CN104610085B - 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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Abstract
The invention provides a kind of polymerisable monomer and its preparation method and application.Described polymerisable monomer has the structure shown in formula (I), and wherein, n is the integer of 15, and R is C5‑C25Alkyl.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 still there is higher apparent viscosity, it can be seen that, it has the resistant and salt performance of excellence.
Description
Technical field
The present invention relates to a kind of polymerisable monomer and its preparation method and application.
Background technology
Radical polymerization is to prepare one of polyvinyl most efficient method.Currently used vinyl
Polymer have 70% be above being obtained by radical polymerization.Common free radical polymerisation process is main
There are substance law, solwution method, emulsion method and suspension method.Other temperature-resistant anti-salt monomers whether are added according to polymerization,
Radical polymerization can be divided into again homopolymerization and copolymerization two kinds.Radical polymerization has many advantages, such as suitable monomers
Many, polymerizing condition gentleness, simple, its favorable reproducibility of polymerization technique etc., thus from the fifties in last century
Since become the important technology of commercial production macromolecule product, its be widely used in oil, mining,
In the industries such as papermaking, water process and weaving.
Along with the deep development of oil exploitation, each elephant of current China all has been enter into exploiting middle and late stage, adopts
Fuel-displaced moisture content is up to more than 90%, and the salinity in oil field and oil recovery temperature all increase substantially, once,
Secondary oil recovery technology cannot meet growing crude oil demand, therefore, uses tertiary oil recovery technology to carry
High recovery rate has become the grand strategy measure of China Petroleum.
Polymer displacement of reservoir oil is one of the most effective method in tertiary oil recovery technology.Polymer displacement of reservoir oil is wanted
Ask polymer must have excellent thickening property under reservoir conditions, and at temperature, pressure and salt
Effect is lower high viscosity conservation rate.Domestic commonly used be polyacrylamide (PAM) and part
The polyacrylamide (HPAM) of hydrolysis, its mechanism of oil displacement is that aqueous solutions of polymers has at very low concentrations
There is the highest viscosity to reduce the permeability of aqueous phase, control the fluidity of water, improve sweep efficiency, finally
Reach to improve the purpose of oil recovery factor.But this base polymer has shear shinning, pyrolytic, chance salt
The shortcoming of viscosity reduction, and at tertiary phase, oil reservoir well temperature deeper, oily is high, and PAM makes
Not can exceed that 75 DEG C by temperature, and be susceptible to be separated in the oil reservoir that salinity is higher, cause molten
Fluid viscosity acutely declines.
Therefore, study and develop that thickening property is good, heatproof, anti-salt and cheap etc. comprehensive
Polymer oil-displacing agent that can be good is extremely urgent.In order to improve the viscosity of polyacrylamide further, improve
Its heat and salt resistance, by being an effective approach with new type functional monomer copolymerization method.
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 (I) institute
The structure shown:
Wherein, n is the integer of 1-5, and R is C5-C25Alkyl.
Present invention also offers the preparation method of a kind of polymerisable monomer, the method comprises the following steps:
(1) under the conditions of condensation reaction, by the aromatic diamines with structure shown in formula (II) with formula it is
The carboxylic acid contact of R-COOH, obtains the intermediate M with structure shown in formula III；
(2) under amidation reaction condition, described intermediate M is contacted with acryloyl chloride；
Wherein, n is the integer of 1-5, and R is C5-C25Alkyl.
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 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 preparing gained 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 hydrophilic (amide group) parent
Oil (C5-C25Alkyl) emulsifying group, complete polymerization after, molecule will not occur again resolve, have
Well stability, and acrylic amide polymerisable emulsifier has reactivity height, resulting polymers
The particular advantages such as molecular weight is high.The polymerisable monomer present invention provided is with other temperature-resistant anti-salt monomers altogether
Poly-, the Polymer Used For Oil Displacement of available excellent performance.
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):
Wherein, n is the integer of 1-5, and R is C5-C25Alkyl.
Preferably, n is 0 or 1, and R is C11-C24Alkyl；It is further preferred that R is C11-C24
Alkyl or C11-C24Alkylene；It is highly preferred that R is C11-C24Straight chained alkyl or C11-C24's
Straight monoene alkyl.From the angle that raw material is ready availability, R is particularly preferably undecyl or 8-17
Thiazolinyl.
The preparation method of the polymerisable monomer that the present invention provides comprises the following steps:
(1) under the conditions of condensation reaction, by the aromatic diamines with structure shown in formula (II) with formula it is
The carboxylic acid contact of R-COOH, obtains the intermediate M with structure shown in formula III；
(2) under amidation reaction condition, described intermediate M is contacted with acryloyl chloride；
Wherein, n is the integer of 1-5, and R is C5-C25Alkyl.
