CN103275270A - Method for preparing fluorocarbon-modified polyacrylamide by using soap-free emulsion method - Google Patents
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Abstract
The invention discloses a method for preparing fluorocarbon-modified cationic polyacrylamide by a soap-free emulsion polymerization method and belongs to the technical field of water-soluble polymer synthesis. The method comprises the following steps of: adopting a free radical polymerization method, taking pure water as a solvent, and taking potassium persulphate (KPS) as an initiator; dispersing a novel fluorocarbon/hydrocarbon mixed cationic surface active monomer with surface activity in the system in the form of a micelle; copolymerizing the novel fluorocarbon/hydrocarbon mixed cationic surface active monomer with acrylamide (AM) in the absence of an emulsifier and in the presence of a single solvent, namely pure water, thus successfully synthesising a perfluorocarbon-modified amphoteric hydrophobic associated polymer with temperature-resistant, viscosity-increasing and anti-shearing performances; and carrying out simple treatments to obtain the powder product. The prepared fluorocarbon-modified hydrophobic associated polymer can be widely applied to the fields of oilfield development, coating, fire-fighting, printing, electroplating, daily-use chemical industry, medicine, and the like.
Description
Technical field
The present invention relates to a kind of fluorine-carbon modified Preparation of Polyacrylamide method, be specifically related to prepare by the emulsifier-free emulsion polymerization method method of fluorine-carbon modified cationic polyacrylamide, belong to the water-soluble polymer synthesis technical field.
Background technology
Fluorine-carbon modified polyacrylamide refers to introduce at the polyacrylamide macromolecular chain class water-soluble polymers of perfluor hydrophobic grouping.Fluorine carbon hydrophobic grouping is compared with hydrocarbon hydrophobic grouping, has more excellent hydrophobic association performance, and this is because cohesive energy density(CED) and surface energy between the fluorine carbon atom are less, is easy to form complicated reticulated structure, thereby strengthens viscosity and the anti-shear performance of polymkeric substance.Simultaneously, extremely strong thermostability and the chemical stability of fluorine carbon alkyl chain also gives fluorine-carbon modified polyacrylamide good heatproof chemical resistance.In addition, fluorine-carbon modified polyacrylamide generally can be reduced to 30mN/m with the surface tension of water also having shown unique character aspect the surface tension that reduces water, is therefore having broad application prospects aspect the preparation polymeric surface active agent.Because fluorine-carbon modified polypropylene amine has these excellent chemical property and particular rheological properties matter, so caused people's extensive concern in the application aspect oil-displacing agent, drilling fluid and the coating.
The main difficulty of synthetic fluorine-carbon modified polyacrylamide comes from the water-soluble relatively poor of fluorine carbon hydrophobic monomer.Up to now, most investigator adopts the preparation of micellar copolymerization (micellar copolymerization) technology.In this system, fluorine carbon hydrophobic monomer is dissolved in the micella of tensio-active agent formation, then with the acrylamide copolymerization that is dissolved in the water, obtains having the acrylamide copolymer of micro-block structure.Yet there is distinct disadvantage in this traditional micellar copolymerization.For example, it must adopt complicated last handling process to remove tensio-active agent to obtain pure copolymerization product.In addition, common tensio-active agent and impurity thereof also can bring disadvantageous effect to polymerization process.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of emulsifier-free emulsion polymerization method to prepare the method for fluorine-carbon modified polyacrylamide, having surface-active novel fluoro-carbon/hydrocarbon mixed type cation surface active monomer is dispersed in the aqueous systems with micelle form, under the emulsifier-free existence condition with the acrylamide copolymerization, the synthetic perfluor modified amphoteric hydrophobic associated polymer with heatproof, tackify and anti-shear performance of success can obtain powder product again through simple process.
Terminological interpretation:
The monomer molar sum refers to the mole number sum of novel fluoro-carbon/hydrocarbon mixed type cation surface active monomer and acrylamide.
The system cumulative volume refers to the volume of aqueous solvent.
Molar feed ratio refers to the per-cent of feed intake mole number and the monomer molar sum of monomer.
Total monomer concentration refers to the mole number sum of novel fluoro-carbon/hydrocarbon mixed type cation surface active monomer and acrylamide and the ratio of system cumulative volume.
