CN103396284A - Hydrophobic monomer for synthesizing temperature sensitive polymer oil-displacing agent and preparation method thereof - Google Patents
Hydrophobic monomer for synthesizing temperature sensitive polymer oil-displacing agent and preparation method thereof Download PDFInfo
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- CN103396284A CN103396284A CN2013103124105A CN201310312410A CN103396284A CN 103396284 A CN103396284 A CN 103396284A CN 2013103124105 A CN2013103124105 A CN 2013103124105A CN 201310312410 A CN201310312410 A CN 201310312410A CN 103396284 A CN103396284 A CN 103396284A
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Abstract
The invention discloses a hydrophobic monomer for synthesizing a temperature sensitive polymer oil-displacing agent and a preparation method thereof, which belong to the technical field of the design of oilfield chemical agents. In order to solve the problems of bad temperature resistance, salt resistance and anti-shear ability of a part of hydrolyzed polyacrylamide serving as an oil-displacing agent and solve the problems of complex synthesis method, dissolution difficulty and high cost of modified temperature-resistant and salt-resistant polymer oil-displacing agents, the invention provides a method for synthesizing a temperature sensitive polymer oil-displacing agent with a thermo-thickening function by copolymerizing poly N-alkyl acrylamide, acrylamide and a temperature-resistant, salt-resistant and hydrophobic monomer. According to the design, n-butylbenzene is used as a raw material, and the hydrophobic monomer p-n-butylbenzene ethylene is synthesized through three chemical reactions of Friedel-Crafts acylation, negative hydrogen transfer reduction and dehydration of alcohol to alkene. The reaction conditions are mild, the purification method is simple, the product is pure, and the requirements of temperature resistance and salt resistance of the hydrophobic monomer for forming the temperature sensitive polymer oil-displacing agent can be met.
Description
Technical field
The present invention relates to a kind ofly for synthetic hydrophobic monomer of temperature sensing polymer oil-displacing agent and preparation method thereof, belong to the Oilfield Chemicals design field.
Background technology
Polymer oil-displacing agent is the chemical agent that is widely used in the tertiary oil recovery operation.Commercial Industrial products mainly contain partially hydrolyzed polyacrylamide (HPAM) and xanthan gum (XG) at present, and wherein, partially hydrolyzed polyacrylamide is because price is lower, and application performance is better, in China oil production, is widely used.And xanthan gum because injection is poor, thermotolerance and germ resistance poor, cost is higher, fewer as polymer oil-displacing agent.But partially hydrolyzed polyacrylamide exists the poor defect of temperature tolerance, salt tolerance and anti-shear ability as oil-displacing agent.In recent years, to the development of thermal resisting anti-salt type polymer oil-displacing agent, give great concern both at home and abroad, mainly contained amphiphilic polymers, heat-resistant salt-resistant modified monomer polymkeric substance, hydrophobic associated polymer, the comb-shaped polymer etc.Though product temperature tolerance, salt tolerance and anti-shear ability through modification increase, but still there are the problems such as synthetic method is complicated, dissolving is more difficult, cost is high.
No matter be the polymer-modified of partially hydrolyzed polyacrylamide or thermal resisting anti-salt type, the characteristics of its aqueous solution are all that increase, the shearing rate along with temperature increases, salts contg is increased to the characteristics that viscosity degradation to a certain degree occurs.And the poly-N-alkyl acrylamide base polymer aqueous solution shows the phenomenon that viscosity increases with the temperature increase, it is a kind of temperature sensing polymer of typical hot thickening, this base polymer is mainly used in the fields such as medicament slow release, feed separation purification, temperature sensitive film, the fixing and immunoassay of enzyme, intelligent weaving, the relevant report of also not applying in tertiary oil recovery at present.In view of the hot thickening effect of this base polymer, if can for tertiary oil recovery, be expected greatly to improve the temperature tolerance of thickening material, meet the needs on high temperature and high salt stratum, play good Efficient Adhesive Promotion.And the hot thickening effect of poly-N-alkyl acrylamide class temperature sensing polymer mainly relies on polymkeric substance to contain a certain proportion of hydrophilic radical and hydrophobic grouping, both meetings produce interaction with the water molecules in the aqueous solution, when temperature during lower than critical temperature, hydrophilic radical and water molecules in polymkeric substance are had an effect, existence due to hydrogen bond and intermolecular Van der Waals force, make polymer macromolecule water molecules on every side form the solvation shell that is connected by hydrogen bond, make polymkeric substance show a kind of ball of string structure of stretching, extension, and present the characteristic that can be dissolved in water.When temperature raises, the hydrogen bond rupture that forms between hydrophilic radical and water molecules, solvated layer is destroyed, present hydrophobic property, the part hydrogen bond is destroyed, and the solvated layer of macromolecular chain hydrophobic part is destroyed, and water molecules shows as phase transformation from the discharge of solvated layer, and become micelle shape structure closely by a ball of string, produce the phenomenon of thickening.
