CN103087236A - Method for preparing high-molecular-weight anionic polyacrylamide through ultralow-temperature initiation - Google Patents
Method for preparing high-molecular-weight anionic polyacrylamide through ultralow-temperature initiation Download PDFInfo
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Abstract
The invention provides a method for preparing high-molecular-weight anionic polyacrylamide through ultralow-temperature initiation. According to the invention, a pluralistic initiator and various auxiliary agents are added into an acrylamide aqueous solution; high-purity nitrogen gas is delivered for carrying our aqueous solution polymerization; polymerization and aging are carried out for a certain period of time; an obtained colloid is granulated; a hydrolysis agent is added and mixed into the granules, and hydrolysis is carried out under heating; and granulation, drying, crushing, and sieving are carried out, such that anionic polyacrylamide with a molecular weight exceeding 25000000 is produced. The method has the advantage of smooth polymerization reaction, such that chain growth is facilitated, such that high-molecular-weight product can be obtained. Therefore, the defects of slow heating or non-uniform heating speed caused by single azo initiator are overcome, and an initiation temperature is low.
Description
Technical field
The invention belongs to the chemical synthesis process of water-soluble polyacrylamide polymkeric substance, particularly relate to a kind of method for preparing the ultra high molecular weight anion-type polyacrylamide of relative molecular mass more than 2,500 ten thousand.
Background technology
The high molecular anion type polycrylamide industrial production is comparative maturity, but it is also more difficult that the Industrial products molecular weight is stabilized in more than 2,500 ten thousand.At present domestic and international anionic polyacrylamide gets production technique and mainly is divided into front hydrolysis and two kinds of methods of rear hydrolysis: front hydrolysis adds the hydrolytic reagents such as sodium carbonate, sodium bicarbonate or sodium hydroxide exactly in acrylamide solution, add the various auxiliary agents such as initiator to carry out aqueous solution polymerization after logical nitrogen deoxygenation, the post-heating hydrolysis is completed in polymerization, produce again the method for polyacrylamide through granulation, drying, pulverizing, screening, as open in CN1168894.The advantages such as it is simple that the method has technique, and facility investment is less.But no matter use which kind of initiator system, adopt the sort of initiation method, front hydrolysis all is difficult to obtain high molecular weight polyacrylamide, and general molecular weight is less than 1,700 ten thousand.Rear hydrolysis adds the various auxiliary agents such as initiator to carry out polymerization exactly in acrylamide solution, after aging for some time of polymerization, colloid is added the hydrolytic reagent Hybrid Heating such as sodium hydroxide to be hydrolyzed through granulation, produce again afterwards the method for polyacrylamide through granulation, drying, pulverizing, screening.As open in CNl057059A.Although the method can be produced the higher molecular weight anion-type polyacrylamide, molecular weight also is difficult to surpass 2,000 ten thousand.
Summary of the invention
The object of the invention is to avoid the deficiency of above-mentioned technology, and a kind of method of preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation is provided.
The object of the present invention is achieved like this: add polynary initiator, various auxiliary agent in acrylamide solution, and pass into high pure nitrogen and carry out aqueous solution polymerization.Add the hydrolytic reagent Hybrid Heating to be hydrolyzed through granulation in colloid after aging for some time of polymerization, produce again afterwards molecular weight through granulation, drying, pulverizing, screening and surpass 2,500 ten thousand anionic polyacrylamide.
Purpose of the present invention can also realize like this:
A kind of method of preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation, hydrolytic reagent are solid sodium hydroxide, the weight percent 10-20% of add-on, and add-on can be by the degree of hydrolysis adjustment of polypropylene phthalein amine.Polynary initiator is comprised of oxygenant, reductive agent, multiple water-soluble azo class initiator, and oxygenant is persulphate, and as Potassium Persulphate, Sodium Persulfate, ammonium persulphate, add-on is to 0.0001-0.5% of acrylamide monomer solution weight; Reductive agent is sulphite, and as S-WAT, ammonium sulphite, potassium sulfite, sodium bisulfite, Sodium Metabisulfite, potassium metabisulfite, add-on is to 0.0005-0.25% of acrylamide monomer solution weight; Water-soluble azo class initiator is 2,2 '-azo (2-amidine propane) dihydrochloride, 2,2 '-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, 2,2 '-azo [2-methyl-N-(2-methacrylic acid) propionic acid amide], add-on is to 0.001-0.5% of acrylamide monomer solution weight.The weight ratio of three kinds of azo initiators is 4:4:2.Auxiliary agent urea add-on is to 0.10-0.50% of acrylamide monomer solution weight, the ammoniacal liquor add-on is to 0.005-0.20% of acrylamide monomer solution weight, and the disodium ethylene diamine tetraacetate add-on is to 0.005-0.05% of acrylamide monomer solution weight.
