CN107973746A - A kind of vinyl monomer and polymer and its preparation method and application - Google Patents
A kind of vinyl monomer and polymer and its preparation method and application Download PDFInfo
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- CN107973746A CN107973746A CN201610921294.0A CN201610921294A CN107973746A CN 107973746 A CN107973746 A CN 107973746A CN 201610921294 A CN201610921294 A CN 201610921294A CN 107973746 A CN107973746 A CN 107973746A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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- C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
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- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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Abstract
The present invention relates to petrochemical industry, and in particular to a kind of vinyl monomer and polymer and its preparation method and application.The vinyl monomer has structure shown in formula (1)：N is 1 or 2, R1And R2It is each independently the alkenyl group of H or C1 C20.The preparation method of the vinyl monomer includes：Work as R1And R2When being H, the salt of acetylene and a aminolactams and/or a aminolactams is subjected to addition reaction；Work as R1And R2When not being H, alkylating reagent after the salt of a aminolactams and/or a aminolactams and acetylene progress addition reaction with C1 C20 is alkylated reaction, or the alkylating reagent of the salt of a aminolactams and/or a aminolactams and C1 C20 is alkylated after reaction and carries out addition reaction with acetylene.Polymer provided by the invention has more preferable temperature-resistant anti-salt performance.
Description
Technical field
The present invention relates to petrochemical industry, and in particular, to a kind of vinyl monomer and polymer and preparation method thereof
And application.
Background technology
Acrylamide copolymer (PAM) is a kind of multiduty water soluble polymer, suitable for dyeing, papermaking, food,
The industries such as building, metallurgy, ore dressing, coal dust, oil field, aquatic products processing and fermentation, have a wide range of applications in the industry.Opened in oil field
In adopting, acrylamide copolymer has excellent performance as oil recovery auxiliary agent in tertiary oil recovery, is China's oilfield stable production, volume increase
Important function is played.
At this stage, China Petroleum is faced with the mining problem of high temperature and high salt oil deposit, based on current severe energy ring
How border, exploit the oil reservoir under harsh geological environment, has become the huge challenge of petroleum industry.Prepare high molecular weight and have
The acrylamide copolymer type oil recovery auxiliary agent of heat and salt resistance is the main method for tackling the challenge at present.
The molecular weight and structure of acrylamide copolymer have significant impact to the viscosity of polymer solution.It is meanwhile single
Body structure also has heat endurance, the hydrolytic resistance of acrylamide copolymer the influence of highly significant, more steady by adding
Fixed benzene radicals, the isostructural acrylamide copolymer of sulfonic acid group have more preferable heat and salt resistance, such as AMPS and third
Acrylamide copolymer will be substantially better than common acrylamide copolymerization in salt tolerance, shear resistant and raising recovery ratio
Thing.
In order to meet the requirement of current temperature-resistant anti-salt, scientific and technical research personnel have synthesized many novel functional monomers, such as resistance to
Warm salt resistance monomer, zwitterionic monomer and hydrophobic monomer etc., then these novel functional monomers and acrylamide are copolymerized, by carrying
The ratio of high function monomer improves solution viscosity.But the purity of these function monomers, solubility property and steric hindrance effect
Multiple aggregation system should can be made to become more complicated, result in molecular weight of product and be difficult to improve, and limit acrylamide and be total to
The improvement of polymer configurations, so as to limit the raising of copolymer comprehensive performance.Therefore to solve the problems, such as tertiary oil recovery, use work(
, it is necessary to overcome product temperature-resistant anti-salt performance to be difficult to the technological deficiency improved, to obtain heatproof while energy monomer is to increase side chain
The preferable product of anti-salt property, so as to improve the comprehensive performance of copolymer.
The content of the invention
In order to overcome the temperature-resistant anti-salt performance of existing acrylamide copolymer to be difficult to the technological deficiency improved, the present invention carries
A kind of new vinyl monomer and polymer and its preparation method and application are supplied.
Usually, be copolymerized using hydrophobic monomer and acrylamide to form hydrophobic associated polymer can be from molecular structure
Change the performance of polymer, so as to achieve the purpose that to increase polymer viscosity.Hydrophobic associated polymer is in polymer hydrophilicity
The water-soluble polymer of a small amount of hydrophobic grouping is carried on macromolecular chain, its solution has unique performance, in aqueous, such
The hydrophobic grouping of polymer is assembled due to hydrophobic effect, macromolecular chain is produced intramolecular and Interpolymer Association；When poly-
After compound concentration is higher than a certain critical concentration (CAC), macromolecular chain is assembled by heat resistance and salt tolerance, is formed with Interpolymer Association
Based on supramolecular structure-dynamic physical cross-linked network, hydrodynamic volume increase, solution viscosity significantly raises, small molecule
The addition of electrolyte and the rise of temperature can increase the polarity of solvent, strengthen heat resistance and salt tolerance.
But the present inventor has found under study for action, the high-temperature stability and salt tolerant of hydrophobic associated polymer are stablized
Poor, the acrylamide facile hydrolysis on hydrophobic associated polymer chain of property.
The present inventor under study for action it was unexpectedly found that：By the lactams cyclic structure containing vinyl double bond
The polymer that monomer (vinyl monomer) is obtained with acrylamide polymerization has preferable temperature-resistant anti-salt performance, and analysis reason is probably
Due to：Amide groups is protected by cyclic structure in the vinyl monomer, not only inhibits the degraded of construction unit, but also is inhibited
The hydrolysis of acrylamide and the degraded of main chain, ensure that the stability of whole strand on chain so that polymer has preferable
Temperature-resistant anti-salt performance.In the case of additionally, it is preferred that, in the vinyl monomer presence of hydrophobic alkyl enhance hydrophobic association work
With and then the viscosity of polymer can be strengthened, so as to get polymer there is more excellent Oil Displacing Capacity.