Preferably, n is 0 or 1, and R is C11-C24Alkyl；It is further preferred that R is C11-C24
Alkyl or C11-C24Alkylene；It is highly preferred that R is C11-C24Straight chained alkyl or C11-C24's
Straight monoene alkyl.When n is 0, the aromatic diamines with structure shown in formula (II) is p-phenylenediamine；
When n is 1, the aromatic diamines with structure shown in formula (II) is p dimethylamine.It is easy to get from raw material
The angle of property is set out, and R is particularly preferably undecyl or 8-17 thiazolinyl, now, with formula is
The material that the carboxylic acid of R-COOH is corresponding is lauric acid and oleic acid.
For the sake of difference, carboxylic acid and amine are obtained the reaction of amide and claim by the present invention by sloughing a part water
For condensation reaction, the reaction that acyl chlorides and amine obtain amide by sloughing a part HCl is referred to as amidatioon
Reaction.
The present invention consumption to the carboxylic acid that the aromatic diamines described in step (1) and formula are R-COOH
It is not particularly limited, as long as the intermediate M with structure shown in formula III can be obtained,
Such as, described aromatic diamines and formula be the mol ratio of the carboxylic acid of R-COOH can be 1:1-1.2, more
It is preferably 1:1-1.15.In the present invention, it is R-COOH's by controlling described aromatic diamines with formula
The additional proportion of carboxylic acid carrys out the-NH controlling in described aromatic diamines as far as possible within the above range2With
Carboxylic acid reaction, obtains intermediate M.
According to the present invention, described condensation reaction condition can be the conventional selection of this area, specifically can lead to
Cross used aromatic diamines and the kind of carboxylic acid and character selects.As a rule, described condensation
Reaction condition includes: reaction temperature can be 100-150 DEG C, preferably 120-140 DEG C；Response time can
Think 2-6 hour, preferably 3-5 hour.
According to the present invention, so that the condensation reaction in step (1) more easily controls, described contracting
Close reaction to carry out the most in presence of organic solvent.The consumption of described organic solvent can be according to monomer
Consumption is adjusted, and such as, described aromatic diamines can be 1:5-30 with the mol ratio of organic solvent,
It is preferably 1:10-25.Described organic solvent can be the existing various material that can act as reaction medium,
Such as, organic solvent can be selected from acetone, ethyl acetate, benzene, dimethylbenzene, dichloromethane, three chloromethanes
One or more in alkane.
According to the present invention, after described condensation reaction completes, condensation reaction products first can be purified and obtain
Described intermediate M, the intermediate M after purifying the most again carry out amidation process with acryloyl chloride；
Directly the most purified condensation product containing intermediate M and acryloyl chloride can also be carried out amidatioon
Reaction.
The consumption of acryloyl chloride described in step (2) is not particularly limited, as long as can by the present invention
Obtain the polymerisable monomer with structure shown in formula (I), such as, described aromatic diamines and propylene
The mol ratio of acyl chlorides can be 1:1-1.2, preferably 1:1-1.15.
According to the present invention, described amidation reaction condition can be the conventional selection of this area, such as, institute
State amidation reaction condition and include 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 80-110 DEG C, more preferably 90-100 DEG C.Response time
The raising extending the yield being conducive to the conversion ratio of reactant or product, but the response time is long
To the conversion ratio of reactant or the increase rate of the yield of product inconspicuous, therefore, from every side
Considering, the described response time is preferably 4-8 hour, more preferably 6-7 hour.Additionally, in order to
Making reaction raw materials be fully utilized with reaction medium, described amidation process is preferably having counterflow condition
Under carry out.
According to the present invention, owing to the reaction between acryloyl chloride and intermediate M is more violent, therefore,
Typically require to be placed in described amidation process and carry out in presence of organic solvent.It should be noted that
It is organic molten that described amidation process carries out being not limited to addition in step (2) in the presence of an organic
, as long as there is solvent in the amidation process system of step (2) in agent.Such as, when step (1)
Carry out in presence of organic solvent and the product of step (1) is directly used in step (2) without isolation
Time, the organic solvent in step (2) can be organic molten in above-mentioned steps (1) gained product
Agent.And when the condensation reaction of step (1) is carried out the most in presence of organic solvent, need in step
(2) organic solvent is added in.The consumption of the organic solvent in step (2) can be according to step (1)
The consumption of middle aromatic diamines is adjusted, such as, and described aromatic diamines and organic solvent in step (2)
Mol ratio can be 1:20-30, preferably 1:20-25.Described organic solvent can be existing respectively
Kind can act as the material of reaction medium, such as, organic solvent can be selected from acetone, ethyl acetate, benzene,
One or more in dimethylbenzene, dichloromethane, chloroform.When step (1) and step (2) are equal
When carrying out in the presence of an organic, the organic solvent of two steps can be the same or different.
