CN103509154A - Preparation method of zwitterionic polyacrylamide - Google Patents
Preparation method of zwitterionic polyacrylamide Download PDFInfo
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- CN103509154A CN103509154A CN201210216409.8A CN201210216409A CN103509154A CN 103509154 A CN103509154 A CN 103509154A CN 201210216409 A CN201210216409 A CN 201210216409A CN 103509154 A CN103509154 A CN 103509154A
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Abstract
The invention relates to a preparation method of zwitterionic polyacrylamide, and belongs to the field of high-molecular polymerization. The preparation method is characterized by comprising the following steps of: charging, namely adding deionized water into a polymerization reactor, and adding a 30wt% acrylamide water solution, a cationic monomer, an anionic monomer, a cosolvent and a chain transfer agent while stirring, and regulating the pH value of the system by use of alkali; introducing nitrogen for deoxygenization, and then, adding an initiator; performing adiabatic polymerization reaction, namely controlling the initiation temperature to be 2-25 DEG C, after 2-6 hours, terminating the reaction when the polymerization system temperature rises no longer, thereby obtaining the polymer gel; granulating, baking, smashing and sieving the gel to obtain zwitterionic polyacrylamide products with high intrinsic viscosity. The invention provides a preparation method of zwitterionic polyacrylamide with high intrinsic viscosity, and in the preparation method, azo initiator initiates a polymerization technology at a lower temperature, the operation technology is simple, and the intrinsic viscosity of the prepared product is not less than 2000ml/g.
Description
Technical field
The present invention relates to a kind of preparation method of amphoteric ionic polyacrylamide, belong to high molecular polymerization field.
Background technology
Amphoteric ionic polyacrylamide, as water-soluble polymer product anti-collapse and anti-falling filtration in sewage disposal, solid-liquid separation, drilling well, is used widely in the industry such as industrial polymer flooding, papermaking, weaving, printing and dyeing, coal washing of recovering the oil.Especially in the sewage disposal as flocculation agent, because its suitable acidity value is wider, than cationic polyacrylamide better effects if.In oil production, tertiary phase particularly, high intrinsic viscosity amphoteric ionic polyacrylamide, for more complicated high salinity, the hot environment of oil reservoir situation, can be obtained obvious temperature resistant antisalt effect.In paper industry, add after zwitter-ion polyacrylamide the neutral high-quality paper of can manufacturing paper with pulp out.Preparation technology of the prior art is also difficult to reach intrinsic viscosity >=2300ml/g technical indicator.
At present, the preparation method of amphoteric ionic polyacrylamide mainly uses following two kinds of methods:
The first is two-step approach, first, by acrylamide homopolymerization, makes non-ionic polyacrylamide, and then by this non-ionic polyacrylamide modification, as Mannich reaction and sulfomethylation, finally obtains amphoteric ionic polyacrylamide dilute aqueous soln.The amphoteric ionic polyacrylamide that the method is obtained not only intrinsic viscosity is low, is generally no more than 2000ml/g, and the finished product dilute solution that is 1%～5%, and the storage time is short, and giving the transportation of this product and storing has all increased difficulty.
Second method is the single stage method of ternary or multi-component copolymer.In acrylamide solution, add one or more cationic monomers, anionic monomer and various auxiliary agent, with acid, alkali, adjust pH value after preset value, letting nitrogen in and deoxidizing, adds composite initiator polymerization, makes amphoteric ionic polyacrylamide.In this composite initiation system, generally that redox initiator carries out initial stage low temperature initiation, although the method is simple, cannot overcome that redox initiator brings because initiator wear rate is too fast, monomer conversion reduces, and reductive agent easily participates in the drawback of chain transfer reaction.Thereby cause polymer intrinsic viscosity to reduce, be difficult to obtain the product of high intrinsic viscosity.
A kind of initiator system of preparing zwitter-ion polyacrylamide is disclosed in Chinese patent CN 1061013C, its object is a kind of efficient flocculant of preparation, and its result of use has larger flocs unit diameter and lower filter cake moisture content than the cationic flocculant using at present.This initiator system is comprised of sequestrant, oxygenant, reductive agent and azo initiator, and polymerization temperature, at 25 ℃～60 ℃, belongs to middle temperature polymerization.