Technical scheme of the present invention is as follows:
Fluorine-carbon modified Preparation of Polyacrylamide method, adopt the method for radical polymerization, be solvent with the pure water, Potassium Persulphate (KPS) is initiator, synthetic novel fluoro-carbon/hydrocarbon mixed type the cation surface active monomer in this laboratory is hydrophobic monomer, with acrylamide (AM) copolymerization in the single solvent pure water.The chemical structural formula that novel fluoro-carbon/hydrocarbon mixed type cation surface active monomer is hydrophobic monomer is as follows:
Acrylamide (AM) is as follows with novel fluoro-carbon/hydrocarbon mixed type cation surface active monomer copolyreaction formula:
Step is as follows:
(1) immigration of 80mL deionized water is equipped with in the 250mL four-hole round-bottomed flask of mechanical stirring rod, spherical condensation tube, nitrogen ventpipe, thermometer, taking by weighing a certain amount of acrylamide changes in the four-hole bottle, the molar feed ratio of acrylamide is 98.5mol%～99.9mol%, and the optimum molar feed ratio is 99.0mol%～99.9mol%.Feed N
2, stirring at room 1h.
(2) take by weighing a certain amount of fluorine carbon/hydrocarbon mixed type cation surface active monomer, be dissolved in the 10mL deionized water, fully the dissolving back be yellow clear solution, changes in the four-hole bottle after leaving standstill 10min, washes residual solution repeatedly with the 10mL deionized water again and foam also changes in the reaction system together.The molar feed ratio of fluorine carbon/hydrocarbon mixed type cation surface active monomer is 0.1mol%～1.5mol%, and the optimum molar feed ratio is 0.1mol%～1mol%.Reaction system is warming up to 50～65 ℃, continues to stir N
2Protection keeps 15～30min.
(3) take by weighing a certain amount of Potassium Persulphate (KPS), change over to rapidly in the four-hole bottle, the molar feed ratio of KPS is 1～4mmol/L, and the optimum molar feed ratio is 1～3mmol/L.Behind about 30s, reaction soln begins to become muddy by faint yellow settled solution, and about 1h afterreaction system becomes faint yellow emulsion, and along with the carrying out of reaction, emulsion is thickness more and more, foam showed increased in the system.
(4) behind reaction 6～24h, stopped reaction obtains the transparent faint yellow viscous fluid.Viscous fluid is changed in the large beaker that 400～600mL dehydrated alcohol is housed while hot, obtain faint yellow netted soft solid, shred into cotton-shaped chip with scissors immediately, mechanical stirring 12～24h is to remove unreacted fluoro-carbon surface active monomer and acrylamide in dehydrated alcohol.
(5) suction filtration is removed dehydrated alcohol, obtains faint yellow soft chip, and 25～40 ℃ of following vacuum-drying 24～48h obtain faint yellow flake light solid, obtain the faint yellow solid powder of fluorine-carbon modified polyacrylamide after the pulverizing.
In above-mentioned emulsifier-free emulsion polymerization system, the reaction monomers total concn is controlled to be 1.0mol/L.
Optimum temps is 55～60 ℃ in the above-mentioned steps (2), can successful initiated polymerization.
Time is according to the difference of conditions such as monomer ratio in the polymeric system and concentration, initiator concentration, polymer temperature in the above-mentioned steps (4), the complete required time of polymerization is also different, can be 6～24h, if feed intake by above-mentioned top condition, best polymerization time is 12～18h.
Novel fluoro-carbon/hydrocarbon mixed type cation surface active monomer selected in the fluorine-carbon modified Preparation of Polyacrylamide method of the present invention is this experiment oneself preparation, with N, N-dimethyl-ethylenediamine, 6-bromo-1-hexene, perfluoro-hexyl iodide alkane and allyl acetate are starting raw material, synthetic fluorine carbon/hydrocarbon mixed type cation surface active monomer, reaction equation is as follows:
The preparation method is as follows:
Step (i), (popular name: the Boc acid anhydrides) to N, the amino of N-dimethyl-ethylenediamine is protected, and amino is changed into the more stable amide group of chemical property to utilize tert-Butyl dicarbonate.
