CN102807503A - Polymerizable monomer with surface activity and tackifying copolymer with surface activity as well as preparation methods and application thereof - Google Patents
Polymerizable monomer with surface activity and tackifying copolymer with surface activity as well as preparation methods and application thereof Download PDFInfo
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- CN102807503A CN102807503A CN2011101482455A CN201110148245A CN102807503A CN 102807503 A CN102807503 A CN 102807503A CN 2011101482455 A CN2011101482455 A CN 2011101482455A CN 201110148245 A CN201110148245 A CN 201110148245A CN 102807503 A CN102807503 A CN 102807503A
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Abstract
The invention discloses a polymerizable monomer with surface activity, a tackifying copolymer with surface activity as well as preparation methods and application of the polymerizable monomer and the tackifying copolymer. The polymerizable monomer with surface activity has a structure shown in formula (I) shown in the specification, has high surface activity and high polymerization activity, and can be copolymerized with other monomers to obtain the tackifying copolymer surface activity. The solution of the tackifying copolymer with surface activity has excellent temperature resistance, salt resistance and apparent viscosity, and can effectively exert actions of solubilizing, dispersing and the like on crude oil when used as an oil-displacing agent, so as to carry and draw remnant crude oil difficult to displace and improve the displacement efficiency.
Description
Technical field
The present invention relates to surfactivity polymerisable monomer, surfactivity tackify multipolymer and preparation method thereof; Particularly, relate to a kind of surfactivity polymerisable monomer and preparation method thereof, a kind of surfactivity tackify multipolymer and preparation method thereof and this application of surfactivity tackify multipolymer in oil-displacing agent.
Background technology
Large-scale oil fields such as China's grand celebration, triumph, Central Plains, North China, huge port have all got into the exploitation middle and later periods at present; Extraction oil water ratio is up to more than 90%; Temperature and salinity all increase substantially; First and second oil recovery technique can't satisfy growing crude oil demand again, therefore, adopts tertiary oil recovery technology to improve the grand strategy measure that RF has become China Petroleum.
Polymer flooding is one of efficient ways the most in the tertiary oil recovery technology.This method requires polymkeric substance under reservoir condition, must have good thickening property, and high viscosity conservation rate will be arranged under the effect of temperature, pressure and salt.It is domestic that what generally adopt is the SEPIGEL 305 (HPAM) of SEPIGEL 305 (PAM) and partly hydrolysed; Its oil-displacement mechanism is that aqueous solutions of polymers has very high viscosity to reduce the rate of permeation of water under very low concentration; The degree of mobilization of control water; Improve sweep efficiency, finally reach the purpose that improves oil recovery factor.But this base polymer has the shortcoming of shear shinning, pyrolytic decomposition, chance salt viscosity reduction; And at tertiary phase; Oil reservoir is dark, the interior temperature of oil well is high; The use temperature of PAM can not surpass 75 ℃, and in the higher oil reservoir of salinity, is separated easily, causes soltion viscosity acutely to descend.
In addition; Except using hydrophilic polymers such as PAM and HPAM to carry out the displacement of reservoir oil; Also commonly used all have the surface-active polymer of affinity to come the displacement of reservoir oil as oil-displacing agent to water, oil phase, and this surface-active polymer comprises amphiphilic block water-soluble polymkeric substance and hydrophobic associated water-soluble polymer two big classes.In order to overcome the above-mentioned shortcoming of SEPIGEL 305; Domestic and international research personnel have done number of research projects; Disclose like US4814096 and a kind ofly to prepare the multipolymer of acrylic amide, vinylformic acid and lauryl methacrylate(LMA) with method of emulsion polymerization, its hydrophobic association effect makes polymkeric substance have the anti-shearing property of temperature resistant antisalt preferably.Zhao Yong (the synthetic and performance study of hydrophobic association type SEPIGEL 305 in the reverse micro emulsion; " polymer journal "; 2000, (5): 550-553) synthesized the SEPIGEL 305 of hydrophobically modified with the conversed phase micro emulsion copolymerization method, this multipolymer gets the aqueous solution and has good tackify characteristic.But water-fast hydrophobic monomer has all been used in the preparation of above-mentioned hydrophobic associated water-soluble polymer, therefore needs to consume a large amount of tensio-active agents, causes industrial cost huge, and the later stage tensio-active agent is difficult for removal and destroys environment.
The various deficiencies that exist when solving a large amount of use tensio-active agent; The multipolymer with ionogenic surfactant side chain that a kind of employing obtains by monomer copolymerizations such as polymerizable surfactants monomer and the acrylic amides method as oil-displacing agent has been proposed; This analog copolymer obtains good salt resistance through the congregation that salt brings out the tensio-active agent side chain, can be used for the oil-displacing agent under high temperature and the high salinity formation condition.Wang Yupeng (AM/AA/AMPS/AMC
14The preparation of S multipolymer and sign, " Qingdao University of Science and Technology's journal ", 2006,27 (1): 1-4) prepare polymerisable surface active monomer AMC
14S; Utilize the method for micellar copolymerization to prepare the higher tetrapolymer of molecular weight; Under low temperature and low mineralization, aqueous copolymers solution shows tackify character preferably, but this tetrapolymer tackifying under high temperature and high salt is relatively poor; And solvability is bad, big limitations its in Application in Oilfield.