Chinese patent CN101514239 adopts aqueous solution dispersion copolymerization method, take water as reaction medium, not with an organic solvent and tensio-active agent, reduced the pollution to environment, prepared product is that polymer active constituent is even in water, the liquid of stable dispersion, solid content 20～30%, is easy to preparation and uses.In its polymerization technique, drip and feed in raw material at twice, initiator is persulphate, 50～80 ℃ of polymerization temperatures, and the weight-average molecular weight of polymkeric substance is 5,000,000～18,000,000.
Summary of the invention
According to the deficiencies in the prior art, the technical problem to be solved in the present invention is: the preparation method that a kind of amphoteric ionic polyacrylamide is provided, stable polymerization reaction, efficiency of initiation is high, the polymer intrinsic viscosity obtaining is high, aspect product application, the suitable pH value scope of sewage disposal is wider than cationic polymers, and oil extraction in oil field more can adapt to high temperature, high salinity media.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of amphoteric ionic polyacrylamide is provided, it is characterized in that comprising the following steps:
(1) feed intake: deionized water is dropped in polymerization reactor, under agitation condition, once drop into raw materials quality mark and be 30% acrylamide solution, cationic monomer, anionic monomer, solubility promoter, chain-transfer agent, with alkali, carry out the pH value of regulation system; After logical nitrogen deoxygenation, add initiator;
(2) adiabatic polymerisation reaction: it is 2～25 ℃ that kick off temperature is controlled at, 2 ~ 6h post polymerization system temperature no longer raises and is reaction end, obtains polymeric colloid;
(3), by granulating from colloid, oven dry, pulverizing, screening, obtain high intrinsic viscosity amphoteric ionic polyacrylamide product.
Wherein the add-on of ionized water is formula ratio.
The present invention can obtain the high intrinsic viscosity amphoteric ionic polyacrylamide product of intrinsic viscosity >=2000ml/g.
Intrinsic viscosity described in the present invention adopts viscosimetry to measure, and according to GB12005.1-89, measures intrinsic viscosity.
High intrinsic viscosity amphoteric ionic polyacrylamide solvability prepared by the present invention is better, and the copolymerization process adopting is simple and practical, easy to operate, is easy to large-scale industrial production.
Initiator described in step (1) is water-soluble azo initiator, described water-soluble azo initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-isobutyrate hydrochloride, azo diisopropylamidinateand Cuo quinoline hydrochloride, azo two NSC 18620 Cuo quinoline hydrochlorides or azo two isocyano-valeric acids, and its consumption is 0.005%～0.075% of starting monomer quality.
Cationic monomer described in step (1) is one or more in acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride or dimethyl diallyl ammonium chloride, and its add-on accounts for 10%～60% of starting monomer total mass.
Anionic monomer described in step (1) is one or more in 2-acrylamido 2-methyl propane sulfonic acid, vinylformic acid or sodium acrylate, and its add-on accounts for 1%～30% of starting monomer total mass.
Described in step (1), solubility promoter is urea, and its add-on accounts for 0.1%～5% of starting monomer total mass.
Chain-transfer agent described in step (1) is that in sodium formiate, β-dimethylamino butyronitrile or Virahol, its add-on accounts for 0.01%～0.07% of starting monomer total mass.
Alkali described in step (1) is sodium hydroxide, is used for regulating pH value, and its add-on is adjusted to 4～8 with pH value and is as the criterion;
Polymerization technology condition described in step (2) is as follows:
Kick off temperature ℃ 2～25
Pass into nitrogen amount m
3/ m
3360 ~ 80
Drying temperature ℃ 40～80
Wherein pass into the volume that nitrogen amount refers to the nitrogen that every cubic metre of polymeric solution passes into.
Preferably 5 ~ 20 ℃ of kick off temperatures described in step (2).
The invention has the beneficial effects as follows:
1, provide a kind of azo initiator initiated polymerization technique at low temperatures, operating procedure is simple, makes the preparation method of the high intrinsic viscosity amphoteric ionic polyacrylamide of product performance viscosity number >=2000ml/g.
2, be applicable to anti-collapse in sewage disposal, solid-liquid separation, oil drilling and fall the polymer flooding of high temperature and high salt in leak-off, tertiary oil production in oil field, and the industry such as papermaking, weaving, printing and dyeing.