Step (ii); the N that amino has been protected by Boc; N-dimethyl-ethylenediamine and 6-bromo-1-hexene carry out quaterisation, after reaction finishes, and removal of solvent under reduced pressure; add anhydrous diethyl ether; ice bath stirred 2～12 hours, separated out white solid, suction filtration; obtain the white solid powder, namely have the compound I of polymerizable groups (ethylene linkage).
Step is (iii) utilized HCl-Et
2The O saturated solution takes off Boc to compound I, and after reaction finished, removal of solvent under reduced pressure added anhydrous diethyl ether, and ice bath stirred 2～12 hours, separated out white solid, and suction filtration obtains the white solid powder, i.e. compound I I.
Step (iv); under initiator dibenzoyl peroxide (BPO) effect; iodine and ethanoyl are sloughed in perfluoro-hexyl iodide alkane and allyl acetate generation addition reaction then under the effect of KOH, filter; the filtrate decompression distillation; collect 77～80 ℃/40mmHg cut, be colourless liquid, i.e. compound III; 3-(perfluor n-hexyl)-1,2 epoxy prapane.
(v), compound I I and compound III are carried out ring-opening reaction, removal of solvent under reduced pressure adds the anhydrous diethyl ether precipitation to step, obtains compound IV, is yellow thickness lotion.
Raw materials used: N, N-dimethyl-ethylenediamine (99%, Beijing lark prestige Science and Technology Ltd.), tert-Butyl dicarbonate (99%, Beijing lark prestige Science and Technology Ltd.), N, dinethylformamide (99.8%, Beijing lark prestige Science and Technology Ltd.), 6-bromo-1-hexene (98%, Tianjin method Moses Science and Technology Ltd.), perfluoro-hexyl iodide alkane (97%, Beijing lark prestige Science and Technology Ltd.), allyl acetate (99%, Beijing lark prestige Science and Technology Ltd.), sulfuric acid (95～98% Yantai City are chemical industry company limited in pairs), hydrochloric acid (37%, the Yantai City is chemical industry company limited in pairs).Above reagent all obtains from commercial channels, and does not do and be further purified processing.
Following reagent also obtains from commercial channels, and is further purified processing: dibenzoyl peroxide (BPO) is available from the chemical company limited of A Faaisha (Tianjin), uses with after chloroform and the recrystallizing methanol 3 times; KOH is available from the chemical company limited of A Faaisha (Tianjin), and KOH is ground to powder with sheet, uses after the vacuum-drying; Methyl alcohol, dehydrated alcohol, anhydrous diethyl ether, normal hexane are analytical pure available from Tianjin Fu Yu Fine Chemical Co., Ltd, with reference to Purification of Laboratory Chemicals, 5
ThEd (Chai, C.L.L.; Armarego, W.L.F., Butterwirth-Heinemann:New York, 2003.) use of processing back.
In above-mentioned preparation method, the described N of step (i), the mol ratio of N-dimethyl-ethylenediamine and tert-Butyl dicarbonate can be 1: (1.1～1.5), solvent can be N, dinethylformamide (DMF), acetone, methyl alcohol or ethanol, N, the N-dimethyl-ethylenediamine can be 1 with the massfraction ratio of described solvent: (16～25), temperature of reaction can be 25～40 ℃, reaction times can be 0.5～2 hour, and feeding mode is that tert-Butyl dicarbonate is dissolved in an amount of solvent, dropwise splashes into N in 0.5～1 hour, in the reaction system that the N-dimethyl-ethylenediamine exists, be reflected under the nitrogen atmosphere and carry out.
In above-mentioned preparation method, step is (ii) directly carried out after step (i) reaction finishes, and namely utilizes one kettle way synthetic compound I.N, the mol ratio of N-dimethyl-ethylenediamine and 6-bromo-1-hexene can be 1: (1.1～1.3), no longer add solvent, temperature of reaction remains unchanged, reaction times can be 24～72 hours, feeding mode is that 6-bromo-1-hexene was dropwise splashed in the reaction system of step (i) in 0.5～1 hour, is reflected under the nitrogen atmosphere and carries out.
