CN104628611B - A kind of acrylamide monomers and its preparation method and application - Google Patents
A kind of acrylamide monomers and its preparation method and application Download PDFInfo
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- CN104628611B CN104628611B CN201310573160.0A CN201310573160A CN104628611B CN 104628611 B CN104628611 B CN 104628611B CN 201310573160 A CN201310573160 A CN 201310573160A CN 104628611 B CN104628611 B CN 104628611B
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- acrylamide
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- 239000000178 monomer Substances 0.000 title claims abstract description 89
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- 239000011591 potassium Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229920002401 polyacrylamide Polymers 0.000 claims description 15
- 238000010276 construction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229920006322 acrylamide copolymer Polymers 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 9
- 238000010008 shearing Methods 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- -1 polypropylene Polymers 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- OBNZQBVPDZWAEB-UHFFFAOYSA-N 2-phenylprop-1-ene-1-sulfonic acid Chemical group OS(=O)(=O)C=C(C)C1=CC=CC=C1 OBNZQBVPDZWAEB-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- RTJKEOKLFIWBTE-UHFFFAOYSA-N CC(=C)C1=CC=CC=C1.[S] Chemical compound CC(=C)C1=CC=CC=C1.[S] RTJKEOKLFIWBTE-UHFFFAOYSA-N 0.000 description 1
- 0 CCC(C)(*)C(NC(*)(*)c1ccc(*)cc1)=O Chemical compound CCC(C)(*)C(NC(*)(*)c1ccc(*)cc1)=O 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000302 molecular modelling Methods 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000009818 secondary granulation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of acrylamide monomers and its preparation method and application, wherein, this monomer has the structure shown in formula (1), wherein, R1For the alkyl of C1 C8, R2For hydrogen or the alkyl of C1 C4, M1And M2It is each independently at least one in hydrogen, potassium and sodium.Experiment shows that this monomer carries out being polymerized the acrylamide copolymer obtained and has higher molecular weight and excellent temperature-resistant anti-salt performance and resistant to shearing performance, can be as high temperature and high salt oil deposit Flooding Agent for EOR.
Description
Technical field
The present invention relates to a kind of acrylamide monomers and its preparation method and application.
Background technology
Polymer flooding, mainly by injecting the polymer solution of certain scale, increases displacing fluid viscosity, fall
Low oil-reservoir water phase permeability reduces mobility ratio, adjusts intake profile, to reach to improve displacing phase volume
Purpose, and then improve recovery ratio.As main polymer oil-displacing agent, water-soluble portion hydrolysis polypropylene
Amide (HPAM) in conventional oil reservoir tertiary oil recovery (EOB) technology, obtained large-scale promotion and
Application, has played important function for oilfield stable production and volume increase.Along with the minimizing of conventional reservoir reserve, high temperature
High salinity reservoir makes the application of HPAM be faced with many difficult problems, is mainly reflected in exploitation high temperature and high salt oil deposit
Time high temperature, high salt, dissolved oxygen compound action when shearing and prepare solution make HPAM solution viscosity
It is greatly reduced, causes oil displacement efficiency the most notable.
For above-mentioned performance shortcomings, research worker has carried out a large amount of study on the modification to HPAM.Wherein,
By acrylamide and temperature-resistant anti-salt monomer copolymerization, HPAM copolymer introduces temperature-resistant anti-salt group,
It it is the important channel enhanced product performance.The temperature-resistant anti-salt monomer developed include sulfonic acid type monomer,
Hydrophobic association monomer and zwitterionic monomer etc..The most entitled " the low temperature synthesis of AMPS/AM copolymer
And performance " (Chang Zhiying, polymer material science and engineering, 1997,13,16) article in report
Can show with acrylamide copolymerization with 2-acrylamide-2-methylpro panesulfonic acid (AMPS) sulfonic acid type monomer
Write the serviceability improving HPAM.But the correlational study " height of water solublity AM/AA/AMPS copolymer
Warm water solution " (Zhu Linyong, applied chemistry, 2000,17,2) simultaneously it was also found that at the high temperature bar of 90 DEG C
Under part, being subject to close on the Molecular modelling effect of acrylic acid (AA) unit, also there is water in AMPS unit
Solving reaction, in copolymer, acrylic acid structure unit ratio increases, and improves its Thermo-sensitive and the quick performance of salt,
Therefore the application under the conditions of this base polymer high temperature and high salt more than hydrolysis temperature is limited.Hydrophobic association
Polymer utilizes molecular structure to make its viscosity the most really have an obvious thickening effect, but its
Extemporaneous preparation requirement fresh water or heating dissolution, make troubles to construction, and this base polymer there is also in addition
Easily block stratum, under the conditions of high temperature and high salt poor resistance shortcoming (Wang Zhonghua, fine and specialty chemicals,
2006,14,24).Amphoteric ion copolymer has a salt consistence energy that polyampholyte is unique, but because of
There is positive charge in its structure, there is adsorption with surface of stratum negative charge, add loss.
