CN104557587B - A kind of polymerisable monomer and its preparation method and application - Google Patents
A kind of polymerisable monomer and its preparation method and application Download PDFInfo
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- CN104557587B CN104557587B CN201310478608.0A CN201310478608A CN104557587B CN 104557587 B CN104557587 B CN 104557587B CN 201310478608 A CN201310478608 A CN 201310478608A CN 104557587 B CN104557587 B CN 104557587B
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Abstract
The invention provides a kind of polymerisable monomer and its preparation method and application.Described polymerisable monomer has the structure shown in formula (Ι), and wherein, n is the integer of 15, and m is the integer of 1 10.The polymer that the polymerisable monomer using the present invention to provide prepares, temperature be 85 DEG C, salinity be 32868mg/L under conditions of there is higher apparent viscosity.Formula (Ι).
Description
Technical field
The present invention relates to a kind of polymerisable monomer and its preparation method and application.
Background technology
Oil is one of most important energy of contemporary world, especially in the China that auto industry is fast-developing,
The demand of oil the most rapidly increases.Recover the oil from oil reservoir and be generally divided into three phases: primary oil recovery is
The natural energy relying on stratum is fuel-displaced, and tar productivity is below 30%；Secondary oil recovery uses water filling, gas injection skill
It is fuel-displaced that art supplements oils energy, and recovery ratio is up to 40-50%；Tertiary oil recovery i.e. intensified oil reduction, can make to adopt
Yield brings up to 80-85%.At present, China's intensified oil reduction relies primarily on chemical flooding, wherein polymer flooding
Proportion is higher.Scientific research both domestic and external and production practices show, polymer flooding is that a kind of oil that improves is adopted
Yield effective ground method.This base polymer is under the conditions of hiding oil, it is necessary to have excellent thickening property,
And under the effect of temperature, pressure and salt, there is high viscosity conservation rate.
At present, conventional flooding polymers mainly has two classes: one be with polyacrylamide (PAM) and
Partially hydrolyzed polyacrylamide (PHPA) (HPAM) is the synthetic polymer of representative.But HPAM heat and salt resistance
Can be undesirable, the ultimate-use (limiting service) temperature under reservoir condition is only 75 DEG C, and in the presence of having salt, viscosity acutely declines,
Bivalent metal ion also can make it produce precipitation and lose viscosity.It addition, HPAM meeting under shear action
There is molecular chain rupture, cause its tackifying ability to reduce.Research shows, the thermostability of HPAM, anti-salt
The poor-performing such as property and shear resistant so that it is application conditions is restricted.Two with Xanthan gun as representative
Biopolymer.Xanthan gun has certain anti-salt resistant to shearing performance, but Xanthan gun meeting in high-temperature stratum
Thermal oxidative degradation occurs, and the formation temperature for tertiary oil recovery typically should not be higher than 60 DEG C.Additionally Xanthan gun
Price be 5 times of HPAM, also limit its popularization.Therefore, study and develop thickening property
The polymer displacement of reservoir oil that the combination properties such as salt good, heat-resisting, anti-, serviceability are excellent and cheap are good
Agent is extremely urgent.
Summary of the invention
It is an object of the invention to overcome the polymer oil-displacing agent heat resistance of prior art and anti-salt property relatively
The defect of difference, and a kind of new polymerisable monomer and its preparation method and application is provided.By described polymerizable
Monomer and other temperature-resistant anti-salt monomer copolymerizations, the copolymerization product of gained has the resistant and salt performance of excellence.
The invention provides a kind of polymerisable monomer, wherein, described polymerisable monomer has formula (Ι) institute
The structure shown:
Formula (Ι)
Wherein, n is the integer of 1-5, and m is the integer of 1-10.
Present invention also offers the preparation method of a kind of polymerisable monomer, wherein, the method includes following step
Rapid:
(1) under amidation reaction condition, will have the aromatic diamines and third of structure shown in formula II
Alkene acyl chlorides contacts, and obtains the intermediate M with structure shown in formula III；
Formula II
Formula III
(2) under the conditions of condensation reaction, by described intermediate M with there is structure shown in formula IV
Binary of fatty acids contacts；
HOOC-(CH2)m-COOH formula IV
Wherein, n is the integer of 1-5, and m is the integer of 1-10.
Present invention also offers the polymerisable monomer prepared by said method.
Additionally, present invention also offers the application in preparing Polymer Used For Oil Displacement of the described polymerisable monomer.