Embodiment
Below in conjunction with embodiment, the present invention is described further:
Embodiment 1
56g deionized water is added in aggregation container, under agitation add successively the acrylamide of 133g30%, the acrylyl oxy-ethyl-trimethyl salmiac of 6.25g80% (DAC), 5g 2-acrylamido 2-methyl propane sulfonic acid (AMPS), 1g urea, 0.015g sodium formiate, the pH value of adjusting system with NaOH is 6.5, adjust system kick off temperature to 10 ℃ simultaneously, under nitrogen flow 4L/min, pass into after 15min, add through 10 minutes pretreated initiator azo-bis-isobutyrate hydrochloride 0.005g of 50 ℃ of constant temperature, approximately crossing 3min polymerization system starts polymerization and is clamminess, heat up, 2 ~ 6h post polymerization system temperature reaches 70 ℃, then system temperature starts to decline, continue to keep 2h at this temperature, then the colloid obtaining is carried out to granulation, at 50 ℃ by drying materials, pulverizing obtains the amphoteric ionic polyacrylamide dry powder of intrinsic viscosity 2376ml/g.Other several important technology indexs are:
Solid content (testing standard GB12005.2-89) 88.63%
Dissolution rate (testing standard GB12005.8-89) 40min
Residual monomer content (testing standard GB/T 22312-2008) 0.035%
(same under testing standard)
Embodiment 2
According to the method for embodiment 1 and step, difference is that the starting temperature of embodiment 2 is 5 ℃, and each technical indicator of gained amphoteric ionic polyacrylamide dry powder is as follows:
Embodiment 3
According to the method for embodiment 1 and step, difference is that the starting temperature of embodiment 3 is 20 ℃, and each technical indicator of gained amphoteric ionic polyacrylamide dry powder is as follows:
Embodiment 4
56g deionized water is added in aggregation container, under agitation add successively the acrylamide of 133g30%, the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 6.25g80% (DMC), 5g vinylformic acid, 1g urea, 0.015g sodium formiate, the pH value of adjusting system with NaOH is 6.5, adjust system kick off temperature to 20 ℃ simultaneously, under nitrogen flow 4L/min, pass into after 15min, add through 5 minutes pretreated initiator azo-bis-isobutyrate hydrochloride 0.045g of 60 ℃ of constant temperature, approximately crossing 3min polymerization system starts polymerization and is clamminess, heat up, 2 ~ 6h post polymerization system temperature reaches 70 ℃, then system temperature starts to decline, continue to keep 2h at this temperature, then the colloid obtaining is carried out to granulation, at 50 ℃ by drying materials, pulverizing obtains amphoteric ionic polyacrylamide dry powder, each technical indicator is as follows:
Embodiment 5
560g deionized water is added in aggregation container, under agitation add successively the acrylamide of 1333g30%, the DAC of 62.5g80%, 50gAMPS, 10g urea, 0.15g sodium formiate, the pH value of adjusting system with NaOH is 6.5, pass into nitrogen to remove the dissolved oxygen in reaction system, adjust system kick off temperature to 10 ℃ simultaneously, , after logical nitrogen 15min, add through 10 minutes pretreated initiator azo-bis-isobutyrate hydrochloride 0.10g of 60 ℃ of constant temperature, approximately crossing 3min polymerization system starts polymerization and is clamminess, heat up, 2h～6h post polymerization system temperature reaches 70 ℃, then system temperature starts to decline, continue to keep 2h at this temperature, then the colloid obtaining is carried out to granulation, at 50 ℃ by drying materials, pulverizing obtains amphoteric ionic polyacrylamide dry powder.Its technical indicator is:
Embodiment 6
According to the method for embodiment 5 and step, difference is that the starting temperature of embodiment 6 is 20 ℃, and each technical indicator of gained amphoteric ionic polyacrylamide dry powder is as follows
Embodiment 7
879.5g deionized water is added in aggregation container, under agitation add successively the acrylamide of 833g30%, the DAC of 187.5g80%, 100gAMPS, 10g urea, 0.15g sodium formiate, the pH value of adjusting system with NaOH is 6.0, pass into nitrogen to remove the dissolved oxygen in reaction system, adjust system kick off temperature to 15 ℃ simultaneously, , after logical nitrogen 15min, add through 10 minutes pretreated initiator azo-bis-isobutyrate hydrochloride 0.10g of 50 ℃ of constant temperature, approximately crossing 3min polymerization system starts polymerization and is clamminess, heat up, 2h～6h post polymerization system temperature reaches 70 ℃, then system temperature starts to decline, continue to keep 2h at this temperature, then the colloid obtaining is carried out to granulation, at 50 ℃ by drying materials, pulverizing obtains amphoteric ionic polyacrylamide dry powder.