Based on above-mentioned discovery, the present invention provides a kind of vinyl monomer, which has the structure shown in formula (1)：
Wherein, n is 1 or 2, R1And R2It is each independently the alkenyl group of H or C1-C20.
Present invention also offers a kind of preparation method of vinyl monomer, wherein, which has shown in formula (1)
Structure：
Wherein, n is 1 or 2, R1And R2The alkenyl group of H or C1-C20 are each independently,
Work as R1And R2When being H, this method includes：Under alkali and/or alkali metal and solvent existence condition, by acetylene with
The salt of a- aminolactams and/or a- aminolactams carries out addition reaction；
Work as R1And R2When not being H, this method includes：Under alkali and/or alkali metal and solvent existence condition, by acetylene
Addition reaction is carried out with the salt of a- aminolactams and/or a- aminolactams, is then again obtained the addition reaction mixed
The alkylating reagent of compound and C1-C20 are alkylated reaction；Alternatively, by a- aminolactams and/or a- aminolactams
The alkylating reagent of salt and C1-C20 are alkylated reaction, will then under alkali and/or alkali metal and solvent existence condition
The mixture that the alkylated reaction obtains carries out addition reaction with acetylene.
Invention further provides a kind of polymer, wherein, the polymer contain vinyl monomer construction unit and
Acrylamide construction unit, the vinyl monomer construction unit have the structure shown in formula (2)：
Wherein, n is 1 or 2, R1And R2It is each independently the alkenyl group of H or C1-C20.
Present invention also offers a kind of preparation method of polymer, this method includes：In the presence of initiator, by monomer
Mixture carries out polymerisation, wherein, the monomer mixture contains acrylamide and monomer A, and the monomer A carries for the present invention
The vinyl monomer of confession.
Present invention also offers the polymer being prepared by the above method.
Present invention also offers application of the above-mentioned polymer in oil displacement agent is prepared.
The present invention uses with lactams cyclic structure and preferably comprises the vinyl monomer and acrylamide of alkyl side chain
Polymer is prepared with optional temperature-resistant anti-salt monomer copolymerization, which there can be the intrinsic viscosity of 17-30dl/g, polymerize
Thing concentration is 1500mg/L, salinity is under 30000mg/L and temperature is that apparent viscosity at 90 DEG C is 9-13mPas, and only
The apparent viscosity of the acrylamide copolymer prepared by acrylamide and temperature-resistant anti-salt monomer copolymerization under the same conditions is only
4.7mPa·s.Therefore, it is provided by the invention to use with lactams cyclic structure and preferably comprise the vinyl list of alkyl side chain
The more existing temperature-resistant anti-salt acrylamide of polymer that body is prepared with acrylamide and optional temperature-resistant anti-salt monomer copolymerization is total to
Polymers, has more preferable temperature-resistant anti-salt performance, so as to improve the comprehensive performance of Flooding Agent for EOR.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the product that embodiment 1 obtains1H-NMR spectrum.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of vinyl monomer, which has the structure shown in formula (1)：
Wherein, n is 1 or 2, R1And R2It is each independently the alkenyl group of H or C1-C20.
Formula (1) compound according to the present invention, wherein, in a preferred case, the R1And R2Independently of one another
For the alkenyl group of C1-C6, for example, can be methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, amyl group, isopentyl,
Base or dissident's base.
In accordance with the present invention it is preferred that the R1And R2It is identical, it is further preferred that the R1And R2It is methyl or second
Base.
Present invention also offers a kind of preparation method of vinyl monomer, wherein, which has shown in formula (1)
Structure：
Wherein, n is 1 or 2, R1And R2The alkenyl group of H or C1-C20 are each independently,
Work as R1And R2When being H, this method includes：Under alkali and/or alkali metal and solvent existence condition, by acetylene with
The salt of a- aminolactams and/or a- aminolactams carries out addition reaction；
Work as R1And R2When not being H, this method includes：Under alkali and/or alkali metal and solvent existence condition, by acetylene
Addition reaction is carried out with the salt of a- aminolactams and/or a- aminolactams, is then again obtained the addition reaction mixed
The alkylating reagent of compound and C1-C20 are alkylated reaction；Alternatively, by a- aminolactams and/or a- aminolactams
The alkylating reagent of salt and C1-C20 are alkylated reaction, will then under alkali and/or alkali metal and solvent existence condition
The mixture that the alkylated reaction obtains carries out addition reaction with acetylene.
Preparation method according to the present invention, it is preferable that on the basis of the acetylene of 100 molar parts, alkali and/or alkali metal
Dosage be 100-300 molar parts, the dosage of the salt of a- aminolactams and/or a- aminolactams is 80-200 molar parts,
The dosage of the alkylating reagent of C1-C20 is 80-200 molar parts；It is highly preferred that on the basis of the acetylene of 100 molar parts, alkali and/
Or the dosage of alkali metal is 100-150 molar parts, the dosage of the salt of a- aminolactams and/or a- aminolactams is 80-120
Molar part, the dosage of the alkylating reagent of C1-C20 is 80-120 molar parts.
In the case of specified otherwise, when alkali and alkali metal while in use, the dosage of the alkali and/or alkali metal refers to
Total dosage of alkali and alkali metal；When alkali and alkali metal are used alone, the dosage of the alkali and/or alkali metal refers to alkali or alkali
The dosage of metal.