The chain length of the polymerisable monomer that the present invention provides is longer, and easy shape between the amide group on strand
Becoming hydrogen bond, therefore, it polymer prepared has higher viscosity.Additionally, the present invention provides
Polymerisable monomer be a kind of monomer with emulsification function, be also called polymerisable emulsifier, its molecule tie
In structure in addition to containing the reactive group that can participate in radical polymerization, possibly together with the emulsified base of hydrophilic and oleophilic
Group, after completing polymerization, molecule will not occur resolving again, has good stability, and acrylamide
Class polymerisable emulsifier has the particular advantages such as reactivity is high, resulting polymers molecular weight is high.By this
The polymerisable monomer of bright offer and other temperature-resistant anti-salt monomer copolymerizations, the displacement of reservoir oil of available excellent performance is with poly-
Compound.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the polymerisable monomer prepared by preparation example 1.
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 polymerisable monomer that the present invention provides has a structure shown in formula (Ι):
Formula (Ι)
Wherein, n is the integer of 1-5, and m is the integer of 1-10；Preferably, n is 0 or 1, and m is
The integer of 4-8.
The preparation method of the polymerisable monomer that the present invention provides comprises the following steps:
(1) under amidation reaction condition, will have the aromatic diamines and third of structure shown in formula II
Alkene acyl chlorides contacts, and obtains the intermediate M with structure shown in formula III；
Formula II
Formula III
(2) under the conditions of condensation reaction, by described intermediate M with there is structure shown in formula IV
Binary of fatty acids contacts；
HOOC-(CH2)m-COOH formula IV
Wherein, n is the integer of 1-5, and m is the integer of 1-10；Preferably, n is 0 or 1, and m is
The integer of 4-8.
For the sake of difference, acyl chlorides and amine are obtained the reaction of amide by sloughing a part HCl by the present invention
Being referred to as amidation process, the reaction that carboxylic acid and amine obtain amide by sloughing a part water is referred to as condensation
Reaction.
The consumption of the aromatic diamines described in step (1) with acryloyl chloride is limited by the present invention the most especially
Fixed, as long as the intermediate shown in formula III can be obtained, such as, described aromatic diamines and propylene
The mol ratio of acyl chlorides can be 1:1-1.2, preferably 1:1-1.1.
According to the present invention, described amidation reaction condition can be the conventional selection of this area, such as, institute
State amidation reaction condition to generally include: reaction temperature can be 80-110 DEG C, preferably 90-100 DEG C；
Response time can be 4-8 hour, preferably 6-7 hour.
The consumption of the binary of fatty acids described in step (2) is not particularly limited by the present invention, as long as
Can obtain that there is the polymerisable monomer shown in formula (Ι), such as, described binary of fatty acids and virtue
The mol ratio of fragrant diamidogen can be 1:1-1.2, preferably 1:1-1.1.
According to the present invention, described condensation reaction condition can be the popular response condition of this area.Such as,
Described condensation reaction condition includes reaction temperature and response time.Under normal circumstances, in order to be beneficial to further
The carrying out of reaction, described reaction temperature is preferably 110-160 DEG C, more preferably 130-150 DEG C.During reaction
Between the raising extending the yield being conducive to the conversion ratio of reactant or product, but response time mistake
The increase rate of the yield of the long conversion ratio to reactant or product is the most inconspicuous, therefore, from each side
Face considers, and the described response time is preferably 2-6 hour, more preferably 3-5 hour.
According to the present invention, in order to regulate reaction rate, the amidation process of described step (1) and/or step
Suddenly the condensation reaction of (2) is carried out the most in presence of organic solvent.Owing to described organic solvent is main
As reaction medium, its consumption can be adjusted according to the consumption of monomer.Such as, in step (1)
In, described aromatic diamines can be 1:20-30, preferably 1:20-25 with the mol ratio of organic solvent；
In step (2), described binary of fatty acids can be 1:20-30 with the mol ratio of organic solvent, excellent
Elect 1:20-25 as.Described organic solvent can be the existing various material that can act as reaction medium,
Such as, described organic solvent can be selected from acetone, ethyl acetate, benzene, dimethylbenzene, dichloromethane and three
One or more in chloromethanes.
According to the present invention, in order to prevent the polymerisable monomer generated from autohemagglutination, step occurring in course of reaction
(1) amidation process is preferably carried out in the presence of polymerization inhibitor.
Kind and the consumption of described polymerization inhibitor are not particularly limited by the present invention, prevent as long as can play
Autohemagglutination is there is in the polymerisable monomer generated in course of reaction.Such as, described polymerization inhibitor and acryloyl
The weight ratio of chlorine can be 0.05-0.1:1, preferably 0.05-0.08:1.Described polymerization inhibitor is preferably selected from
One or more in hydroquinone, 1,4-benzoquinone and MEHQ.
According to the present invention, described amidation process and condensation reaction can be in existing various conventional reactor
In carry out, for example, it is possible to carry out in various flasks or reactor.Additionally, in order to be more beneficial for reaction
Being fully contacted between thing, described amidation process and condensation reaction are the most under agitation carried out.
