polyoxyethylene, quaterisation cationic monomer and initiator are polymerized, wherein the relative molecular weight of the polyoxyethylene is 0.7million-3million. The initiator is the initiator of a redox system or the salt of a rare-earth element, and the mass ratio of the acrylamide monomer and the polyoxyethylene is 1:0.02-1:0.05. The cationic polyacrylamide polymer can be cross linked for a long time to form more three-dimensional network structures, so the retention efficiency is effectively improved.
Description
Technical field
The present invention is concrete relates to a kind of cationic polyacrylamide polymer.
Background technology
Huge variation has taken place in the modern paper machine structure, and like the use of two net formers, the high turbulent flow of formation can be smashed straight-chain polymer, but traditional retention filtration adjuvant is main with the SEPIGEL 305 and the verivate thereof of straight chain mainly.Therefore, the high effective retention flocculating aids of research under high turbulent flow is extremely urgent.Because cultural paper mainly is under alkaline condition, to manufacture paper with pulp, therefore the retention filtration adjuvant of research needs normal use the under alkaline condition.
The retention filtration adjuvant of the general usefulness of paper manufacturing systems is SEPIGEL 305 and verivate thereof, and like cationic polyacrylamide, but cationic polyacrylamide is prone to curl, unite phenomenon, and the influence wadding gathers effect.
SEPIGEL 305 can adopt method preparations such as free yl solution polymerization or inverse emulsion polymerization, inverse suspension polymerization, and aqueous solution polymerization technology is simple, and percent polymerization is high, but is difficult to prepare the SEPIGEL 305 of high molecular weight.Require viscosity-average molecular weight greater than 3,000,000 as paper retention and filter aid, the viscosity-average molecular weight of polyacrylamide amine system reaches 3,000,000 when above, and the viscosity of system will reach 100Pas, be prone to the generation implode, poorly water-soluble.Though effectively addressing these problems of reversed-phase emulsion, use organic solvent in a large number, exist and pollute and the production cost problem, and the poorly water-soluble of product, use very difficulty.
Summary of the invention
Technical problem to be solved by this invention is that cationic polyacrylamide is prone to curl, unite phenomenon in the existing paper manufacturing systems in order to overcome; Influence the defective of flocculating effect, and a kind of cationic polyacrylamide polymer is provided.Preparing method of the present invention can be crosslinked lastingly, thereby make the more three-dimensional net structure of formation in the polyacrylamide polymers that makes, and effectively improves and keep efficient; And the polyacrylamide polymers that makes also can reach good solubility, can be dissolved in the water rapidly.
The present invention relates to a kind of preparation method of cationic polyacrylamide polymer, it comprises the following step: in water, and with acrylamide monomer, polyoxyethylene, cationic monomer and initiator carry out polyreaction, get final product; Wherein, the viscosity-average molecular weight of polyoxyethylene is 700,000～3,000,000 (preferred 700,000～1,000,000); The structure of acrylamide monomer is following:
Wherein, R is hydrogen, methyl or ethyl; Cationic monomer is quaternized cationic monomer, and described initiator is the salt of redox system initiator or REE, and the mass ratio of acrylamide monomer and above-mentioned polyoxyethylene is 1: 0.02～1: 0.05.
Preferable, in above-mentioned polyreaction, can also add viscosity-average molecular weight and be 10000～50000 polyoxyethylene, what acrylamide monomer and this polyoxyethylated mass ratio were preferable is 1: 0.5～1: 2.
Among the present invention, what described quaternized cationic monomer was preferable is dimethyl diallyl ammonium chloride, and its structure is following:
Perhaps methylacryoyloxyethyl trimethyl ammonium chloride.
Described redox system initiator can be this area redox system initiator commonly used; Preferable is persulphate and bisulfite salt system (like Sodium Persulfate and sodium sulfite anhy 96); Persulphate and primary amine system, perhaps persulphate and tertiary alkanolamine system.The salt of described REE also can be used as initiator and uses, and what wherein REE was preferable is lanthanon, and like cerium, lanthanum or praseodymium etc., the salt of described REE can be any salt that contains above-mentioned rare earth element ion, and preferable is nitrate salt.What the mass ratio of acrylamide monomer and initiator was preferable is 100: 1～20: 1.
What the mass ratio of described acrylamide monomer and water was preferable is 1: 4～1: 10.What the mass ratio of described acrylamide monomer and cationic monomer was preferable is 2: 1～10: 1.
What the temperature of described polyreaction was preferable is 50 ℃～90 ℃.What the time of reaction was preferable is 4～6 hours.
The invention still further relates to the cationic polyacrylamide polymer that makes by above-mentioned preparation method.