Similarly, when the salt of a- aminolactams and a- aminolactams is at the same time in use, a- aminolactams and/or a-
The dosage of the salt of aminolactam refers to total dosage of the salt of a- aminolactams and a- aminolactams；When acyl in a- amino
When the salt of amine and a- aminolactams is used alone, the dosage of the salt of the a- aminolactams and/or a- aminolactams refers to
Be a- aminolactams or a- aminolactams salt dosage.
Method according to the present invention, has no particular limits the alkali and/or alkali metal, as long as can be with a- ammonia
The salt of base lactams and/or a- aminolactams reacts to obtain lactams anion, and preferably described alkali is selected from hydrogenation
At least one of sodium, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate and saleratus, further preferably
For potassium carbonate and/or sodium carbonate；It is preferred that the alkali metal is sodium and/or potassium.
Method according to the present invention, has no particular limits the solvent, as long as can be with dissolved acetylene and a- ammonia
The salt of base lactams and/or a- aminolactams, preferably described solvent are selected from halogenated hydrocarbons, dimethylformamide (DMF), two
At least one of methylacetamide (DMAC), 1-methyl-2-pyrrolidinone, tetrahydrofuran and dioxane, are further preferably selected from
C1-C2 chlorohydrocarbons, chlorobenzene, dimethylformamide, dimethylacetylamide, 1-methyl-2-pyrrolidinone, tetrahydrofuran and dioxy six
At least one of ring, is most preferably dimethylformamide.
In the present invention, shown in the structure such as formula (3) of the a- aminolactams：
Wherein, n is 1 or 2.
The salt of the a- aminolactams can be the salt of various a- aminolactams commonly used in the art, preferably described a-
The salt of aminolactam is selected from least one of hydrochloride, sulfate and acetate of a- aminolactams.
A kind of preferred embodiment according to the present invention, total dosage of the salt of the a- aminolactams and a- aminolactams
It is 1 with the weight ratio of alkali and total dosage of alkali metal：1-5, more preferably 1：1-1.2.
In the present invention, the alkylating reagent is had no particular limits, any alkyl that can be known in the art
Change reagent, preferably described alkylating reagent is selected from least one of halogenated hydrocarbons, sulfuric ester, aldehyde and acid of C1-C20, preferably institute
State the chloralkane that halogenated hydrocarbons is C1-C6, preferably described sulfuric ester be dialkyl sulfate, preferably described aldehyde be formaldehyde and/or
Acetaldehyde, preferably described acid is formic acid and/or acetic acid.
The present invention has no particular limits the alkylation reaction condition, and preferably described alkylation reaction condition includes：
Temperature is -78 DEG C to 150 DEG C, pressure 0-0.5MPa, when the time is 0.5-24 small；More preferably include：Temperature is -10 DEG C to 60
DEG C, pressure is normal pressure, when the time is 0.5-12 small.
The present invention has no particular limits the addition condition, as long as can be so that reactant carries out addition reaction with acetylene
, preferably described addition reaction condition includes：Temperature is 130-200 DEG C, pressure 0.2-2.0MPa, and the time is small for 2-12
When, more preferably include：Temperature is 150-180 DEG C, pressure 0.5-1.5MPa, when the time is 3-9 small.
In the present invention, unless otherwise specified, the pressure refers both to gauge pressure.
The preparation method of the vinyl monomer provided according to the present invention, works as R1And R2After not being H and using elder generation's addition reaction
When alkylated reaction prepares vinyl monomer, preferably this method is additionally included in before being alkylated reaction, first by addition reaction
Obtained mixture is washed, extracted and dried successively；And work as R1And R2It is not H and uses addition after first alkylated reaction
When reaction prepares vinyl monomer, preferably this method is additionally included in before carrying out addition reaction, first obtains alkylated reaction
Mixture is washed, extracted and dried successively.The purity of reaction product can so be improved.Wherein, it is described washing, extraction and
Dry specific operation process and operating condition all can be this area conventional selection, this those skilled in the art can be known
Know, therefore not to repeat here.
In the present invention, R is worked as1And R2When being H, by the salt of acetylene and a- aminolactams and/or a- aminolactams into
After row addition reaction, can the isolated compound with structure shown in formula (1) by means commonly known in the art, for example,
Separated method can include：Reaction raw materials are removed by extracting, then removes solvent by way of vacuum distillation and obtains formula (1)
The compound of shown structure.
In the present invention, R is worked as1And R2When not being H, in the alkylation for the mixture and C1-C20 for obtaining addition reaction
, can be with alternatively, after the mixture that obtains alkylated reaction carries out addition reaction with acetylene after reagent is alkylated reaction
The compound of structure shown in isolated formula (1) by means commonly known in the art, for example, separated method can include：It is logical
Cross extraction and remove reaction raw materials, then remove solvent by way of vacuum distillation and obtain the compound of structure shown in formula (1).
One important use of vinyl monomer provided by the invention is for resisting with acrylamide and optional heatproof
Salt monomer is copolymerized to prepare acrylamide copolymer.
Invention further provides a kind of polymer, the polymer contains vinyl monomer construction unit and acryloyl
Amine structure unit, the vinyl monomer construction unit have the structure shown in formula (2)：
Wherein, n is 1 or 2, R1And R2It is each independently the alkenyl group of H or C1-C20.
Polymer according to the present invention, it is preferable that the R1And R2The alkenyl group of C1-C6 is each independently, into
The preferred R of one step1And R2It is identical, particularly preferred R1And R2It is methyl or ethyl.