According to the present invention, in order to obtain sterling, the preparation method of the polymerisable monomer that the present invention provides also may be used
To include the step of the product purification obtained.The method of described purification can be the conventional choosing of this area
Select, for example, it is possible to the product that step (2) obtains is carried out recrystallization.The method of described recrystallization and
Condition can be the conventional selection of this area, such as, the solvent used by recrystallization can be selected from ethanol,
One or more in acetone and hexane.
Present invention also offers the polymerisable monomer prepared by said method.
Additionally, present invention also offers the application in polymer oil-displacing agent of the above-mentioned polymerisable monomer.This
In bright, described " polymerisable monomer is in the application of polymer oil-displacing agent " both included using polymerisable monomer as
Prepare the monomer of the polymer of the displacement of reservoir oil, the polymer formed be used as oil displacement agent and by gathering of being formed
Compound and other polymer oil-displacing agents with the use of.
It was found by the inventors of the present invention that by polymerisable monomer of the present invention and other temperature-resistant anti-salt monomers
Copolymerization, can arrive heat-resisting, the copolymer of anti-salt property with excellence.
According to the present invention, with other temperature-resistant anti-salt monomers of the described polymerisable monomer copolymerization that the present invention provides
Can be any monomer that can improve polymer displacement of reservoir oil performance, under preferable case, other heatproofs described resist
Salt monomer is selected from acrylamide (AM), acrylic acid, acrylic ester monomer, styrene, 2-acryloyl
Amine-2-methyl propane sulfonic acid (AMPS), NVP (NVP) and N-N-dimethyl allene acyl
One or more in amine (DMAM).The angle being easy to get from raw material, other temperature-resistant anti-salts described
Monomer is particularly preferably acrylamide (AM) and/or 2-acrylamide-2-methyl propane sulfonic (AMPS).
Additionally, described acrylic ester monomer can be such as acrylic acid methyl ester., ethyl acrylate, acrylic acid fourth
One or more in ester and 2-(Acryloyloxy)ethanol.
The condition of described copolyreaction is not particularly limited by the present invention, such as, and described copolyreaction
Condition generally includes: reaction temperature can be 0-80 DEG C；Response time can be 1-24 hour；PH value
Can be 4-11, preferably 8-11.The method of the pH value of regulation reaction system can be according to this area skill
Known in art personnel, method is carried out, and such as, is adjusted by adding alkaline matter in reaction system.Institute
Stating alkaline matter can be such as the one in potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate or many
Kind.Above-mentioned alkaline matter can use in solid form, it is also possible to uses with the form of its aqueous solution.
When using in form of an aqueous solutions, its concentration can be that 10 weight % are to saturated concentration.
According to the present invention, in order to overcome oxygen inhibition, obtain the copolymerization product of larger molecular weight, described copolymerization
Reaction is carried out the most in an inert atmosphere.Described inert atmosphere refers to not occur chemistry anti-with reactant and product
Any one gas answered or admixture of gas, in nitrogen, helium and periodic table of elements zero group gas
One or more.Keep inert atmosphere method can be passed through in reaction system above-mentioned not with reactant
Any one gas or admixture of gas with product generation chemical reaction.
The present inventor finds under study for action, takes following condition can obtain super high molecular weight random
Copolymer, i.e. preferably, described copolyreaction includes two stages carried out successively, the first stage
Reaction condition includes that reaction temperature is 0-20 DEG C, and the response time is 1-8 hour；The reaction bar of second stage
Part includes that reaction temperature is 40-80 DEG C, and the response time is 1-4 hour.
According to the present invention, the initiator used by described copolyreaction can be that existing various free radicals cause
Agent.Described radical initiator includes azo-initiator, peroxide type initiators and oxidoreduction class
Initiator.Wherein, described azo-initiator is selected from azo-bis-iso-dimethyl, azo two 2,2-Dimethylaziridine
Hydrochlorate, azodicarbonamide, azo diisopropyl imidazoline hydrochloride, azo isobutyl cyano group Methanamide,
Azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo diisopropyl imidazoline, azodiisobutyronitrile,
One or more in AMBN and 2,2'-Azobis(2,4-dimethylvaleronitrile).Described peroxide type initiators is selected from
Hydrogen peroxide, Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate, benzoyl peroxide and benzoyl peroxide
One or more in the tert-butyl ester.Described redox type initiators is selected from sulfate-sulphite, mistake
One or more in sulfate-thiourea, persulfate-organic salt and Ammonium persulfate .-fatty amine.Wherein,
Described sulfate-sulphite can be selected from sodium sulfate-sodium sulfite, potassium sulfate-potassium sulfite and ammonium sulfate
One or more in-ammonium sulfite；Persulfate-thiourea can be selected from sodium peroxydisulfate-thiourea, persulfuric acid
One or more in potassium-thiourea and Ammonium persulfate .-thiourea；Persulfate-organic salt can be selected from persulfuric acid
One or more in sodium-potassium acetate, potassium peroxydisulfate-potassium acetate and Ammonium persulfate .-ammonium acetate；Ammonium persulfate.