And the used for tertiary oil recovery oil-displacing agent not only requires polymkeric substance to have good thickening effectiveness, and requires polymkeric substance to have temperature resistant antisalt, and the selection of hydrophobic monomer is that temperature sensitive polymer can be as the key of polymer oil-displacing agent.Hydrophobic monomer commonly used mainly contains following several at present: N-dodecyl acrylamide, N, N-bis-(dodecyl) acrylamide, N-is to the n-butylphenyl acrylamide, vinylformic acid perfluoro capryl ethyl ester, PhEA, to tert-butylbenzene ethene, to vinyl biphenyl etc., it can be for carrying out free-radical polymerizedly with acrylamide or derivative, and the chemical structural formula of these hydrophobic monomers is:
(a) N-dodecyl acrylamide, (b) N, N-bis-(dodecyl) acrylamide, (c) N-is to the n-butylphenyl acrylamide, (d) vinylformic acid perfluoro capryl ethyl ester, (e) PhEA, (f) to tert-butylbenzene ethene, (g) to vinyl biphenyl;
Visible from the said structure formula, hydrophobic monomer (a), (b), (c), (d), (e) contain amido linkage or ester bond or the carbonyl of facile hydrolysis, easy hydrolytic cleavage and slough hydrophobic grouping under the stimulation of the external environments such as temperature, shearing, salt, lose hydrophobic effect.And (f), (g) contain benzene ring structure, has certain rigidity, can improve the temperature resistant antisalt ability of polymkeric substance, but wherein (f)-short to tert-butylbenzene vinyl alkyl chain, hydrophobicity a little less than, (g)-to vinyl biphenyl owing to containing two phenyl ring, water-soluble can variation.The rigid radical that the requirement that therefore, meet the polymer oil-displacing agent temperature resistant antisalt must contain in polymer chain; Meet the thickening characteristic of temperature sensitive polymer, will carry the hydrophobic performance of suitable high hydrophobic monomer.
Summary of the invention
In order to meet above-mentioned requirements, the present invention is directed to the deficiencies in the prior art and provide a kind of for synthetic hydrophobic monomer of temperature sensing polymer oil-displacing agent and preparation method thereof.
The present invention proposes to utilize n-butylbenzene to be raw material, and by the Fu Ke acylation reaction, Hydride transfer reduction reaction and dehydration of alcohols become the conventional chemical reaction of alkene reaction three step, vinyl are introduced to the contraposition of n-butylbenzene, and the hydrophobic synthetic monomer aligns butylstyrene.To hydrophobic monomer, align butylstyrene and can become the temperature sensitive polymer oil-displacing agent with N-alkyl acrylamide, acrylamide.The phenyl ring that aligns in the butylstyrene molecule can improve the copolymer molecule chain rigidity, the molecular chain of aqueous copolymers solution is unfolded, be conducive to improve the temperature resistant antisalt ability of multipolymer, phenyl ring is also hydrophobic grouping simultaneously, can make multipolymer produce the hydrophobic association effect, the hydrophobic grouping normal-butyl that is in contraposition is further strengthened the hydrophobic effect of multipolymer, produces temperature sensitive thickening power.Align the molecular structure of butylstyrene:
The present invention is achieved through the following technical solutions above-mentioned purpose.
