CN102702401B - 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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- CN102702401B CN102702401B CN201210232218.0A CN201210232218A CN102702401B CN 102702401 B CN102702401 B CN 102702401B CN 201210232218 A CN201210232218 A CN 201210232218A CN 102702401 B CN102702401 B CN 102702401B
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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 dimethylamine, diethylamine and piperidines modify, belong to Polymer Synthesizing field.
Background technology
Cationic-type polyacrylamide has that positive charge density is high, good water solubility, limiting viscosity number be compared with advantages of higher, is widely used in the industries such as papermaking, oil recovery, sewage disposal and drinking water treatment.Synthesizing cationic type polyacrylamide mainly contains copolymerization method and modification method at present.The synthetic polyacrylamide solid content of copolymerization method is relatively high, but electrical charge rejection effect between ionic group makes the high molecular of product and high ionization degree not get both conventionally.The methods such as inverse emulsion polymerization, inverse suspension polymerization and " water Bao Shui " letex polymerization of having developed conventionally have need to be with an organic solvent or inorganic salt content cross the shortcomings such as high, and in copolymerization method, cationic monomer cost of material is higher.And modification method can be carried out cationization to the polyacrylamide of different molecular weight, can be according to material rate control cationic degree, and cost is lower, and raw material is easy to get.
Because polymkeric substance viscosity is larger, in report, participated in mass percentage concentration lower (1% ~ 8%) conventionally of the polyacrylamide of reaction in the past, amination reagent used is generally dimethylamine.In " Treatment of Industrial Water " (1993 the 5th phases of the volume end of the year 13,23 ~ 26 pages) " the synthetic and throwing out of amine methyl polyacrylamide is investigated ", report the cation-modified of polyacrylamide that dimethylamine is 8% to mass percentage concentration; The positively charged ion of having reported the polyacrylamide that dimethylamine is 1% to mass percentage concentration in " oil and gas chemical industry " (the 33rd the 2nd phase of volume in 2004,137 ~ 141 pages) " preparation of polyacrylamide modified flocculant and applied research thereof " transforms; " oil-gas field environment protection " (the 18th the 2nd phase of volume in 2008; 29 ~ 31 pages) report the cationization of the polyacrylamide that dimethylamine is 3% to mass percent concentration in " the synthetic and flocculating property research of cationic PAM "; although can obtain ion degree and be 62% ~ 83% cationic polyacrylamide; but material molar ratio is polyacrylamide: formaldehyde: dimethylamine=1: 1.06: 2.50 ~ 1: 1.40: 2.50; need that formaldehyde is excessive and dimethylamine 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 formaldehyde residual volume, improve the cationic degree of product, the novel method of the cationic polyacrylamide that synthetic ion degree is 65% ~ 78%.
In order to realize goal of the invention, technical solution of the present invention is as follows: under the inexcessive condition of formaldehyde, take pre-prepared methylol amine intermediate method, formaldehyde and secondary amine are reacted to generation methylol amine intermediate in advance, then intermediate mixing solutions is added drop-wise in polyacrylamide solution, polyacrylamide continues to react with methylol amine generation Amino-methylated Polyacrylamide, and concrete steps are as follows:
(1) preparation of methylol amine intermediate: formaldehyde solution is reacted 30 ~ 40 minutes after mixing under 20 ~ 25 ℃ of water bath condition with secondary amine.
(2) add distilled water that polyacrylamide solution is diluted to being equipped with in the reactor of polyacrylamide solution.Stir and heating condition under, methylol amine intermediate is added drop-wise in reactor in 20 ~ 30 minutes, dropwise 40 ~ 45 ℃ of rear maintenance temperature of reaction and continue to react 3 ~ 4 hours.Optimal reaction temperature is 45 ℃.
While participating in reaction in step (2), the mass percent concentration of polyacrylamide solution is 8.2% ~ 20%.Polyacrylamide solution molecular weight ranges used is 3 × 10
4~ 100 × 10
4.
Reactant molar ratio is polyacrylamide: formaldehyde: secondary amine=1: 1: 1.2.
Described secondary amine is dimethylamine, diethylamine or piperidines.
Be 65% ~ 78% according to colloid titration products obtained therefrom cationic degree.
Beneficial effect of the present invention is: by technological improvement, take pre-prepared methylol amine intermediate method, reduce the probability that crosslinking reaction occurs, reduce formaldehyde residual volume; Under the inexcessive condition of formaldehyde, be polyacrylamide: formaldehyde: secondary amine mol ratio=1: under the condition of 1: 1.2, obtain macroion degree cationic polyacrylamide, not only synthesize the cationic polyacrylamide of dimethylamine, diethylamine modification, also realize piperidines the positively charged ion of such polyacrylamide is transformed, the cationic degree of products obtained therefrom is 65% ~ 78%.