-fatty amine can be selected from the one in Ammonium persulfate .-N, N-tetramethylethylenediamine and Ammonium persulfate .-diethylamine
Or it is multiple.
The consumption of described initiator is not particularly limited by the present invention, can be according to the use of monomer mixture
Amount selects, and as a rule, the consumption of described initiator can be monomer mixture gross weight
0.01-0.1%, preferably 0.02-0.08%.
By following example, the present invention will be described in further detail below.
In following example and comparative example, in polymer, the content of each construction unit is according to the inventory of monomer
Calculate.
Reagent used in preparation example, embodiment and comparative example is commercially available chemically pure reagent.
In following example and comparative example, in polymer, the content of each construction unit is according to the inventory of monomer
Calculate.
In embodiment and comparative example, the intrinsic viscosity of polymer is surveyed according to GB12005.1-89 intrinsic viscosity
The method of determining is measured；Viscosity-average molecular weight is according to formula M η=([η]/K)1\α, wherein, K=4.5 × 10-3,
α=0.80 is calculated；The apparent viscosity of aqueous solutions of polymers passes through BROOKFIELD DV-III
Viscosity apparatus is 7.34s in rotating speed perseverance-1, temperature measures under conditions of being 85 DEG C and obtains, wherein, and test condition
Including: polymer concentration is 1500mg/L, and solution total salinity is 32868mg/L.
Preparation example 1
The preparation method of the polymerisable monomer that this preparation example provides for the present invention is described.
(1) preparation of intermediate:
Under agitation, 150 milliliters of dimethylbenzene are mixed homogeneously with the p-phenylenediamine of 0.1mol, and drips
0.1mol acryloyl chloride, after dropping, rises to temperature at 80 DEG C and back flow reaction 8 hours,
To intermediate M1.
(2) preparation of polymerisable monomer:
Under agitation, intermediate M1 and 0.1mol decanedioic acid step (1) obtained is mixed homogeneously,
It is heated to 110 DEG C to react 6 hours, then steams solvent and be dried, with acetone solvent to product at 70 DEG C
Thing carries out recrystallization, obtains polymerisable monomer D1.
Characterizing D1 with infrared spectrometry, result is as shown in Figure 1.Wherein, 2859.6cm-1、2956.0
cm-1For methyl, the symmetrically and asymmetrically stretching vibration absworption peak of methylene, 1372.6cm-1、1404.4
cm-1、1470.7cm-1For methyl, the in-plane bending vibration peak of methylene；1709.9cm-1For C=O's
Stretching vibration peak；1628.6cm-1、1586.4cm-1Stretching vibration peak for C=C double bond；3063.4cm-1
For the stretching vibration peak of c h bond on C=C-H, these demonstrate that the existence of double bond；3419.2cm-1For
The stretching vibration peak of the upper O-H of COOH, it was demonstrated that the existence of carboxyl；3290.3cm-1It it is N-H key
Stretching vibration peak, 1539.1cm-1It it is then the in-plane bending vibration of N-H.
Preparation example 2
The preparation method of the polymerisable monomer that this preparation example provides for the present invention is described.
(1) preparation of intermediate:
Under agitation, the p dimethylamine of 0.1mol is mixed homogeneously with 0.1mol acryloyl chloride, and adds
Heat, to 110 DEG C of back flow reaction 4 hours, obtains intermediate M2.
(2) preparation of polymerisable monomer:
Under agitation, intermediate M2 step (1) obtained and 150 milliliters of dichloromethane mixing are all
Even, and drip the decanedioic acid of 0.1mol, then temperature is risen to 160 DEG C react 2 hours, then steam molten
Agent is also dried at 70 DEG C, with acetone solvent, product is carried out recrystallization, obtains polymerisable monomer D2.With
D2 is characterized by infrared spectrometry, and result infrared spectrum is similar with Fig. 1.
Preparation example 3
The preparation method of the polymerisable monomer that this preparation example provides for the present invention is described.
(1) preparation of intermediate:
Under agitation, by 250 milliliters of xylol, the p-phenylenediamine of 0.1mol and 0.1mol propylene
Acyl chlorides mix homogeneously, and temperature is risen to 100 DEG C of back flow reaction 6 hours, steam solvent and at 70 DEG C
It is dried, obtains intermediate M3.
