CN105085309A - Method for preparing polymerisable monomer and application thereof - Google Patents
Method for preparing polymerisable monomer and application thereof Download PDFInfo
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Abstract
The invention provides a method for preparing a polymerisable monomer and application thereof. The method comprises the following steps: (1) enabling diamine with the general formula of NH2-(CH2)n-NH2 and aliphatic dibasic acid with the general formula of HOOC-(CH2)m-COOH to be in contact under the condition of condensation reaction so as to obtain an intermediate M represented by a formula (I) shown in the description; and (2) enabling the intermediate M to be in touch with acrylic acid under the condition of amidation reaction so as to obtain the polymerisable monomer represented by a formula (II) shown in the description, wherein n is an integer of 1 to 6, and m is an integer of 1 to 8. According to the method, the purity and yield of the obtained product are relatively high, and the production cost is relatively low; and through copolymerizing the polymerisable monomer provided by the invention with other monomers, a polymer for oil displacement with high molecular weight, high apparent viscosity and excellent heat resistance and salt resistance can be obtained, and an oil displacement agent, which is formed through compounding the polymer and a surfactant, has relatively high viscosity and excellent heat resistance and salt resistance.
Description
Technical field
The present invention relates to a kind of preparation method and application of polymerisable monomer.
Background technology
Oil is one of most important energy of contemporary world, especially in the China of automotive industry fast development, and the demand rapid growth especially of oil.Recover the oil from oil reservoir and be generally divided into 3 stages: primary oil recovery relies on the natural energy on stratum fuel-displaced, and tar productivity is below 30%; It is fuel-displaced that secondary oil recovery adopts water filling, air insufflation techiques supplements oils energy, and recovery ratio can reach 40-50%; Tertiary oil recovery and intensified oil reduction, can make recovery ratio bring up to 80-85%.At present, China's intensified oil reduction mainly relies on chemical flooding, and wherein polymer flooding proportion is higher.Scientific research both domestic and external and production practice show, polymer flooding is a kind of effective ground method of raising oil recovery.This base polymer, under the deep-fried twisted dough sticks part of Tibetan, must have excellent thickening property, and will have high viscosity conservation rate under the effect of temperature, pressure and salt.
At present, conventional flooding polymers mainly contains two classes: one is the synthetic polymer that is representative with polyacrylamide (PAM) and partially hydrolyzed polyacrylamide (HPAM).But HPAM temperature resistant antisalt performance is undesirable, the ultimate-use temperature under reservoir condition is only 75 DEG C, and when having salt to exist, viscosity acutely declines, divalent-metal ion also can make its produce precipitation and loses viscosity.In addition, can there is molecular rupture in HPAM under shearing action, causes its tackifying ability to reduce.Research shows, the thermotolerance of HPAM, the poor-performing such as salt resistance and shear resistant, make its application conditions be restricted.Two is take xanthocyte gum as the biological polymer of representative.Xanthocyte gum has certain anti-salt resistant to shearing performance, but xanthocyte gum thermooxidative degradation can occur in high-temperature stratum, and the formation temperature for tertiary oil recovery generally should not higher than 60 DEG C.The price of xanthocyte gum is 5 times of HPAM in addition, also limit its popularization.
A kind of polymerisable monomer and its preparation method and application is disclosed in CN102775324A.But the defect of the preparation method of this monomer is mainly that refer to the extremely active acrylate chloride of chemical property in preparation process participates in reaction, this can cause byproduct of reaction more, and reaction is fierce and controllability is poor, thus causes the purity of prepared polymerisable monomer and yield greatly lower; Simultaneously when utilizing this polymerisable monomer to prepare Polymer Used For Oil Displacement, the reduction of purity has also had a strong impact on molecular weight and the performance thereof of polymkeric substance.In addition, because the price of acrylate chloride is higher, the production cost of the polymerisable monomer causing the method to prepare is higher, thus limits the promotion and application of this polymerisable monomer.
Summary of the invention
The yield and the purity that the object of the invention is to overcome polymerisable monomer in prior art are lower, production cost is high and react uppity defect provides a kind of preparation method of polymerisable monomer and the polymerisable monomer prepared by the method is preparing the application in polymer oil-displacing agent.
A first aspect of the present invention provides a kind of preparation method of polymerisable monomer, and the method comprises the following steps:
(1) under condensation reaction condition, be NH by general formula
2-(CH
2)
n-NH
2diamines and general formula be HOOC-(CH
2)
mthe binary of fatty acids contact of-COOH, obtains the intermediate M shown in formula (Ι);
(2) under amidation reaction condition, described intermediate M is contacted with vinylformic acid, obtain the polymerisable monomer shown in formula (II);
Wherein, n is the integer of 1-6, and m is the integer of 1-8.
A second aspect of the present invention provides the polymerisable monomer prepared by aforesaid method and is preparing the application in polymer oil-displacing agent.
The preparation method of polymerisable monomer provided by the invention, simple to operate, react easy to control gently, by product is few, and purity and the yield of product are higher, and production cost is lower.