Polymer according to the present invention, the content of the vinyl monomer construction unit and acrylamide construction unit
It can be made choice in wider range, it is preferable that on the basis of the gross weight of the polymer, the vinyl construction unit
Content be 0.1-99.9 weight %, the content of the acrylamide construction unit is 0.1-99.9 weight %；It is highly preferred that with
On the basis of the gross weight of the polymer, the content of the vinyl construction unit is 10-30 weight %, the acrylamide knot
The content of structure unit is 70-90 weight %.Using the preferable content, it is more advantageous to giving full play to vinyl monomer construction unit
Effect, and then obtain the more preferable polymer of temperature-resistant anti-salt performance.
A preferred embodiment of the invention, in order to improve the temperature-resistant anti-salt performance of polymer of the present invention,
The polymer can also contain temperature-resistant anti-salt construction unit, the temperature-resistant anti-salt construction unit by temperature-resistant anti-salt monomer polymerization and
Into.
The temperature-resistant anti-salt monomer can be various temperature-resistant anti-salt monomers commonly used in the art, be preferably selected from 2- acrylamides
Base -2- methyl propane sulfonic acids, n-vinyl pyrrolidone, dimethylamino ethyl acrylate, acrylic acid diethylaminoethyl, methyl-prop
One or more in olefin(e) acid dimethylamino ethyl ester, diethylaminoethyl base ethyl ester and N, N- dimethacrylamide.
A preferred embodiment of the invention, on the basis of the gross weight of the polymer, the temperature-resistant anti-salt
The content of construction unit is 5-50 weight %, more preferably 10-30 weight %.
In addition, polymer provided by the invention can be random copolymer, can be block copolymer, or alternately
Copolymer, can also be graft copolymerization.
According to the present invention, the polymer can have the intrinsic viscosity of 17-30dl/g, preferably with 19-24dl/g's
Intrinsic viscosity.It should be noted that the intrinsic viscosity in the present invention is special according to GB12005.1-89 acrylamide copolymers
Property the numerical value that measures of viscosity number assay method, which is used for the molecular size range for characterizing polymer.
Present invention also offers a kind of preparation method of polymer, this method includes：In the presence of initiator, by monomer
Mixture carries out polymerisation, wherein, the monomer mixture contains acrylamide and monomer A, and the monomer A is as described above
Vinyl monomer with formula (1) structure.
The preparation method of polymer according to the present invention, wherein, the weight of the monomer mixture and the initiator
Amount ratio has no particular limits, and is preferably 1：(1×10-6-5×10-4), more preferably 1：(1×10-5-4×10-4)。
The preparation method of polymer according to the present invention, it is preferable that there are bar in reagent and additive in polymerization for the polymerisation
Under part.At this time, the weight ratio of the monomer mixture, the initiator and the reagent and additive in polymerization has no particular limits, preferably
For 1：(1×10-6-5×10-4)：(1×10-6-2×10-4), more preferably 1：(1×10-5-4×10-4)：(5×10-6-
1.6×10-4)。
The preparation method of polymer according to the present invention, wherein, the reagent and additive in polymerization can improve the efficiency of polymerization,
The species of the reagent and additive in polymerization has no particular limits, under preferable case, the reagent and additive in polymerization for disodium ethylene diamine tetraacetate and/
Or urea.
The preparation method of polymer according to the present invention, wherein, the condition of the polymerisation does not limit particularly
Make, under preferable case, the condition of the polymerisation includes：Reaction temperature can be 0-80 DEG C, and the reaction time can be 2-20
Hour.
The most preferred embodiment of the preparation method of polymer according to the present invention, the polymerisation include low temperature
High temperature section polymerisation after section polymerisation and low-temperature zone polymerisation, the condition of the low-temperature zone polymerisation include：
Reaction temperature is 0-20 DEG C, when the reaction time is 4-12 small；The condition of the high temperature section polymerisation includes：Reaction temperature is
60-80 DEG C, when the reaction time is 1-2 small, the viscosity of polymer can be so further improved, so that the polymer has
More excellent temperature-resistant anti-salt performance.
The preparation method of polymer according to the present invention, wherein, the species of the initiator has no particular limits,
But in order to improve the comprehensive performance of polymer, under preferable case, the initiator is redox initiator, wherein, the oxygen
Change reduction initiator to be made of Oxidizing and Reducing Agents, the weight ratio of the oxidant and the reducing agent can be 1：0.2-5,
Preferably 1:0.5-2.In addition, the oxidant can be ammonium persulfate and/or potassium peroxydisulfate, it is preferably ammonium persulfate；It is described
Reducing agent can be iron ammonium sulfate and/or sodium hydrogensulfite, be preferably sodium hydrogensulfite.
A preferred embodiment of the invention, the initiator can be that redox initiator and azo trigger
The composite initiator of agent, the weight ratio of the redox initiator and azo initiator can be 1：0.1-10, is preferably 1:
0.5-2；The redox initiator is made of Oxidizing and Reducing Agents, and the weight ratio of the oxidant and the reducing agent can
Think 1:0.2-5, is preferably 1:0.5-2；The oxidant can be ammonium persulfate and/or potassium peroxydisulfate, be preferably persulfuric acid
Ammonium；The reducing agent can be iron ammonium sulfate and/or sodium hydrogensulfite, be preferably sodium hydrogensulfite；The azo initiator
Can be azodiisobutyronitrile and/or azo diisobutyl amidine hydrochloride.
The preparation method of polymer according to the present invention, wherein, do not have to the weight ratio of the monomer A and acrylamide
There is special limitation, be preferably 0.1-99.9：1, more preferably 0.11-0.42：1.