Therefore from MOLECULE DESIGN angle, temperature-resistant anti-salt performance is good, easily generate high molecular weight product in exploitation
Temperature-resistant anti-salt monomer will be a HPAM long-standing issues entering study on the modification.
Summary of the invention
It is an object of the invention to overcome the drawbacks described above of prior art, it is provided that a kind of acrylamide monomers
And its preparation method and application.
The invention provides a kind of acrylamide monomers, wherein, this monomer has shown in formula (1)
Structure:
Wherein, R1For the alkyl of C1-C8, R2For hydrogen or the alkyl of C1-C4, M1And M2The most solely
It is on the spot at least one in hydrogen, potassium and sodium.
Present invention also offers the preparation method of a kind of acrylamide monomers, wherein, the method includes:
Under conditions of temperature is-5 DEG C to 30 DEG C, by knot shown in the monomer of structure shown in formula (2), formula (3)
The monomer of structure and sulfonating agent react 2-16 hour,
Wherein, R1For the alkyl of C1-C8, R2For hydrogen or the alkyl of C1-C4, M1For hydrogen, potassium and sodium
In at least one.
Present invention also offers a kind of acrylamide polymer, this acrylamide polymer contains formula (4)
Shown construction unit:
Wherein, R1For the alkyl of C1-C8, R2For hydrogen or the alkyl of C1-C4, M1And M2The most solely
It is on the spot at least one in hydrogen, potassium and sodium.
Present invention also offers the application in polymer oil-displacing agent of the aforesaid propylene amide polymer.
Experiment shows that the acrylamide monomers of the present invention carries out being polymerized the acrylamide copolymer obtained and exists
Having higher apparent viscosity under high temperature, high ore deposit degree and high-rate of shear, the heatproof therefore with excellence resists
Salt performance and anti-shear performance.This is likely due in the acrylamide monomers of the present invention around amide groups
An alkyl and the hydrophobic interaction of a phenyl and space steric effect greatly improve hot conditions
The anti-hydrolytic performance of lower monomer self.Additionally, the disulfonic acid base in this monomer is insensitive to divalent salts ion,
Thus the anti-salt property of copolymer solution can be significantly improved when synthesis of acrylamide analog copolymer.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of acrylamide monomers, wherein, this monomer has shown in formula (1)
Structure:
Wherein, R1For the alkyl of C1-C8, R2For hydrogen or the alkyl of C1-C4, M1And M2The most solely
It is on the spot at least one in hydrogen, potassium and sodium.
In the present invention, the alkyl of described C1-C4 can be straight chain, it is also possible to be side chain.Described
The example of the alkyl of C1-C4 may include that methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, secondary
Butyl, isobutyl group and the tert-butyl group.
In the present invention, the alkyl of described C1-C8 can be straight chain, it is also possible to be side chain.Described
The example of the alkyl of C1-C8 can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, just
Butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, just oneself
Base, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1,2-dimethylbutyl, 1,3-dimethyl
Butyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,
1,1,2-thmethylpropyl, 1,2,2-thmethylpropyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-ethyl-2-
Methyl-propyl, n-heptyl and n-octyl.
In the present invention, in order to when preparing acrylamide copolymer, obtain high conversion further
Product, under preferable case, in the acrylamide monomers shown in formula (1), R1Alkane for C1-C4
Base, R2For hydrogen or methyl, M1For hydrogen or sodium.
Present invention also offers the preparation method of a kind of acrylamide monomers, wherein, the method includes:
Under conditions of temperature is-5 DEG C to 30 DEG C, by knot shown in the monomer of structure shown in formula (2), formula (3)
The monomer of structure and sulfonating agent react 2-16 hour,
Wherein, R1For the alkyl of C1-C8, R2For hydrogen or the alkyl of C1-C4, M1For hydrogen, potassium and sodium
In at least one.