(1) the Fu Ke acylation reaction of phenyl ring contraposition is synthetic to the n-butylbenzene ethyl ketone
Take maleic anhydride as acylating agent, under the catalytic condition of aluminum trichloride (anhydrous), n-butylbenzene is carried out to the Fu Ke acylation reaction, in the contraposition of n-butylbenzene, introduce ethanoyl, obtain the first step reaction product to the n-butylbenzene ethyl ketone, reaction equation is shown below:
(2) the synthetic 1-methyl of the Hydride transfer reduction reaction of carbonyl is to n-butylbenzene methyl alcohol
Take sodium borohydride as reductive agent, will be alcohol to the carbonyl reduction of n-butylbenzene ethyl ketone, obtain second step reaction product 1-methyl to n-butylbenzene methyl alcohol, reaction equation is shown below:
(3) dehydration of alcohols becomes the synthetic n-butylbenzene ethene of reaction of alkene
Under the katalysis of p-methyl benzenesulfonic acid monohydrate, the 1-methyl, in the n-butylbenzene methanol molecules, sloughing a part water, obtains final product and aligns butylstyrene, and reaction equation is shown below:
The present invention compared with prior art has following beneficial effect:
1, to adopt the commercialization n-butylbenzene be starting raw material in the present invention, and raw material is easy to get, and cost is low.
2, n-butylbenzene ethene of the present invention contains two keys, has good reactive behavior, energy and acrylamide, N-alkyl acrylamide generation copolyreaction.
3, the phenyl ring in n-butylbenzene ethylene molecule of the present invention can improve temperature sensitive copolymer molecule chain rigidity, the molecular chain of aqueous copolymers solution is unfolded, can improve the temperature resistant antisalt ability of multipolymer, the hydrophobic grouping normal-butyl of phenyl ring and contraposition can be strengthened the hydrophobic interaction of temperature sensitive multipolymer simultaneously, produces hot thickening effect.
4, it is popular response that the Fu Ke acidylate of the present invention's employing, Hydride transfer reduction and dehydration of alcohols become alkene three step chemical reactions, and reaction conditions is gentle, the product purification method is simple, product is pure, can meet synthetic requirement.
The accompanying drawing explanation
Fig. 1 is n-butylbenzene and the first step reaction product infrared spectrogram to the n-butylbenzene ethyl ketone;
Fig. 2 is to n-butylbenzene ethyl ketone and the second step reaction product 1-methyl infrared spectrogram to n-butylbenzene methyl alcohol;
Fig. 3 is that the 1-methyl aligns the infrared spectrogram of butylstyrene to n-butylbenzene methyl alcohol and three-step reaction product;
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
(1) synthesizing the n-butylbenzene ethyl ketone
In the 500ml three-necked bottle of magnetic agitation is housed, in 0 ℃, 56.75g (0.44mol) aluminum trichloride (anhydrous) is added in the 200ml methylene dichloride and dissolves 30min, slowly add again 22.45g (0.22mol) solution of acetic anhydride that is dissolved in the 25ml methylene dichloride, in 0 ℃, continue to stir 15min, then slowly drip and be dissolved in 13.4g (0.1mol) the n-butylbenzene solution 30min in the 25ml methylene dichloride, rise to room temperature reaction 5h.Mixture after reaction is completed pours on the trash ice of 375ml, the organic solution part of separating is used the hydrochloric acid soln of 125ml10wt% successively, the saturated sodium carbonate solution of 125ml, the saturated nacl aqueous solution washing of 125ml 2 times, gained solution revolves to steam through the anhydrous magnesium sulfate drying final vacuum removes methylene dichloride, obtain product liquid to the n-butylbenzene ethyl ketone, with reference to figure 1.
(2) 1-methyl synthesizing n-butylbenzene methyl alcohol
In the 500ml three-necked bottle of magnetic agitation is housed, in 0 ℃, 13.2g (0.075mol) is added in 250ml methyl alcohol the n-butylbenzene ethyl ketone, then in 5min, add successively the 0.85g(0.0225mol that is divided into ten deciles) sodium borohydride, temperature is risen to 60 ℃ of reaction 2h.Mixture after reaction is completed revolves to steam removes methyl alcohol, be dissolved in again in the normal hexane of 250ml, use successively the hydrochloric acid soln of 125ml10wt%, the saturated nacl aqueous solution washing of 125ml 2 times, gained solution revolves to steam through the anhydrous magnesium sulfate drying final vacuum removes normal hexane, obtain product liquid 1-methyl to n-butylbenzene methyl alcohol (need carry out twice this reaction, reactant is fully reduced).With reference to figure 2.