The polymerisable monomer obtained by method provided by the invention and other monomer copolymerizations, can obtain having high molecular, high apparent viscosity and the resistance toheat of excellence and the Polymer Used For Oil Displacement of anti-salt property.In addition, the polymkeric substance being used for oil-displacing agent prepared by polymerisable monomer provided by the invention and surfactant compound can be formed compound oil displacement agent, because this polymkeric substance and tensio-active agent give full play to synergistic effect, make this compound oil displacement agent have higher viscosity, excellent resistance toheat and anti-salt property, therefore there is in tertiary oil recovery field higher application prospect.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of polymerisable monomer, the method comprises the following steps:
(1) under condensation reaction condition, be NH by general formula
2-(CH
2)
n-NH
2diamines and general formula be HOOC-(CH
2)
mthe binary of fatty acids contact of-COOH, obtains the intermediate M shown in formula (Ι);
(2) under amidation reaction condition, described intermediate M is contacted with vinylformic acid, obtain the polymerisable monomer shown in formula (II);
Wherein, n is the integer of 1-6, and m is the integer of 1-8; Preferably, n is the integer of 2-6, and m is the integer of 4-8.
It should be noted that, for the purpose of difference, binary of fatty acids and amine are obtained acid amides by the present invention reaction by sloughing a part water is called condensation reaction, and reaction vinylformic acid and amine being obtained acid amides by sloughing a part water is called amidate action.
The present invention is NH to described general formula
2-(CH
2)
n-NH
2diamines and general formula be HOOC-(CH
2)
mthere is no particular limitation for the consumption of the binary of fatty acids of-COOH, can change in wider scope, and can obtain the intermediate shown in formula (Ι) as long as meet, under preferable case, described general formula is NH
2-(CH
2)
n-NH
2diamines and the mol ratio of described binary of fatty acids can be 1:1-1.2, more preferably 1:1-1.1.In the present invention, by being NH by described general formula
2-(CH
2)
n-NH
2diamines and general formula be HOOC-(CH
2)
mthe mol ratio of the binary of fatty acids of-COOH controls in above-mentioned scope to make general formula for NH
2-(CH
2)
n-NH
2diamines in-a NH
2react with-the COOH of in binary of fatty acids, obtain described intermediate M.
According to the present invention, the condensation reaction condition of described step (1) can be the popular response condition of this area.Under normal circumstances, in order to the yield of the transformation efficiency or reaction product that improve reactant, described condensation reaction condition comprises: temperature of reaction can be 110-160 DEG C, is preferably 130-150 DEG C.The prolongation in reaction times is conducive to the transformation efficiency of reactant or the yield raising of reaction product, but the reaction times long increase rate to the transformation efficiency of reactant or the yield of reaction product is also not obvious, therefore, the reaction times can be 2-6 hour, is preferably 3-5 hour.
According to the present invention, after described condensation reaction completes, condensation reaction products first can be purified and obtain described intermediate M, and then the intermediate M after purification and vinylformic acid are carried out amidate action; Also directly amidate action can be carried out by without the condensation product containing intermediate M of purifying and vinylformic acid.
According to the present invention, in order to control speed of reaction, described condensation reaction and/or amidate action carry out in presence of organic solvent.The consumption of described organic solvent can adjust according to the consumption of reaction monomers, and such as, in step (1), described general formula is NH
2-(CH
2)
n-NH
2diamines and the mol ratio of organic solvent can be 1:20-30, be preferably 1:20-25; In step (2), the mol ratio of described vinylformic acid and organic solvent can be 1:20-30, is preferably 1:20-25.It should be noted that, amidate action carries out in the presence of an organic but is not limited to add organic solvent in step (2), as long as there is organic solvent in step (2).Such as, when step (1) is carried out in the presence of an organic and the reaction product of step (1) is directly used in step (2) without separation, organic solvent in step (2) can be the organic solvent in step (1) gained reaction product, and when the condensation reaction of step (1) is not carried out in presence of organic solvent, need to add organic solvent in step (2).Consumption of organic solvent in step (2) can adjust according to the consumption of the organic solvent in step (1).Described organic solvent can be existingly variously can be used as the material of reaction medium, such as, described organic solvent can be selected from acetone, ethyl acetate, benzene, dimethylbenzene, methylene dichloride and trichloromethane one or more.When step (1) and step (2) all exist organic solvent, the organic solvent in step (1) and step (2) can be identical or different.
According to the present invention, the organic solvent in described step (1) can steam after condensation reaction terminates, and also can not steam and directly carry out step (2) together with condensation product, removes finally by revolving the evaporation of steaming instrument.
To the acrylic acid amount added in step (2), there is no particular limitation in the present invention, and can obtain the polymerisable monomer shown in formula (II) as long as meet, under preferable case, the general formula described in step (1) is NH
2-(CH
2)
n-NH
2diamines and step (2) in acrylic acid mol ratio can be 1:1-1.2, more preferably 1:1-1.1.
Main improvements of the present invention are to adopt vinylformic acid and described intermediate M to carry out amidate action, thus make the purity of the polymerisable monomer adopting method provided by the invention to prepare and yield higher, production cost is lower; And the reaction times is shorter, temperature of reaction is lower, and reaction is easy to control gently.Described amidation reaction condition comprises: temperature of reaction can be 60-80 DEG C, is preferably 65-75 DEG C; The described reaction times can be 2-4 hour, is preferably 2-3 hour.
According to the present invention, the preparation method of described polymerisable monomer also comprises the product described for step (2) intermediate M being contacted gained with vinylformic acid and contacts with the moisture removed in product with siccative, improves purity and the yield of polymerisable monomer.Described siccative can be calcium oxide and/or anhydrous cupric sulfate.
According to the present invention, in order to prevent the polymerisable monomer generated from reaction process, autohemagglutination occurring, under preferable case, the amidate action of described step (2) carries out under the existence of stopper.