Summary of the invention
The objective of the invention is for the relatively poor shortcoming of tackifying under the high temperature and high salt that overcomes the resulting multipolymers of monomer copolymerization such as utilizing existing surface active monomer and acrylic amide, a kind of surfactivity surface of good reactive, polymerizable monomer is provided and the surface active block copolymer and preparation method thereof of strong, the favorable solubility of thickening property under high temperature and high salt.
The present invention improves a kind of surfactivity polymerisable monomer, and wherein, this surfactivity polymerisable monomer has the structure shown in the formula (1),
Wherein, R is H or CH
3, n1 is 2 or 3, n2 is the integer of 4-18.
The present invention also provides a kind of preparation method of surfactivity polymerisable monomer; Wherein, this preparation method comprises: under alkylation reaction condition, under alkaline condition; Acrylic amide shown in the formula (2) is contacted in organic solvent with the haloalkyl sulfonic acid alkali metal salts shown in the formula (3)
X-(CH
2)
N2-SO
3 -Y
+Formula (3)
Wherein, in the formula (2), R is H or CH
3, n1 is 2 or 3; In the formula (3), n2 is the integer of 4-18, and X is a halogen, and Y is a basic metal.
The present invention also provides a kind of surfactivity tackify multipolymer; Wherein, this multipolymer contains the structural unit B shown in structural unit A shown in the formula (4) and the formula (5), is benchmark with this multipolymer; The content of said structural unit B is 0.1-20 weight %; The mol ratio of said structural unit A and structural unit B is 30-1000: 1, and the intrinsic viscosity of said multipolymer [η] is 1200-2600mL/g
formula (4)
Wherein, in the formula (4), R
1', R
2' and R
3' be the alkyl of hydrogen or carbonatoms 1-3 independently of one another, R
4' for being selected from-CONH
2,-COOH and-CONHC (CH
3)
2CH
2SO
3Any one group among the H; In the formula (5), R is H or CH
3, n1 is 2 or 3, n2 is the integer of 4-18.
The present invention also provides a kind of preparation method of surfactivity tackify multipolymer, and wherein, this method comprises: under polymeric reaction condition; In the presence of initiator; Make a kind of monomer mixture in water, carry out polyreaction, said monomer mixture contains the monomer shown in the formula (6) and above-mentioned according to surfactivity polymerisable monomer of the present invention, and is benchmark with said monomer mixture; The consumption of said surfactivity polymerisable monomer is 0.1-20 weight %; The mol ratio of monomer shown in the formula (6) and described surfactivity polymerisable monomer is 30-1000: 1, and the condition of polyreaction makes that the intrinsic viscosity [η] of gained multipolymer is 1200-2600mL/g
Wherein, in the formula (6), R
1', R
2' and R
3' be the alkyl of hydrogen or carbonatoms 1-3 independently of one another, R
4' for being selected from-CONH
2,-COOH and-CONHC (CH
3)
2CH
2SO
3Any one group among the H.
Surfactivity polymerisable monomer of the present invention has hydrophilic radical and hydrophobic grouping simultaneously on molecular structure; Therefore have the surface of good activity, this surfactivity polymerisable monomer has the effect from solubilising when being used to prepare polymkeric substance, need not to add tensio-active agent; Can obtain to have surfactivity micro-block structure and the good multipolymer of solubility property; And this surfactivity polymerisable monomer belongs to the verivate of acrylic amide, is prone to and the acrylamide monomers copolymerization, and is substituted macoradical on the acid amides N; Strengthen the resistance to hydrolysis of itself and multipolymer, thereby improved the stability of multipolymer when high temperature.
Surfactivity tackify multipolymer of the present invention is through in the aqueous solution, making said surfactivity polymerisable monomer and making like acrylic acid or the like and/or acrylamide monomers polymerization in homogeneous phase; The preparation process is simple; Need not to add the exhibiting high surface promoting agent, greatly reduce production cost.In addition; The temperature resistant antisalt property and the AV of this copolymer solution are good; This possibly be because the introducing of sulfonic acid fundamental mode reinforcing yin essence ionic hydrophilic property group and fat or aryl hydrophobic side chain has increased macromolecular hydrodynamic radius through its intermolecular charge repulsion and association.This surfactivity tackify multipolymer can also play effects such as solubilising, dispersion effectively, thereby can carry, pull the irreducible oil that difficulty is driven as oil-displacing agent the time to crude oil, improve its oil displacement efficiency.This surfactivity tackify multipolymer of the present invention can be used as polymer oil-displacing agent, is applicable to oil reservoir behind high temperature and high salt oil deposit and the polymer flooding, in TOR, further improves oil recovery factor.
Description of drawings
Fig. 1 is the figure of the relation of expression tackify multipolymer of the present invention and the AV of existing tackify multipolymer under different concns;
Fig. 2 is the figure of the relation of expression tackify multipolymer of the present invention and the AV of existing tackify multipolymer under differing temps.
