CN102702401A - Synthesis method of cationic polyacrylamide with ionic degree of 65-78% - Google Patents
Synthesis method of cationic polyacrylamide with ionic degree of 65-78% Download PDFInfo
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- CN102702401A CN102702401A CN2012102322180A CN201210232218A CN102702401A CN 102702401 A CN102702401 A CN 102702401A CN 2012102322180 A CN2012102322180 A CN 2012102322180A CN 201210232218 A CN201210232218 A CN 201210232218A CN 102702401 A CN102702401 A CN 102702401A
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- polyacrylamide
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Abstract
The invention belongs to the field of polymer synthesis and relates to a synthesis method of cationic polyacrylamide with an ionic degree of 65-78%. The synthesis method comprises the steps of: reacting formaldehyde with secondary amine in advance by using a method for pre-preparing a hydroxymethylamine intermediate based on polyacrylamide, formaldehyde and secondary amine as raw materials to generate the hydroxymethylamine intermediate; continuously reacting a polyacrylamide solution with hydroxymethylamine to finally obtain cationic polyacrylamide with the ionic degree of 65-78% under the conditions that formaldehyde is not excessive. With the adoption of the synthesis method, the hydroxymethylation polyacrylamide intermediate liable to crosslinking can be avoided, the occurrence of cross-linking reaction is reduced, a residual formaldehyde amount is reduced, and the cationic degree of the cationic polyacrylamide is improved. The obtained cationic polyacrylamide can be used as an oil extraction auxiliary agent, a papermaking auxiliary agent, an urban sewage treating agent and the like.
Description
Technical field
The present invention relates to a kind of ion degree and be the synthetic of 65% ~ 78% cationic polyacrylamide, comprise the synthetic of cationic polyacrylamide that n n dimetylaniline, diethylamine and piperidines are modified, belong to the Polymer Synthesizing field.
Background technology
Cationic-type polyacrylamide has positive charge density height, good water solubility, limiting viscosity number than advantages such as height, is widely used in industries such as papermaking, oil recovery, WWT and drinking water treatment.Synthesizing cationic type SEPIGEL 305 mainly contains copolymerization method and modification method at present.Copolymerization method synthetic SEPIGEL 305 solid content is higher relatively, but the electrical charge rejection effect between the ionic group makes the HMW of product and macroion degree not get both usually.Methods such as the inverse emulsion polymerization that has developed, inverse suspension polymerization and " water Bao Shui " letex polymerization have usually need be with an organic solvent or inorganic salt content cross high shortcoming, and the cationic monomer cost of material is higher in the copolymerization method.And the modification method can be carried out cationization to the SEPIGEL 305 of different molecular weight, can control cationic degree according to material rate, and cost is lower, and raw material is easy to get.
Because the polymkeric substance viscosity is bigger, in the report, participated in the mass percentage concentration lower usually (1% ~ 8%) of the SEPIGEL 305 of reaction in the past, used amination reagent is generally n n dimetylaniline.Reported in " Treatment of Industrial Water " (the 5th phases of volume 1993 end of the year 13,23 ~ 26 pages) " the synthetic and throwing out of amine methyl SEPIGEL 305 is investigated " that n n dimetylaniline is the cation-modified of 8% SEPIGEL 305 to mass percentage concentration; Reported in " oil and gas chemical industry " (2004 the 33rd volume the 2nd phase, 137 ~ 141 pages) " preparation of SEPIGEL 305 modified flocculant and applied research thereof " that n n dimetylaniline is that the positively charged ion of 1% SEPIGEL 305 transforms to mass percentage concentration; " fld environment protection " (2008 the 18th the 2nd phases of volume; 29 ~ 31 pages) reported that n n dimetylaniline is the cationization of 3% SEPIGEL 305 to mass percent concentration in " the synthetic and flocculating property research of cationic PAM "; Though can access ion degree and be 62% ~ 83% cationic polyacrylamide; But material molar ratio is a SEPIGEL 305: formaldehyde: n n dimetylaniline=1: 1.06: 2.50 ~ 1: 1.40: 2.50; Promptly need formaldehyde excessive and n n dimetylaniline is excessive greatly, be unfavorable for environment protection.
Summary of the invention
The object of the present invention is to provide a kind of generation that reduces crosslinking reaction, reduce the formaldehyde residual volume, improve the cationic degree of product, synthetic ion degree is the novel method of 65% ~ 78% cationic polyacrylamide.