The alkyl of described C1-C4 is all identical with foregoing description with the alkyl of C1-C8.
In the present invention, in order to obtain the acrylamide monomers of structure shown in the formula (1) of high yield,
Under preferable case, R in the monomer of structure shown in formula (2)1For the alkyl of C1-C4, M1For hydrogen or sodium；
R in the monomer of structure shown in formula (3)2For hydrogen or methyl；It is further preferred that knot shown in formula (2)
The monomer of structure is α-methyl styrene sulfonic acid, and shown in formula (3), the monomer of structure is acrylonitrile.
In the present invention, the structure of described α-methyl styrene sulfonic acid is as the formula (5):
According to the present invention, the present invention kind particularly requirement to sulfonating agent, various in prior art
Sulfonating agent all can realize the purpose of the present invention, it is contemplated that the sulfonating agent with highly acid and strong oxidizing property can
To improve the productivity of reaction, it is preferable that described sulfonating agent is the sulphuric acid of concentration 95-140 weight % or is fuming
Sulphuric acid.
According to the present invention, in order to obtain the acrylamide monomers of high yield, under preferable case, described instead
Two stages carried out successively should be included: under conditions of the first stage is for being-5 DEG C to 10 DEG C in temperature, will
Sulfonating agent contacts with the monomer of structure shown in formula (3), obtains the first solution；And at the bar less than 10 DEG C
Under part, in the first obtained solution, add the monomer of structure shown in formula (2), make the first solution with
Shown in formula (2), the monomer reaction of structure 1-8 hour, obtains the second solution；Second stage is to gained
To the second solution in add water, under conditions of temperature is 10-30 DEG C, continue reaction 1-8 hour.
In the present invention, at the monomer of structure shown in formula (2), the monomer of formula (3) depicted structure and sulphur
After agent reaction, in the acrylamide monomers of structure shown in the formula (1) obtained, M2For hydrogen, basis
The technical staff in field could be aware that, works as M2During for hydrogen, the acidity of described acrylamide monomer is relatively
By force, easily polymeric kettle is caused corrosion in the course of the polymerization process, need product is neutralized.
In the case of it is therefore preferable that, described method is additionally included in the monomer of structure shown in formula (2), formula (3)
After the monomer of depicted structure reacts with sulfonating agent, by anti-with inorganic alkaline compound for the product obtained
Should, generate corresponding alkali metal salt.
In the present invention, described inorganic alkaline compound is preferably sodium hydroxide, potassium hydroxide and sodium carbonate
In one or more, more preferably sodium hydroxide.
Under normal circumstances, the inorganic alkaline compound used makes the monomer of structure shown in formula (1) exist
M2During for hydrogen, the pH value of the solution being configured to is 4-12, preferably 6-9.
According to the present invention, the present invention is shown to the monomer of structure shown in formula (2), sulfonating agent and formula (3)
The mol ratio of the monomer of structure is not particularly limited, as long as can realize obtaining structure shown in formula (1)
Acrylamide monomers, under preferable case, the monomer of structure, sulfonating agent and formula shown in formula (2)
(3) mol ratio of the monomer of depicted structure is 1:0.8-1.2:5-25, more preferably 1:1-1.2:
10-20。
In the present invention, in order to make acrylamide monomers of the present invention easily stored, under preferable case,
Described method farther includes to carry out filtering, wash and drying by above-mentioned reaction products therefrom.
Described filtration, wash and dry as the conventional method of ability, do not repeat them here.
According to the preferred embodiment of the present invention, the preparation method of acrylamide monomers of the present invention can
To comprise the following steps:
(1) under stirring, sulfonating agent is slowly added into the list of structure shown in the formula (3) of excess
In body, obtaining the first solution, the temperature controlling the first solution is-5 DEG C to 10 DEG C.Delay in the first solution
Slowly add the monomer of structure shown in formula (2), adition process control reacting liquid temperature and is less than 10 DEG C,
React 1-8 hour, obtain the second solution.
(2) in the second solution, add suitable quantity of water, under normal temperature condition, continue reaction 1-8 hour, quiet
Only, crystal is had to separate out.