Embodiment
The present invention provides a kind of surfactivity polymerisable monomer, and wherein, this surfactivity polymerisable monomer has the structure shown in the formula (1),
Wherein, R is H or CH
3, n1 is 2 or 3, n2 is the integer of 6-18.
Under the preferable case, R is H, and n1 is 2, and n2 is the integer of 6-12; Perhaps R is CH
3, n1 is 2, n2 is the integer of 6-12; Perhaps R is H, and n1 is 3, and n2 is the integer of 6-12; Perhaps R is CH
3, n1 is 3, n2 is the integer of 6-12.
The present invention also provides a kind of preparation method of surfactivity polymerisable monomer; Wherein, this preparation method comprises: under alkylation reaction condition, under alkaline condition; Acrylic amide shown in the formula (2) is contacted in organic solvent with the haloalkyl sulfonic acid alkali metal salts shown in the formula (3)
X-(CH
2)
N2-SO
3 -Y
+Formula (3)
Wherein, in the formula (2), R is H or CH
3, n1 is 2 or 3; In the formula (3), n2 is the integer of 6-18, and X is a halogen, and Y is a basic metal.
Under the preferable case, in the formula (3), n2 is the integer of 6-12;
In the formula (3), X is preferably chlorine, bromine or iodine; Chlorine or bromine more preferably.
In the formula (3), Y is an alkali metal, is preferably sodium element.
According to the preparation method of surfactivity polymerisable monomer, the consumption of the haloalkyl sulfonic acid alkali metal salts shown in acrylic amide shown in the said formula (2) and the formula (3) can in very large range change.Under preferred situation, the consumption mol ratio of the haloalkyl sulfonic acid alkali metal salts shown in the acrylic amide shown in the said formula (2) and the formula (3) is 0.7-2.5: 1, and preferred 0.75-1.5: 1,0.8-1.3 more preferably: 1, further be preferably 1.0-1.2: 1.The consumption of the haloalkyl sulfonic acid alkali metal salts shown in acrylic amide shown in the said formula (2) and the formula (3) is in above-mentioned scope the time, and the surfactivity polymerisable monomer solvability that obtains is better, surfactivity is higher.
Preparing method according to the surfactivity polymerisable monomer; Acrylic amide shown in the said formula (2) can be N; N-dimethylamino propyl acrylamide, N; N-dimethylamino-propyl USAF RH-1, N, N-dimethylaminoethyl acrylic amide and N, one or more in the N-dimethylaminoethyl USAF RH-1.
According to the preparation method of surfactivity polymerisable monomer of the present invention, under the preferred situation, said alkaline condition is meant that the pH value is 9-11.Said alkaline condition for example can be realized (for example NaOH, KOH etc.) through in mixture, adding basic cpd, as long as can reach desired pH value scope.
Preparing method according to surfactivity polymerisable monomer of the present invention; Under preferred situation; The mol ratio of the total amount of the haloalkyl sulfonic acid alkali metal salts shown in acrylic amide shown in said organic solvent and the said formula (2) and the formula (3) can be 1-50: 1; 1.5-20 more preferably: 1, further be preferably 2-10: 1.
Above-mentioned organic solvent can be all kinds of SOLVENTS known in the field.Under preferred situation, be selected from ethanol, Virahol, THF, ether, chloroform, ETHYLE ACETATE, N, benzene and the toluene one or more.
Preparing method according to surfactivity polymerisable monomer of the present invention; Acrylic amide shown in the said formula (2) comprises the temperature of contact and the time that contacts with the condition that the haloalkyl sulfonic acid alkali metal salts shown in the formula (3) contacts, and the temperature of said contact can be selected in awide temperature range.The temperature that contacts under the preferred situation is 10-50 ℃, more preferably 30-45 ℃; The prolongation of duration of contact helps the raising of reaction yield, but duration of contact is long to its yield increase rate and not obvious, and under the therefore general preferable case, the time of contact can be 10-20 hour, more preferably 10-14 hour.
According to the preparation method of surfactivity polymerisable monomer of the present invention, this method also comprise with the contact after product carry out solid-liquid separation through after the room temperature cooling, vacuum-drying obtains surfactivity polymerisable monomer of the present invention.In order further to improve the purity of the surfactivity polymerisable monomer that obtains, under the preferred situation, can also the solid that above-mentioned solid-liquid separation obtains be carried out after the crystallization treatment dry again.
The mode of above-mentioned filtration, vacuum-drying, recrystallization or method all can adopt this area mode or method commonly used, and the present invention does not have particular requirement.For example, the solvent of said recrystallization can be in ethanol, acetone, Virahol, the ETHYLE ACETATE one or more.
Because being the reaction through dehydrohalogenation between halohydrocarbon and the organic amine, the present invention prepares the surfactivity polymerisable monomer; And this reaction to be organic chemistry filed very conventional and study very sophisticated reaction; Therefore to need not special structural characterization with solid product after the haloalkyl sulfonic acid alkali metal salts shown in the formula (3) contacts be that provable its is the structure shown in the formula (1) to the acrylic amide shown in the said formula (2); But also can characterize, as confirming through nucleus magnetic resonance and infrared spectrum.