In order to realize goal of the invention; Technical scheme of the present invention is following: under the inexcessive condition of formaldehyde, take pre-prepared methylol amine midbody method; Formaldehyde and secondary amine are reacted generation methylol amine midbody in advance; Then the midbody mixing solutions is added drop-wise in the polyacrylamide solution, SEPIGEL 305 continues to generate amine-methylated SEPIGEL 305 with the reaction of methylol amine, and concrete steps are following:
(1) preparation of methylol amine midbody: formaldehyde solution was mixed afterreaction 30 ~ 40 minutes with secondary amine under 20 ~ 25 ℃ of water bath condition.
(2) in the reactor drum that polyacrylamide solution is housed, adding zero(ppm) water dilutes polyacrylamide solution.Stir with heating condition under, methylol amine midbody is added drop-wise in the reactor drum in 20 ~ 30 minutes, dropwise the back and keep temperature of reaction to continue for 40 ~ 45 ℃ to react 3 ~ 4 hours.Optimal reaction temperature is 45 ℃.
The mass percent concentration of polyacrylamide solution is 8.2% ~ 20% when participating in reaction in the step (2).Used polyacrylamide solution molecular weight ranges is 3 * 10
4~ 100 * 10
4
Reactant molar ratio is a SEPIGEL 305: formaldehyde: secondary amine=1: 1: 1.2.
Described secondary amine is n n dimetylaniline, diethylamine or piperidines.
According to colloid titration products obtained therefrom cationic degree is 65% ~ 78%.
Beneficial effect of the present invention is: through technological improvement, take pre-prepared methylol amine midbody method, reduce the probability that crosslinking reaction takes place, reduce the formaldehyde residual volume; Under the inexcessive condition of formaldehyde; Be SEPIGEL 305: formaldehyde: under the condition of secondary amine mol ratio=1: 1: 1.2; Obtain macroion degree cationic polyacrylamide; The cationic polyacrylamide that not only synthesizes n n dimetylaniline, diethylamine modification realizes that also piperidines transforms the positively charged ion of such SEPIGEL 305, and the cationic degree of products obtained therefrom is 65% ~ 78%.
Embodiment
For the present invention will be described better, it is following to enumerate embodiment:
Embodiment 1
(1) the 13.7g massfraction be 37% formaldehyde solution with the 27.6g massfraction is that 33% dimethylamine solution mixes under 20 ℃ of water bath condition, keeps 20 ℃ of reactions 40 minutes.
(2) be that (molecular weight is 8.0 * 10 for 32% polyacrylamide solution to the 37.5g massfraction is housed
4) reactor drum in add 55.3g zero(ppm) water.Stir with 45 ℃ of conditions under, through constant pressure funnel methylol amine midbody is added drop-wise in the reactor drum in 30 minutes, the massfraction that dropwises the back SEPIGEL 305 is 10%, keeps temperature of reaction to be 45 ℃ and continues to react 3 hours.
According to colloid titration products obtained therefrom cationic degree is 74%.
Embodiment 2
With embodiment 1, the consumption of zero(ppm) water changes 15.4g in the step (2), and (molecular weight is 8.0 * 10 to SEPIGEL 305
4) massfraction of end reaction is 15%, is 68% according to the cationic degree of colloid titration products obtained therefrom.
Embodiment 3
With embodiment 1, the consumption of zero(ppm) water changes 2.1g in the step (2), and (molecular weight is 8.0 * 10 to SEPIGEL 305
4) massfraction of end reaction is 18%, is 65% according to the cationic degree of colloid titration products obtained therefrom.
Embodiment 4
(1) the 13.7g massfraction be 37% formaldehyde solution with the 27.6g massfraction is that 33% dimethylamine solution mixes under 25 ℃ of water bath condition, keeps 25 ℃ of reactions 30 minutes.
(2) be that (molecular weight is 3.0 * 10 for 37% polyacrylamide solution to the 32.3g massfraction is housed
4) reactor drum in add 0.6g zero(ppm) water.Stir with 43 ℃ of conditions under, through constant pressure funnel methylol amine midbody is added drop-wise in the reactor drum in 30 minutes, the massfraction that dropwises the back SEPIGEL 305 is 20%, keeps temperature of reaction to be 43 ℃ and continues to react 4 hours.
Cationic degree according to the colloid titration products obtained therefrom is 72%.
Embodiment 5
(1) the 6.9g massfraction be 37% formaldehyde solution with the 13.8g massfraction is that 33% dimethylamine solution mixes under 25 ℃ of water bath condition, keeps 25 ℃ of reactions 30 minutes.