(2) preparation of polymerisable monomer:
Under agitation, intermediate M3 step (1) obtained and 150 milliliters of dichloromethane mixing are all
Even, and drip the suberic acid of 0.1mol, it is again heated to 140 DEG C and reacts 4 hours, then steam solvent also
It is dried at 70 DEG C, with acetone solvent, product is carried out recrystallization, obtain polymerisable monomer D3.With infrared
D3 is characterized by spectrographic method, and result infrared spectrum is similar with Fig. 1.
Preparation example 4
The preparation method of the polymerisable monomer that this preparation example provides for the present invention is described.
(1) preparation of intermediate:
Under agitation, by 250 milliliters of xylol, the p dimethylamine of 0.1mol and 0.1mol third
Alkene acyl chlorides mix homogeneously, and temperature is risen to 80 DEG C of back flow reaction after 8 hours, steam solvent and 70
It is dried at DEG C, obtains intermediate M4.
(2) preparation of polymerisable monomer:
Under agitation, intermediate M4 step (1) obtained and 150 milliliters of dichloromethane mixing are all
Even, and drip 0.1mol suberic acid, be again heated to 110 DEG C and react 6 hours, then steam solvent and
It is dried at 70 DEG C, with acetone solvent, product is carried out recrystallization, obtain polymerisable monomer D4.Use infrared light
D4 is characterized by spectrometry, and result infrared spectrum is similar with Fig. 1.
Preparation example 5
The preparation method of the polymerisable monomer that this preparation example provides for the present invention is described.
(1) preparation of intermediate:
Under agitation, the p-phenylenediamine of 0.1mol is mixed homogeneously with 0.1mol acryloyl chloride, and by temperature
Degree rose to 110 DEG C of back flow reaction after 4 hours, obtained intermediate M5.
(2) preparation of polymerisable monomer:
Under agitation, intermediate M5 step (1) obtained and 150 milliliters of dichloromethane mixing are all
Even, and drip the adipic acid of 0.1mol, it is again heated to 160 DEG C and reacts 2 hours, then steam solvent also
It is dried at 70 DEG C, with acetone solvent, product is carried out recrystallization, obtain polymerisable monomer D5.With infrared
D5 is characterized by spectrographic method, and result infrared spectrum is similar with Fig. 1.
Preparation example 6
The preparation method of the polymerisable monomer that this preparation example provides for the present invention is described.
(1) preparation of intermediate:
Under agitation, the p dimethylamine of 0.1mol is mixed homogeneously with 0.1mol acryloyl chloride, and will
Temperature rose to 100 DEG C of back flow reaction after 6 hours, obtained intermediate M6.
(2) preparation of polymerisable monomer:
Under agitation, intermediate M6 step (1) obtained and 150 milliliters of dichloromethane mixing are all
Even, and drip 0.1mol adipic acid, be again heated to 140 DEG C and react 4 hours, then steam solvent and
It is dried at 70 DEG C, with acetone solvent, product is carried out recrystallization, obtain polymerisable monomer D6.Use infrared light
D6 is characterized by spectrometry, and result infrared spectrum is similar with Fig. 1.
Preparation example 7
The preparation method of the polymerisable monomer that this preparation example provides for the present invention is described.
Identical with the preparation method of preparation example 1, except for the difference that, at dropping acryloyl chloride in step (1)
Before be initially charged 0.006 gram of 1,4-benzoquinone, obtain polymerisable monomer D7.With infrared spectrometry, D7 is carried out table
Levying, result infrared spectrum is similar with Fig. 1.
Embodiment 1
This embodiment illustrates the polymer for oil displacement agent prepared by polymerisable monomer provided by the present invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS)
Mixing with 50 grams of deionized waters, stirring makes monomer be completely dissolved, by the hydroxide that concentration is 20 weight %
The pH value of sodium water solution regulation system is 8, and said mixture and 0.15 gram is prepared by preparation example 1
Polymerisable monomer D1 and the mixing of 1 milligram of azo-bis-isobutyrate hydrochloride, under nitrogen protection, add
2 milligrams of Ammonium persulfate .s, are first polymerized 2 hours at temperature 20 DEG C, then are warming up to 40 DEG C, continue polymerization 4
Hour, gained colloid is taken out, pelletize, dry, pulverize at 50 DEG C, obtain white granular copolymerization
Product, is designated as polymer P 1.Characterizing P1 with infrared spectrometry, result shows, three kinds of monomers
The characteristic absorption peak of construction unit be both present in infrared spectrum, show that this copolymer is by these three structure
Unit forms.In described polymer on the basis of the total mole number of construction unit, acrylamide construction unit
The content that content is 89.97mol%, 2-acrylamide-2-methyl propane sulfonic construction unit be
9.69mol%, the content derived from the construction unit of polymerisable monomer D1 is 0.34mol%.
