CN102796222B - Synthesis method of hydrophobically associated polyacrylamide - Google Patents
Synthesis method of hydrophobically associated polyacrylamide Download PDFInfo
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- CN102796222B CN102796222B CN201210311190.XA CN201210311190A CN102796222B CN 102796222 B CN102796222 B CN 102796222B CN 201210311190 A CN201210311190 A CN 201210311190A CN 102796222 B CN102796222 B CN 102796222B
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Abstract
The invention belongs to the field of water-soluble high molecular materials, and particularly relates to a synthesis method of hydrophobically associated polyacrylamide, which comprises the following steps: preparing a polyacrylamide reverse emulsion, modifying the polyacrylamide reverse emulsion, and introducing long-chain alkyl hydrophobic group and cation group to prepare a hydrophobically associated polyacrylamide reverse emulsion, thereby preparing nonionic, anionic, cationic or amphoteric hydrophobically associated polyacrylamide reverse emulsion series products. The products can be widely used in the fields of traditional polyacrylamide with poor properties, and especially in the aspects of oilfield assistants, water treatment, paper making retention, cosmetics and the like. Since the product form is still reverse emulsion, the hydrophobically associated polyacrylamide is convenient to use, has the advantage of low cost, can easily implement industrial production, and has wide application prospects.
Description
Technical field
The present invention relates to water-soluble high-molecular material field, particularly a kind of hydrophobic association polyacrylamide.
Background technology
Current domestic widely used polyacrylamide carries out displacement of reservoir oil operation and has obtained good effect in low temperature less salt oil field, but while using under the environment of high temperature and high salt, fall flat, the temperature resistant antisalt performance that therefore improves polyacrylamide amine product is very necessary.Hydrophobic association polyacrylamide refers to by acrylamide and the hydrophobic monomer copolymerization that contains two keys or by chemical modification, on polyacrylamide segment, introduces a kind of polymkeric substance that a small amount of hydrophobic grouping obtains.In the aqueous solution, uncompatibility because of hydrophobic grouping and water, between hydrophobic grouping, occur assemble or associate, make a macromole ball of string in the aqueous solution, form reversible space reticulated structure, be similar to supramolecular aggregation, not only make the viscosity of this polymkeric substance significantly improve, also make the temperature resistant antisalt ability of this polymkeric substance greatly strengthen.
< < chemical industry environmental protection > > discloses the preparation of amphiprotic polyacrylamide reversed-phase emulsion December in 2011 on 31 6 phase of volume paper, do not relate to the synthetic method of hydrophobically modified polyacrylamide reversed-phase emulsion.CN101132756A patent discloses acceptable composition in a kind of cosmetic that comprises one or more hydrophobically modified polyacrylamides, is that the amide group of polyacrylamide turns amido with hydrophobic amine and reacts, to generate the polyacrylamide of hydrophobically modified.Wherein said hydrophobic amine is selected from C
6-C
22group that the siloxanes of alkylamine and aminofunctional the forms secondary amine used from this patent is different, and all different in reaction conditions, reaction mechanism from this patent.
The main production method of hydrophobic association polyacrylamide is micella copolymerization and reversed-phase emulsion/Reversed Phase Micro Emulsion Copolymerization at present, these two kinds of methods are except all being used expensive hydrophobic monomer, also has following characteristics: the product of micella copolymerization be take dry powder form as main, it is long that this series products in use exists dissolution time, needs to be equipped with the special drawbacks such as dry powder dissolver; Reversed-phase emulsion/Reversed Phase Micro Emulsion Copolymerization is water in oil external phase system, is characterized in " instant ", easy to use, but exists the relative molecular mass of product lower, the more high deficiency of production cost.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of synthetic method of simple and safe, hydrophobic association polyacrylamide that production cost is low is provided.
A synthetic method for hydrophobic association polyacrylamide, is characterized in that comprising the steps:
1, the preparation of reversed phase latex of polyacrylamide
In the container of agitator, thermometer, spherical condenser and import and export of nitrogen is housed, adding successively mass concentration is the acrylamide solution of 20-50%, by needed negatively charged ion degree, add the 2-acrylamide-2-methylpro panesulfonic acid that accounts for acrylamide molar weight 0-50%, the pH value of the aqueous sodium hydroxide solution regulation system that is 10-50% by mass concentration is 4-7, then adds and account for the sorbitan mono-laurate of monomer total mass 20-50% and polyoxyethylene octylphenol ether as emulsifying agent.Open and stir, until reactant mixes, then add the hexanaphthene or the solvent oil that account for acrylamide solution volume 60-120%, logical nitrogen or carbon dioxide flooding oxygen, control temperature is 5-35 ℃, stir 20-40min, chemistry causes or UV-irradiation initiated polymerization, makes the reversed phase latex of polyacrylamide of different anions degree.