(2) in reactor drum, adding the 58.8g massfraction is that (molecular weight is 62 * 10 for 10% polyacrylamide solution
4).Stir with 40 ℃ of conditions under, through constant pressure funnel methylol amine midbody is added drop-wise in the reactor drum in 20 minutes, the massfraction that dropwises the back SEPIGEL 305 is 8.2%, keeps temperature of reaction to be 40 ℃ and continues to react 4 hours.
Cationic degree according to the colloid titration products obtained therefrom is 78%.
Embodiment 6
With embodiment 5, the mass percent concentration of SEPIGEL 305 is 10% in the step (2), and molecular weight is 100 * 10
4The massfraction of SEPIGEL 305 end reaction is 8.2%, is 76% according to the cationic degree of colloid titration products obtained therefrom.
Embodiment 7
(1) the 6.9g massfraction is that 37% formaldehyde solution is mixed under 25 ℃ of water bath condition with the 7.4g diethylamine, keeps 25 ℃ of reactions 30 minutes.
(2) be that (molecular weight is 8.0 * 10 for 32% polyacrylamide solution to the 18.8g massfraction is housed
4) reactor drum in add 36.9g zero(ppm) water.Stir with 45 ℃ of conditions under, through constant pressure funnel methylol amine midbody is added drop-wise in the reactor drum in 20 minutes, the massfraction that dropwises the back SEPIGEL 305 is 10%, keeps temperature of reaction to be 45 ℃ and continues to react 3 hours.
The cationic degree that records the product of diethylamine modification according to colloid titration method is 73%.
Embodiment 8
With embodiment 7, secondary amine is a piperidines in the step (1), and consumption is 8.6g.
The cationic degree that records the product of piperidines modification according to colloid titration method is 68%.
Claims (5)
1. an ion degree is the compound method of 65% ~ 78% cationic polyacrylamide, and it is characterized by: concrete steps are following:
(1) preparation of methylol amine midbody: formaldehyde solution was mixed afterreaction 30 ~ 40 minutes with secondary amine under 20 ~ 25 ℃ of water bath condition;
(2) in the reactor drum that polyacrylamide solution is housed, adding zero(ppm) water dilutes polyacrylamide solution; Stir with heating condition under, methylol amine midbody is added drop-wise in the reactor drum in 20 ~ 30 minutes, dropwise the back and keep temperature of reaction to continue for 40 ~ 45 ℃ to react 3 ~ 4 hours; Each reactant mole proportioning is: SEPIGEL 305: formaldehyde: secondary amine=1: 1: 1.2.
2. according to the method for the said cationic polyacrylamide of claim 1, it is characterized in that described secondary amine is respectively n n dimetylaniline, diethylamine or piperidines.
3. according to the method for the said cationic polyacrylamide of claim 1, it is characterized in that the molecular weight ranges of SEPIGEL 305 is 3 * 10
4~ 100 * 10
4
4. according to the method for the said cationic polyacrylamide of claim 1, it is characterized in that the mass percent concentration of polyacrylamide solution is 8.2% ~ 20% when participating in reaction in the step (2).
5. according to the method for the said cationic polyacrylamide of claim 1, it is characterized in that the optimal reaction temperature of step (2) is 45 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231132A (en) * | 2013-06-21 | 2014-12-24 | 中国石油天然气股份有限公司 | Multifunctional oil-repellent polymer and preparation method thereof |
| CN107417816A (en) * | 2017-03-20 | 2017-12-01 | 浙江工商大学 | One kind grafting PAMA and its preparation method and application |
| CN107686151A (en) * | 2017-07-25 | 2018-02-13 | 上海颢羟环保科技有限公司 | A kind of preparation method of water process coagulant |
-
2012
- 2012-07-06 CN CN201210232218.0A patent/CN102702401B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 王薇等: "《阳离子PAM的合成及絮凝性能研究》", 《油气田环境保护》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231132A (en) * | 2013-06-21 | 2014-12-24 | 中国石油天然气股份有限公司 | Multifunctional oil-repellent polymer and preparation method thereof |
| CN107417816A (en) * | 2017-03-20 | 2017-12-01 | 浙江工商大学 | One kind grafting PAMA and its preparation method and application |
| CN107417816B (en) * | 2017-03-20 | 2019-05-14 | 浙江工商大学 | A kind of grafting anionic polyacrylamide and its preparation method and application |
| CN107686151A (en) * | 2017-07-25 | 2018-02-13 | 上海颢羟环保科技有限公司 | A kind of preparation method of water process coagulant |
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