Embodiment 2
This embodiment illustrates the polymer for oil displacement agent prepared by polymerisable monomer provided by the present invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS)
Mixing with 50 grams of deionized waters, stirring makes monomer be completely dissolved, by the hydroxide that concentration is 20 weight %
The pH value of sodium water solution regulation system is 8, and said mixture and 0.15 gram is prepared by preparation example 2
Polymerisable monomer D2 and the mixing of 1 milligram of azodiisobutyronitrile, under nitrogen protection, add 2 milligrams
Potassium peroxydisulfate, is first polymerized 8 hours at temperature 5 DEG C, then is warming up to 60 DEG C, continues polymerization 2 hours,
Gained colloid is taken out, pelletize, dry, pulverize at 40 DEG C, obtain white granular copolymerization product,
It is designated as polymer P 2.Characterizing P2 with infrared spectrometry, result shows, the structure of three kinds of monomers
The characteristic absorption peak of unit is both present in infrared spectrum, shows that this copolymer is by these three construction unit group
Become.In described polymer on the basis of the total mole number of construction unit, the content of acrylamide construction unit
Content for 89.99mol%, 2-acrylamide-2-methyl propane sulfonic construction unit is 9.69mol%, derivative
It is 0.32mol% from the content of the construction unit of polymerisable monomer D2.
Embodiment 3
This embodiment illustrates the polymer for oil displacement agent prepared by polymerisable monomer provided by the present invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS)
Mixing with 50 grams of deionized waters, stirring makes monomer be completely dissolved, by the hydroxide that concentration is 20 weight %
The pH value of sodium water solution regulation system is 8, and said mixture and 0.15 gram is prepared by preparation example 3
Polymerisable monomer D3 and the mixing of 1 milligram of AMBN, under nitrogen protection, add 2 milligrams
Ammonium persulfate .-diethylamine, is first polymerized 5 hours at temperature 10 DEG C, then is warming up to 80 DEG C, continues polymerization
1 hour, gained colloid is taken out, pelletize, dry, pulverize at 50 DEG C, obtain white granular altogether
Poly-product, is designated as polymer P 3.Characterizing P3 with infrared spectrometry, result shows, three kinds of lists
The characteristic absorption peak of the construction unit of body is both present in infrared spectrum, shows that this copolymer is tied by these three
Structure unit forms.In described polymer on the basis of the total mole number of construction unit, acrylamide structure list
The content that content is 89.95mol%, 2-acrylamide-2-methyl propane sulfonic construction unit of unit is
9.68mol%, the content derived from the construction unit of polymerisable monomer D3 is 0.37mol%.
Embodiment 4
This embodiment illustrates the polymer for oil displacement agent prepared by polymerisable monomer provided by the present invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS)
Mixing with 50 grams of deionized waters, stirring makes monomer be completely dissolved, by the hydroxide that concentration is 20 weight %
The pH value of sodium water solution regulation system is 11, and said mixture and 0.15 gram is prepared by preparation example 4
Polymerisable monomer D4 and the mixing of 1 milligram of azo-bis-isobutyrate hydrochloride, under nitrogen protection, add
2 milligrams of Ammonium persulfate .s, are first polymerized 2 hours at temperature 20 DEG C, then are warming up to 40 DEG C, continue polymerization 4
Hour, gained colloid is taken out, pelletize, dry, pulverize at 60 DEG C, obtain white granular copolymerization
Product, is designated as polymer P 4.Characterizing P4 with infrared spectrometry, result shows, three kinds of monomers
The characteristic absorption peak of construction unit be both present in infrared spectrum, show that this copolymer is by these three structure
Unit forms.In described polymer on the basis of the total mole number of construction unit, acrylamide construction unit
The content that content is 89.97mol%, 2-acrylamide-2-methyl propane sulfonic construction unit be
9.69mol%, the content derived from the construction unit of polymerisable monomer D4 is 0.34mol%.
Embodiment 5
This embodiment illustrates the polymer for oil displacement agent prepared by polymerisable monomer provided by the present invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS)
Mixing with 50 grams of deionized waters, stirring makes monomer be completely dissolved, by the hydroxide that concentration is 20 weight %
The pH value of sodium water solution regulation system is 8, and said mixture and 0.15 gram is prepared by preparation example 5
Polymerisable monomer D5 and the mixing of 1 milligram of azodiisobutyronitrile, under nitrogen protection, add 2 milligrams
Potassium peroxydisulfate, is first polymerized 8 hours at temperature 5 DEG C, then is warming up to 60 DEG C, continues polymerization 2 hours,
Gained colloid is taken out, pelletize, dry, pulverize at 50 DEG C, obtain white granular copolymerization product,
It is designated as polymer P 5.Characterizing P5 with infrared spectrometry, result shows, the structure of three kinds of monomers
The characteristic absorption peak of unit is both present in infrared spectrum, shows that this copolymer is by these three construction unit group
Become.In described polymer on the basis of the total mole number of construction unit, the content of acrylamide construction unit
Content for 89.91mol%, 2-acrylamide-2-methyl propane sulfonic construction unit is 9.68mol%, derivative
It is 0.41mol% from the content of the construction unit of polymerisable monomer D5.