(3) align the synthetic of butylstyrene
In the mono-neck bottle of the 500ml that magnetic agitation and water trap are housed, add 350ml toluene, add successively the p-methyl benzenesulfonic acid monohydrate of 6.489g (0.0364mol) 1-methyl to n-butylbenzene methyl alcohol and 0.2077g (3mol%), reactant is heated to 160 ℃ of condensing reflux 2h again.Mixture after reaction is completed is cooled to room temperature, with 340ml distilled water wash 1 time, gained solution revolves to steam through the anhydrous magnesium sulfate drying final vacuum removes toluene, and products therefrom is take normal hexane as chromatographic solution, through the silica gel column chromatography separating-purifying, obtain the ultimate aim product and align butylstyrene.With reference to figure 3.
Embodiment 2
At first by acrylamide: N, N diethyl acrylamide: the monomer mole ratio that aligns butylstyrene=79:20:1, add successively in there-necked flask, be dissolved in deionized water and obtain monomer solution, the monomer oeverall quality accounts for 30% of monomer solution total mass, then adds the sodium laurylsulfonate of monomer total mass 1.5% and 1% oxidation-reduction initiator system (Potassium Persulphate: the S-WAT mass ratio is 1:1).Control 100 rev/mins of stirring velocitys, 45 ℃ of temperature of reaction, reacted 10 hours, product washing with acetone 3 times, then dry under 80 ℃ of conditions, can obtain with the cinnamic temperature sensing polymer oil-displacing agent of normal-butyl.Synthetic temperature sensitive polymer is configured to 0.8% deionized water solution, when temperature surpasses 50 ℃ (phase transition temperature), viscosity sharply rises to 256.9mpa.s. from 98.5mpa.s. and demonstrates stronger hot thickening effect, increases temperature to 100 ℃, the viscosity loss rate only has 5%, at 50 ℃, 170s
-1Under shearing rate, sheared 30 minutes, the viscosity loss rate only has 8%, in system, add 3% sodium-chlor, the salt of 1% calcium chloride, viscosity does not only descend, 5% rising is arranged on the contrary, and the character of aqueous solutions of polymers demonstrates the rigidity hydrophobic monomer and has stronger anti-shear ability.
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improve and conversion all should belong to the protection domain of claims of the present invention.
Claims (5)
1. the preparation method for the synthetic hydrophobic monomer of temperature sensing polymer oil-displacing agent, is characterized in that, comprises the following steps:
(1) with the commercialization n-butylbenzene, be starting raw material, synthetic to the n-butylbenzene ethyl ketone by the Fu Ke acylation reaction of phenyl ring contraposition;
(2) with the n-butylbenzene ethyl ketone after purifying, by the Hydride transfer reduction reaction of carbonyl, synthesize the 1-methyl to n-butylbenzene methyl alcohol;
(3) the 1-methyl becomes the synthetic butylstyrene that aligns of reaction of alkene by dehydration of alcohols to n-butylbenzene methyl alcohol.
2. preparation method according to claim 1; it is characterized in that; in described step (1); adopting the commercialization n-butylbenzene is raw material; take maleic anhydride as acylating agent, aluminum trichloride (anhydrous) is catalyzer, and synthetic product is used hydrochloric acid soln successively; saturated sodium carbonate solution, saturated sodium-chloride washs.
3. preparation method according to claim 1, it is characterized in that, in described step (2), take sodium borohydride as reductive agent, in reaction process, in 5min, add successively the 0.85g sodium borohydride that is divided into ten deciles, then temperature is risen to 60 ℃ of reaction 2h, product washs with the hydrochloric acid soln saturated nacl aqueous solution.
4. the preparation method described according to claim 1, is characterized in that, in described step (3), with the p-methyl benzenesulfonic acid monohydrate, make catalyzer, reactant is heated to 160 ℃ of condensing reflux 2h, and products therefrom is take normal hexane as chromatographic solution, through the silica gel column chromatography separating-purifying.