The invention further relates to the application of cationic polyacrylamide polymer of the present invention as retention filtration adjuvant.For example, it can be used as the reasonable high-speed paper machine system that is used for of retention filtration adjuvant.
Among the preparation method of the present invention, above-mentioned each optimum condition can promptly get each preferred embodiments of the present invention in arbitrary combination under the prerequisite of this area general knowledge.
To sum up, the present invention has prepared the cationic polyacrylamide polymer of high side chain with acrylamide monomer, cationic monomer and high-molecular weight polyoxyethylene generation graft copolymerization, is a kind of retention filtration adjuvant that is used for the wet cloth of papermaking of high side chain.
And; The present invention also can be dissolved in acrylic amide and cationic monomer etc. in the low-molecular-weight polyethylene oxide solutions and react, and through the interaction of polymkeric substance and dispersion medium, system is separated; Improve institute's synthetic polymer relative molecular mass; Reduction system viscosity, the cationic polyacrylamide polymer that makes simultaneously also has good solubility, can be dissolved in the water rapidly.
Except that specified otherwise, raw material that the present invention relates to and reagent are all commercially available to be got.
Positive progressive effect of the present invention is:
1, the cationic polyacrylamide polymer that makes of the present invention is a kind of retention filtration adjuvant that is used for the wet cloth of papermaking of high side chain, has and keeps efficient preferably, can use in high pH, high shear, plain boiled water height closed system.
2, preparation method of the present invention can improve the relative molecular mass of institute's synthetic polymer, reduces the system viscosity, and the cationic polyacrylamide polymer that makes simultaneously also has good solubility, can be dissolved in the water rapidly.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Below relative molecular mass or relative molecular weight among each embodiment be viscosity-average molecular weight.
Embodiment 1
Being 50000 polyoxyethylene with acrylamide monomer and relative molecular mass at first mixes by 1: 2 mass ratio; Adding the aqueous solution then, to make the content of acrylamide monomer be 25% (wt%); The relative molecular mass that add the cationic monomer diallyldimethylammonChloride Chloride of acrylamide monomer quality 50% again, adds acrylamide monomer quality 5% again is 700,000 polyoxyethylene and 3% initiator ammonium persulfate, gets final product in 5 hours 90 ℃ of polyreactions.
With the product insulation that obtains 24 hours, detect, solid content is 95%, viscosity is 30cp.With potassium bromate Potassium Bromide method conversion rate of products is measured; Transformation efficiency surpasses 95%, with acid the product percentage of grafting is measured, and percentage of grafting is 78%; Solvability to product makes an experiment; In 100g water, add this polymkeric substance milky emulsion of 2g, stir gently, be dissolved as clear solution rapidly.
This product application in kp softwood pulp, is processed handsheet, put into air dry oven, measure the paper stock retention in 105 ℃ times dry 5 hours.Through experiment, when adding 0.05% (mass percent) product, the paper stock retention is 90%.
Embodiment 2
Being 40000 polyoxyethylene with acrylamide monomer and relative molecular mass at first mixes by 1: 1.8 mass ratio; Adding the aqueous solution then, to make the content of acrylamide monomer be 20% (wt%); The relative molecular mass that add the cationic monomer diallyldimethylammonChloride Chloride of acrylamide monomer quality 40% again, adds acrylamide monomer quality 2% again is 800,000 polyoxyethylene and 2.4% initiator potassium persulfate, gets final product in 5.5 hours 70 ℃ of polyreactions.
With the product insulation that obtains 24 hours, detect, solid content is 92%, viscosity is 28cp.。With potassium bromate Potassium Bromide method conversion rate of products is measured, transformation efficiency surpasses 95%, with acid the product percentage of grafting is measured, and percentage of grafting is 79%.Solvability to product makes an experiment, and in 100g water, adds this polymkeric substance milky emulsion of 2g, stirs gently, is dissolved as clear solution rapidly.
This product application in old corrugated containers(OCC) paperboard slurry, is processed handsheet, put into air dry oven, measure the paper stock retention in 105 ℃ times dry 5 hours.Through experiment, when adding 0.05% (mass percent) product, the paper stock retention is 80%.
Embodiment 3
Being 30000 polyoxyethylene with acrylamide monomer and relative molecular mass at first mixes by 1: 1.5 mass ratio; Adding the aqueous solution then, to make the content of acrylamide monomer be 18% (wt%); The relative molecular mass that add the cationic monomer diallyldimethylammonChloride Chloride of acrylamide monomer quality 45% again, adds acrylamide monomer quality 3% again is 900,000 polyoxyethylene and 5% initiator potassium persulfate, gets final product in 4 hours 80 ℃ of polyreactions.