According to the present invention, in order to prevent the polymerisable monomer generated from autohemagglutination, step occurring in course of reaction
(2) 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, with the weight of described acryloyl chloride
On the basis of amount, the consumption of described polymerization inhibitor can be 0.05-0.1 weight %.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.
The amidation process and the condensation that relate to due to the preparation method of the polymerisable monomer of present invention offer are anti-
Should all be known in the art and reaction that the Direction of Reaction is the clearest and the most definite, therefore the polymerisable monomer of the present invention
The structure of structure and intermediate M can be confirmed by raw material association reaction principle, it is also possible to passes through
Nuclear-magnetism and/or infrared spectrum confirm.
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 temperature-resistant anti-salts described
Monomer is selected from acrylamide (AM), acrylic acid, acrylic ester monomer, styrene, 2-acrylamide
-2-methyl propane sulfonic acid (AMPS), NVP (NVP) and N-N-DMAA
(DMAM) one or more in.The angle being easy to get from raw material, other temperature-resistant anti-salt lists described
Body 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, preferably 0-60 DEG C；Response time can be
1-24 hour, preferably 4-18 hour；PH value can be 4-11, preferably 8-11.Regulation reactant
The method of the pH value of system can be carried out according to method as well known to those skilled in the art, such as, by instead
Addition alkaline matter in system is answered to be adjusted.Described alkaline matter can be such as potassium hydroxide, hydrogen-oxygen
Change one or more in sodium, potassium carbonate and sodium carbonate.Above-mentioned alkaline matter can make in solid form
With, it is also possible to use with the form of its aqueous solution.When using in form of an aqueous solutions, its concentration is permissible
It is 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.
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 joined the p-phenylenediamine added with 0.1mol and 0.1mol
In the there-necked flask of oleic acid, and temperature is risen to 130 DEG C of reactions 2 hours, obtain containing structure such as formula IV
The product of shown intermediate M1.
(2) preparation of polymerisable monomer:
In step (1) products therefrom, add 0.006g MEHQ, and drip 0.12mol
Acryloyl chloride, then temperature is risen to 80 DEG C reaction 6 hours after filter, then with acetone solvent to filter institute
The product obtained carries out recrystallization, obtains the polymerisable monomer D1 of 0.09mol.
Characterizing D1 with infrared spectrometry, result is as shown in Figure 1.Wherein, 2922.4cm-1、2854.5
cm-1For methyl, the symmetrically and asymmetrically stretching vibration absworption peak of methylene, 1321.7cm-1、1405.0
cm-1、1508.6cm-1For methyl, the in-plane bending vibration peak of methylene；1700.3cm-1For C=O's
Stretching vibration peak；1628.0cm-1、1539.6cm-1Stretching vibration peak for C=C double bond；3082.5cm-1
For the stretching vibration peak of c h bond on phenyl ring；3027.4cm-1For the stretching vibration of c h bond on C=C-H
Peak；3380.4cm-1For the stretching vibration peak of O-H on COOH, it was demonstrated that the existence of carboxyl；3283.5
cm-1It it is the stretching vibration peak of N-H key.
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, 150 milliliters of dimethylbenzene are joined the p dimethylamine added with 0.1mol and 0.1mol
In the there-necked flask of oleic acid, and temperature is risen to 150 DEG C of reactions 6 hours, obtain containing structure such as formula (V)
The product of shown intermediate M2.
(2) preparation of polymerisable monomer:
In step (1) products therefrom, add 0.006g MEHQ, and drip 0.12mol
Acryloyl chloride, then temperature is risen to 90 DEG C reaction 5 hours after filter, then with acetone solvent to filter institute
The product obtained carries out recrystallization, obtains the polymerisable monomer D2 of 0.09mol.With infrared spectrometry to D2
Characterizing, 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, 150 milliliters of dimethylbenzene are joined the p-phenylenediamine added with 0.1mol and 0.1mol
In the there-necked flask of lauric acid mixing, and temperature is risen to 140 DEG C of reactions 4 hours, obtain containing structure such as
The product of the intermediate M3 as shown in formula VI.
