CN100413895C

CN100413895C - Preparation of high molecular weight anion polyacrylamide

Info

Publication number: CN100413895C
Application number: CNB2004100503882A
Authority: CN
Inventors: 尹海滨; 崔祜徽; 孙艳霞; 程芹; 车吉泰
Original assignee: GUANGHUI CHEMISTRY CO Ltd DALIAN
Current assignee: GUANGHUI CHEMISTRY CO Ltd DALIAN
Priority date: 2004-09-06
Filing date: 2004-09-06
Publication date: 2008-08-27
Anticipated expiration: 2024-09-06
Also published as: CN1746198A

Abstract

The present invention relates to method of preparing anionic polyacrylamide with high molecular weight. 15 to 26% of sodium carbonate as a hydrolytic reagent is added; multiple initiator is composed of an oxidizing agent, a reducing agent, ammonia water and water-solubility azo initiator, wherein the oxidizing agent is persulphate, and the addition of persulphate is from 0.0001 to 0.5%; the reducing agent is sulfite such as sodium sulfite, ammonium sulfite, potassium sulfite, sodium bisulfite, offset sodium sulfite, offset potassium sulfite, and the addition of the reducing agent is from 0.0005 to 0.25%; the reducing agent can be also organic amine such as ethylenediamine, diethylamine, triethylamine, ethanolamine, pyridinium and 4-cyanopyridine, and the addition of the reducing agent is from 0.01 to 1.0%; the water-solubility azo initiator is 2, 2,-azodi(2-methyl propyl ether) dihydrochloride, 4, 4,-azobis(4-cyano pentanoic acid) with 0.001-0.5%, and the addition of the water-solubility azo initiator is from 0.001 to 0.5%; the addition of the ammonia water is from 0.005 to 0.20%; a chain transferring agent is beta-dimethybutylcyan, and the addition of the chain transferring agent is from 0.005 to 0.20%. initiation temperature is from 5 to 25 DEG C, adiabatic polymerization time is from 2 to 6h, and the hydrolyzation is sustained for 3 to 5h; anionic polyacrylamide whose molecular weight is larger than 2000 million, solubility is good and insoluble matter content is low is obtained by the steps of granulating, drying and pulverization.

Description

The preparation method of high molecular anion type polycrylamide

The invention belongs to the synthetic field of water-soluble polymers, particularly relate to a kind of relative molecular mass 2 * 10 ⁷The preparation method of above ultra high molecular weight anion-type polyacrylamide.

At present, the preparation high molecular anion type polycrylamide mainly contains following three kinds of methods both at home and abroad: first method, carry out the aqueous solution polymerization hydrolysis and make " single stage method " as in acrylamide solution, adding various auxiliary agents such as hydrolytic reagent such as yellow soda ash or sodium hydroxide and initiator, though this method is simple, can not get high molecular weight polyacrylamide.And for example CN1168894 is open, in acrylamide solution, add various auxiliary agents such as yellow soda ash and polynary initiator, and the pH value of feeding carbonic acid gas controlled polymerization system, carry out reheat hydrolysis behind the adiabatic polymerisation, obtain product through granulation, oven dry, pulverizing then, though this method technology is simple, molecular weight product not high (＜1,600 ten thousand) is used CO ₂Regulate pH value, make troubles to suitability for industrialized production; Second method, open as JP57202308, CN1057059A, CN1057057A, CN1498908A, in acrylamide solution, add various auxiliary agents such as initiator and carry out polymerization, " two-step approach " that then colloid is added the first polymerization posthydrolysis of hydrolytic reagent Hybrid Heating hydrolysis such as sodium hydroxide through granulation, though this method can be prepared high molecular anion type polycrylamide, but there is the equipment complexity, technical process is long, production cycle is long, energy consumption is big, produce a large amount of ammonia flavors, the shortcoming of serious environment pollution; The third method, open as CN1114628C, adding yellow soda ash and initiator etc. in acrylamide solution carries out aqueous solution adiabatic polymerisation and polymeric colloid is moved on to is hydrolyzed in the microwave field and makes, though this method obtains the high molecular weight anionic polyacrylamide, but owing to increased the microwave equipment investment, again colloid is moved on in the microwave field, many procedures, industrial production is subjected to certain limitation.

The object of the present invention is to provide a kind of preparation method of high molecular anion type polycrylamide, it can remedy the deficiency of aforesaid method.

The present invention adopts " single stage method " that adds hydrolytic reagent polymerization hydrolysis, just adds hydrolytic reagent, polynary initiator, chain propagation agent, quick-dissolving agent in acrylamide solution, and the feeding high pure nitrogen carries out aqueous solution polymerization.