According to the present invention, the kind of described stopper and consumption can be conventional kind known in those skilled in the art and consumption, prevent the polymerisable monomer generated from reaction process, autohemagglutination occurring as long as can play, under preferable case, with the acrylic acid weight in step (2) for benchmark, the consumption of described stopper is 0.05-0.1 % by weight, is preferably 0.06-0.08 % by weight.Described stopper be preferably selected from Resorcinol, para benzoquinone and MEHQ one or more.
According to the present invention, described condensation reaction and amidate action can carry out in various conventional reactor, such as, can carry out in various flask or reactor.In order to make fully to contact between reactant, described condensation reaction and amidate action preferably under agitation carry out.
According to the present invention, in order to obtain sterling, method provided by the invention can also comprise the step of the product purification obtained, the method of described purifying can adopt and well known to a person skilled in the art various purification process, under preferable case, the polymerisable monomer that the present invention can be obtained carries out recrystallization, the method of described recrystallization and condition can adopt the method for well known to a person skilled in the art and condition, such as, the solvent that recrystallization is used can one or more for being selected from ethanol, acetone and hexane.
According to a second aspect of the invention, present invention also offers the polymerisable monomer prepared by aforesaid method and prepare the application in polymer oil-displacing agent.
The present inventor finds, by described polymerisable monomer of the present invention and other monomer copolymerizations, can obtain the multipolymer of the heat-resisting and anti-salt property with high molecular, high apparent viscosity and excellence.
According to the present invention, can be able to be any monomer that can improve polymer flooding performance with other monomers of polymerisable monomer copolymerization provided by the invention, under preferable case, other monomers described be selected from acrylamide, vinylformic acid, 2-acrylamide-2-methyl propane sulfonic (AMPS), NVP (NVP) and N-N-DMAA (DMAM) one or more.
According to the present invention, the condition of described copolyreaction can be the copolyreaction condition of this area routine, but, under preferable case, in order to overcome oxygen inhibition, obtain the copolymerization product with larger molecular weight, under preferable case, described copolyreaction is carried out in an inert atmosphere, described inert atmosphere refer to not with any one gas or the gaseous mixture of reactant and product generation chemical reaction, as one or more in nitrogen, helium and periodic table of elements zero group gas.Keep the method for inert atmosphere can for pass in reaction system above-mentioned not with any one gas or the gaseous mixture of reactant and product generation chemical reaction.The condition of described copolyreaction can comprise the pH value of temperature of reaction and reaction times and reaction system, and such as, described temperature of reaction can be 0-80 DEG C, and the described reaction times can be 1-24 hour, and pH value can be 4-11.The method regulating the method for pH value of reaction system to be known to the skilled person, such as, regulates by adding alkali in reaction system, described alkali be preferably selected from sodium hydroxide and sodium carbonate one or more.
The present inventor finds under study for action, takes following condition can obtain ultra-high molecular weight random copolymers, namely, preferably, described copolyreaction comprises two stages of carrying out successively, and it is 0-20 DEG C that the reaction conditions of first stage comprises temperature of reaction, and the reaction times is 2-8 hour; It is 50-80 DEG C that the reaction conditions of subordinate phase comprises temperature of reaction, and the reaction times is 1-6 hour.
According to the present invention, described copolyreaction initiator used can be one or more in the various radical initiator in this area; Described radical initiator comprises azo-initiator, peroxide type initiators and redox type initiators.Wherein, described azo-initiator is selected from one or more in azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121, azo di-isopropyl imidazoline hydrochloride, azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile); Described peroxide type initiators is selected from hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, one or more in benzoyl peroxide and the benzoyl peroxide tert-butyl ester; Described redox type initiators be selected from vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide one or more.Wherein, described vitriol-sulphite can be selected from one or more in sodium sulfate-S-WAT, potassium sulfate-potassium sulfite, ammonium sulfate-ammonium sulphite; Persulphate-thiocarbamide can be selected from Sodium Persulfate-thiocarbamide, Potassium Persulphate-thiocarbamide, ammonium persulphate-thiocarbamide one or more; Persulphate-organic salt can be selected from Sodium Persulfate-Potassium ethanoate, Potassium Persulphate-Potassium ethanoate, ammonium persulphate-ammonium acetate one or more; Ammonium persulphate-aliphatic amide can be selected from ammonium persulphate-N, one or more in N-Tetramethyl Ethylene Diamine and ammonium persulphate-diethylamine.
The consumption of the present invention to described initiator is not particularly limited, and under preferable case, the consumption of described initiator is preferably the 0.01-0.1% of monomer mixture gross weight, more preferably 0.02-0.08%.
In addition, the present inventor also finds under study for action, the random copolymers obtained by polymerisable monomer provided by the invention and other monomer copolymerizations and surfactant compound can be formed compound oil displacement agent, polymkeric substance provided by the invention and tensio-active agent give full play to synergistic effect, make this oil-displacing agent have higher viscosity, excellent resistance toheat and anti-salt property, therefore there is in tertiary oil recovery field higher application prospect.
According to the present invention, described tensio-active agent can be the various tensio-active agents that can be used for improving oil recovery known in those skilled in the art, under preferable case, described tensio-active agent be selected from alkylaryl sulphonate, alkylaryl sulfonate, polyethenoxy ether sulphonate, sulphosuccinates, sulfonated petro-leum, petroleum carboxylate, amido amine yl carboxylic acid salt, polyethenoxy ether carboxylate and polyoxyethylene phosphoric acid salt one or more.
According to the present invention, above-mentioned random copolymers and the content of tensio-active agent can change within a large range.In preferred situation, with the gross weight of oil-displacing agent composition for benchmark, the content of described random copolymers can be 30-90 % by weight, more preferably 60-90 % by weight; The content of described tensio-active agent can be 10-70 % by weight, more preferably 10-40 % by weight.