In above-mentioned preparation method, step (iii) described reaction solvent is methyl alcohol, compound I and can be 1 with the massfraction ratio of solvent: (4～7), HCl-Et
2The volume ratio of O saturated solution and solvent is 1: (2.5～5), temperature are 10～25 ℃, and the reaction times can be 6～12 hours, and feeding mode is with HCl-Et
2The O saturated solution dropwise splashed in 0.5～1 hour in the reaction system of compound I existence.
In above-mentioned preparation method, the step (iv) mol ratio of described perfluoro-hexyl iodide alkane and allyl acetate is 1: 1, the two is mixed stirring (not adding solvent herein), after being warming up to 95 ℃, solution to be mixed kept several minutes, add BPO afterwards, the mol ratio of BPO and perfluoro-hexyl iodide alkane can be 1: after (50～100), question response sharply are warming up to 160～170 ℃, be cooled to 120～130 ℃, kept 30～60 minutes.In above-mentioned reaction system, add normal hexane and KOH successively then, normal hexane is solvent, and can be (2.5～3) with mol ratio that the massfraction ratio of perfluoro-hexyl iodide alkane can be (1.5～2): 1, KOH and perfluoro-hexyl iodide alkane: 1, reaction times can be 4～6 hours, and temperature is 70～80 ℃.
In above-mentioned preparation method, (v) the mol ratio of described compound I I and compound III can be 1 to step: (3～5), solvent can be methyl alcohol or ethanol, compound I I can be 1 with the massfraction ratio of described solvent: (100～120), temperature of reaction is can 80～90 ℃, reaction times can be 5～7 days, and described being reflected under the nitrogen atmosphere carried out.
Principle to the inventive method is described as follows below:
The preparation of fluorine-containing modified soluble polymkeric substance, generally by three kinds of methods: (1) is emulsifying agent with the tensio-active agent, makes the water-soluble and hydrophilic monomer copolymerization of hydrophobic monomer.(2) hydrophilic monomer and hydrophobic monomer are dissolved in common single solvent realization copolymerization.(3) synthetic itself have surface-active polymerisable fluorine-containing surfactants monomer, carries out the soap-free emulsion copolymerization with hydrophilic monomer.During method (1) polymerization, an importance is to need to select suitable tensio-active agent.Usually, fluorine surfactant is a kind of preferably, but such tensio-active agent is relatively more expensive.In addition, also can select to have the tensio-active agent of longer hydrophobic segment, but this type of tensio-active agent requires harshness to reaction conditions, cause reaction wayward.And the exhibiting high surface promoting agent that adds in the emulsion copolymerization has very big influence to the association behavior of polymkeric substance, removes the complicacy that these tensio-active agents will increase last handling processes such as separation and purifying.During method (2) polymerization, need to select appropriate organic solvent, dissolve fluorine-containing hydrophobic monomer and hydrophilic monomer simultaneously.Because the existence of organic solvent, this method feature of environmental protection is poor, and the later stage is removed the complicacy that organic solvent also will increase treating processess such as separation and purifying.So the present invention is mainly by the fluorine-containing modified soluble polymkeric substance of method (3) preparation.
With N, the N-dimethyl-ethylenediamine is initial reactant, 3-(perfluor n-hexyl) propylene oxide is that fluoro-containing intermediate has synthesized and has surface-active polymerisable fluorocarbon/hydrocarbon mixed type cation surface active monomer, it can the micelle form stable existence in the aqueous solution, can with acrylamide copolymerization in the aqueous solution.In addition, C-F key force of cohesion is little, and is strong with the reactive force of polar molecule, and fluorine atom has very big electronegativity, bond energy is big, and bond length is short, and molecular chain is difficult for rupturing, improved the stability of its polymkeric substance greatly, and fluorocarbon chain is compared with the hydrocarbon chain of equal length, has lower cohesive energy density(CED) and surface energy, and its hydrophobic association effect is stronger than hydrocarbon chain, the viscosity of the polyacrylamide of fluorocarbon chain modification contains the copolymerization object height of hydrocarbon chain more accordingly, has better thickening effectiveness.
Preparation method provided by the invention has the following advantages:
1. raw material is easy to get, and toxicity is low, uses safety, and it is convenient to store, environmental protection.