Acrylamide solution concentration in the present invention is controlled at 15-35%, and kick off temperature is 0-5 ℃, and the adiabatic polymerisation time is 1-5h.Aging 1-3h after adiabatic polymerisation is completed adds sodium hydrate solid to mix after preliminary granulation, is heated to hydrolysis temperature and is 85-105 ℃, and hydrolysis time is 2-6h., obtain molecular weight greater than 2,500 ten thousand anion-polyacrylamide through granulation, oven dry, pulverizing, screening.
Compared with prior art, advantage of the present invention is:
1, the initiator system that adopts redox to coordinate with multiple azo initiator, stable polymerization reaction is conducive to the growth of chain, forms high molecular weight products;
2, use uses that proportion of multiple azo initiator in initiator, overcome single azo initiator and heated up slowly or the inhomogeneous shortcoming of heat-up rate, improved the overall performance of initiator system;
3, kick off temperature is low, is conducive to the raising of molecular weight product.
Embodiment
Further illustrate embodiments of the invention below by embodiment.
Embodiment 1
In the cooling batching kettle of the jacketed of 15 cubic metres, add 30% acrylamide 6600kg, pure water 2200kg, urea 5kg under stirring, ammoniacal liquor 6kg, disodium ethylene diamine tetraacetate 400g, 2,2 '-azo (2-amidine propane) dihydrochloride 320g, 2,2 '-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride 320g, 2,2 '-azo [2-methyl-N-(2-methacrylic acid) propionic acid amide] 160g, pass into-10 ℃ of refrigerated water coolings in chuck, adjust 3 ℃ of kick off temperatures.the acrylamide soln for preparing is put into polymeric kettle, pass into high pure nitrogen to remove dissolved oxygen in reaction system, add ammonium persulphate 120g after logical nitrogen 30min, after 5min, add sodium bisulfite 90g, continue to stop nitrogen after logical nitrogen 15min, in still, material begins to heat up, 2.5h rear temperature in the kettle reaches 71.3 ℃, carry out granulation after aging 1 hour, polyacrylamide after granulation is put into the hydrolyzer of 85 ℃ of chuck heating, add solid sodium hydroxide 320kg under stirring, 85 ℃ of hydrolysis 4h of rear maintenance stir, pass through afterwards granulation, dry, pulverize, screening obtains molecular weight 2,694 ten thousand, the high molecular wt. anionic polyacrylamide product of degree of hydrolysis 24.1%.
Embodiment 2
In the cooling batching kettle of the jacketed of 15 cubic metres, add 30% acrylamide 6600kg under stirring, pure water 2200kg,, 5kg urea, ammoniacal liquor 6kg, disodium ethylene diamine tetraacetate 200g, 2,2 '-azo (2-amidine propane) dihydrochloride 300g, 2,2 '-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride 300g, 2,2 '-azo [2-methyl-N-(2-methacrylic acid) propionic acid amide] 150g, pass into-10 ℃ of refrigerated water coolings in chuck, adjust 5 ℃ of kick off temperatures.the acrylamide soln for preparing is put into polymeric kettle, pass into high pure nitrogen to remove dissolved oxygen in reaction system, add ammonium persulphate 150g after logical nitrogen 30min, after 5min, add S-WAT 120g, continue to stop nitrogen after logical nitrogen 15min, in still, material begins to heat up, after 2h, temperature in the kettle reaches 73.2 ℃, carry out granulation after aging 1 hour, polyacrylamide after granulation is put into the hydrolyzer of 85 ℃ of chuck heating, add solid sodium hydroxide 290kg under stirring, 85 ℃ of hydrolysis 4h of rear maintenance stir, pass through afterwards granulation, dry, pulverize, screening obtains molecular weight 2,587 ten thousand, the high molecular wt. anionic polyacrylamide product of degree of hydrolysis 22.5%.