With the product insulation that obtains 24 hours, detect, solid content is 92%, viscosity is 27cp.。With potassium bromate Potassium Bromide method conversion rate of products is measured, transformation efficiency surpasses 95%, with acid the product percentage of grafting is measured, and percentage of grafting is 76%.Solvability to product makes an experiment simultaneously, in 100g water, adds this polymkeric substance milky emulsion of 2g, stirs gently, is dissolved as clear solution rapidly.
This product application in the vitriol hardwood pulp, is processed handsheet, put into air dry oven, measure the paper stock retention in 105 ℃ times dry 5 hours.Through experiment, when adding 0.05% (mass percent) product, the paper stock retention is 88%.
Embodiment 4
Being 10000 polyoxyethylene with acrylamide monomer and relative molecular mass at first mixes by 1: 0.5 mass ratio; Adding the aqueous solution then, to make the content of acrylamide monomer be 10% (wt%); The relative molecular mass that add the cationic monomer diallyldimethylammonChloride Chloride of acrylamide monomer quality 10% again, adds acrylamide monomer quality 4% again is 1,000,000 polyoxyethylene and 0.9% initiator Sodium Persulfate and sodium sulfite anhy 96, gets final product in 6 hours 50 ℃ of polyreactions.
With the product insulation that obtains 24 hours, detect, solid content is 92%, viscosity is 28cp.With potassium bromate Potassium Bromide method conversion rate of products is measured, transformation efficiency surpasses 95%, with acid the product percentage of grafting is measured, and percentage of grafting is 80%.Solvability to product makes an experiment simultaneously, in 100g water, adds this polymkeric substance milky emulsion of 2g, stirs gently, is dissolved as clear solution rapidly.
This product application in news paper pulp, is processed handsheet, put into air dry oven, measure the paper stock retention in 105 ℃ times dry 5 hours.Through experiment, when adding 0.05% (mass percent) product, the paper stock retention is 86%.
Embodiment 5
Initiator changes praseodymium nitrate into, and remaining same instance 1 is identical.
With the product insulation that obtains 24 hours, detect, solid content is 94%, viscosity is 28cp.With potassium bromate Potassium Bromide method conversion rate of products is measured, transformation efficiency surpasses 97%, with acid the product percentage of grafting is measured, and percentage of grafting is 98%.Solvability to product makes an experiment simultaneously, in 100g water, adds this polymkeric substance milky emulsion of 2g, stirs gently, is dissolved as clear solution rapidly.
This product application in kp softwood pulp, is processed handsheet, put into air dry oven, measure the paper stock retention in 105 ℃ times dry 5 hours.Through experiment, when adding 0.05% (mass percent) product, the paper stock retention is up to more than 97%.
Embodiment 6
Initiator changes Lanthanum trinitrate into, and remaining same instance 1 is identical.
With the product insulation that obtains 24 hours, detect, solid content is 94%, viscosity is 28cp.With potassium bromate Potassium Bromide method conversion rate of products is measured, transformation efficiency surpasses 97%, with acid the product percentage of grafting is measured, and percentage of grafting is 98%.Solvability to product makes an experiment simultaneously, in 100g water, adds this polymkeric substance milky emulsion of 2g, stirs gently, is dissolved as clear solution rapidly.
This product application in paper waste, is processed handsheet, put into air dry oven, measure the paper stock retention in 105 ℃ times dry 5 hours.Through experiment, when adding 0.05% (mass percent) product, the paper stock retention is up to more than 95%.
Control Example
The removal relative molecular mass is 700,000 polyoxyethylene, and remaining same embodiment 5 is identical.
With the product insulation that obtains 24 hours, detect, solid content is 94%, viscosity is 28cp.With potassium bromate Potassium Bromide method conversion rate of products is measured, transformation efficiency surpasses 97%.Solvability to product makes an experiment simultaneously, in 100g water, adds this polymkeric substance milky emulsion of 2g, stirs gently, is dissolved as clear solution rapidly.
This product application in kp softwood pulp, is processed handsheet, put into air dry oven, measure the paper stock retention in 105 ℃ times dry 5 hours.Through experiment, when adding 0.05% (mass percent) product, the paper stock retention is 80%.
Claims (14)
1. the preparation method of a cationic polyacrylamide polymer is characterized in that comprising the following step: in water, and with acrylamide monomer, polyoxyethylene, quaternized cationic monomer and initiator carry out polyreaction, get final product; Wherein, the viscosity-average molecular weight of polyoxyethylene is 700,000～3,000,000; The structure of acrylamide monomer is following:
Wherein, R is hydrogen, methyl or ethyl; Described initiator is the salt of redox system initiator or REE, and the mass ratio of acrylamide monomer and described polyoxyethylene is 1: 0.02～1: 0.05.