Its technical indicator is:
Embodiment 8
According to the method for embodiment 7 and step, difference is that embodiment 8 colloid bake out temperatures are 60 ℃, and each technical indicator of gained amphoteric ionic polyacrylamide dry powder is as follows
Comparative example 1
560g deionized water is added in aggregation container, under agitation add successively the acrylamide of 1333g30%, the DAC of 62.5g80%, 50gAMPS, 10g urea, 0.15g sodium formiate, the pH value of adjusting system with NaOH is 6.5, pass into nitrogen to remove the dissolved oxygen in reaction system, adjust system kick off temperature to 30 ℃ simultaneously, , after logical nitrogen 15min, add initiator ammonium persulfate 0.1g, sodium bisulfite 0.1g, not pretreated initiator azo-bis-isobutyrate hydrochloride 0.05g, approximately crossing 2min polymerization system starts polymerization and is clamminess, heat up, 1h post polymerization system temperature reaches 70 ℃, then system temperature starts to decline, continue to keep 3h at this temperature, then the colloid obtaining is carried out to granulation, dry, pulverizing obtains amphoteric ionic polyacrylamide dry powder.
Its technical indicator is:
Comparative example 2
According to the method for comparative example 1 and step, difference is that the starting polymerization temperature of comparative example 2 is 40 ℃, and each technical indicator of gained amphoteric ionic polyacrylamide dry powder is as follows
Comparative example 3
560g deionized water is added in aggregation container, under agitation add successively the acrylamide of 1333g30%, the DAC of 62.5g80%, 50gAMPS, 10g urea, 0.15g sodium formiate, the pH value of adjusting system with NaOH is 6.5, pass into nitrogen to remove the dissolved oxygen in reaction system, adjust system kick off temperature to 20 ℃ simultaneously, after logical nitrogen 15min, add not pretreated initiator azo-bis-isobutyrate hydrochloride 0.10g, result polymerization is slow, and polymerization is incomplete, clear liquid is about 30%, cannot test each technical indicator.
Claims (9)
1. a preparation method for amphoteric ionic polyacrylamide, is characterized in that comprising the following steps:
(1) feed intake: deionized water is dropped in polymerization reactor, under agitation condition, once drop into raw materials quality mark and be 30% acrylamide solution, cationic monomer, anionic monomer, solubility promoter, chain-transfer agent, with alkali, carry out the pH value of regulation system; After logical nitrogen deoxygenation, add initiator;
(2) adiabatic polymerisation reaction: it is 2～25 ℃ that kick off temperature is controlled at, 2 ~ 6h post polymerization system temperature no longer raises and is reaction end, obtains polymeric colloid;
(3), by granulating from colloid, oven dry, pulverizing, screening, obtain high intrinsic viscosity amphoteric ionic polyacrylamide product.
2. the preparation method of amphoteric ionic polyacrylamide according to claim 1, it is characterized in that the initiator described in step (1) is water-soluble azo initiator, described water-soluble azo initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-isobutyrate hydrochloride, azo diisopropylamidinateand Cuo quinoline hydrochloride, azo two NSC 18620 Cuo quinoline hydrochlorides or azo two isocyano-valeric acids, and its consumption is 0.005%～0.075% of starting monomer quality.
3. the preparation method of amphoteric ionic polyacrylamide according to claim 1, it is characterized in that the cationic monomer described in step (1) is one or more in acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride or dimethyl diallyl ammonium chloride, its add-on accounts for 10%～60% of starting monomer total mass.
4. the preparation method of amphoteric ionic polyacrylamide according to claim 1, it is characterized in that anionic monomer described in step (1) is one or more in 2-acrylamido 2-methyl propane sulfonic acid, vinylformic acid or sodium acrylate, its add-on accounts for 1%～30% of starting monomer total mass.
5. the preparation method of amphoteric ionic polyacrylamide according to claim 1, is characterized in that described in step (1), solubility promoter is urea, and its add-on accounts for 0.1%～5% of starting monomer total mass.