(2) preparation of polymerisable monomer:
In step (1) products therefrom, add 0.006g 1,4-benzoquinone and 150 milliliters of dichloromethane, stir
Mix mix homogeneously, and drip 0.1mol acryloyl chloride, then temperature is risen to 100 DEG C of back flow reaction 4 hours,
Rotation is evaporated off dichloromethane and xylene solvent, then heavily ties the product of gained with acetone solvent
Crystalline substance, obtains the polymerisable monomer D3 of 0.08mol.Characterizing D3 with infrared spectrometry, result is red
Outer spectrogram 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, 150 milliliters of dimethylbenzene are joined the p dimethylamine added with 0.1mol and 0.1mol
In the there-necked flask of lauric acid mixing, and temperature is risen to 140 DEG C of reactions 4 hours, obtain containing structure such as
The product of the intermediate M4 shown in formula (VII).
(2) preparation of polymerisable monomer:
In step (1) products therefrom, add 0.006g 1,4-benzoquinone and 150 milliliters of dichloromethane, stir
Mix mix homogeneously, and drip 0.12mol acryloyl chloride, then temperature is risen to 90 DEG C of back flow reaction 5 hours,
Rotation is evaporated off dichloromethane and xylene solvent, then heavily ties the product of gained with acetone solvent
Crystalline substance, obtains the polymerisable monomer D4 of 0.09mol.Characterizing D4 with infrared spectrometry, result is red
Outer spectrogram 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 4.75 grams of acrylamides (AM), 5.25 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS)
Mixing with 50 grams of deionized waters, stirring makes monomer dissolve, with the sodium hydroxide water that concentration is 20 weight %
Solution, by the pH regulator of system to 8, adds 0.15 gram of monomer D1 and 3.0 prepared by preparation example 1
Milligram azo-bis-isobutyrate hydrochloride (AIBA), under nitrogen protection, adds 6.0 milligrams of Ammonium Persulfate 98.5s,
First it is polymerized 1 hour at temperature 20 DEG C, then is warming up to 80 DEG C of continuation polymerizations 1 hour, by gained colloid
Taking-up, pelletize, be dried and pulverize, obtain granular copolymer, be designated as polymer P 1.With described
In polymer on the basis of the total mole number of construction unit, the content of acrylamide construction unit is
The content of 72.24mol%, 2-acrylamide-2-methyl propane sulfonic construction unit is 27.38mol%, derivative
It is 0.38mol% from the content of the construction unit of polymerisable monomer D1.
Embodiment 2
This embodiment illustrates the polymer for oil displacement agent prepared by polymerisable monomer provided by the present invention.
By 4.75 grams of acrylamides (AM), 5.25 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS)
Mixing with 50 grams of deionized waters, stirring makes monomer dissolve, with the sodium hydroxide water that concentration is 20 weight %
The pH value of system is regulated to 8 by solution, adds 0.15 gram of monomer D2 and 3.0 prepared by preparation example 2
Milligram azo-bis-isobutyrate hydrochloride (AIBA), under nitrogen protection, adds 6.0 milligrams of Ammonium Persulfate 98.5s,
First it is polymerized 6 hours at temperature 0 DEG C, then is warming up to 40 DEG C of continuation polymerizations 2 hours, gained colloid is taken
Go out, pelletize, be dried and pulverize, obtain the copolymer of white granular, be designated as polymer P 2.With institute
Stating in polymer on the basis of the total mole number of construction unit, the content of acrylamide construction unit is
The content of 72.26mol%, 2-acrylamide-2-methyl propane sulfonic construction unit is 27.38mol%, derivative
It is 0.36mol% 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 4.75 grams of acrylamides (AM), 5.25 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS)
Mixing with 50 grams of deionized waters, stirring makes monomer dissolve, with the sodium hydroxide water that concentration is 20 weight %
The pH value of system is regulated to 11 by solution, adds 0.15 gram of monomer D3 and 3.0 prepared by preparation example 3
Milligram azo-bis-isobutyrate hydrochloride (AIBA), under nitrogen protection, adds 6.0 milligrams of Ammonium Persulfate 98.5s,
First it is polymerized 8 hours at temperature 0 DEG C, then is warming up to 40 DEG C of continuation polymerizations 4 hours, gained colloid is taken
Go out, pelletize, be dried and pulverize, obtain the copolymer of white granular, be designated as polymer P 3.With institute
Stating in polymer on the basis of the total mole number of construction unit, the content of acrylamide construction unit is
The content of 72.21mol%, 2-acrylamide-2-methyl propane sulfonic construction unit is 27.37mol%, derivative
It is 0.42mol% from the content of the construction unit of polymerisable monomer D3.