Embodiment 6
This embodiment illustrates the polymer for oil displacement agent prepared by polymerisable monomer provided by the present invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS)
Mixing with 50 grams of deionized waters, stirring makes monomer be completely dissolved, by the hydroxide that concentration is 20 weight %
The pH value of sodium water solution regulation system is 8, and said mixture and 0.15 gram is prepared by preparation example 6
Polymerisable monomer D6 and the mixing of 1 milligram of AMBN, under nitrogen protection, add 2 milligrams
Ammonium persulfate .-diethylamine, is first polymerized 5 hours at temperature 10 DEG C, then is warming up to 80 DEG C, continues polymerization
1 hour, gained colloid is taken out, pelletize, dry, pulverize at 70 DEG C, obtain white granular altogether
Poly-product, is designated as polymer P 6.Characterizing P6 with infrared spectrometry, result shows, three kinds of lists
The characteristic absorption peak of the construction unit of body is both present in infrared spectrum, shows that this copolymer is tied by these three
Structure unit forms.In described polymer on the basis of the total mole number of construction unit, acrylamide structure list
The content that content is 89.95mol%, 2-acrylamide-2-methyl propane sulfonic construction unit of unit is
9.68mol%, the content derived from the construction unit of polymerisable monomer D6 is 0.37mol%.
Embodiment 7
This embodiment illustrates the polymer for oil displacement agent prepared by polymerisable monomer provided by the present invention.
Random copolymer is prepared, except for the difference that, by prepared by preparation example 1 according to the method for embodiment 1
The polymerisable monomer D7 prepared by preparation example 7 of polymerisable monomer D1 identical weight part substitutes,
To white granular copolymerization product, it is designated as polymer P 7.With infrared spectrometry, P7 is characterized, knot
Fruit shows, the characteristic absorption peak of the construction unit of three kinds of monomers is both present in infrared spectrum, shows that this is altogether
Polymers is made up of these three construction unit.In described polymer on the basis of the total mole number of construction unit,
The content of acrylamide construction unit is 89.97mol%, 2-acrylamide-2-methyl propane sulfonic construction unit
Content be 9.69mol%, the content derived from the construction unit of polymerisable monomer D7 is 0.34mol%.
Embodiment 8
The preparation of the random copolymer that this embodiment provides for the present invention is described.
Random copolymer is prepared according to the method for embodiment 1, except for the difference that, the use of polymerisable monomer D1
Amount is 18.44 grams, obtains white granular copolymerization product, is designated as polymer P 8.With infrared spectrometry pair
P8 characterizes, and result shows, the characteristic absorption peak of the construction unit of three kinds of monomers is both present in infrared
In spectrum, show that this copolymer is made up of these three construction unit.With construction unit in described polymer
On the basis of total mole number, the content of acrylamide construction unit is 63.20mol%, 2-acrylamide-2-first
The content of base propane sulfonic acid construction unit is 6.80mol%, derived from the construction unit of polymerisable monomer D1
Content is 30mol%.
Comparative example 1
The polymer for oil displacement agent of this comparative example explanation reference.
Prepare copolymer according to the method for embodiment 1, except for the difference that, be added without polymerisable monomer D1,
Thus obtain the copolymer DP of AM and AMPS.
Test case 1-8
Test case 1-8 is for illustrating the viscosity-average molecular weight of polymer and the test of apparent viscosity.
The intrinsic viscosity of the polymer P 1-P8 that embodiment 1-8 prepares is according to GB12005.1-89
Intrinsic Viscosity Measurements method is measured；Viscosity-average molecular weight is according to formula M=([η]/K)1\α, wherein
K=4.5×10-3, α=0.80 is calculated；The apparent viscosity of aqueous solutions of polymers is passed through
BROOKFIELD DV-III viscosity apparatus is 7.34s in rotating speed perseverance-1, temperature is carried out under conditions of being 85 DEG C
Mensuration obtains, and wherein, test condition includes: polymer concentration is 1500mg/L, solution total salinity
For 32868mg/L.Test result is as shown in table 1.
Contrast test example 1
This contrast test example is for illustrating the viscosity-average molecular weight of reference polymer and the test of apparent viscosity.