6. the preparation method of amphoteric ionic polyacrylamide according to claim 1, it is characterized in that chain-transfer agent described in step (1) is that in sodium formiate, β-dimethylamino butyronitrile or Virahol, its add-on accounts for 0.01%～0.07% of starting monomer total mass.
7. the preparation method of amphoteric ionic polyacrylamide according to claim 1, is characterized in that the alkali described in step (1) is sodium hydroxide, is used for regulating pH value, and its add-on is adjusted to 4～8 with pH value and is as the criterion.
8. the preparation method of amphoteric ionic polyacrylamide according to claim 1, is characterized in that the polymerization technology condition described in step (2) is as follows:
Kick off temperature ℃ 2～25
Pass into nitrogen amount m
3/ m
3360 ~ 80
Drying temperature ℃ 40～80
Wherein pass into the volume that nitrogen amount refers to the nitrogen that every cubic metre of polymeric solution passes into.
9. according to the preparation method of the amphoteric ionic polyacrylamide described in claim 1 or 8, it is characterized in that preferably 5 ~ 20 ℃ of the kick off temperatures described in step (2).
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Cited By (11)
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| CN105153361A (en) * | 2015-08-07 | 2015-12-16 | 中国石油化工股份有限公司胜利油田分公司勘探开发研究院 | Partially-branched and partially-crosslinked polymer oil displacement agent and preparation method thereof |
| CN106478870A (en) * | 2016-10-25 | 2017-03-08 | 湖南省核农学与航天育种研究所 | A kind of production technology for preparing amphiprotic polyacrylamide using γ-ray-initiated polymerization |
| CN107746378A (en) * | 2016-10-14 | 2018-03-02 | 中国石油大学(华东) | A kind of polymerizable quaternaries cation monomer and preparation method thereof |
| CN107746446A (en) * | 2016-10-14 | 2018-03-02 | 中国石油大学(华东) | A kind of preparation method of ternary polymerization amphiprotic polyacrylamide |
| CN108341911A (en) * | 2017-05-10 | 2018-07-31 | 新疆华油技术服务股份有限公司 | A kind of multifunctional polymer oil displacement agent and its preparation method and application |
| CN108485639A (en) * | 2018-04-28 | 2018-09-04 | 中国石油集团川庆钻探工程有限公司 | A kind of amphoteric ion polymer thickening agent and preparation method thereof |
| CN110527028A (en) * | 2019-09-05 | 2019-12-03 | 江苏富淼科技股份有限公司 | A kind of Instant cationic polyacrylamide and preparation method thereof |
| CN112515856A (en) * | 2020-11-30 | 2021-03-19 | 江苏达胜伦比亚生物科技有限公司 | Device and method for preparing hydrogel dressing by radiation method |
| CN116120499A (en) * | 2022-12-22 | 2023-05-16 | 河南亿群环保科技有限公司 | Preparation method of modified polyacrylamide |
| CN116284560A (en) * | 2021-12-20 | 2023-06-23 | 深圳市长隆科技有限公司 | Cationic polyacrylamide for water treatment and preparation method thereof |
| CN116120499B (en) * | 2022-12-22 | 2024-04-26 | 河南亿群环保科技有限公司 | Preparation method of modified polyacrylamide |
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| CN105153361B (en) * | 2015-08-07 | 2019-05-10 | 中国石油化工股份有限公司胜利油田分公司勘探开发研究院 | A kind of part branched moiety cross-linked polymer oil-displacing agent and preparation method thereof |
| CN107746446A (en) * | 2016-10-14 | 2018-03-02 | 中国石油大学(华东) | A kind of preparation method of ternary polymerization amphiprotic polyacrylamide |
| CN107746378A (en) * | 2016-10-14 | 2018-03-02 | 中国石油大学(华东) | A kind of polymerizable quaternaries cation monomer and preparation method thereof |
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| CN110527028A (en) * | 2019-09-05 | 2019-12-03 | 江苏富淼科技股份有限公司 | A kind of Instant cationic polyacrylamide and preparation method thereof |
| CN110527028B (en) * | 2019-09-05 | 2022-01-04 | 江苏富淼科技股份有限公司 | Instant cationic polyacrylamide and preparation method thereof |
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| CN116120499B (en) * | 2022-12-22 | 2024-04-26 | 河南亿群环保科技有限公司 | Preparation method of modified polyacrylamide |
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