The preparation method of polymer according to the present invention, wherein, the polymerisation carries out in water phase, preferably
Ground, the dosage of water can make it that the concentration of acrylamide is 5-50 weight %, be preferably 10-40 weight %.Meanwhile it can pass through
Add alkaline matter, the pH value of aqueous phase liquid during telo merization be 7-9, the alkaline matter can for sodium hydroxide,
One or more in potassium hydroxide and sodium carbonate.
A preferred embodiment of the invention, obtained by improving the preparation method of polymer of the present invention
Polymer temperature-resistant anti-salt performance, the monomer mixture can also contain temperature-resistant anti-salt monomer, the temperature-resistant anti-salt monomer
Selected from 2- acrylamide-2-methylpro panesulfonic acids, n-vinyl pyrrolidone, dimethylamino ethyl acrylate, acrylic acid diethyl
In aminoethyl, Dimethylaminoethyl Methacrylate, diethylaminoethyl base ethyl ester and N, N- dimethacrylamide
One or more, more preferably 2- acrylamide-2-methylpro panesulfonic acids, n-vinyl pyrrolidone and N, N- diformazan
One or more in base acrylamide.
A preferred embodiment of the invention, in the monomer mixture, acrylamide and temperature-resistant anti-salt monomer
Weight ratio can be 1：0.1-10, more preferably 1：0.25-1.
According to the present invention, for the ease of storing and transporting, by obtained polymer prills, can be done after polymerization
Dry and crushing.The granulation, dry and crushing can use routine techniques well known in the art to carry out, of the invention not to be important to
Ask, details are not described herein.
A preferred embodiment of the invention, the preparation method of the polymer can carry out as follows：
1st step, by the acrylamide of 100 parts by weight, formula (1) vinyl monomer of 10-100 parts by weight, 0-50 weights
The temperature-resistant anti-salt monomer of amount part is added in reaction vessel, and it is 5-50 weight % to be dissolved in water as concentration (based on acrylamide)
Solution；
2nd step, nitrogen, deoxygenation 20-30 minutes are passed through into reaction vessel；
3rd step, relative to the acrylamide of 100 parts by weight, by the sodium hydrogensulfite of 0.001-0.01 parts by weight, 0.001-
The persulfate of 0.02 parts by weight, the azo diisobutyl amidine hydrochloride of 0.001-0.02 parts by weight, 0.005-0.01 parts by weight
Disodium ethylene diamine tetraacetate and the urea of 0.005-0.01 parts by weight be added in reaction vessel, and with alkali by the pH of reaction solution
Value is adjusted to 7-9；
4th step, carries out low-temperature zone polymerisation, reaction time in the range of the temperature of reaction vessel is maintained 0-20 DEG C
For 4-12 it is small when；
5th step, the temperature of reaction vessel is raised and maintains 60-80 DEG C, carries out high temperature section polymerisation, reaction time
For 1-2 it is small when；Obtain gelatinous temperature-resistant anti-salt water-soluble polymer.
Present invention also offers the polymer that the preparation method by above-mentioned polymer obtains.
Polymer according to the present invention, wherein, the polymer can have the intrinsic viscosity of 17-30dl/g, preferably have
There is the intrinsic viscosity of 19-24dl/g.
The present invention still further provides application of the above-mentioned polymer in oil displacement agent is prepared.
According to application of the polymer in oil displacement agent is prepared, wherein, the oil displacement agent contains provided by the invention poly-
Compound, the content of the polymer can make it that the gross weight of the oil displacement agent and the weight ratio of the polymer are 500-
5000：1, it is preferably 500-1000：1.
The oil displacement agent can also contain the materials such as alkaline matter, surfactant, so that as binary composite oil displacement agent
Used with ternary composite driving finish.The alkaline matter and the species of surfactant and dosage are oil displacement agent preparation field
Known content, the present invention repeats no more.
Hereinafter, the present invention is further described by embodiment, it is necessary to indicate, the embodiment of the present invention is served only for
The technical solution illustrated the present invention, the scope of the present invention are not limited in the following example.
It should be noted that the gas volume numerical value in the present invention is scaled the numerical value under standard state.In the present invention
Acrylamide copolymer basic performance indices are determined as follows：Intrinsic viscosity is according to GB12005.1-89 acrylamide copolymers
Intrinsic Viscosity Measurements method is measured；Acrylamide copolymer solution apparent viscosity is used at a temperature of nominative testing
Brookfield viscosimeters measure.
Embodiment 1-3 is used for the method for illustrating the vinyl monomer of formula (1).
Embodiment 1
11.4g a- amino valerolactams are dissolved in anhydrous DMF, 15g Anhydrous potassium carbonates are then added, in condition of ice bath
Under, slow (7.5g/h) adds 30g iodomethane, is warmed to room temperature reaction 24h, and reaction product is washed afterwards, is extracted, is dry
Except obtaining intermediate product after solvent；
Intermediate product is dissolved in 50mL dry N-methylpyrrolidones, 2.4g sodium is then added, is reacted at 125 DEG C
30min, is transferred in autoclave, and acetylene/nitrogen mixture (volume ratio 1 is passed through at 170 DEG C：1) to 0.5MPa, instead
Answer 10 it is small when obtain reaction product, be evaporated under reduced pressure isolated product.
With1H-NMR analyzes the structure of the product, obtains spectrogram shown in Fig. 1.It can be seen that from the spectrogram in chemical shift
It is methyl peak at 2.6 to be the peak of olefinic double bonds at 7.3,6.1 and 4.8, it is consistent with target compound, it was demonstrated that the product is certain
For the vinyl monomer with formula (1) structure.
The structure of the product is analyzed by GC-MS, the molecular weight for confirming the product is 168.3, consistent with target compound,
It with n is 1 and R to prove that the product is really1、R2It is CH3Formula (1) structure vinyl monomer.