To the mixing condition of random copolymers and tensio-active agent, there is no particular limitation in the present invention, as long as make to mix between component, in preferred situation, the condition of described mixing comprises: mixing temperature can be 10-40 DEG C, more preferably 20-30 DEG C; Described mixing time can be 40-150min, more preferably 60-120min.
To be described in further detail the present invention by following examples below.
In following examples and comparative example, in polymkeric substance, the content of each structural unit calculates according to the charging capacity of monomer.
Reagent used in preparation example, embodiment and comparative example is commercially available chemically pure reagent.
In embodiment and comparative example, the intrinsic viscosity of polymkeric substance measures according to GB12005.1-89 For Intrinsic Viscosity Measurements method; Viscosity-average molecular weight is according to formula M=([η]/K)
1 α, wherein K=4.5 × 10
-3, α=0.80 calculates; The apparent viscosity of aqueous solutions of polymers is 7.34s by BROOKFIELDDV-III viscosity apparatus in rotating speed perseverance
-1, temperature is measure under the condition of 85 DEG C to obtain, and wherein, test condition comprises: polymer concentration is 1500mg/L, and solution total mineralization is 32868mg/L.
Preparation example 1
This preparation example is for illustration of the preparation method of polymerisable monomer provided by the invention.
(1) preparation of intermediate
In there-necked flask, first add the quadrol of 0.1mol, then start stirring after adding 0.1mol sebacic acid and make the two mix, be heated to 110 DEG C, react 6 hours, obtain the product containing the intermediate M1 of structure as shown in formula III.
(2) preparation of polymerisable monomer
Under agitation, the product containing intermediate M1 first step (1) obtained is dissolved in 150 milliliters of methylene dichloride, dissolve completely, be heated to 70 DEG C, start to drip 0.1mol vinylformic acid, react 3 hours, steam solvent and with calcium oxide drying at 70 DEG C, with acetone solvent, recrystallization carried out more than three times to product, obtain polymerizable functional monomer D1, be 75.2% with test unit yield as calculated, monomer purity reaches 99.8%.
Preparation comparative example 1
Intermediate and polymerisable monomer is prepared according to the method for preparation example 1, difference is, in step (2), the acrylate chloride starting to drip 0.1mol after being heated to 80 DEG C replaces vinylformic acid, the complete back flow reaction of dropwise reaction 4 hours, obtain contrast polymerisable monomer B1, be 50% with the yield of test unit as calculated, monomer purity reaches 91%.
Preparation example 2
This preparation example is for illustration of the preparation method of polymerisable monomer provided by the invention.
(1) preparation of intermediate
In there-necked flask, first add the hexanediamine of 0.1mol, then start stirring after adding 0.1mol sebacic acid and make the two mix, be heated to 160 DEG C, react 2 hours, obtain the product containing the intermediate M2 of structure as shown in formula IV.
(2) preparation of polymerisable monomer
Under agitation, the product containing intermediate M2 first step (1) obtained is dissolved in 150 milliliters of methylene dichloride, dissolve completely, be heated to 60 DEG C, start to drip 0.1mol vinylformic acid, react 4 hours, steam solvent and with calcium oxide drying at 70 DEG C, with acetone solvent, recrystallization carried out more than three times to product, obtain polymerizable functional monomer D2, be 72.8% with test unit yield as calculated, monomer purity reaches 99.3%.
Preparation example 3
This preparation example is for illustration of the preparation method of polymerisable monomer provided by the invention.
(1) preparation of intermediate
In there-necked flask, first add 250 milliliters of p-Xylol, under agitation, then the quadrol and the 0.1mol suberic acid that add 0.1mol successively mix, be heated to 140 DEG C, react 4 hours, steam solvent and drying at 70 DEG C, obtain containing the product of structure such as formula the intermediate M3 shown in (V).
(2) preparation of polymerisable monomer
Under agitation, the product containing intermediate M3 first step (1) obtained is dissolved in 150 milliliters of methylene dichloride, dissolve completely, be heated to 75 DEG C, start the vinylformic acid dripping 0.1mol, react after 3 hours, steam solvent and with calcium oxide drying at 70 DEG C, with acetone solvent, recrystallization carried out more than three times to product, obtain polymerizable functional monomer D3, be 78.3% with test unit yield as calculated, monomer purity reaches 99.5%.
Preparation example 4
This preparation example is for illustration of the preparation method of polymerisable monomer provided by the invention.
(1) preparation of intermediate
In there-necked flask, first add 250 milliliters of p-Xylol, under agitation, then the hexanediamine and the 0.1mol suberic acid that add 0.1mol successively mix, be heated to 110 DEG C, react 6 hours, steam solvent and drying at 70 DEG C, obtain the product containing the intermediate M4 of structure as shown in formula VI.
(2) preparation of polymerisable monomer
Under agitation, the product containing intermediate M4 first step (1) obtained is dissolved in 150 milliliters of methylene dichloride, dissolve completely, be heated to 65 DEG C, start the vinylformic acid dripping 0.1mol, react after 2 hours, steam solvent and with calcium oxide drying at 70 DEG C, with acetone solvent, recrystallization carried out more than three times to product, obtain polymerizable functional monomer D4, be 77.1% with test unit yield as calculated, monomer purity reaches 99.2%.
Preparation example 5
This preparation example is for illustration of the preparation method of polymerisable monomer provided by the invention.