Embodiment 3
In the cooling batching kettle of the jacketed of 15 cubic metres, add 30% acrylamide monomer 6600kg under stirring, deionized water (electricity is led≤2.0 μ s/cm) 2200kg,, urea 5kg, ammoniacal liquor (content 25-28%) 6kg, disodium ethylene diamine tetraacetate 200g, 2,2 '-azo (2-amidine propane) dihydrochloride 300g, 2,2 '-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride 300g, 2,2 '-azo [2-methyl-N-(2-methacrylic acid) propionic acid amide] 150g, pass into-10 ℃ of refrigerated water coolings in chuck, adjust 1.5 ℃ of kick off temperatures.The acrylamide soln for preparing is put into polymeric kettle, pass into high pure nitrogen (purity 〉=99.999%) to remove dissolved oxygen in reaction system, nitrogen flow 〉=80m
3/ h adds Potassium Persulphate 96g after logical nitrogen 30min, after 5min, adds sodium bisulfite 96g, continues to stop nitrogen after logical nitrogen 15min, and in still, material begins to heat up, and after 3h, temperature in the kettle reaches 70.8 ℃ of top temperatures.Polymerization is completed after aging 1 hour and is carried out granulation, polyacrylamide after granulation is put into the hydrolyzer of 85 ℃ of chuck heating, add solid sodium hydroxide 380kg under stirring, 85 ℃ of hydrolysis 4h of rear maintenance stir, obtain molecular weight 2,783 ten thousand, the high molecular wt. anionic polyacrylamide product of degree of hydrolysis 28.9% through granulation, drying, pulverizing, screening afterwards.
Can find out from above-described embodiment, can produce molecular weight according to the present invention greater than 2,500 ten thousand polyacrylamide Industrial products.
Claims (8)
1. the method for a preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation, employing very low temperature causes, adiabatic polymerisation, rear hydrolysis method, it is characterized in that: adding weight concentration in polymeric kettle is 15-35% acrylamide monomer aqueous solution, initiator, auxiliary agent, passes into nitrogen flooding oxygen and carries out adiabatic polymerisation, adds alkali and be hydrolyzed after preliminary granulation, carry out granulation, oven dry after the hydrolysis certain hour, pulverize, sieve, obtain final product.
2. the method for a kind of preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation according to claim 1, it is characterized in that: the present invention adopts initiator to make by persulphate the polynary initiator system that oxidation-reduction initiating system that oxygenant and sulphite or hydrosulphite form as reductive agent and multiple water-soluble azo class initiator form, wherein the add-on of oxygenant is 0.0001-0.5 % of acrylamide monomer aqueous solution weight, reductive agent is 0.0001-0.25% of acrylamide monomer aqueous solution weight, azo-initiator is 0.001-0.50% of acrylamide monomer aqueous solution weight.
3. the method for a kind of preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation according to claim 1, it is characterized in that: preferred oxidant is Potassium Persulphate or Sodium Persulfate or ammonium persulphate, and add-on is 0.0001-0.5 % of acrylamide monomer aqueous solution weight; Reductive agent is sulphite, and as S-WAT, ammonium sulphite, potassium sulfite, sodium bisulfite, Sodium Metabisulfite or potassium metabisulfite, add-on is to 0.0005-0.25% of acrylamide monomer aqueous solution weight; Water-soluble azo class initiator is 2,2 '-azo (2-amidine propane) dihydrochloride, 2,2 '-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride and 2,2 '-azo [2-methyl-N-(2-methacrylic acid) propionic acid amide], add-on is 0.001-0.5% of acrylamide monomer aqueous solution weight.
4. the method for a kind of preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation according to claim 1, it is characterized in that: water-soluble azo initiator adds by a certain percentage, 2,2 '-azo (2-amidine propane) dihydrochloride, 2,2 '-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, 2, the weight ratio of three kinds of azo initiators of 2 '-azo [2-methyl-N-(2-methacrylic acid) propionic acid amide] is 4:4:2.