2. use pure water to be solvent, economic security, the reaction conditions gentleness, the water-soluble fluorine carbon that can successful initiated polymerization under a little higher than room temperature obtains high molecular is polymer-modified, and the monomer conversion height, and the product aftertreatment is simple.
3. introduced novel fluoro-carbon/hydrocarbon mixed type cation surface active monomer in molecule, fluorine carbon alkyl chain has extremely strong thermostability and chemical stability, so give fluorine-carbon modified polyacrylamide good heatproof chemical resistance.
4. the internal cohesive energy that fluorine carbon hydrophobic grouping is extremely low and surface energy make acrylamide copolymer have excellent hydrophobic association performance, have greatly improved viscosity and the anti-shear performance of polymkeric substance.
5. emulsifying agent is not used in this reaction, reduces production costs, and has save the last handling process except de-emulsifier simultaneously yet; In addition, the acrylamide copolymer of preparation is pure, has avoided in some application process because the disadvantageous effect that the existence of emulsifying agent produces polymkeric substance.
6. Zhi Bei fluorine-carbon modified hydrophobic associated polymer can directly be used in a lot of fields, as oil-field development, coating, fire-fighting, printing, plating, daily-use chemical industry, medicine and other fields.
Above-mentioned many characteristics show that the present invention is suitable for suitability for industrialized production, and are with a wide range of applications.
Description of drawings
Fig. 1 is the fluorine-carbon modified polyacrylamide of embodiment 2 preparations
1The H-NMR spectrogram.
Fig. 2 is the perfluor modified amphoteric hydrophobic associated polymer of embodiment 2 preparations
19The F-NMR spectrogram.
Embodiment
Below in conjunction with concrete embodiment the present invention is done further and to explain.
Used solvent in the following enforcement: deionized water
Used monomer in the following enforcement: fluorine carbon/hydrocarbon mixed type cation surface active monomer makes by embodiment 1 method.Acrylamide (AM), analytical pure, close europeanized chemical reagent work of Tianjin section.
The catalyzer that the following example is used: Potassium Persulphate (KPS), analytical pure, close europeanized chemical reagent work of Tianjin section further uses the pure water recrystallization purifying, and vacuum-drying gets white crystal.
Agents useful for same in the following example 1:
Following reagent all obtains from commercial channels, and do not do and be further purified processing: N, N-dimethyl-ethylenediamine (99%, Beijing lark prestige Science and Technology Ltd.), tert-Butyl dicarbonate (99%, Beijing lark prestige Science and Technology Ltd.), N, dinethylformamide (99.8%, Beijing lark prestige Science and Technology Ltd.), 6-bromo-1-hexene (98%, Tianjin method Moses Science and Technology Ltd.), perfluoro-hexyl iodide alkane (97%, Beijing lark prestige Science and Technology Ltd.), allyl acetate (99%, Beijing lark prestige Science and Technology Ltd.), sulfuric acid (95～98% Yantai City are chemical industry company limited in pairs), hydrochloric acid (37%, the Yantai City is chemical industry company limited in pairs).
Following reagent also obtains from commercial channels, and is further purified processing: dibenzoyl peroxide (BPO) is available from the chemical company limited of A Faaisha (Tianjin), uses with after chloroform and the recrystallizing methanol 3 times; KOH is available from the chemical company limited of A Faaisha (Tianjin), and KOH is ground to powder with sheet, uses after the vacuum-drying; Methyl alcohol, dehydrated alcohol, anhydrous diethyl ether, normal hexane are analytical pure available from Tianjin Fu Yu Fine Chemical Co., Ltd, with reference to Purification ofLaboratory Chemicals, 5
ThEd (Chai, C.L.L.; Armare-go, W.L.F., Butterwirth-Heinemann:New York, 2003.) use of processing back.