(1) preparation of intermediate
In there-necked flask, first add the quadrol of 0.1mol, then start stirring after adding 0.1mol hexanodioic acid and make the two mix, be heated to 150 DEG C, react 3 hours, obtain containing the product of structure such as formula the intermediate M5 shown in (VII).
(2) preparation of polymerisable monomer
Under agitation, the product containing intermediate M5 first step (1) obtained is dissolved in 150 milliliters of methylene dichloride, dissolve completely, be heated to 80 DEG C, start the vinylformic acid dripping 0.1mol, react after 4 hours, steam solvent and with calcium oxide drying at 70 DEG C, with acetone solvent, recrystallization carried out more than three times to product, obtain polymerizable functional monomer D5, be 73.4% with test unit yield as calculated, monomer purity reaches 99.7%.
Preparation example 6
This preparation example is for illustration of the preparation method of polymerisable monomer provided by the invention.
(1) preparation of intermediate
In there-necked flask, first add the hexanediamine of 0.1mol, then start stirring after adding 0.1mol hexanodioic acid and make the two mix, be heated to 140 DEG C, react 4 hours, obtain containing the product of structure such as formula (VIII) intermediate M6.
(2) preparation of polymerisable monomer
Under agitation, the product containing intermediate M6 first step (1) obtained is dissolved in 150 milliliters of methylene dichloride, dissolve completely, be heated to 60 DEG C, start the vinylformic acid dripping 0.1mol, react after 4 hours, steam solvent and with calcium oxide drying at 70 DEG C, with acetone solvent, recrystallization carried out more than three times to product, obtain polymerizable functional monomer D5, be 74.2% with test unit yield as calculated, monomer purity reaches 99.5%.
Preparation example 7
This preparation example is for illustration of the preparation method of polymerisable monomer provided by the invention.
(1) preparation of intermediate
In there-necked flask, first add the quadrol of 0.1mol, then start stirring after adding 0.12mol sebacic acid and make the two mix, be heated to 110 DEG C, react 6 hours, obtain the product containing intermediate M7.
(2) preparation of polymerisable monomer
Under agitation, 0.12mol vinylformic acid is added drop-wise to step (1) obtains containing in the product of intermediate M7, at 80 DEG C, react 2 hours, with acetone solvent, recrystallization is carried out to product, obtain polymerizable functional monomer D7, be 62.2% with test unit yield as calculated, monomer purity reaches 98.9%.
Preparation example 8
This preparation example is for illustration of the preparation method of polymerisable monomer provided by the invention.
(1) preparation of intermediate
In there-necked flask, first add 250 milliliters of p-Xylol, under agitation, then the quadrol and the 0.11mol suberic acid that add 0.1mol successively mix, and are heated to 140 DEG C, react 4 hours, steam solvent and drying at 70 DEG C, obtain the product containing intermediate M8.
(2) preparation of polymerisable monomer
Under agitation, 0.11mol vinylformic acid is added drop-wise to step (1) obtains containing in the product of intermediate M8, at 70 DEG C, react 3 hours, with acetone solvent, recrystallization is carried out to product, obtain polymerizable functional monomer D8, be 64.5% with test unit yield as calculated, monomer purity reaches 98.6%.
Preparation example 9
This preparation example is for illustration of the preparation method of polymerisable monomer provided by the invention.
Identical with the preparation method of preparation example 1, unlike, before dropping vinylformic acid, first add 0.006 gram of para benzoquinone in step (2), obtain polymerizable functional monomer D9, be 78.9% with test unit yield as calculated, monomer purity reaches 99.7%.
Embodiment 1
This embodiment illustrates the polymkeric substance for oil-displacing agent prepared by polymerisable monomer provided by the invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS) mix with 50 grams of deionized waters, stirring makes monomer dissolve completely, be the pH value of the aqueous sodium hydroxide solution regulation system of 20 % by weight by concentration be 8, and said mixture is mixed with 1 milligram of azo-bis-isobutyrate hydrochloride with 0.15 gram of polymerisable monomer D1 obtained by preparation example 1, under nitrogen protection, add 2 milligrams of ammonium persulphates, first be polymerized 2 hours at temperature 20 DEG C, be warming up to 50 DEG C again, continue polymerization 4 hours, gained colloid is taken out, granulation, dry at 50 DEG C, pulverize, obtain white granular copolymerization product, be designated as polymer P 1.Characterize P1 with infrared spectroscopy, result shows, the charateristic avsorption band of the structural unit of three kinds of monomers all appears in infrared spectra, shows that this multipolymer is made up of these three kinds of structural units.With the total mole number of structural unit in described polymkeric substance for benchmark, the content of acrylamide structural unit is 89.88mol%, the content of 2-acrylamide-2-methyl propane sulfonic structural unit is 9.68mol%, and the content derived from the structural unit of polymerisable monomer D1 is 0.44mol%.
Embodiment 2
This embodiment illustrates the polymkeric substance for oil-displacing agent prepared by polymerisable monomer provided by the invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS) mix with 50 grams of deionized waters, stirring makes monomer dissolve completely, be the pH value of the aqueous sodium hydroxide solution regulation system of 20 % by weight by concentration be 8, and said mixture is mixed with 1 milligram of Diisopropyl azodicarboxylate with 0.15 gram of polymerisable monomer D2 obtained by preparation example 2, under nitrogen protection, add 2 milligrams of Potassium Persulphates, first be polymerized 8 hours at temperature 5 DEG C, be warming up to 60 DEG C again, continue polymerization 2 hours, gained colloid is taken out, granulation, dry at 40 DEG C, pulverize, obtain white granular copolymerization product, be designated as polymer P 2.Characterize P2 with infrared spectroscopy, result shows, the charateristic avsorption band of the structural unit of three kinds of monomers all appears in infrared spectra, shows that this multipolymer is made up of these three kinds of structural units.With the total mole number of structural unit in described polymkeric substance for benchmark, the content of acrylamide structural unit is 89.94mol%, the content of 2-acrylamide-2-methyl propane sulfonic structural unit is 9.69mol%, and the content derived from the structural unit of polymerisable monomer D2 is 0.37mol%.