(3) filter off the monomer of structure shown in the formula (3) of excess, obtain thick product, and with formula (3)
Thick product is washed 2-3 time by the monomer of shown structure, and vacuum drying obtains target product.
According to the present invention, the inventive point of the present invention essentially consists in the acrylamide monomers providing above-mentioned, and
The method synthesizing described acrylamide monomers can be the method for this area routine, by of the present invention
The structure of acrylamide monomers of method synthesis such as can pass through Infrared Characterization, at infrared spectrum
In, 1500cm-1Near be the characteristic absorption peak of phenyl ring, 1185cm-1Near be sulfonic acid group feature suction
Receive peak, 1650cm-1Near be the absworption peak of alkene, 1740cm-1Near be the characteristic absorption peak of ester group,
3340cm-1Near be the characteristic absorption peak of amide group, and at 2250cm-1Near itrile group does not occur
Characteristic absorption peak, this illustrates that method of the present invention has synthesized target product.Therefore, in following reality
Execute in example, the most described acrylamide monomers is characterized.
Present invention also offers a kind of acrylamide polymer, this acrylamide polymer contains formula (4)
Shown construction unit:
Wherein, R1For the alkyl of C1-C8, R2For hydrogen or the alkyl of C1-C4, M1And M2The most solely
It is on the spot at least one in hydrogen, potassium and sodium.
According to the present invention, the preparation method of described acrylamide polymer can be the side that this area is conventional
Method, for example, it is possible to by the monomer of structure shown in acrylamide monomer, formula (1) at solution polymerization
Under the conditions of, in the presence of initiator, carry out polyreaction.
In order to increase the temperature-resistant anti-salt performance of acrylamide polymer, under preferable case, described system further
Preparation Method also includes: under hydrolysising condition, by acrylamide polymer and the inorganic base of polyreaction gained
Property compound contact, make the degree of hydrolysis of polymer reach 10-30%.It is well known by those skilled in the art that
By hydrolysis, the acrylamide construction unit in described acrylamide polymer is partially converted into acrylates
Construction unit.
In the present invention, to refer to that the molal quantity of acrylates construction unit accounts for of the present invention for described degree of hydrolysis
The percentage ratio of the total mole number of the construction unit of acrylamide polymer.According to the present invention, described degree of hydrolysis
Determined by the consumption of inorganic alkaline compound.
Those skilled in the art could be aware that, by regulating the consumption of inorganic alkaline compound, and can
To obtain the acrylamide polymer of different degree of hydrolysis.
In the present invention, the molal quantity of described inorganic alkaline compound rubbing equal to acrylates construction unit
That number.
Present invention also offers the application in polymer oil-displacing agent of the aforesaid propylene amide polymer.
Below, by following example, the present invention will be described in more detail.
In following example and comparative example, acrylamide commercially available from Bao Mo biochemical industry limited company,
2-acrylamide-2-methylpro panesulfonic acid commercially available from Xiamen Changtian Enterprise Co., Ltd., 2,2'-azo two isobutyls
Base amidine dihydrochloride is commercially available from Aldrich.
Embodiment 1
Acrylamide monomers that the present embodiment provides for the present invention is described and preparation method thereof
Adding 530 grams of acrylonitrile in temperature-controlled glass reactor, under stirring, dropping concentration is 98%
Concentrated sulphuric acid 100 grams, mixed liquor is cooled to-5 DEG C, after stirring, drip α-methyl styrene sulphur
Acid 198 grams, maintains temperature of reaction system below 10 DEG C.After reacting 6 hours, add suitable quantity of water,
Reaction 4 hours is continued under normal temperature condition.Pure monomer, product yield is obtained through filtering, wash, drying
It is 94.3%.
Embodiment 2
Acrylamide monomers that the present embodiment provides for the present invention is described and preparation method thereof.
Adding 1060 grams of acrylonitrile in temperature-controlled glass reactor, under stirring, dropping concentration is
The concentrated sulphuric acid of 98% 117.6 grams, is cooled to 5 DEG C by mixed liquor, after stirring, drips Alpha-Methyl benzene
Vinyl sulfonic acid 198 grams, maintains temperature of reaction system below 10 DEG C.After reacting 1 hour, add appropriate
Water, continues reaction 8 hours under normal temperature condition.Obtain pure monomer through filtering, wash, drying, produce
Product yield is 95%.