The present invention also provides a kind of surfactivity tackify multipolymer; Wherein, this multipolymer contains the structural unit B shown in structural unit A shown in the formula (4) and the formula (5), is benchmark with this multipolymer; The content of said structural unit B is 0.1-20 weight %; The mol ratio of said structural unit A and structural unit B is 30-1000: 1, and the intrinsic viscosity of said multipolymer [η] is 1200-2600mL/g
Wherein, in the formula (4), R
1', R
2' and R
3' be the alkyl of hydrogen or carbonatoms 1-3 independently of one another, R
4' for being selected from-CONH
2,-COOH and-CONHC (CH
3)
2CH
2SO
3Any one group among the H; In the formula (5), R is H or CH
3, n1 is 2 or 3, n2 is the integer of 4-18.
Under the preferred situation, in the formula (5), R is H, and n1 is 2, and n2 is the integer of 6-12; Perhaps R is CH
3, n1 is 2, n2 is the integer of 6-12; Perhaps R is H, and n1 is 3, and n2 is the integer of 6-12; Perhaps R is CH
3, n1 is 3, n2 is the integer of 6-12.
The surfactivity tackify multipolymer according to the present invention is a benchmark with this multipolymer, and the content of said structural unit B is generally 0.1-20 weight %, is preferably 0.5-10 weight %, further is preferably 5-9 weight %; The mol ratio of said structural unit A and structural unit B is generally 30-1000: 1, be preferably 40-800: and 1, further be preferably 50-650: 1.
The surfactivity tackify multipolymer according to the present invention, the intrinsic viscosity of said multipolymer [η] can be 1200-2600mL/g, is preferably 1800-2600mL/g, more preferably 2200-2600mL/g.
Surfactivity tackify multipolymer of the present invention, concentration are that 1500mg/L and salinity are that the aqueous solution of this surface-active polymer of 30000mg/L is 12-20mPas 75 ℃ AV, are preferably 15-20mPas.Among the present invention, said salinity is meant the summation of inorganic ion content in the aqueous solution, and said mineral ion generally comprises Na
+, K
+, Ca
2+, Mg
2+, C1
-, SO
4 2-, CO
3 2-Deng.
The present invention also provides a kind of preparation method of surfactivity tackify multipolymer, and wherein, this method comprises: under polymeric reaction condition; In the presence of initiator; Make a kind of monomer mixture in water, carry out polyreaction, said monomer mixture contains the monomer shown in the formula (6) and above-mentioned according to surfactivity polymerisable monomer of the present invention, and is benchmark with said monomer mixture; The consumption of said surfactivity polymerisable monomer is 0.1-20 weight %; The mol ratio of monomer shown in the formula (6) and described surfactivity polymerisable monomer is 30-1000: 1, and the condition of polyreaction makes that the intrinsic viscosity [η] of gained multipolymer is 1200-2600mL/g
formula (6)
Wherein, in the formula (6), R
1', R
2' and R
3' be the alkyl of hydrogen or carbonatoms 1-3 independently of one another, R
4' for being selected from-CONH
2,-COOH and-CONHC (CH
3)
2CH
2SO
3Any one group among the H.
In the said monomer mixture, can contain the monomer shown in a kind of formula (6), also can contain the monomer shown in the multiple formula (6).
According to the present invention, be benchmark with said monomer mixture, the consumption of said surfactivity polymerisable monomer is generally 0.1-20 weight %, is preferably 0.5-10 weight %, further is preferably 5-9 weight %; The mol ratio of monomer shown in the formula (6) and surfactivity polymerisable monomer of the present invention is generally 30-1000: 1, be preferably 40-800: and 1, further be preferably 50-650: 1.
In the preparation method of surfactivity tackify multipolymer of the present invention, the monomer shown in the said formula (6) can be in vinylformic acid, methylacrylic acid, acrylic amide, USAF RH-1 and the 2-acrylamido-2-methyl propane sulfonic acid one or more.
In the preparation method of surfactivity tackify multipolymer of the present invention, be benchmark with said monomer mixture, the consumption of said initiator can be 0.0001-0.1 weight %.Said initiator can various initiators known in the field.For example said initiator can be peroxide initiator such as Potassium Persulphate, Sodium Persulfate and Ammonium Persulfate 98.5 etc.; Redox system initiator such as Potassium Persulphate-S-WAT, Sodium Persulfate-S-WAT, Ammonium Persulfate 98.5-S-WAT, Potassium Persulphate-sodium sulfite anhy 96, Sodium Persulfate-sodium sulfite anhy 96 and Ammonium Persulfate 98.5-sodium sulfite anhy 96 etc.; Azo-initiator such as azo diisobutyl amidine hydrochloride etc.; In the present invention, initiator further is preferably one or more in the composite initiator that Potassium Persulphate, Sodium Persulfate, Ammonium Persulfate 98.5, Potassium Persulphate-S-WAT, Sodium Persulfate-S-WAT, Ammonium Persulfate 98.5-S-WAT, Potassium Persulphate-sodium sulfite anhy 96, Sodium Persulfate-sodium sulfite anhy 96 or Ammonium Persulfate 98.5-sodium sulfite anhy 96 and azo diisobutyl amidine hydrochloride form.When adopting above-mentioned composite initiator, more help causing the copolyreaction between acrylic acid or the like and/or acrylamide monomers and the surfactivity polymerisable monomer of the present invention as polymerization starter.