Embodiment 2
11.4g a- aminocaproic lactams are dissolved in 50mL dry N-methylpyrrolidones, then add 2.4g sodium,
30min is reacted at 125 DEG C, is transferred in autoclave, acetylene/nitrogen mixture (volume ratio 1 is passed through at 150 DEG C：1)
To 0.5MPa, when reaction 10 is small, gained reaction product is washed afterwards, is extracted, drying obtains intermediate product after removing solvent；
Intermediate product is dissolved in anhydrous DMF, then adds 15g Anhydrous potassium carbonates, under condition of ice bath, slow (7.5g/
H) 30g iodomethane is added, reaction 24h is warmed to room temperature and obtains reaction product, be evaporated under reduced pressure isolated product afterwards.
Pass through1H-NMR and GC-MS analyzes the structure of the product, it was demonstrated that it with n is 2 and R that the product is really1、R2It is
CH3Formula (1) structure vinyl monomer.
Embodiment 3
11.4g a- aminocaproic lactams are dissolved in 100ml dry N-methylpyrrolidones, then add 2.4g sodium,
30min is reacted at 125 DEG C, is transferred in autoclave, acetylene/nitrogen mixture (volume ratio 1 is passed through at 130 DEG C：1)
To 2.0MPa, reaction 3 obtains reaction product when small, is evaporated under reduced pressure isolated product afterwards.
Pass through1H-NMR and GC-MS analyzes the structure of the product, it was demonstrated that it with n is 2 and R that the product is really1、R2It is H
Formula (1) structure vinyl monomer.
Polymerization Example 1-6 is used to illustrate polymer provided by the invention and preparation method thereof.
Polymerization Example 1
At room temperature, the n that has 8.20 grams of acrylamides, 3.04 grams of embodiments 1 obtained is 1 and R1、R2It is CH3Formula
(1) vinyl monomer of structure and 5.0 grams of N,N-DMAAs (being purchased from Aldrich) are dissolved in 30 grams of water, to anti-
Answer and nitrogen is passed through in container, deoxygenation 20 minutes.Add 0.0005 gram of azo diisobutyl amidine hydrochloride, 0.002 gram of ammonium persulfate,
0.012 gram of 0.006 gram of disodium ethylene diamine tetraacetate and urea.PH is adjusted to 9 with solid sodium hydroxide, is transferred to polymerization bottle
In, letting nitrogen in and deoxidizing depressurizes pump drainage deoxidation after twenty minutes, then leads to nitrogen 20 minutes, adds sodium hydrogensulfite 0.002 afterwards repeatedly for three times
Gram, 8 DEG C reaction 6 it is small when after, be warming up to 70 DEG C reaction 2 it is small when, obtain gum polymers 1, after measured, the gum polymers
Intrinsic viscosity is 21.32dl/g.
It polymerize comparative example 1
At room temperature, 10.20 grams of acrylamides are dissolved in 19 grams of water, nitrogen is passed through into reaction vessel, deoxygenation 20 divides
Clock.Add 0.0005 gram of azo diisobutyl amidine hydrochloride, 0.002 gram of ammonium persulfate, 0.006 gram of disodium ethylene diamine tetraacetate and
0.012 gram of urea.PH is adjusted to 9 with solid sodium hydroxide, is transferred in polymerization bottle, letting nitrogen in and deoxidizing depressurizes pump drainage after twenty minutes
Deoxidation, then logical nitrogen 20 minutes, add 0.002 gram of sodium hydrogensulfite afterwards repeatedly for three times, when 8 DEG C of reactions 6 are small after, be warming up to 70
DEG C reaction 2 it is small when, obtain gum polymers A, after measured, the intrinsic viscosity of the gum polymers is 19.23dl/g.
Polymerization Example 2
At room temperature, the n that has 8.20 grams of acrylamides, 3.04 grams of embodiments 2 obtained is 2 and R1、R2It is CH3Formula
(1) vinyl monomer of structure and 5.0 grams of n-vinyl pyrrolidone (being purchased from Aldrich) are dissolved in 30 grams of water, to reaction
Nitrogen, deoxygenation 20 minutes are passed through in container.Add 0.0005 gram of azo diisobutyl amidine hydrochloride, 0.002 gram of ammonium persulfate, second
0.012 gram of 0.006 gram of edetate disodium and urea.PH is adjusted to 9 with solid sodium hydroxide, is transferred in polymerization bottle,
Letting nitrogen in and deoxidizing depressurizes pump drainage deoxidation after twenty minutes, then leads to nitrogen 20 minutes, adds 0.002 gram of sodium hydrogensulfite afterwards repeatedly for three times,
8 DEG C reaction 6 it is small when after, be warming up to 70 DEG C reaction 2 it is small when, obtain gum polymers 2, after measured, the spy of the gum polymers
Property viscosity number is 20.62dl/g.
Polymerization Example 3
At room temperature, the n that has 11.30 grams of acrylamides, 2.04 grams of embodiments 1 obtained is 1 and R1、R2It is CH3's
The vinyl monomer of formula (1) structure and 4.0 grams of 2- acrylamide-2-methylpro panesulfonic acids (being purchased from Aldrich) are dissolved in 19 grams
In water, nitrogen, deoxygenation 20 minutes are passed through into reaction vessel.Add 0.0005 gram of azo diisobutyl amidine hydrochloride, persulfuric acid
0.012 gram of 0.002 gram of ammonium, 0.006 gram of disodium ethylene diamine tetraacetate and urea.PH is adjusted to 7.5 with solid sodium hydroxide, is turned
Move on in polymerization bottle, letting nitrogen in and deoxidizing depressurizes pump drainage deoxidation after twenty minutes, then leads to nitrogen 20 minutes, adds sulfurous acid afterwards repeatedly for three times
0.002 gram of hydrogen sodium, 8 DEG C reaction 6 it is small when after, be warming up to 70 DEG C reaction 2 it is small when, obtain gum polymers 3, after measured, the glue
The intrinsic viscosity of shaped polymer is 24.20dl/g.