In principal character step 1, if the 2-acrylamide-2-methylpro panesulfonic acid adding is 0, do not add anionic copolymerization monomer, can make non-ionic polyacrylamide reversed-phase emulsion.
2, the preparation of hydrophobic functional group reagent
Measure a kind of first with acid moieties neutralization in the di-n-propylamine, Di-n-Butyl Amine, two n-amylamines of certain volume, more in molar ratio for 0.8-1.2 adds formalin, control temperature of reaction at 20-50 ℃, make hydrophobic functional group reagent after reacting 4-6h.
In principal character step 2, acid used is a kind of in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, carbonic acid.
3, the preparation of Cationic functional groups reagent
33% dimethylamine agueous solution is added in the container of belt stirrer, for 0.8-1.2, add paraformaldehyde in molar ratio in batches, control temperature of reaction at 20-50 ℃.After paraformaldehyde dissolves completely, add the stablizer dicyandiamide of paraformaldehyde quality 5-20% and Sodium Metabisulfite to stir, after all dissolving, it makes Cationic functional groups reagent.
4, the preparation of hydrophobic association polyacrylamide reversed-phase emulsion
The reversed phase latex of polyacrylamide that step 1 makes adds in the container of belt stirrer, and the 0.5-2mol% hydrophobic functional group reagent that the total monomer amount that accounts for that step 2 is made is slowly adds in above-mentioned reversed-phase emulsion, temperature of reaction 20-40 ℃, reaction times 4-6h; Then slowly add and account for the Cationic functional groups reagent that the step 3 of total monomer amount 0-50mol% makes, temperature of reaction 20-40 ℃, reaction times 4-6h, makes hydrophobic association polyacrylamide reversed-phase emulsion.
In principal character step 4, can synthesize lower several prods as required:
(1) the non-ionic polyacrylamide reversed-phase emulsion that does not add anionic copolymerization monomer to make in step 1, only adds the modification of hydrophobic functional group reagent, does not add Cationic functional groups reagent, can make hydrophobic association non-ionic polyacrylamide reversed-phase emulsion.
(2) the anionic polyacrylamide reversed-phase emulsion that adds anionic copolymerization monomer to make in step 1, only adds the modification of hydrophobic functional group reagent, does not add Cationic functional groups reagent, can make hydrophobic association anionic polyacrylamide reversed-phase emulsion.
(3) the non-ionic polyacrylamide reversed-phase emulsion that does not add anionic copolymerization monomer to make in step 1, adds the modification of hydrophobic functional group reagent, then adds the modification of Cationic functional groups reagent, can make hydrophobic association cationic polyacrylamide reversed-phase emulsion.
(4) the anionic polyacrylamide reversed-phase emulsion that adds anionic copolymerization monomer to make in step 1, adds the modification of hydrophobic functional group reagent, then adds the modification of Cationic functional groups reagent, can make hydrophobic association amphiprotic polyacrylamide reversed-phase emulsion.
The present invention adopts reversed emulsion polymerization to obtain nonionic or anionic polyacrylamide reversed-phase emulsion product, add afterwards hydrophobic functional group reagent, or add again Cationic functional groups reagent to carry out modification to emulsion, thereby prepare nonionic, negatively charged ion, positively charged ion or both sexes hydrophobic association polyacrylamide reversed-phase emulsion series product, product can be widely used in conventional polypropylene acid amides but the field of poor performance, particularly at aspects such as oilfield additive, water treatment, Papermaking Retention and makeup.
Embodiment
Provide four most preferred embodiments of the present invention below:
Example one
1, the acrylamide solution, 30g Arlacel-20 and the 7.5g polyoxyethylene octylphenol ether that in the 1000ml four-hole boiling flask with agitator, thermometer, spherical condenser and import and export of nitrogen, add successively 300g42.5%, stir after 10min, add hexanaphthene 350ml, control 25 ℃ of bath temperatures and stir 30min, logical high pure nitrogen is with the oxygen in the system of removing simultaneously.The aqueous solution of sodium bisulfite 0.8ml that adds 1% ammonium persulfate aqueous solution 0.2ml and 5% causes, and rises to after top temperature, and 60 ℃ of insulation reaction 1h, make non-ionic polyacrylamide reversed-phase emulsion.