In the preparation method of surfactivity tackify multipolymer of the present invention; Said polymerizing condition can be for making the various conditions of polymerization reaction take place between monomer shown in the formula (6) and the surfactivity polymerisable monomer of the present invention; Under preferred situation; Said polyreaction comprises first polymerization reaction zone and second polymerization reaction zone of carrying out successively, and the condition of said first polymerization reaction zone comprises that polymerization temperature is 5-30 ℃, is preferably 5-15 ℃; Polymerization time can be 2-16 hour, is preferably 8-16 hour, and the condition of said second polymerization reaction zone comprises that polymerization temperature can be 40-55 ℃, is preferably 45-55 ℃; Polymerization time can be 1-8 hour, is preferably 2-6 hour, further is preferably 2-4 hour.
In the preparation method of surfactivity tackify multipolymer of the present invention; In order further to promote the carrying out of polyreaction, under preferred situation, the control reaction system is an alkalescence; For example can use sodium hydroxide, yellow soda ash, salt of wormwood, ammoniacal liquor or their aqueous solution that the pH value of reaction system is regulated; Under preferred situation, the pH of control reaction system is in the 7.1-10.5 scope, and preferred pH is 7.4-9.0.
In the preparation method of surfactivity tackify multipolymer of the present invention; In order to suppress the generation of side reaction; Improve the transformation efficiency of reaction; Under preferred situation, said polyreaction is carried out under inert conditions, for example can guarantee that polymerization reaction system is an inert atmosphere through the mode that in reaction system, feeds rare gas elementes such as nitrogen or argon gas.
In the preparation method of surfactivity tackify multipolymer of the present invention, under the preferred situation, said monomer mixture only is made up of monomer shown in the formula (6) and surfactivity polymerisable monomer of the present invention.
According to the application of surfactivity tackify multipolymer of the present invention in polymer oil-displacing agent; Surfactivity tackify multipolymer of the present invention can be applicable to oil reservoir behind high temperature and high salt oil deposit and the polymer flooding as polymer oil-displacing agent, in TOR, further improves oil recovery factor.
In the present invention, said polymer oil-displacing agent can also contain this area various Tackified polymerics with displacement of reservoir oil effect commonly used except containing surfactivity tackify multipolymer of the present invention, for example SEPIGEL 305 etc.
Through specific embodiment the present invention is further described in detail below.
Aliphatic amide that in following each embodiment, uses or arylamine are available from Beijing chemical reagent factory, and haloalkyl sulfonic acid alkali metal salts, acrylic amide, vinylformic acid and 2-acrylamido-2-methyl propane sulfonic acid are all available from Aladdin reagent company; Initiator is available from chemical reagents corporation of traditional Chinese medicines group.
The dissolution time of multipolymer is measured by GB12005.8-89; The intrinsic viscosity of multipolymer [η] is measured according to GB12005.1-89 SEPIGEL 305 intrinsic viscosity measuring method: measure (10 weight %NaCl solution) with Ubbelohde viscometer down at 25 ℃; The AV of multipolymer is with Brookfield DV-III viscometer, with 1500mg/L concentration, is that 30000mg/L, rotating speed are 6rmin at 80 ℃, salinity
-1Condition under measure.
Embodiment 1
Present embodiment is used to explain surfactivity polymerisable monomer of the present invention and surfactivity tackify multipolymer and their preparation method.
(1) preparation of surfactivity polymerisable monomer:
With 1mol N, N-dimethylamino propyl acrylamide, 0.85mol 6-chlorine hexyl sodium sulfonate, 300mL ethanol, 20g sodium hydroxide joins in the 1L there-necked flask; The pH value of solution is 10.2 in the reactor drum; Reaction is 12 hours under 25 ℃ of temperature, and cooled and filtered obtains solid, confirms that through nuclear magnetic resonance spectroscopy this solid is that R is H in the formula of the present invention (1); N1 is 3, and n2 is 6 surfactivity polymerisable monomer BH-1.
(2) preparation of copolymer p S-1:
In polymerization reactor, add acrylic amide 13.2g, vinylformic acid 5.6g and the above-mentioned monomers B H-11.6g that obtains, add deionized water 55ml, using 20% sodium hydroxide solution to regulate its pH is 7.4, feeds the deoxygenation of high pure nitrogen bubbling then; Add after half a hour by Potassium Persulphate, S-WAT and azo diisobutyl amidine hydrochloride composite initiator 2.6mg with mol ratio=form at 1: 1: 0.5; Under 6 ℃, carried out polyreaction 10 hours; Then be warming up to 45 ℃ and continue reaction 2 hours; Obtain gum polymers, obtain surfactivity tackify copolymer p S-1 after section, drying, the pulverizing, parameter is seen table 1.