Polymerization Example 4
Polymer is prepared according to the method described in Polymerization Example 1, unlike, it is added without 5.0 grams of N, N- dimethyl propylenes
Acrylamide, obtains gum polymers 4, and after measured, the intrinsic viscosity of the gum polymers product is 19.54dl/g.
Polymerization Example 5
Polymer is prepared according to the method described in Polymerization Example 1, unlike, what addition embodiment 1 obtained is with n
1 and R1、R2It is CH3The amount of vinyl monomer of formula (1) structure be 0.82g, obtain gum polymers 5, after measured, the glue
The intrinsic viscosity of shaped polymer is 19.13dl/g.
Polymerization Example 6
Polymer is prepared according to the method described in Polymerization Example 1, unlike, the vinyl that will be obtained by embodiment 1
Monomer use identical weight part by embodiment 3 obtain have n for 2 and R1、R2It is the vinyl monomer of formula (1) structure of H
Substitute, obtain gum polymers 6, after measured, the intrinsic viscosity of the gum polymers product is 17.90dl/g.
Testing example
This testing example is used for the specific viscosity number and at different temperatures and not for measuring polymer 1-6 and polymer A
With the apparent viscosity under the conditions of salinity.
(1) intrinsic viscosity：
Intrinsic viscosity is measured according to GB12005.1-89 acrylamide copolymer Intrinsic Viscosity Measurements methods, institute
The results are shown in Table 1；
(2) apparent viscosity：
Using sodium chloride solution as simulation mineral reserve water, the concentration of the sodium chloride solution is mineralising angle value；Respectively with not
Simulation mineral reserve water with salinity is solvent by polymer 1-6 and the copolymer solution of polymer A compound concentrations 1500mg/L, room
When stirring 2 is small at 25 DEG C of temperature；The apparent viscosity of copolymer solution at different temperatures is measured, investigates copolymer solution apparent viscosity
Situation about changing with the change of temperature and salinity.
Apparent viscosity is measured by the III ULTRA type rotation viscometers of DV- of BROOKFIELD companies, shear rate during measurement
Constant is 7.34s-1。
Table 1 give the solution of polymer 1-6 and polymer A polymer concentration be 1500mg/L, under different salinities,
Apparent viscosity data at 25 DEG C.Table 2 give the solution of polymer 1-6 and polymer A polymer concentration be 1500mg/L,
Salinity is the delta data of apparent viscosity with temperature under 3000mg/L.
Table 1
Although embodiment 1 and the contrast of 1 data of comparative example can be seen that polymer 1 and the viscosity of polymer A from table 1
Under the conditions of low mineralization relatively, but with the increase of salinity, the apparent viscosity bigger of polymer 1 in embodiment 1,
And the viscosity suppression ratio of polymer A is more significant in comparative example 1.Compared with polymer A, polymer 1-6 is in salinity 30000mg/L
When, viscosity higher is still kept, this illustrates that polymer provided by the present invention has excellent anti-salt property.
Table 2
From Table 2, it can be seen that in 25-90 DEG C of Range of measuring temp, the apparent viscosity of polymer 1-6 is consistently higher than poly-
Compound A, illustrates that polymer provided by the invention has good heat resistance.
It can be seen from the results above that polymer provided by the invention has good anti-salt temperature-resistant performance, therefore can
As Heat-resistant salt-tolerant oil displacement agent.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (18)
1. a kind of vinyl monomer, it is characterised in that the monomer has the structure shown in formula (1)：
Wherein, n is 1 or 2, R1And R2It is each independently the alkenyl group of H or C1-C20.
2. vinyl monomer according to claim 1, wherein, the R1And R2It is each independently the alkane of C1-C6
Base；
Preferably, R1And R2It is identical.
3. a kind of preparation method of vinyl monomer, wherein, which has the structure shown in formula (1)：
Wherein, n is 1 or 2, R1And R2The alkenyl group of H or C1-C20 are each independently,
Work as R1And R2When being H, this method includes：Under alkali and/or alkali metal and solvent existence condition, by acetylene and a- ammonia
The salt of base lactams and/or a- aminolactams carries out addition reaction；
Work as R1And R2When not being H, this method includes：Under alkali and/or alkali metal and solvent existence condition, by acetylene and a-
The salt of aminolactam and/or a- aminolactams carries out addition reaction, the mixture for then again obtaining the addition reaction
Reaction is alkylated with the alkylating reagent of C1-C20；Alternatively, by the salt of a- aminolactams and/or a- aminolactams with
The alkylating reagent of C1-C20 is alkylated reaction, then under alkali and/or alkali metal and solvent existence condition, by described in
The mixture that alkylated reaction obtains carries out addition reaction with acetylene.
4. preparation method according to claim 3, wherein, on the basis of the acetylene of 100 molar parts, the alkali and/or alkali
The dosage of metal is 100-300 molar parts, and the dosage of the salt of the a- aminolactams and/or a- aminolactams is 80-200
Molar part, the dosage of the alkylating reagent of the C1-C20 is 80-200 molar parts.