Embodiment 3
Acrylamide monomers that the present embodiment provides for the present invention is described and preparation method thereof.
Adding 636 grams of acrylonitrile in temperature-controlled glass reactor, under stirring, dropping concentration is 98%
Concentrated sulphuric acid 107.8 grams, mixed liquor is cooled to 5 DEG C, after stirring, drip α-methyl styrene
Sulfonic acid 198 grams, maintains temperature of reaction system below 10 DEG C.After reacting 3 hours, add suitable quantity of water,
Reaction 6 hours is continued under normal temperature condition.Obtaining pure monomer through filtering, wash, drying, product is received
Rate is 96.3%.
Embodiment 4
Acrylamide monomers that the present embodiment provides for the present invention is described and preparation method thereof.
Acrylamide monomers is prepared according to the method described in embodiment 1, except that, with 102%
Oleum replace concentration be the concentrated sulphuric acid of 98%, the consumption of oleum is 96 grams, through filter,
Washing, drying obtain pure monomer, and the yield of product is 96.5%.
Embodiment 5
Acrylamide monomers that the present embodiment provides for the present invention is described and preparation method thereof.
Acrylamide monomers is prepared according to the method described in embodiment 1, except that, at room temperature bar
After reacting 6 hours under part, after being 7 with the pH value of sodium hydroxide regulation system further, through filtering,
Washing, drying obtain pure monomer, and the yield of product is 93.5%.
Experimental example
Add 1000 grams of acrylamides, acrylamide monomers 10 of embodiment 1 gained in the reactor
Gram and 3030 grams of water, under stirring, control solution temperature 15 DEG C, add sodium hydroxide solution regulation
PH to 9.Add 1010 milligrams of 2,2'-azo diisobutyl amidine dihydrochlorides and 1010 milligrams of N, N, N ', N '-
Tetramethylethylenediamine, logical high pure nitrogen deoxygenation 0.5 hour, add 1010 milligrams of sodium sulfitees and 1010
Milligram Ammonium persulfate., continues logical nitrogen until thermocouple starts to warm up in reactor, 2 hours response time,
Obtain acrylamide copolymer.The acrylamide copolymer obtained is taken out, becomes 4-6 by granulator granulation
The little micelle of millimeter.By degree of hydrolysis 20%, by the copolymer micelle obtained and the sodium hydroxide grain of respective amount
Alkali mediates contact, hydrolyzes 1 hour, after secondary granulation, 70 DEG C of hot blast conditions at temperature 90 DEG C
Under be dried 2 hours, by crushing and screening the acrylamide copolymer obtaining 20-80 mesh.According to inventory
Calculating determines, in acrylamide copolymer, acrylamide construction unit, acrylates construction unit with
Shown in formula (4), the mass ratio of construction unit is 800:265:10, the viscosity-average molecular weight of resulting polymers
Being 25,000,000, the apparent viscosity of polymer solution is 15.0mPa.s.
Comparative example
Acrylamide copolymer is prepared according to the method described in experimental example, except that, use equal mass
2-acrylamide-2-methylpro panesulfonic acid replace acrylamide monomers obtained by embodiment 1, gained
The viscosity-average molecular weight of polymer is 22,000,000, and the apparent viscosity of polymer solution is 11.5mPa.s.
In above experimental example and comparative example: the intrinsic viscosity of polymer is according to People's Republic of China's oil sky
So in gas industry standard SY/T5862-2008, the method for regulation measures；Polymer viscosity-average molecular weight according to
The method of regulation in SY/T5862-2008, uses formula M=([η]/0.000373)1.515Calculate, wherein,
M is viscosity-average molecular weight, and [η] is intrinsic viscosity；The apparent viscosity of polymer solution is to use salinity
After polymer is made into the solution of 1500mg/L by the saline of 32000mg/L, use Brookfield viscometer
At 95 DEG C, 7.34s-1Under the conditions of measure.
From above experimental example and comparative example it can be seen that synthesized by the acrylamide monomers of the present invention third
Acrylamide polymer has the advantages that molecular weight is high, and the acrylamide copolymer obtained is at high temperature, Gao Kuangdu
With there is under high-rate of shear higher apparent viscosity, illustrate that the acrylamide polymer of the present invention has excellent
Different temperature-resistant anti-salt performance and resistant to shearing performance, can be as high temperature and high salt oil deposit Flooding Agent for EOR.