Viscous equal molecule according to the method for the test case 1-8 copolymer DP to being prepared by comparative example 1
Amount is tested with apparent viscosity.Test result is as shown in table 1.
Table 1
| Numbering | Mη(×104) | Apparent viscosity (mPa s) |
| P1 | 2500 | 32.7 |
| P2 | 2450 | 31.9 |
| P3 | 2300 | 28.4 |
| P4 | 2200 | 26.8 |
| P5 | 2100 | 24.7 |
| P6 | 2000 | 22.5 |
| P7 | 2450 | 31.5 |
| P8 | 2430 | 30.8 |
| DP | 1100 | 11.8 |
By the data in table 1 it can be seen that the aqueous solution of the polymer P 1-P8 prepared by the present invention
Apparent viscosity at high temperature (85 DEG C), the condition of high salinity (32868mg/L) still can reach
More than 22.5mPa s, and under identical testing conditions, comparative example 1 the polymer DP1's prepared
Apparent viscosity is only 11.8mPa s.
As can be seen here, the polymerizable that the polymerisable monomer of the present invention can be used for preparing oil displacement agent is used with other
The apparent viscosity of the copolymerization product obtained after monomer copolymerization is significantly larger than the polymerisable monomer without the present invention
Copolymerization product, it can be said that bright, the present invention provide polymerisable monomer there is good thickening power,
The viscosity of copolymerization product can be improved.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a polymerisable monomer, it is characterised in that described polymerisable monomer has shown in formula (Ι)
Structure:
Wherein, n is the integer of 0-5, and m is the integer of 1-10.
Polymerisable monomer the most according to claim 1, wherein, n is 0 or 1, and m is 4-8's
Integer.
3. the preparation method of the polymerisable monomer described in a claim 1 or 2, it is characterised in that
The method comprises the following steps:
(1) under amidation reaction condition, will have the aromatic diamines and third of structure shown in formula II
Alkene acyl chlorides contacts, and obtains the intermediate M with structure shown in formula III；
(2) under the conditions of condensation reaction, by described intermediate M with there is structure shown in formula IV
Binary of fatty acids contacts；
HOOC-(CH2)m-COOH formula IV
Wherein, n is the integer of 0-5, and m is the integer of 1-10.
Preparation method the most according to claim 3, wherein, n is 0 or 1, and m is the whole of 4-8
Number.
Preparation method the most according to claim 3, wherein, described aromatic diamines and acryloyl chloride
Mol ratio be 1:1-1.2.
6. according to the preparation method described in any one in claim 3-5, wherein, described amidatioon
Reaction condition includes: reaction temperature is 80-110 DEG C, and the response time is 4-8 hour.
Preparation method the most according to claim 3, wherein, described binary of fatty acids and fragrance two
The mol ratio of amine is 1:1-1.2.
8. according to the preparation method described in claim 3 or 7, wherein, described condensation reaction condition bag
Including: reaction temperature is 110-160 DEG C, the response time is 2-6 hour.
9. according to the method described in claim 3 or 4, wherein, in step (1), described amidatioon
Reaction is carried out in the presence of polymerization inhibitor, and described polymerization inhibitor is 0.05-0.1:1 with the weight ratio of acryloyl chloride.
Method the most according to claim 9, wherein, described polymerization inhibitor is selected from hydroquinone, right
One or more in benzoquinone and MEHQ.
The application in polymer oil-displacing agent of the polymerisable monomer described in 11. claim 1 or 2.
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| CN1470504A (en) * | 2003-06-07 | 2004-01-28 | 石油大学(华东) | Functional monomer compound for preparing acrylamide derivatives |
| CN101664657A (en) * | 2008-12-11 | 2010-03-10 | 齐齐哈尔大学 | Carboxylate gemini surfactant and preparation method thereof |
| CN102775324A (en) * | 2011-05-13 | 2012-11-14 | 中国石油化工股份有限公司 | Polymerisable monomer, its preparation method and application |
| CN102775323A (en) * | 2011-05-13 | 2012-11-14 | 中国石油化工股份有限公司 | Polymerisable monomer, its preparation method and application |
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| US4223108A (en) * | 1976-11-03 | 1980-09-16 | Snia Viscosa Societa' Nazionale Industria Applicazioni Viscosa S.P.A. | Glossy fibres of the modacrylic type having reduced inflammability, and compositions of matter and process for producing the same |
| CN1470504A (en) * | 2003-06-07 | 2004-01-28 | 石油大学(华东) | Functional monomer compound for preparing acrylamide derivatives |
| CN101664657A (en) * | 2008-12-11 | 2010-03-10 | 齐齐哈尔大学 | Carboxylate gemini surfactant and preparation method thereof |
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