Comparative Examples 1
According to the method for preparing tackify copolymer p S-1 among the embodiment 1, the copolymer A M-AA of preparation acrylic amide (AM) and vinylformic acid (AA), different is not add BH-1, obtains acrylic amide and acrylic acid multipolymer DB, parameter is seen table 1.
Embodiment 2
Present embodiment is used to explain surfactivity polymerisable monomer of the present invention and surfactivity tackify multipolymer and their preparation method.
(1) preparation of surfactivity polymerisable monomer:
With 1mol N, N-dimethylaminoethyl acrylic amide, 0.90mol 8-chlorine sodium octyl, 300mL ethanol, 20g sodium hydroxide joins in the 1L there-necked flask; The pH value of solution is 10.2 in the reactor drum; Reaction is 10 hours under 25 ℃ of temperature, and cooled and filtered obtains solid, confirms that through nuclear magnetic resonance spectroscopy this solid is that R is H in the formula of the present invention (1); N1 is 3, and n2 is 8 surfactivity polymerisable monomer BH-2.
(2) preparation of copolymer p S-2:
In polymerization reactor, add acrylic amide 13.2g, vinylformic acid 5.6g and the above-mentioned monomers B H-21.2g that obtains, add deionized water 55ml, using 20% sodium hydroxide solution to regulate its pH is 7.6, feeds the deoxygenation of high pure nitrogen bubbling then; Add after half a hour by Potassium Persulphate, S-WAT and azo diisobutyl amidine hydrochloride composite initiator 2.6mg with mol ratio=form at 1: 1: 0.5; Under 5 ℃, carried out polyreaction 14 hours; Then be warming up to 45 ℃ and continue reaction 3 hours; Obtain gum polymers, obtain surfactivity tackify copolymer p S-2 after section, drying, the pulverizing, parameter is seen table 1.
Embodiment 3
Present embodiment is used to explain surfactivity polymerisable monomer of the present invention and surfactivity tackify multipolymer and their preparation method.
(1) preparation of surfactivity polymerisable monomer:
With 1mol N, N-dimethylamino propyl acrylamide, 0.95mol 8-bromine sodium octyl, 300mL ethanol, 18g sodium hydroxide joins in the 1L there-necked flask; The pH value of solution is 10.2 in the reactor drum; Reaction is 10 hours under 35 ℃ of temperature, and cooled and filtered obtains solid, confirms that through nuclear magnetic resonance spectroscopy this solid is that R is H in the formula of the present invention (1); N1 is 3, and n2 is 8 surfactivity polymerisable monomer BH-3.
(2) preparation of copolymer p S-3:
In polymerization reactor, add acrylic amide 13.2g, vinylformic acid 5.6g and the above-mentioned monomers B H-31.2g that obtains, add deionized water 55ml, using 20% sodium hydroxide solution to regulate its pH is 7.6, feeds the deoxygenation of high pure nitrogen bubbling then; Add after half a hour by Potassium Persulphate, S-WAT and azo diisobutyl amidine hydrochloride composite initiator 2.6mg with mol ratio=form at 1: 1: 0.5; Under 8 ℃, carried out polyreaction 9 hours; Then be warming up to 45 ℃ and continue reaction 3 hours; Obtain gum polymers, obtain surfactivity tackify copolymer p S-3 after section, drying, the pulverizing, parameter is seen table 1.
Embodiment 4
(1) preparation of surfactivity polymerisable monomer:
The method for preparing surface active monomer according to embodiment 3 prepares surface active monomer; That different is N, and the N-dimethylamino propyl acrylamide is by N, and N-dimethylamino-propyl USAF RH-1 replaces; Etoh solvent is replaced by methyl alcohol, and the surface active monomer that obtains is that R is CH in the formula of the present invention (1)
3, n1 is 3, n2 is 8 surface active monomer BH-4.
(2) preparation of tackifier PS-4:
Method according to embodiment 3 prepares tackifier, and different is that BH-3 is replaced by the surface active monomer BH-40.2g that embodiment 4 obtains, and obtains surfactivity tackify copolymer p S-4, and parameter is seen table 1.
Embodiment 5
(1) preparation of surfactivity polymerisable monomer:
With 1mol N, N-dimethylamino-propyl USAF RH-1,1.25mol 12-bromo-dodecane base sodium sulfonate, 350mL ethanol, 22g sodium hydroxide joins in the 1L there-necked flask; The pH value of solution is 10.8 in the reactor drum; Reaction is 12 hours under 40 ℃ of temperature, and cooled and filtered obtains solid, confirms that through nuclear magnetic resonance spectroscopy this solid is that R is H in the formula of the present invention (1); N1 is 3, and n2 is 12 surfactivity polymerisable monomer BH-5.