2, at 100ml, in the there-necked flask with agitator and thermometer, add Di-n-Butyl Amine 20ml, first add the hydrochloric acid neutralization of 13ml, then add 3.2g paraformaldehyde, control bath temperature 40 ℃ of left and right, after reaction 5h, make hydrophobic functional group reagent.
3, get non-ionic polyacrylamide reversed-phase emulsion 30ml in 100ml in the there-necked flask with agitator and thermometer, control temperature 25 ℃ of left and right, drip hydrophobic functional group reagent 1ml, be warming up to 40 ℃, reaction 5h, makes hydrophobic association non-ionic polyacrylamide reversed-phase emulsion.
Example two
1, the acrylamide solution that adds successively 300g42.5% in the 1000ml four-hole boiling flask with agitator, thermometer, spherical condenser and import and export of nitrogen, 30g Arlacel-20 and 7.5g polyoxyethylene octylphenol ether, after stirring, add 74.35g2-acrylamide-2-methylpro panesulfonic acid, the pH value of the aqueous sodium hydroxide solution regulation system with 15% is 5.0.Stir after 20min, add solvent oil 350ml, control 25 ℃ of bath temperatures and stir 30min, logical carbonic acid gas is with the oxygen in the system of removing simultaneously.Add st-yrax (3mg is in 0.3ml Glacial acetic acid), by the high voltage mercury lamp radiation system of 250W, make it to cause, after rising to top temperature, 60 ℃ of insulation reaction 1h, make anionic polyacrylamide reversed-phase emulsion.
2, at 100ml, in the there-necked flask with agitator and thermometer, add Di-n-Butyl Amine 20ml, first add the neutralization of 6.5ml acetic acid, then add 37% formalin 8.5ml, control bath temperature 40 ℃ of left and right, after reaction 5h, make hydrophobic functional group reagent.
3, get anionic polyacrylamide reversed-phase emulsion 30ml in 100ml in the there-necked flask with agitator and thermometer, control temperature 25 ℃ of left and right, drip hydrophobic functional group reagent 1ml, be warming up to 40 ℃, reaction 5h, makes hydrophobic association anionic polyacrylamide reversed-phase emulsion.
Example three
1, with 1 in example one.
2, with 2 in example one.
3, at 100ml, in the there-necked flask with agitator and thermometer, add 33% dimethylamine agueous solution 70ml, add paraformaldehyde 12.5g in batches, control bath temperature 30 ℃ of left and right, after solid dissolves completely, add 1g dicyandiamide and 1g Sodium Pyrosulfite further to dissolve completely, make Cationic functional groups reagent.
4, get non-ionic polyacrylamide reversed-phase emulsion 30ml in 100ml in the there-necked flask with agitator and thermometer, control temperature 25 ℃ of left and right, first drip hydrophobic functional group reagent 1ml, drip again Cationic functional groups reagent 20ml, 1h dropwises, be warming up to 40 ℃, reaction 5h, makes hydrophobic association cationic polyacrylamide reversed-phase emulsion.
Example four
1, with 1 in example two.
2, with 2 in example two.
3, at 100ml, in the there-necked flask with agitator and thermometer, add 33% dimethylamine agueous solution 70ml, add paraformaldehyde 12.5g in batches, control bath temperature 30 ℃ of left and right, after solid dissolves completely, add 1g dicyandiamide and 1g Sodium Metabisulfite further to dissolve completely, make Cationic functional groups reagent.
4, get anionic polyacrylamide reversed-phase emulsion 30ml in 100ml in the there-necked flask with agitator and thermometer, control temperature 25 ℃ of left and right, first drip hydrophobic functional group reagent 1ml, drip again Cationic functional groups reagent 20ml, 1h dropwises, be warming up to 40 ℃, reaction 5h, makes hydrophobic association amphiprotic polyacrylamide reversed-phase emulsion.