The preparation of embodiment 1. fluorine carbon/hydrocarbon mixed type cation surface active monomer
(1) preparation of compound I
Take by weighing 0.88g (10mmol) N, the N-dimethyl-ethylenediamine is dissolved in 15ml DMF, change over to be equipped with prolong (on meet CaCl
2Drying tube), in three mouthfuls of round-bottomed flasks of 50ml of logical nitrogen tube, constant pressure funnel, put into 25 ℃ water bath with thermostatic control then, add rotor, start stirring, feed nitrogen deoxygenation 30min.Take by weighing 2.62g (12mmol) Boc acid anhydrides and be dissolved in 10ml DMF, change over to then in the 25ml constant pressure funnel.Open cock, the Boc acid anhydrides that will be dissolved in DMF dropwise splashes in the there-necked flask, and 0.5h drips off, and removes constant pressure funnel.Behind the thing reaction 1h to be mixed, 2.45g (15mmol) 6-bromo-1-hexene is dissolved in 5ml DMF changes in the 10ml constant pressure funnel.Open cock, dropwise splash in the above-mentioned there-necked flask, 1h drips off, and removes constant pressure funnel.Behind the reaction mixture normal-temperature reaction 72h, stopped reaction.Removal of solvent under reduced pressure adds anhydrous diethyl ether, and ice bath stirs 12h, separates out white solid, and suction filtration obtains the white solid powder, continues to obtain the pure compound I of 3.01g with anhydrous diethyl ether washing three times, and yield is 85.7%.
(2) preparation of compound I I
Build the gas generating unit of HCl gas, utilize the vitriol oil and concentrated hydrochloric acid to prepare saturated HCl-diethyl ether solution 25ml.Take by weighing 2.81g (8mmol) compound I and be dissolved in 10ml methyl alcohol, change over to be equipped with prolong (on meet CaCl
2Drying tube), in three mouthfuls of round-bottomed flasks of 50ml of constant pressure funnel, put into 0 ℃ of ice-water bath then, add rotor, slowly stir.Pipette the saturated HCl-diethyl ether solution of 5ml, change the 10ml constant pressure funnel over to, open cock, dropwise splash in the above-mentioned there-necked flask, 0.5h drips off.Slowly be warming up to room temperature then, stopped reaction behind the reaction 12h.Methyl alcohol, ether, HCl are removed in underpressure distillation, add anhydrous diethyl ether, and ice bath stirred 12 hours, separated out white solid, and suction filtration obtains the white solid powder, continue to obtain the pure compound I I of 2.19g with anhydrous diethyl ether washing three times, and yield is 95.1%.
(3) preparation of compound III
13.38g perfluoro-hexyl iodide alkane (30mmol), 3.03g allyl acetate (0.3mol) adding are equipped with in the 100ml four-hole bottle of spherical condensation tube, thermometer, drying tube, stirring rake, are heated to 95 ℃ and kept several minutes.Add 0.145g BPO (0.6mmol) rapidly, after the rapid heat release of question response is warming up to 160 ℃, be cooled to 120 ℃, keep reaction 30min.Add 35ml normal hexane and 4.05g potassium hydroxide (72mmol) then, back flow reaction 4h.After reaction finishes, cold filtration, filter cake washs with a small amount of normal hexane, and 77～80 ℃/40mmHg cut 7.58g is collected in the filtrate decompression distillation, is colourless transparent liquid, yield 67.2% (in perfluoro-hexyl iodide alkane).
(4) preparation of compound IV
With 1.15g (4mmol) compound I I, 7.52g (20mmol) compound III and 150ml dehydrated alcohol add be equipped with prolong (on meet CaCl
2Drying tube), in three mouthfuls of round-bottomed flasks of 250ml of logical nitrogen tube, add rotor and stir, feed nitrogen, temperature of reaction is 85 ℃, stopped reaction behind the reaction 6d.After reaction finished, ethanol was removed in underpressure distillation, added anhydrous diethyl ether, left standstill, separate out yellow transparent thickness lotion, vacuum-drying 72h gets the transparent thickness lotion of safran 2.57g, productive rate is 97.3%.
(1) immigration of 80ml deionized water is equipped with in the 250ml four-hole round-bottomed flask of mechanical stirring rod, spherical condensation tube, nitrogen ventpipe, thermometer, the acrylamide that takes by weighing 7.0582g (99.3mmol) changes in the four-hole bottle, feeds N
2, stirring at room 1h.
(2) take by weighing fluorine carbon/hydrocarbon mixed type cation surface active monomer of 0.4391g (0.7mmol), be dissolved in the 10ml deionized water, fully the dissolving back is yellow clear solution, change in the four-hole bottle after leaving standstill 10min, wash residual solution and foam repeatedly with the 10ml deionized water again and change in the reaction system together.Reaction system is warming up to 65 ℃, continues to stir N
2Protection keeps 30min.