Embodiment 3
This embodiment illustrates the polymkeric substance for oil-displacing agent prepared by polymerisable monomer provided by the invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS) mix with 50 grams of deionized waters, stirring makes monomer dissolve completely, be the pH value of the aqueous sodium hydroxide solution regulation system of 20 % by weight by concentration be 8, and said mixture is mixed with 1 milligram of 2,2'-Azobis(2,4-dimethylvaleronitrile) with 0.15 gram of polymerisable monomer D3 obtained by preparation example 3, under nitrogen protection, add 2 milligrams of ammonium persulphate-diethylamine, first be polymerized 5 hours at temperature 10 DEG C, be warming up to 80 DEG C again, continue polymerization 1 hour, gained colloid is taken out, granulation, dry at 50 DEG C, pulverize, obtain white granular copolymerization product, be designated as polymer P 3.Characterize P3 with infrared spectroscopy, result shows, the charateristic avsorption band of the structural unit of three kinds of monomers all appears in infrared spectra, shows that this multipolymer is made up of these three kinds of structural units.With the total mole number of structural unit in described polymkeric substance for benchmark, the content of acrylamide structural unit is 89.84mol%, the content of 2-acrylamide-2-methyl propane sulfonic structural unit is 9.67mol%, and the content derived from the structural unit of polymerisable monomer D3 is 0.49mol%.
Embodiment 4
This embodiment illustrates the polymkeric substance for oil-displacing agent prepared by polymerisable monomer provided by the invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS) mix with 50 grams of deionized waters, stirring makes monomer dissolve completely, be the pH value of the aqueous sodium hydroxide solution regulation system of 20 % by weight by concentration be 11, and said mixture is mixed with 1 milligram of azo-bis-isobutyrate hydrochloride with 0.15 gram of polymerisable monomer D4 obtained by preparation example 4, under nitrogen protection, add 2 milligrams of ammonium persulphates, first be polymerized 2 hours at temperature 20 DEG C, be warming up to 50 DEG C again, continue polymerization 4 hours, gained colloid is taken out, granulation, dry at 60 DEG C, pulverize, obtain white granular copolymerization product, be designated as polymer P 4.Characterize P4 with infrared spectroscopy, result shows, the charateristic avsorption band of the structural unit of three kinds of monomers all appears in infrared spectra, shows that this multipolymer is made up of these three kinds of structural units.With the total mole number of structural unit in described polymkeric substance for benchmark, the content of acrylamide structural unit is 89.91mol%, the content of 2-acrylamide-2-methyl propane sulfonic structural unit is 9.68mol%, and the content derived from the structural unit of polymerisable monomer D4 is 0.41mol%.
Embodiment 5
This embodiment illustrates the polymkeric substance for oil-displacing agent prepared by polymerisable monomer provided by the invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS) mix with 50 grams of deionized waters, stirring makes monomer dissolve completely, be the pH value of the aqueous sodium hydroxide solution regulation system of 20 % by weight by concentration be 8, and said mixture is mixed with 1 milligram of Diisopropyl azodicarboxylate with 0.15 gram of polymerisable monomer D5 obtained by preparation example 5, under nitrogen protection, add 2 milligrams of Potassium Persulphates, first be polymerized 8 hours at temperature 5 DEG C, be warming up to 60 DEG C again, continue polymerization 2 hours, gained colloid is taken out, granulation, dry at 50 DEG C, pulverize, obtain white granular copolymerization product, be designated as polymer P 5.Characterize P5 with infrared spectroscopy, result shows, the charateristic avsorption band of the structural unit of three kinds of monomers all appears in infrared spectra, shows that this multipolymer is made up of these three kinds of structural units.With the total mole number of structural unit in described polymkeric substance for benchmark, the content of acrylamide structural unit is 89.78mol%, the content of 2-acrylamide-2-methyl propane sulfonic structural unit is 9.67mol%, and the content derived from the structural unit of polymerisable monomer D5 is 0.55mol%.
Embodiment 6
This embodiment illustrates the polymkeric substance for oil-displacing agent prepared by polymerisable monomer provided by the invention.
By 7.23 grams of acrylamides (AM), 2.27 grams of 2-acrylamide-2-methyl propane sulfonics (AMPS) mix with 50 grams of deionized waters, stirring makes monomer dissolve completely, be the pH value of the aqueous sodium hydroxide solution regulation system of 20 % by weight by concentration be 8, and said mixture is mixed with 1 milligram of 2,2'-Azobis(2,4-dimethylvaleronitrile) with 0.15 gram of polymerisable monomer D6 obtained by preparation example 6, under nitrogen protection, add 2 milligrams of ammonium persulphate-diethylamine, first be polymerized 5 hours at temperature 10 DEG C, be warming up to 80 DEG C again, continue polymerization 1 hour, gained colloid is taken out, granulation, dry at 70 DEG C, pulverize, obtain white granular copolymerization product, be designated as polymer P 6.Characterize P6 with infrared spectroscopy, result shows, the charateristic avsorption band of the structural unit of three kinds of monomers all appears in infrared spectra, shows that this multipolymer is made up of these three kinds of structural units.With the total mole number of structural unit in described polymkeric substance for benchmark, the content of acrylamide structural unit is 89.88mol%, the content of 2-acrylamide-2-methyl propane sulfonic structural unit is 9.68mol%, and the content derived from the structural unit of polymerisable monomer D6 is 0.44mol%.