Claims (2)
1. a synthetic method for hydrophobic association polyacrylamide, is characterized in that comprising the following steps:
(1) get a kind of first with acid neutralization in di-n-propylamine, Di-n-Butyl Amine, two n-amylamines, more in molar ratio for 0.8-1.2 adds formalin, control temperature of reaction at 20-50 ℃, make hydrophobic functional group reagent after reacting 4-6h; In 33% dimethylamine agueous solution in molar ratio for 0.8-1.2 adds paraformaldehyde, stir and control temperature of reaction at 20-50 ℃, after paraformaldehyde dissolves completely, add stablizer dicyandiamide and the Sodium Metabisulfite of formaldehyde quality 5-20% to stir, after it all dissolves, make Cationic functional groups reagent;
(2) with acrylamide, be principal monomer, 2-acrylamide-2-methylpro panesulfonic acid is comonomer, add sorbitan mono-laurate and polyoxyethylene octylphenol ether as emulsifying agent, employing organic hydrocarbon is oil phase, by UV-irradiation, cause or use chemical initiator initiated polymerization, preparing the reversed phase latex of polyacrylamide of different anions degree;
(3) reversed phase latex of polyacrylamide step (2) being made adds in the container of belt stirrer, the total monomer amount that accounts for that step (1) is made is that the hydrophobic functional group reagent of 0.5-2mol% slowly adds in above-mentioned reversed-phase emulsion, temperature of reaction 20-40 ℃, reaction times 4-6h, then slowly add and account for the Cationic functional groups reagent that the step (1) of total monomer amount 0-50mol% makes, temperature of reaction 20-40 ℃, reaction times 4-6h, makes hydrophobic association polyacrylamide reversed-phase emulsion.
2. the synthetic method of a kind of hydrophobic association polyacrylamide according to claim 1, in its characterization step (1), acid used is a kind of in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, carbonic acid.
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| CN104277174B (en) * | 2013-07-09 | 2017-02-08 | 中国石油化工股份有限公司 | Polyacrylamide nanometer microballoon system and preparation method thereof |
| CN103641951A (en) * | 2013-12-13 | 2014-03-19 | 山东大学 | Synthesis method of amphiprotic hydrophobic association terpolymer |
| CN106866881B (en) * | 2015-12-14 | 2019-12-10 | 中国石油化工股份有限公司 | hydrophobic association acrylamide polymer emulsion and preparation method thereof |
| CN107868170B (en) * | 2016-09-26 | 2020-10-16 | 中国石油化工股份有限公司 | Block type hydrophobic association polyacrylamide and preparation method thereof |
| CN106823985B (en) * | 2017-01-20 | 2019-01-01 | 中国科学院化学研究所 | Non-ionic biomass-based surfactant of one kind and preparation method thereof |
| CN106957641A (en) * | 2017-03-28 | 2017-07-18 | 四川光亚聚合物化工有限公司 | A kind of Water-In-Oil association type acidifying concentration thickening agent and preparation method thereof |
| CN106833591A (en) * | 2017-03-28 | 2017-06-13 | 四川光亚聚合物化工有限公司 | A kind of oil-in-water association type displacement of reservoir oil concentration thickener and preparation method thereof |
| CN106833590A (en) * | 2017-03-28 | 2017-06-13 | 四川光亚聚合物化工有限公司 | A kind of Water-In-Oil association type displacement of reservoir oil concentration thickener and preparation method thereof |
| CN114773543B (en) * | 2022-06-17 | 2022-09-02 | 山东诺尔生物科技有限公司 | Modified polyacrylamide papermaking retention and drainage aid and preparation method thereof |
| CN115651104B (en) * | 2022-10-28 | 2024-02-13 | 武汉理工大学 | Heavy metal stabilizer and preparation method and application thereof |
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| CN101132756A (en) * | 2005-01-27 | 2008-02-27 | 纳尔科公司 | Personal care composition containing hydrophobically modified polymers |
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| CN101132756A (en) * | 2005-01-27 | 2008-02-27 | 纳尔科公司 | Personal care composition containing hydrophobically modified polymers |
Non-Patent Citations (2)
| Title |
|---|
| 两性聚丙烯酰胺反相乳液的制备及其脱色性能;冯维红等;《化工环保》;20111215;第31卷(第6期);第561～564页 * |
| 冯维红等.两性聚丙烯酰胺反相乳液的制备及其脱色性能.《化工环保》.2011,第31卷(第6期),第561～564页. |
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