Embodiment
For the present invention will be described better, enumerate embodiment as follows:
Embodiment 1
(1) dimethylamine solution that the formaldehyde solution that 13.7g massfraction is 37% is 33% with 27.6g massfraction 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 37.5g massfraction is housed
4) reactor in add 55.3g distilled water.Stir and 45 ℃ of conditions under, by constant pressure funnel, methylol amine intermediate is added drop-wise in reactor in 30 minutes, the massfraction that dropwises rear polyacrylamide is 10%, keeps temperature of reaction to be 45 ℃ and continues to react 3 hours.
Be 74% according to colloid titration products obtained therefrom cationic degree.
Embodiment 2
With embodiment 1, in step (2), the consumption of distilled water changes 15.4g into, and (molecular weight is 8.0 × 10 to polyacrylamide
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, in step (2), the consumption of distilled water changes 2.1g into, and (molecular weight is 8.0 × 10 to polyacrylamide
4) massfraction of end reaction is 18%, is 65% according to the cationic degree of colloid titration products obtained therefrom.
Embodiment 4
(1) dimethylamine solution that the formaldehyde solution that 13.7g massfraction is 37% is 33% with 27.6g massfraction 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 32.3g massfraction is housed
4) reactor in add 0.6g distilled water.Stir and 43 ℃ of conditions under, by constant pressure funnel, methylol amine intermediate is added drop-wise in reactor in 30 minutes, the massfraction that dropwises rear polyacrylamide is 20%, keeps temperature of reaction to be 43 ℃ and continues to react 4 hours.
Be 72% according to the cationic degree of colloid titration products obtained therefrom.
Embodiment 5
(1) dimethylamine solution that the formaldehyde solution that 6.9g massfraction is 37% is 33% with 13.8g massfraction mixes under 25 ℃ of water bath condition, keeps 25 ℃ of reactions 30 minutes.
(2) be that (molecular weight is 62 × 10 for 10% polyacrylamide solution to adding 58.8g massfraction in reactor
4).Stir and 40 ℃ of conditions under, by constant pressure funnel, methylol amine intermediate is added drop-wise in reactor in 20 minutes, the massfraction that dropwises rear polyacrylamide is 8.2%, keeps temperature of reaction to be 40 ℃ and continues to react 4 hours.
Be 78% according to the cationic degree of colloid titration products obtained therefrom.
Embodiment 6
With embodiment 5, in step (2), the mass percent concentration of polyacrylamide is 10%, and molecular weight is 100 × 10
4.The massfraction of polyacrylamide end reaction is 8.2%, is 76% according to the cationic degree of colloid titration products obtained therefrom.
Embodiment 7
(1) formaldehyde solution that 6.9g massfraction is 37% is mixed under 25 ℃ of water bath condition with 7.4g diethylamine, keeps 25 ℃ of reactions 30 minutes.
(2) be that (molecular weight is 8.0 × 10 for 32% polyacrylamide solution to 18.8g massfraction is housed
4) reactor in add 36.9g distilled water.Stir and 45 ℃ of conditions under, by constant pressure funnel, methylol amine intermediate is added drop-wise in reactor in 20 minutes, the massfraction that dropwises rear polyacrylamide 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, in step (1), secondary amine is piperidines, 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. a synthetic method for the cationic polyacrylamide that ion degree is 65% ~ 78%, is characterized by: concrete steps are as follows:
(1) preparation of methylol amine intermediate: formaldehyde solution is reacted 30 ~ 40 minutes after mixing under 20 ~ 25 ℃ of water bath condition with secondary amine;
(2) add distilled water that polyacrylamide solution is diluted to being equipped with in the reactor of polyacrylamide solution; Stir and heating condition under, methylol amine intermediate is added drop-wise in reactor in 20 ~ 30 minutes, dropwise 40 ~ 45 ℃ of rear maintenance temperature of reaction and continue to react 3 ~ 4 hours; Each reactant mole proportioning is: polyacrylamide: formaldehyde: secondary amine=1: 1: 1.2.
2. according to the method for cationic polyacrylamide described in claim 1, it is characterized in that, described secondary amine is respectively dimethylamine, diethylamine or piperidines.
3. according to the method for cationic polyacrylamide described in claim 1, it is characterized in that, the molecular weight ranges of polyacrylamide is 3 × 10
4~ 100 × 10
4.
4. according to the method for cationic polyacrylamide described in claim 1, it is characterized in that, while participating in reaction in step (2), the mass percent concentration of polyacrylamide solution is 8.2% ~ 20%.
5. according to the method for cationic polyacrylamide described in claim 1, it is characterized in that, the optimal reaction temperature of step (2) is 45 ℃.
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| 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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Non-Patent Citations (2)
| Title |
|---|
| 《阳离子PAM的合成及絮凝性能研究》;王薇等;《油气田环境保护》;20081231;第18卷(第2期);29-31 * |
| 王薇等.《阳离子PAM的合成及絮凝性能研究》.《油气田环境保护》.2008,第18卷(第2期),29-31. |
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