(3) take by weighing the Potassium Persulphate (KPS) of 0.0541g (2mmol/L), change in the four-hole bottle rapidly, behind about 30s, reaction soln begins to become muddy by faint yellow settled solution, about 1h afterreaction system becomes faint yellow emulsion, along with the carrying out of reaction, emulsion is thickness more and more, foam showed increased in the system.，
(4) behind the reaction 24h, stopped reaction obtains the transparent faint yellow viscous fluid.Viscous fluid is changed in the large beaker that the 500ml dehydrated alcohol is housed while hot, obtain faint yellow netted soft solid, shred into cotton-shaped chip with scissors immediately, mechanical stirring 24h is to remove unreacted fluoro-carbon surface active monomer and acrylamide in dehydrated alcohol.
(5) suction filtration is removed dehydrated alcohol, obtains faint yellow soft chip, and 40 ℃ of following vacuum-drying 24h obtain faint yellow flake light solid, obtains the faint yellow solid powder 7.2871g of fluorine-carbon modified polyacrylamide after the pulverizing, and yield is 97.2%.
As described in embodiment 2, difference is that the monomeric charge ratio changes fluorine carbon/hydrocarbon mixed type cation surface active monomer 0.2509g into, and acrylamide 7.0795g obtains fluorine-carbon modified polyacrylamide pale yellow powder 7.0880g, and yield is 96.7%.
As described in embodiment 2, difference is that the monomeric charge ratio changes fluorine carbon/hydrocarbon mixed type cation surface active monomer 0.0626g into, and acrylamide 7.1001g obtains fluorine-carbon modified polyacrylamide pale yellow powder 7.0920g, and yield is 99.0%.
As described in embodiment 2, difference is that the quality of initiator potassium persulfate (KPS) changes 0.0811g (3mmol/L) into, obtains fluorine-carbon modified polyacrylamide pale yellow powder 7.3548g, and yield is 98.1%.
Claims (4)
1. fluorine-carbon modified Preparation of Polyacrylamide method, feature have provided the perfluor modification hydrophobic associated polymer that the emulsifier-free emulsion polymerization legal system is equipped with heatproof, tackify and anti-shear performance.Adopting the method for radical polymerization, is solvent with the pure water, and Potassium Persulphate (KPS) is initiator, and novel fluoro-carbon/hydrocarbon mixed type cation surface active monomer is hydrophobic monomer, with acrylamide (AM) copolymerization in the single solvent pure water.
2. fluorine-carbon modified Preparation of Polyacrylamide method as claimed in claim 1, it is characterized in that binary copolymerization in the single solvent pure water, total monomer is 1.0mol/L, fluorine carbon/hydrocarbon mixed type cation surface active monomer content is 0.1mol%～1.0mol%, and acrylamide content is 99.0mol%～99.9mol%.
3. fluorine-carbon modified Preparation of Polyacrylamide method as claimed in claim 1 is characterized in that not using emulsifying agent in the reaction process, has reduced production cost, also saves the last handling process except de-emulsifier simultaneously; In addition, the acrylamide copolymer of preparation is pure, has avoided in some application process because the disadvantageous effect that the existence of emulsifying agent produces polymkeric substance.
4. fluorine-carbon modified Preparation of Polyacrylamide method as claimed in claim 1 is characterized in that it is 1～3mmol/L that used initiator potassium persulfate (KPS) has been used.
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| CN105504153B (en) * | 2015-12-25 | 2017-06-20 | 长江大学 | A kind of fluorine-containing hydrophobic association surface-active polyacrylamide and preparation method thereof |
| CN106467601A (en) * | 2016-09-29 | 2017-03-01 | 陕西科技大学 | A kind of hydrophobic association type PAMC and its preparation method and application |
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| US11911761B2 (en) | 2021-01-22 | 2024-02-27 | Saudi Arabian Oil Company | Microfluidic chip with mixed porosities for reservoir modeling |
| CN112897947A (en) * | 2021-01-29 | 2021-06-04 | 江苏中砼新材料科技有限公司 | High-strength anti-cracking environment-friendly concrete and preparation process thereof |
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