2. preparation method as claimed in claim 1 is characterized in that: in polyreaction, also add viscosity-average molecular weight and be 10000～50000 polyoxyethylene.
3. preparation method as claimed in claim 2 is characterized in that: acrylamide monomer and viscosity-average molecular weight are that 10000～50000 polyoxyethylated mass ratio is 1: 0.5～1: 2.
4. like each described preparation method of claim 1～3, it is characterized in that: described quaternized cationic monomer is a dimethyl diallyl ammonium chloride, and its structure is following:
Perhaps methylacryoyloxyethyl trimethyl ammonium chloride.
5. like each described preparation method of claim 1～3, it is characterized in that: the viscosity-average molecular weight of described polyoxyethylene is 700,000～1,000,000.
6. like each described preparation method of claim 1～3, it is characterized in that: described redox system initiator is persulphate and bisulfite salt system, persulphate and primary amine system, perhaps persulphate and tertiary alkanolamine system.
7. like each described preparation method of claim 1～3, it is characterized in that: in the salt of described REE, described REE is a lanthanon.
8. preparation method as claimed in claim 7 is characterized in that: described lanthanon is cerium, lanthanum or praseodymium, and the salt of described REE is nitrate salt.
9. like each described preparation method of claim 1～3, it is characterized in that: the mass ratio of acrylamide monomer and initiator is 100: 1～20: 1.
10. like each described preparation method of claim 1～3, it is characterized in that: the mass ratio of described acrylamide monomer and water is 1: 4～1: 10.
11. like each described preparation method of claim 1～3, it is characterized in that: the mass ratio of described acrylamide monomer and cationic monomer is 2: 1～10: 1.
12. like each described preparation method of claim 1～3, it is characterized in that: the temperature of described polyreaction is 50 ℃～90 ℃; The time of reaction is 4～6 hours.
13. the cationic polyacrylamide polymer that makes like each described preparation method of claim 1～12.
14. cationic polyacrylamide polymer as claimed in claim 13 is as the application of retention filtration adjuvant.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106111088A (en) * | 2016-07-11 | 2016-11-16 | 常州大学 | A kind of preparation method of silicon dioxide/cationic-type polyacrylamide hybrid sorbents |
| CN112142923A (en) * | 2020-09-29 | 2020-12-29 | 浙江皇马科技股份有限公司 | Preparation method of polycarboxylate superplasticizer macromonomer suitable for normal-temperature polymerization |
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| CN101033593A (en) * | 2007-04-13 | 2007-09-12 | 陕西科技大学 | Method of preparing cationic polyacrylamide remaining and filling assistant agent |
| CN101463109A (en) * | 2008-12-30 | 2009-06-24 | 上海东升新材料有限公司 | Cation polyacrylamide and preparation thereof |
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2011
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Patent Citations (2)
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| CN101033593A (en) * | 2007-04-13 | 2007-09-12 | 陕西科技大学 | Method of preparing cationic polyacrylamide remaining and filling assistant agent |
| CN101463109A (en) * | 2008-12-30 | 2009-06-24 | 上海东升新材料有限公司 | Cation polyacrylamide and preparation thereof |
Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106111088A (en) * | 2016-07-11 | 2016-11-16 | 常州大学 | A kind of preparation method of silicon dioxide/cationic-type polyacrylamide hybrid sorbents |
| CN106111088B (en) * | 2016-07-11 | 2019-03-22 | 常州大学 | A kind of preparation method of silica/cationic-type polyacrylamide hybrid sorbents |
| CN112142923A (en) * | 2020-09-29 | 2020-12-29 | 浙江皇马科技股份有限公司 | Preparation method of polycarboxylate superplasticizer macromonomer suitable for normal-temperature polymerization |
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| CN102585089B (en) | 2014-09-10 |
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Owner name: SHANGHAI EMPEROR OF CLEANING TECH. CO., LTD. Free format text: FORMER OWNER: SHANGHAI PUTAI CHEMICAL INDUSTRIAL CO., LTD. Effective date: 20140211 |
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Effective date of registration: 20140211 Address after: 200437 5F, B, Bai Shu Building, No. 1230, Bei Bei Road, Hongkou District, Shanghai, Zhongshan Applicant after: Shanghai Emperor of Cleaning Tech Co., Ltd. Address before: 200437, building 6, block B, Bai Shu Building, No. 1230, Bei Bei Road, Shanghai, Zhongshan Applicant before: Shanghai Putai Chemical Industrial Co., Ltd. |
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