Claims (12)
1. an acrylamide monomers, wherein, this monomer has a structure shown in formula (1):
Wherein, R1For the alkyl of C1-C8, R2For hydrogen or the alkyl of C1-C4, M1And M2The most solely
It is on the spot at least one in hydrogen, potassium and sodium.
Acrylamide monomers the most according to claim 1, wherein, R1For the alkyl of C1-C4,
R2For hydrogen or methyl, M1For hydrogen or sodium.
3. the preparation method of the acrylamide monomers described in a claim 1, it is characterised in that
The method includes: in temperature under conditions of-5 DEG C to 30 DEG C, by the monomer of structure shown in formula (2),
Shown in formula (3), the monomer of structure reacts 2-16 hour with sulfonating agent,
Wherein, R1For the alkyl of C1-C8, R2For hydrogen or the alkyl of C1-C4, M1For hydrogen, potassium and sodium
In at least one.
Method the most according to claim 3, wherein, R1For the alkyl of C1-C4, R2For hydrogen or
Methyl, M1For hydrogen or sodium.
Method the most according to claim 3, wherein, described sulfonating agent is concentration 95-140 weight
The sulphuric acid of % or oleum.
Method the most according to claim 3, wherein, described reaction includes two carried out successively
Stage: the first stage is under conditions of temperature is for-5 DEG C to 10 DEG C, shown in sulfonating agent and formula (3)
The monomer contact of structure, obtains the first solution；And under conditions of less than 10 DEG C, to obtained first
Solution adds the monomer of structure shown in formula (2), makes the monomer of the first solution and structure shown in formula (2)
React 1-8 hour, obtain the second solution；Second stage is addition water in the second obtained solution,
Under conditions of temperature is 10-30 DEG C, continue reaction 1-8 hour.
Method the most according to claim 3, wherein, described method further includes at formula (2)
After shown in the shown monomer of structure, formula (3), the monomer of structure reacts with sulfonating agent, anti-by obtain
Product is answered to react with inorganic alkaline compound.
Method the most according to claim 7, wherein, described inorganic alkaline compound is hydroxide
At least one in sodium, potassium hydroxide and sodium carbonate.
9. according to the method described in any one in claim 3-8, wherein, structure shown in formula (2)
Monomer, the mol ratio of monomer of structure shown in sulfonating agent and formula (3) be 1:0.8-1.2:5-25.
Method the most according to claim 9, wherein, the monomer of structure, sulphur shown in formula (2)
Agent is 1:1-1.2:10-20 with the mol ratio of the monomer of structure shown in formula (3).
11. 1 kinds of acrylamide polymers, wherein, this acrylamide polymer contains shown in formula (4)
Construction unit:
Wherein, R1For the alkyl of C1-C8, R2For hydrogen or the alkyl of C1-C4, M1And M2The most solely
It is on the spot at least one in hydrogen, potassium and sodium.
12. the application that the acrylamide polymer described in claim 11 is in polymer oil-displacing agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1053256A (en) * | 1975-11-06 | 1979-04-24 | Donald L. Murfin | Amine and quaternary ammonium salts of acrylamidoalkanesulfonic acids and polymers thereof |
| CN1470504A (en) * | 2003-06-07 | 2004-01-28 | 石油大学(华东) | Functional monomer compound for preparing acrylamide derivatives |
| JP2007177154A (en) * | 2005-12-28 | 2007-07-12 | Toagosei Co Ltd | Acrylic acid copolymer, method for producing the same, and use thereof |
| CN101528888A (en) * | 2006-10-23 | 2009-09-09 | 美国海博公司 | Functional polymer for enhanced oil recovery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1053256A (en) * | 1975-11-06 | 1979-04-24 | Donald L. Murfin | Amine and quaternary ammonium salts of acrylamidoalkanesulfonic acids and polymers thereof |
| CN1470504A (en) * | 2003-06-07 | 2004-01-28 | 石油大学(华东) | Functional monomer compound for preparing acrylamide derivatives |
| JP2007177154A (en) * | 2005-12-28 | 2007-07-12 | Toagosei Co Ltd | Acrylic acid copolymer, method for producing the same, and use thereof |
| CN101528888A (en) * | 2006-10-23 | 2009-09-09 | 美国海博公司 | Functional polymer for enhanced oil recovery |
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