Embodiment 7
This embodiment illustrates the polymkeric substance for oil-displacing agent prepared by polymerisable monomer provided by the invention.
Random copolymers is prepared according to the method for embodiment 1, unlike, replace the polymerisable monomer D1 obtained by preparation example 1 with the polymerisable monomer D7 obtained by preparation example 7 of identical weight part, obtain white granular copolymerization product, be designated as polymer P 7.Characterize P7 with infrared spectroscopy, result shows, the charateristic avsorption band of the structural unit of three kinds of monomers all appears in infrared spectra, shows that this multipolymer is made up of these three kinds of structural units.With the total mole number of structural unit in described polymkeric substance for benchmark, the content of acrylamide structural unit is 89.88mol%, the content of 2-acrylamide-2-methyl propane sulfonic structural unit is 9.68mol%, and the content derived from the structural unit of polymerisable monomer D7 is 0.44mol%.
Embodiment 8
This embodiment illustrates the polymkeric substance for oil-displacing agent prepared by polymerisable monomer provided by the invention.
Random copolymers is prepared according to the method for embodiment 1, unlike, replace the polymerisable monomer D1 obtained by preparation example 1 with the polymerisable monomer D8 obtained by preparation example 8 of identical weight part, obtain white granular copolymerization product, be designated as polymer P 8.Characterize P8 with infrared spectroscopy, result shows, the charateristic avsorption band of the structural unit of three kinds of monomers all appears in infrared spectra, shows that this multipolymer is made up of these three kinds of structural units.With the total mole number of structural unit in described polymkeric substance for benchmark, the content of acrylamide structural unit is 89.84mol%, the content of 2-acrylamide-2-methyl propane sulfonic structural unit is 9.67mol%, and the content derived from the structural unit of polymerisable monomer D8 is 0.49mol%.
Embodiment 9
This embodiment illustrates the polymkeric substance for oil-displacing agent prepared by polymerisable monomer provided by the invention.
Random copolymers is prepared according to the method for embodiment 1, unlike, replace the polymerisable monomer D1 obtained by preparation example 1 with the polymerisable monomer D9 obtained by preparation example 9 of identical weight part, obtain white granular copolymerization product, be designated as polymer P 9.Characterize P9 with infrared spectroscopy, result shows, the charateristic avsorption band of the structural unit of three kinds of monomers all appears in infrared spectra, shows that this multipolymer is made up of these three kinds of structural units.With the total mole number of structural unit in described polymkeric substance for benchmark, the content of acrylamide structural unit is 89.88mol%, the content of 2-acrylamide-2-methyl propane sulfonic structural unit is 9.68mol%, and the content derived from the structural unit of polymerisable monomer D9 is 0.44mol%.
Embodiment 10
This embodiment is for illustration of the preparation of random copolymers provided by the invention.
Random copolymers is prepared according to the method for embodiment 1, unlike, the consumption of polymerisable monomer D1 is 18.44 grams, obtains white granular copolymerization product, is designated as polymer P 10.Characterize P10 with infrared spectroscopy, result shows, the charateristic avsorption band of the structural unit of three kinds of monomers all appears in infrared spectra, shows that this multipolymer is made up of these three kinds of structural units.With the total mole number of structural unit in described polymkeric substance for benchmark, the content of acrylamide structural unit is 58.30mol%, the content of 2-acrylamide-2-methyl propane sulfonic structural unit is 6.28mol%, and the content derived from the structural unit of polymerisable monomer D10 is 35.42mol%.
Comparative example 1
This comparative example illustrates the polymkeric substance for oil-displacing agent of reference.
Multipolymer is prepared according to the method for embodiment 1, unlike, do not add polymerisable monomer D1, thus obtain the multipolymer DP-1 of AM and AMPS.
Comparative example 2
This comparative example is for illustration of the polymkeric substance for oil-displacing agent of reference.
Multipolymer is prepared according to the method for embodiment 1, unlike, obtaining polymerisable monomer B1 by preparation comparative example 1 and replace polymerisable monomer D1 by identical weight, thus obtain multipolymer DP-2.
Test case 1
The viscosity-average molecular weight of test case 1 for illustration of polymkeric substance and the test of apparent viscosity.
The intrinsic viscosity of multipolymer DP-1, DP-2 that the polymer P 1-P10 that embodiment 1-10 prepares and comparative example 1-2 prepares measures according to GB12005.1-89 For Intrinsic Viscosity Measurements method; Viscosity-average molecular weight is according to formula M=([η]/K)
1 α, wherein K=4.5 × 10
-3, α=0.80 calculates;
The apparent viscosity of aqueous solutions of polymers is 7.34s by BROOKFIELDDV-III viscosity apparatus in rotating speed perseverance
-1, be carry out mensuration under the condition of 25 DEG C and 85 DEG C to obtain respectively in temperature, wherein, test condition comprises: polymer concentration is 1500mg/L, and solution total mineralization is 32868mg/L.Test result is as shown in table 1.