(2) preparation of copolymer p S-5:
In polymerization reactor, add acrylic amide 13.2g, vinylformic acid 5.6g and the above-mentioned monomers B H-51.8g that obtains, add deionized water 55ml, using 20% sodium hydroxide solution to regulate its pH is 7.8, feeds the deoxygenation of high pure nitrogen bubbling then; Add after half a hour by Potassium Persulphate, S-WAT and azo diisobutyl amidine hydrochloride composite initiator 2.6mg with mol ratio=form at 1: 1: 0.5; Under 15 ℃, carried out polyreaction 8 hours; Then be warming up to 55 ℃ and continue reaction 2 hours; Obtain gum polymers, obtain surfactivity tackify copolymer p S-5 after section, drying, the pulverizing, parameter is seen table 1.
Embodiment 6
Present embodiment is used to explain surfactivity tackify multipolymer of the present invention and preparation method.
The preparation of copolymer p S-6:
In polymerization reactor, add the monomers B H-31.2g that obtains among acrylic amide 13.2g, 2-acrylamido-2-methyl propane sulfonic acid 6.0g and the embodiment 3; Add deionized water 55ml; Using 20% sodium hydroxide solution to regulate its pH is 7.8, feeds the deoxygenation of high pure nitrogen bubbling then; Add after half a hour by Potassium Persulphate, S-WAT and azo diisobutyl amidine hydrochloride composite initiator 2.6mg with mol ratio=form at 1: 1: 0.5; Under 6 ℃, carried out polyreaction 10 hours; Then be warming up to 45 ℃ and continue reaction 3 hours; Obtain gum polymers, obtain surfactivity tackify copolymer p S-6 after section, drying, the pulverizing, parameter is seen table 1.
Embodiment 7
Present embodiment is used to explain surfactivity polymerisable monomer of the present invention and surfactivity tackify multipolymer and their preparation method.
The preparation of copolymer p S-7:
In polymerization reactor, add the monomers B H-51.8g that obtains among acrylic amide 13.2g, 2-acrylamido-2-methyl propane sulfonic acid 6.0g and the embodiment 3; Add deionized water 55ml; Using 20% sodium hydroxide solution to regulate its pH is 8.0, feeds the deoxygenation of high pure nitrogen bubbling then; Add after half a hour by Potassium Persulphate, S-WAT and azo diisobutyl amidine hydrochloride composite initiator 2.6mg with mol ratio=form at 1: 1: 0.5; Under 10 ℃, carried out polyreaction 8 hours; Then be warming up to 45 ℃ and continue reaction 4 hours; Obtain gum polymers, obtain surfactivity tackify copolymer p S-7 after section, drying, the pulverizing, parameter is seen table 1.
The SOLUTION PROPERTIES of table 1. amphiphilic SEPIGEL 305 tackifier PS
Experimental example 1
With 1000mg/L salinity salt solution the multipolymer DB for preparing in surfactivity tackify multipolymer (PS-1)～(PS-7) for preparing among the embodiments of the invention 1-7 and the Comparative Examples 1 is mixed with the polymer viscosified agent solution that concentration is respectively 200mg/L, 500mg/L, 1000mg/L, 1500mg/L, 2000mg/L, 2500mg/L, 3000mg/L separately respectively; At 75 ℃, rotating speed is 6rmin
-1Detect the AV of the polymer viscosified agent solution of different concns down.The relation of the AV of tackify multipolymer under different concns in surfactivity tackify multipolymer of the present invention and the Comparative Examples 1 is as shown in Figure 1.
As can beappreciated from fig. 1, surfactivity tackify multipolymer of the present invention all is higher than the AV of multipolymer DB under each concentration in the AV under each concentration.
Experimental example 2
With 30000mg/L salinity salt solution the multipolymer DB for preparing in surfactivity tackify multipolymer (PS-1)-(PS-7) for preparing among the embodiments of the invention 1-7 and the Comparative Examples 1 is mixed with the polymer viscosified agent solution that concentration is 1500mg/L respectively, at 6rmin
-1Rotating speed detect down the AV of each polymer viscosified agent solution under 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃.The relation of the AV of tackify multipolymer under differing temps in surfactivity tackify multipolymer of the present invention and the Comparative Examples 1 is as shown in Figure 2.
As can beappreciated from fig. 2; The AV of surfactivity tackify multipolymer of the present invention under each temperature and high salt all is higher than multipolymer DB at each temperature AV, further is the AV that the AV of surfactivity tackify multipolymer of the present invention under high temperature and high salt all is higher than multipolymer DB.
Claims (11)
1. a surfactivity polymerisable monomer is characterized in that, this surfactivity polymerisable monomer has the structure shown in the formula (1),
Wherein, R is H or CH
3, n1 is 2 or 3, n2 is the integer of 4-18;
Preferred R is H, and n1 is 2, and n2 is the integer of 6-12; Perhaps R is CH
3, n1 is 2, n2 is the integer of 6-12; Perhaps R is H, and n1 is 3, and n2 is the integer of 6-12; Perhaps R is CH
3, n1 is 3, n2 is the integer of 6-12.