5. the hydrophobic monomer for preparing of according to claim 1-4 arbitrary described preparation methods.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104531118A (en) * | 2014-12-25 | 2015-04-22 | 郑州正佳能源环保科技有限公司 | Method for preparing intelligent nanometer oil-displacing agent |
| CN106317340A (en) * | 2015-07-07 | 2017-01-11 | 中国石油化工股份有限公司 | Thermosensitive polymer, preparation method and application thereof, and method for displacing oil from oil pool |
| CN106349181A (en) * | 2015-07-16 | 2017-01-25 | 中国石油化工股份有限公司 | Phenyl and fluorocarbon chain-containing hydrophobic monomer and polymer based on phenyl and fluorocarbon chain-containing hydrophobic monomer |
| CN106749886A (en) * | 2015-11-24 | 2017-05-31 | 中国石油天然气股份有限公司 | It is a kind of can the thickening of heat/salt copolymer and preparation method thereof |
| CN109762171A (en) * | 2019-01-28 | 2019-05-17 | 中石化石油工程技术服务有限公司 | Temperature sensitive polymer and preparation method thereof, drilling fluid flow pattern regulator composition, drilling fluid flow pattern regulator and preparation method thereof |
| CN110078594A (en) * | 2019-04-19 | 2019-08-02 | 新昌县泰如科技有限公司 | A kind of synthetic method of p-hydroxyphenylethanol |
| CN110655605A (en) * | 2019-10-12 | 2020-01-07 | 青岛大学 | Preparation method of novel reverse temperature-sensitive gel oil displacement agent |
| CN111778004A (en) * | 2020-08-12 | 2020-10-16 | 中国石油大学(北京) | Amphiphilic block polymer ultra-low permeability agent and intelligent temporary plugging type water-based drilling fluid |
| CN112143478A (en) * | 2019-06-28 | 2020-12-29 | 中国石油化工股份有限公司 | Temperature-sensitive salt-sensitive oil displacement composition, displacement fluid, preparation method and application thereof |
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| CN104531118A (en) * | 2014-12-25 | 2015-04-22 | 郑州正佳能源环保科技有限公司 | Method for preparing intelligent nanometer oil-displacing agent |
| CN104531118B (en) * | 2014-12-25 | 2017-09-12 | 河南正佳能源环保股份有限公司 | A kind of preparation method of intelligent nano oil displacement agent |
| CN106317340A (en) * | 2015-07-07 | 2017-01-11 | 中国石油化工股份有限公司 | Thermosensitive polymer, preparation method and application thereof, and method for displacing oil from oil pool |
| CN106349181A (en) * | 2015-07-16 | 2017-01-25 | 中国石油化工股份有限公司 | Phenyl and fluorocarbon chain-containing hydrophobic monomer and polymer based on phenyl and fluorocarbon chain-containing hydrophobic monomer |
| CN106349181B (en) * | 2015-07-16 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of hydrophobic monomer containing phenyl and fluorocarbon chain and the polymer based on the monomer |
| CN106749886A (en) * | 2015-11-24 | 2017-05-31 | 中国石油天然气股份有限公司 | It is a kind of can the thickening of heat/salt copolymer and preparation method thereof |
| CN109762171A (en) * | 2019-01-28 | 2019-05-17 | 中石化石油工程技术服务有限公司 | Temperature sensitive polymer and preparation method thereof, drilling fluid flow pattern regulator composition, drilling fluid flow pattern regulator and preparation method thereof |
| CN109762171B (en) * | 2019-01-28 | 2021-08-17 | 中石化石油工程技术服务有限公司 | Temperature-sensitive polymer and preparation method thereof, drilling fluid flow pattern regulator composition, drilling fluid flow pattern regulator and preparation method thereof |
| CN110078594A (en) * | 2019-04-19 | 2019-08-02 | 新昌县泰如科技有限公司 | A kind of synthetic method of p-hydroxyphenylethanol |
| CN110078594B (en) * | 2019-04-19 | 2022-07-15 | 新昌县泰如科技有限公司 | Synthetic method of p-hydroxyphenylethanol |
| CN112143478A (en) * | 2019-06-28 | 2020-12-29 | 中国石油化工股份有限公司 | Temperature-sensitive salt-sensitive oil displacement composition, displacement fluid, preparation method and application thereof |
| CN112143478B (en) * | 2019-06-28 | 2022-09-30 | 中国石油化工股份有限公司 | Temperature-sensitive salt-sensitive oil displacement composition, displacement fluid, preparation method and application thereof |
| CN110655605A (en) * | 2019-10-12 | 2020-01-07 | 青岛大学 | Preparation method of novel reverse temperature-sensitive gel oil displacement agent |
| CN111778004A (en) * | 2020-08-12 | 2020-10-16 | 中国石油大学(北京) | Amphiphilic block polymer ultra-low permeability agent and intelligent temporary plugging type water-based drilling fluid |
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Application publication date: 20131120 |