Embodiment 4
This embodiment illustrates the polymer for oil displacement agent prepared by polymerisable monomer provided by the present invention.
Polymer is prepared according to the method for embodiment 1, except for the difference that, preparation example 1 monomer prepared
The monomer D4 prepared by preparation example 4 of D1 identical weight part substitutes, and obtains the copolymerization of white granular
Thing, is designated as polymer P 4.In described polymer on the basis of the total mole number of construction unit, acryloyl
The content of amine structure unit is the content of 72.23mol%, 2-acrylamide-2-methyl propane sulfonic construction unit
For 27.38mol%, the content derived from the construction unit of polymerisable monomer D4 is 0.39mol%.
Embodiment 5
This embodiment illustrates the polymer for oil displacement agent prepared by polymerisable monomer provided by the present invention.
Preparing polymer according to the method for embodiment 1, except for the difference that, the consumption of polymerisable monomer D1 is
16.83 grams, obtain the copolymer of white granular, be designated as polymer P 5.With structure in described polymer
On the basis of the total mole number of unit, the content of acrylamide construction unit is 50.76mol%, 2-acryloyl
The content of amine-2-methyl propane sulfonic acid construction unit is 19.24mol%, derived from the knot of polymerisable monomer D1
The content of structure unit 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 1-5
Test case 1-5 is for illustrating the viscosity-average molecular weight of polymer and the test of apparent viscosity.
The intrinsic viscosity of the polymer P 1-P5 that embodiment 1-5 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, it is 25 DEG C and 85 in temperature respectively
Being measured under conditions of DEG C obtaining, wherein, test condition includes: polymer concentration is 1500mg/L,
Solution total salinity is 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 1-5 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) | η25(mPa·s) | η85(mPa·s) |
| P1 | 2000 | 38.2 | 21.3 |
| P2 | 1900 | 36.5 | 20.4 |
| P3 | 1750 | 32.7 | 17.9 |
| P4 | 1600 | 30.6 | 16.2 |
| P5 | 1800 | 35.5 | 19.8 |
| DP | 1300 | 22.9 | 12.4 |
Note: M in table 1ηThe viscosity-average molecular weight of representation polymer, it is water-soluble that η 25 represents polymer at 25 DEG C
The apparent viscosity of liquid, η 85 represents the apparent viscosity of aqueous solutions of polymers at 85 DEG C.
The comparison of the data of embodiment P1-P5 from table 1 and the data of comparative example DP it can be seen that
The polymer P 1-P5 (25 DEG C) at normal temperatures using the method for the present invention to prepare has the highest table
See viscosity, and still can under conditions of high temperature (85 DEG C), high salinity (32868mg/L) when it
The apparent viscosity that enough holdings are the highest, therefore, its heat resistance with excellence and salt resistant character.
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 (I)
Structure:
Wherein, n is the integer of 0-5, and R is C5-C25Alkyl.
Polymerisable monomer the most according to claim 1, wherein, n is 0 or 1, and R is C11-C24
Alkyl.
3. there is a preparation method for the polymerisable monomer of structure shown in formula (I), the method include with
Lower step:
(1) under the conditions of condensation reaction, by having the aromatic diamines of structure shown in formula (II) with formula it is
The carboxylic acid contact of R-COOH, obtains the intermediate M with structure shown in formula III；
(2) under amidation reaction condition, described intermediate M is contacted with acryloyl chloride；
Wherein, n is the integer of 0-5, and R is C5-C25Alkyl.
Preparation method the most according to claim 3, wherein, n is 0 or 1, and R is C11-C24
Alkyl.
5. according to the preparation method described in claim 3 or 4, wherein, described aromatic diamines and formula
Mol ratio for the carboxylic acid of R-COOH is 1:1-1.2.
6. according to the preparation method described in claim 3 or 4, wherein, described condensation reaction condition bag
Including: reaction temperature is 100-150 DEG C, the response time is 2-6 hour.
Preparation method the most according to claim 3, wherein, described aromatic diamines and acryloyl chloride
Mol ratio be 1:1-1.2.
8. according to the preparation method described in claim 3 or 7, wherein, described amidation reaction condition
Including: reaction temperature is 80-110 DEG C, and the response time is 4-8 hour.
9. according to the preparation method described in claim 3 or 4, wherein, described amidation process is in resistance
Carrying out in the presence of poly-agent, on the basis of the weight of described acryloyl chloride, the consumption of described polymerization inhibitor is
0.05-0.1 weight %.
Preparation method the most according to claim 9, wherein, described polymerization inhibitor selected from hydroquinone,
One or more in 1,4-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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| 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 |
| 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 |
| 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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