Hydrolytic reagent among the present invention is the weight percent 15-26% of yellow soda ash add-on, and add-on can be by adjusting arbitrarily in HYDROLYSIS OF POLYACRYLAMIDE AND ITS COPOLYMERS degree 20～35% scopes.Polynary initiator is made up of oxygenant, reductive agent, ammoniacal liquor, water-soluble azo class initiator, and oxygenant is a persulphate, and as Potassium Persulphate, Sodium Persulfate, ammonium persulphate, add-on is to 0.0001～0.5% of acrylamide monomer weight; Reductive agent is a sulphite, as S-WAT, ammonium sulphite, potassium sulfite, sodium bisulfite, Sodium Metabisulfite, potassium metabisulfite, add-on is to 0.0005～0.25% of acrylamide monomer weight, reductive agent is organic amine also, as quadrol, diethylamine, triethylamine, thanomin, pyridine, 4-cyanopyridine, add-on is 0.01～1.0%; Water-soluble azo class initiator is 2,2 '-two (the 2-methyl-propyl amidine) dihydrochlorides, 4,4 of azo '-azo two (4-cyanopentanoic acid), add-on is 0.001～0.5%; The ammoniacal liquor add-on is that 0.005～0.20% chain-transfer agent is β-dimethylamino butyronitrile, and add-on is 0.005～0.20%; Quick-dissolving agent is a urea, and add-on is 0.10～0.50%.

Acrylamide solution concentration among the present invention is controlled at 15～35%, and kick off temperature is 5～25 ℃, and the adiabatic polymerisation time is 2～6h.Adiabatic polymerisation is finished post-heating and is warming up to 85～110 ℃ of hydrolysis 3～5h, obtains molecular weight＞2,000 ten thousand, the capable polyacrylamide of the negatively charged ion that solvability is good through granulation, oven dry, pulverizing.

Characteristics of the present invention are: (one) does not need the pH value of controlled polymerization system; (2) owing to adopt new polynary initiator system, make stable polymerization reaction, help the growth of chain; (3) owing to added chain propagation agent, can obtain high molecular weight products; (4) owing to added ammoniacal liquor, in polymerization process, produce nitrogen three acrylamides, it be reductive agent be again chain-transfer agent, also add quick-dissolving agent urea, make the product solvability good, insolubles content is low.

Further specify the present invention below by embodiment.

Embodiment 1, the 126.4kg deionized water is put into still, under agitation add 9.1kg yellow soda ash successively, the 51kg acrylamide, 2kg urea, 1% ammoniacal liquor 2kg, 2% diethylamine 1.5kg, 2% β-dimethylamino butyronitrile 2kg, 1% azo (4-cyanopentanoic acid) 1kg, adjust 16 ℃ of kick off temperatures, feed nitrogen to remove dissolved oxygen in the reaction system, add 0.1% ammonium persulphate 5kg after feeding 30min, crossing the interior material of 20min still approximately begins to be clamminess, and begin to heat up, temperature in the kettle reaches 87.4 ℃ behind the 3h, heat temperature raising to 95 ± 5 ℃, hydrolysis 3h, granulation then, oven dry, pulverizing obtains molecular weight 2,180 ten thousand, the HPAM of insolubles content 0.08%.

Embodiment 2, the 114.5kg deionized water is put into still, under agitation ` adds 9.5kg yellow soda ash successively, the 51kg acrylamide, 3kg urea, 1% ammoniacal liquor 2.5kg, 2% diethanolamine 1.5kg, 2% β-dimethylamino butyronitrile 2kg, 1% azo (4-cyanopentanoic acid) 1kg, adjust 16 ℃ of kick off temperatures, feed nitrogen to remove dissolved oxygen in the reaction system, add 0.1% ammonium persulfate aqueous solution 10kg after feeding 30min, crossing the interior material of 23min still approximately begins to be clamminess, simultaneous temperature rises, temperature in the kettle reaches 84 ℃ behind the polyase 13 h, heat temperature raising to 95 ± 5 ℃, hydrolysis 3h, granulation then, oven dry, pulverizing obtains molecular weight 2,073 ten thousand, the HPAM of insolubles content 0.12%.

Embodiment 3, the 126.5kg deionized water is put into still, under agitation add 9.5kg yellow soda ash successively, the 51kg acrylamide, 3kg urea, 1% ammoniacal liquor 2.5kg, 2%4-cyanopyridine 1.5kg, 2% β-dimethylamino butyronitrile 2.5kg, 1% azo (4-cyanopentanoic acid) 1kg, adjust 15 ℃ of kick off temperatures, feed nitrogen to remove dissolved oxygen in the reaction system, add 0.1% persulfate aqueous solution 2.5kg after feeding 30min, the interior material of still begins to be clamminess after crossing 26min approximately, simultaneous temperature rises, temperature in the kettle reaches 83 ℃ behind the polymerization 4h, heat temperature raising to 95 ± 5 ℃, hydrolysis 3h, granulation then, oven dry, pulverizing obtains molecular weight 2,230 ten thousand, the HPAM of insolubles content 0.07%.