5. the preparation method according to claim 3 or 4, wherein,
The alkali in sodium hydride, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate and saleratus extremely
Few one kind；
The alkali metal is sodium and/or potassium；
The solvent is selected from halogenated hydrocarbons, dimethylformamide, dimethylacetylamide, 1-methyl-2-pyrrolidinone, tetrahydrofuran and two
At least one of six ring of oxygen；
The salt of the a- aminolactams is selected from least one of hydrochloride, sulfate and acetate of a- aminolactams.
6. the preparation method according to claim 3 or 4, wherein, the alkylating reagent is selected from halogenated hydrocarbons, sulfuric ester, aldehyde
At least one of with acid；The alkylation reaction condition includes：Temperature is -78 DEG C to 150 DEG C, pressure 0-0.5MPa, when
Between for 0.5-24 it is small when；The addition reaction condition includes：Temperature is 130 DEG C to 200 DEG C, pressure 0.2-2.0MPa, the time
For 2-12 it is small when.
7. a kind of polymer, it is characterised in that the polymer contains vinyl monomer construction unit and acrylamide structure list
Member, the vinyl monomer construction unit have the structure shown in formula (2)：
Wherein, n is 1 or 2, R1And R2It is each independently the alkenyl group of H or C1-C20；
Preferably, R1And R2It is each independently the alkenyl group of C1-C6；
Preferably, R1And R2It is identical.
8. polymer according to claim 7, wherein, on the basis of the gross weight of the polymer, the vinyl list
The content of body construction unit is 0.1-99.9 weight %, and the content of acrylamide construction unit is 0.1-99.9 weight %.
9. the polymer according to claim 7 or 8, wherein, the polymer also contains temperature-resistant anti-salt construction unit, described
Temperature-resistant anti-salt construction unit is formed by temperature-resistant anti-salt monomer polymerization, and the temperature-resistant anti-salt monomer is selected from 2- acrylamido -2- first
Base propane sulfonic acid, n-vinyl pyrrolidone, dimethylamino ethyl acrylate, acrylic acid diethylaminoethyl, methacrylic acid two
One or more in methylamino ethyl ester, diethylaminoethyl base ethyl ester and N, N- dimethacrylamide；
Preferably, on the basis of the gross weight of the polymer, the content of the temperature-resistant anti-salt construction unit is 5-50 weight %.
10. a kind of preparation method of polymer, this method include：In the presence of initiator, monomer mixture is polymerize
Reaction, it is characterised in that the monomer mixture contains acrylamide and monomer A, the monomer A for described in claim 1 or 2
Vinyl monomer.
11. preparation method according to claim 10, wherein, the weight ratio of the monomer mixture and the initiator is
1：(1×10-6-5×10-4)；
Preferably, the polymerisation carries out in the presence of reagent and additive in polymerization, and the reagent and additive in polymerization is disodium ethylene diamine tetraacetate
And/or urea；
Preferably, the weight ratio of the monomer mixture, the initiator and the reagent and additive in polymerization is 1：(1×10-6-5×10-4)：(1×10-6-2×10-4)。
12. preparation method according to claim 10, wherein, the weight ratio of the monomer A and acrylamide are 0.1-
99.9：1.
13. according to the preparation method described in any one in claim 10-12, wherein, the monomer mixture is also containing resistance to
Warm salt resistance monomer, the temperature-resistant anti-salt monomer are selected from 2- acrylamide-2-methylpro panesulfonic acids, n-vinyl pyrrolidone, third
Olefin(e) acid dimethylamino ethyl ester, acrylic acid diethylaminoethyl, Dimethylaminoethyl Methacrylate, diethylaminoethyl base
One or more in ethyl ester and N, N- dimethacrylamide；
Preferably, in the monomer mixture, the weight ratio of acrylamide and temperature-resistant anti-salt monomer is 1：0.1-10.
14. preparation method according to claim 10, wherein, the initiator is redox initiator, or is oxygen
Change the composite initiator of reduction initiator and azo initiator.
15. preparation method according to claim 10, wherein, the polymerisation includes low-temperature zone polymerisation and low temperature
High temperature section polymerisation after section polymerisation, the condition of the low-temperature zone polymerisation include：Reaction temperature is 0-20 DEG C,
When reaction time is 4-12 small；The condition of the high temperature section polymerisation includes：Reaction temperature is 60-80 DEG C, and the reaction time is
When 1-2 is small.
16. the polymer being prepared as the preparation method described in any one in claim 10-15.
17. polymer according to claim 16, wherein, the polymer has the intrinsic viscosity of 17-30dl/g.
18. application of the polymer in claim 7-9,16 and 17 described in any one in oil displacement agent is prepared.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050926A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Heat-resistant salt-tolerate graft polyacrylamide and preparation method thereof |
| CN103772602A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Temperature-resistant and salt-resistant copolymer and preparation method thereof |
| CN104004122A (en) * | 2014-05-08 | 2014-08-27 | 中国科学院长春应用化学研究所 | Novel temperature-sensitive polymer and method for preparing novel temperature-sensitive polymer from L-lysine as renewable resource |
| CN104558407A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant water-soluble polymer, and preparation and application method thereof |
| CN106588754A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Styrene compound and acrylamide copolymer and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050926A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Heat-resistant salt-tolerate graft polyacrylamide and preparation method thereof |
| CN103772602A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Temperature-resistant and salt-resistant copolymer and preparation method thereof |
| CN104558407A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant water-soluble polymer, and preparation and application method thereof |
| CN104004122A (en) * | 2014-05-08 | 2014-08-27 | 中国科学院长春应用化学研究所 | Novel temperature-sensitive polymer and method for preparing novel temperature-sensitive polymer from L-lysine as renewable resource |
| CN106588754A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Styrene compound and acrylamide copolymer and preparation method and application thereof |
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