5. the method for a kind of preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation according to claim 1, it is characterized in that: outer adding assistant is urea, ammoniacal liquor and disodium ethylene diamine tetraacetate, the urea add-on is 0.10-0.50 % of acrylamide monomer aqueous solution weight, the ammoniacal liquor add-on is 0.005-0.20% of acrylamide monomer aqueous solution weight, and the disodium ethylene diamine tetraacetate add-on is 0.005-0.05 % of acrylamide monomer aqueous solution weight.
6. the method for a kind of preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation according to claim 1, it is characterized in that: kick off temperature is 0-5 ℃.
7. the method for a kind of preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation according to claim 1, it is characterized in that: kick off temperature is preferably 1-3 ℃.
8. the method for a kind of preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation according to claim 1, it is characterized in that: hydrolytic reagent is solid sodium hydroxide, the weight percent 10-20% of add-on;
Hydrolysis temperature is 85-105 ℃, and hydrolysis time is 2-6h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739758A (en) * | 2014-01-09 | 2014-04-23 | 安徽天润化学工业股份有限公司 | Preparation method of polyacrylamide for oil field |
| CN104371054A (en) * | 2014-11-07 | 2015-02-25 | 安徽天润化学工业股份有限公司 | Preparation method of high-molecular-weight anionic polyacrylamide |
| CN107474177A (en) * | 2017-09-07 | 2017-12-15 | 成都金弘诺环保科技有限公司 | A kind of copolymerization composition manufacture method of calcium ions modified anion polyacrylamide |
| CN107857837A (en) * | 2017-12-12 | 2018-03-30 | 成都金弘诺环保科技有限公司 | The copolymerization composition manufacture method of calcium-magnesium-containing compound ion modified anion polyacrylamide |
| CN107973877A (en) * | 2017-12-12 | 2018-05-01 | 成都金弘诺环保科技有限公司 | A kind of copolymerization composition manufacture method of the polyacrylamide of modified anion containing magnesium ion |
| CN110294820A (en) * | 2018-03-21 | 2019-10-01 | 上海四奥化工有限公司 | A kind of preparation method of super high molecular weight polyacrylamide |
| CN111547830A (en) * | 2020-05-11 | 2020-08-18 | 爱森（中国）絮凝剂有限公司 | Modified high-efficiency anionic flocculant and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157736A (en) * | 2007-09-28 | 2008-04-09 | 东营顺通化工（集团）有限公司 | Method for preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157736A (en) * | 2007-09-28 | 2008-04-09 | 东营顺通化工（集团）有限公司 | Method for preparing high molecular weight anion type polyacrylamide by ultralow-temperature initiation |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739758A (en) * | 2014-01-09 | 2014-04-23 | 安徽天润化学工业股份有限公司 | Preparation method of polyacrylamide for oil field |
| CN104371054A (en) * | 2014-11-07 | 2015-02-25 | 安徽天润化学工业股份有限公司 | Preparation method of high-molecular-weight anionic polyacrylamide |
| CN107474177A (en) * | 2017-09-07 | 2017-12-15 | 成都金弘诺环保科技有限公司 | A kind of copolymerization composition manufacture method of calcium ions modified anion polyacrylamide |
| CN107857837A (en) * | 2017-12-12 | 2018-03-30 | 成都金弘诺环保科技有限公司 | The copolymerization composition manufacture method of calcium-magnesium-containing compound ion modified anion polyacrylamide |
| CN107973877A (en) * | 2017-12-12 | 2018-05-01 | 成都金弘诺环保科技有限公司 | A kind of copolymerization composition manufacture method of the polyacrylamide of modified anion containing magnesium ion |
| CN110294820A (en) * | 2018-03-21 | 2019-10-01 | 上海四奥化工有限公司 | A kind of preparation method of super high molecular weight polyacrylamide |
| CN110294820B (en) * | 2018-03-21 | 2022-06-24 | 上海四奥化工有限公司 | Preparation method of polyacrylamide with ultrahigh molecular weight |
| CN111547830A (en) * | 2020-05-11 | 2020-08-18 | 爱森（中国）絮凝剂有限公司 | Modified high-efficiency anionic flocculant and preparation method thereof |
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Application publication date: 20130508 |