Embodiment 4, the 126.6kg deionized water is put into still, under agitation add 10.6kg yellow soda ash successively, the 51kg acrylamide, 3kg urea, 1% ammoniacal liquor 2kg, 2% diethylamine 1kg, 2% pyridine 0.8kg, 2% β-dimethylamino butyronitrile 2kg, 1% azo (4-cyanopentanoic acid) 1kg, adjust 15 ℃ of kick off temperatures, feed nitrogen to remove dissolved oxygen in the reaction system, add 0.1% persulfate aqueous solution 3kg after feeding 30min, the interior material of still begins to be clamminess after crossing 30min inductive phase, simultaneous temperature rises, temperature in the kettle reaches 85 ℃ behind the polymerization 4h, heat temperature raising to 95 ± 5 ℃, hydrolysis 3h, granulation then, oven dry, pulverizing obtains molecular weight 2,317 ten thousand, the HPAM of insolubles content 0.06%.

Comparative example 1, the 128.75kg deionized water is put into still, under agitation add 9.5kg yellow soda ash successively, the 51kg acrylamide, 2kg urea, 1% ammoniacal liquor 2kg, 2% sodium bisulfite 0.75kg, 2% β-dimethylamino butyronitrile 2kg, 1% azo (4-cyanopentanoic acid) 1kg, adjust 16 ℃ of kick off temperatures, feed nitrogen to remove dissolved oxygen in the reaction system, add 1% Potassium Persulphate 5kg after feeding 30min, crossing the interior material of 20min still approximately begins to be clamminess, and begin to heat up, 2.5h back temperature in the kettle reaches 87 ℃, heat temperature raising to 95 ± 5 ℃, hydrolysis 3h, granulation then, oven dry, pulverizing obtains molecular weight 1,289 ten thousand, the HPAM of insolubles content 0.23%.

Comparative example 2, the 130.75kg deionized water is put into still, under agitation add 9.5kg yellow soda ash successively, the 51kg acrylamide, 2kg urea, 1% ammoniacal liquor 2kg, 2% potassium metabisulfite 0.75kg, 1% azo (4-cyanopentanoic acid) 1kg, adjust 16 ℃ of kick off temperatures, feed nitrogen to remove dissolved oxygen in the reaction system, add 1% ammonium persulfate aqueous solution 3kg after feeding 30min, crossing the interior material of 20min still inductive phase begins to be clamminess, simultaneous temperature rises, temperature in the kettle reaches 84 ℃ behind the polymerization 2.5h, heat temperature raising to 95 ± 5 ℃, hydrolysis 3h, granulation then, oven dry, pulverizing obtains molecular weight 9,480,000, the HPAM of insolubles content 0.18%.

Claims

1. the preparation method of a high molecular anion type polycrylamide, adopt low temperature to cause the adiabatic polymerisation mode, adding weight concentration in polymeric kettle is 15～35% acrylamide monomer aqueous solution, hydrolytic reagent, initiator and auxiliary agent, feed nitrogen flooding oxygen and carry out adiabatic polymerisation, be hydrolyzed then, granulation, oven dry and pulverizing obtain final product, kick off temperature is 5～25 ℃, and hydrolytic reagent is Na ₂CO ₃, the weight percent of add-on is 15-26%, and adjusts in degree of hydrolysis 20～35% scopes according to product; It is characterized in that: the multicomponent system that the oxidation that the present invention adopts initiator to be made up of organic amine reductive agent and persulfate oxidation agent---reduction initiating system and ammoniacal liquor and water-soluble azo class initiator are formed, wherein the add-on of oxygenant is 0.0001～0.5% of an acrylamide monomer weight, organic amine reductive agent add-on is the 0.01-1.0% of acrylamide monomer weight, and the azo-initiator add-on is 0.001～0.50% of an acrylamide monomer weight; Described auxiliary agent has chain propagation agent β-dimethylamino butyronitrile, and add-on is 0.005～0.20% of an acrylamide monomer weight; The ammoniacal liquor add-on is 0.005～0.20% of an acrylamide monomer weight; Polymerization time is 2～6h, and hydrolysis temperature is 85～110 ℃, and hydrolysis time is 3～5h.

2. preparation method as claimed in claim 1 is characterized in that: oxygenant is Potassium Persulphate, Sodium Persulfate or ammonium persulphate; The organic amine reductive agent is quadrol, diethylamine, triethylamine, thanomin, pyridine or 4-cyanopyridine; Water-soluble azo class initiator is 2,2 '-two (the 2-methyl-propyl amidine) dihydrochlorides or 4,4 of azo '-azo two (4-cyanopentanoic acid).