2. the preparation method of a surfactivity polymerisable monomer; It is characterized in that this preparation method comprises: under alkylation reaction condition, under alkaline condition; Acrylic amide shown in the formula (2) is contacted in organic solvent with the haloalkyl sulfonic acid alkali metal salts shown in the formula (3)
X-(CH
2)
N2-SO
3 -Y
+Formula (3)
Wherein, in the formula (2), R is H or CH
3, n1 is 2 or 3; In the formula (3), n2 is the integer of 4-18, and preferred n2 is the integer of 6-12; X is a halogen, is preferably chlorine, bromine or iodine; Y is an alkali metal, is preferably sodium element.
3. preparation method according to claim 2; Wherein, The condition of said alkylated reaction comprises: temperature of reaction is 10-50 ℃; Reaction times is 10-20 hour, and the consumption mol ratio of the haloalkyl sulfonic acid alkali metal salts shown in acrylic amide shown in the said formula (2) and the said formula (3) is 0.7-2.5: 1;
The consumption mol ratio of the haloalkyl sulfonic acid alkali metal salts shown in acrylic amide shown in the preferred said formula (2) and the said formula (3) is 0.75-1.5: 1.
4. preparation method according to claim 2; Wherein, Acrylic amide shown in the said formula (2) is N, N-dimethylamino propyl acrylamide, N, N-dimethylamino-propyl USAF RH-1, N; N-dimethylaminoethyl acrylic amide and N, one or more in the N-dimethylaminoethyl USAF RH-1.
5. surfactivity tackify multipolymer; It is characterized in that; This multipolymer contains the structural unit B shown in structural unit A shown in the formula (4) and the formula (5), is benchmark with this multipolymer, and the content of said structural unit B is 0.1-20 weight %; The mol ratio of said structural unit A and structural unit B is 30-1000: 1, and the intrinsic viscosity of said multipolymer [η] is 1200-2600mL/g;
The content of preferred said structural unit B is 0.5-10 weight %, and the mol ratio of said structural unit A and structural unit B is 40-800: 1;
formula (4)
Wherein, in the formula (4), R
1', R
2' and R
3' be the alkyl of hydrogen or carbonatoms 1-3 independently of one another, R
4' for being selected from-CONH
2,-COOH and-CONHC (CH
3)
2CH
2SO
3Any one group among the H; In the formula (5), R is H or CH
3, n1 is 2 or 3, n2 is the integer of 4-18;
Preferred R is H, and n1 is 2, and n2 is the integer of 6-12; Perhaps R is CH
3, n1 is 2, n2 is the integer of 6-12; Perhaps R is H, and n1 is 3, and n2 is the integer of 6-12; Perhaps R is CH
3, n1 is 3, n2 is the integer of 6-12.
6. the preparation method of a surfactivity tackify multipolymer; It is characterized in that this method comprises: under polymeric reaction condition, in the presence of initiator; Make a kind of monomer mixture in water, carry out polyreaction; Said monomer mixture contains monomer shown in the formula (6) and the described surfactivity polymerisable monomer of claim 1, and is benchmark with said monomer mixture, and the consumption of said surfactivity polymerisable monomer is 0.1-20 weight %; The mol ratio of monomer shown in the formula (6) and said surfactivity polymerisable monomer is 30-1000: 1, and the condition of polyreaction makes that the intrinsic viscosity [η] of gained multipolymer is 1200-2600mL/g;
The consumption of preferred said surfactivity polymerisable monomer is 0.5-10 weight %; The mol ratio of monomer shown in the formula (6) and said surfactivity polymerisable monomer is 40-800: 1;
Wherein, in the formula (6), R
1', R
2' and R
3' be the alkyl of hydrogen or carbonatoms 1-3 independently of one another, R
4' for being selected from-CONH
2,-COOH and-CONHC (CH
3)
2CH
2SO
3Any one group among the H.
7. the preparation method of surfactivity tackify multipolymer according to claim 6; Wherein, the monomer shown in the said formula (6) is one or more in vinylformic acid, methylacrylic acid, acrylic amide, USAF RH-1 and the 2-acrylamido-2-methyl propane sulfonic acid.
8. the preparation method of surfactivity tackify multipolymer according to claim 6 wherein, is a benchmark with said monomer mixture, and the consumption of said initiator can be 0.0001-0.1 weight %.
9. the preparation method of surfactivity tackify multipolymer according to claim 6; Wherein, Said polyreaction comprises first polymerization reaction zone and second polymerization reaction zone of carrying out successively, and the condition of said first polymerization reaction zone comprises that polymerization temperature is 5-30 ℃, and polymerization time is 2-16 hour; The condition of said second polymerization reaction zone comprises that polymerization temperature is 45-55 ℃, and polymerization time is 1-8 hour.
10. the preparation method of surfactivity tackify multipolymer according to claim 6, wherein, said polyreaction is to carry out under the condition of 7.1-10.5 at pH.
11. the application of surfactivity tackify multipolymer in oil-displacing agent of any described method preparation among claim 5 described surfactivity tackify multipolymer or the claim 6-10.
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