Table 1
| Numbering | M η(×10 4) | η25(mPa·s) | η85(mPa·s) |
| P1 | 2700 | 72.8 | 36.4 |
| P2 | 3300 | 91.8 | 47.2 |
| P3 | 3100 | 86.2 | 43.5 |
| P4 | 2700 | 72.5 | 36.0 |
| P5 | 3200 | 89.1 | 46.3 |
| P6 | 3000 | 82.7 | 40.9 |
| P7 | 2750 | 74.2 | 35.8 |
| P8 | 2800 | 76.1 | 38.6 |
| P9 | 2850 | 77.2 | 39.0 |
| P10 | 2600 | 70.9 | 35.7 |
| DP-1 | 1300 | 24.6 | 11.8 |
| DP-2 | 1800 | 44.6 | 20.4 |
Note: M in table 1
ηthe viscosity-average molecular weight of representation polymer, η 25 represents the apparent viscosity of aqueous solutions of polymers at 25 DEG C, and η 85 represents the apparent viscosity of aqueous solutions of polymers at 85 DEG C.
The data of the embodiment P1-P10 as can be seen from table 1 compare with the data of comparative example DP-1, DP-2, the polymer P 1-P10 adopting method of the present invention to prepare at normal temperatures (25 DEG C) has very high apparent viscosity, and when it still can keep very high apparent viscosity under the condition of high temperature (85 DEG C), high salinity (32868mg/L), therefore, it has excellent resistance toheat and anti-salt property.
Test case 2
Test case 2 is used as the apparent viscosity of oil-displacing agent for illustration of polymkeric substance provided by the invention and tensio-active agent compound.
Under agitation, at 20 DEG C, multipolymer DP-1, DP-2 that the polymer P 1-P10 prepared by the embodiment 1-10 of 0.3g and comparative example 1 and comparative example 2 prepare respectively with 0.1g sulfonated petro-leum (producer: the great global oilfield technology Services Co., Ltd of grand celebration; The composition of sulfonated petro-leum: actives 60 % by weight, oil 20 % by weight, salt 1.5 % by weight, water 18.5 % by weight, in actives, single sulfonic acid accounts for 90 % by weight, and disulfonic acid and many sulfonic acid account for 10 % by weight) Homogeneous phase mixing 80min, then this mixture is mixed with the aqueous solution.
The apparent viscosity of this aqueous solution is 7.34s by BROOKFIELDDV-III viscosity apparatus in rotating speed perseverance
-1, be carry out mensuration under the condition of 25 DEG C and 85 DEG C to obtain respectively in temperature, wherein, test condition comprises: mixture concentration is 1500mg/L, and solution total mineralization is 32868mg/L.Test result is as shown in table 2.
Table 2
| Numbering | η25(mPa·s) | η85(mPa·s) |
| Compound P1 | 81.2 | 40.8 |
| Compound P2 | 98.9 | 52.6 |
| Compound P3 | 95.4 | 46.8 |
| Compound P4 | 81.5 | 40.2 |
| Compound P5 | 96.2 | 47.6 |
| Compound P6 | 91.6 | 43.2 |
| Compound P7 | 83.9 | 39.8 |
| Compound P8 | 85.1 | 41.9 |
| Compound P9 | 86.5 | 43.2 |
| Compound P10 | 89.2 | 45.1 |
| Compound DP-1 | 32.1 | 16.0 |
| Compound DP-2 | 52.9 | 24.5 |
Data as can be seen from table 2 relatively, the polymer P 1-P10 adopting method of the present invention to prepare and sulfonated petro-leum composite be used as oil-displacing agent at normal temperatures (25 DEG C) there is very high apparent viscosity, and when it still can keep very high apparent viscosity under the condition of high temperature (85 DEG C), high salinity (32868mg/L), therefore, it has excellent resistance toheat and salt resistant character.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. a preparation method for polymerisable monomer, the method comprises the following steps:
(1) under condensation reaction condition, be NH by general formula
2-(CH
2)
n-NH
2diamines and general formula be HOOC-(CH
2)
mthe binary of fatty acids contact of-COOH, obtains the intermediate M shown in formula (Ι);
(2) under amidation reaction condition, described intermediate M is contacted with vinylformic acid, obtain the polymerisable monomer shown in formula (II);
Wherein, n is the integer of 1-6, and m is the integer of 1-8.
2. preparation method according to claim 1, wherein, n is the integer of 2-6, and m is the integer of 4-8.
3. preparation method according to claim 1, wherein, in step (1), the mol ratio of described diamines and binary of fatty acids is 1:1-1.2, is preferably 1:1-1.1.
4. preparation method according to claim 1, wherein, described condensation reaction condition comprises: temperature of reaction is 110-160 DEG C, and the reaction times is 2-6 hour.
5. preparation method according to claim 1, wherein, the acrylic acid mol ratio in diamines described in step (1) and step (2) is 1:1-1.2, is preferably 1:1-1.1.
6. preparation method according to claim 1, wherein, in step (2), described amidation reaction condition comprises: temperature of reaction is 60-80 DEG C, and the reaction times is 2-4 hour.
7. the preparation method according to claim 1 or 6, wherein, in step (2), described amidate action carries out under the existence of stopper, and with acrylic acid weight for benchmark, the consumption of described stopper is 0.05-0.1 % by weight; Described stopper be selected from Resorcinol, para benzoquinone and MEHQ one or more.
8. preparation method according to claim 1, wherein, described condensation reaction and/or amidate action carry out in presence of organic solvent, described organic solvent be selected from acetone, ethyl acetate, benzene, dimethylbenzene, methylene dichloride and trichloromethane one or more.
9. the polymerisable monomer prepared by the method in claim 1-8 described in any one is preparing the application in polymer oil-displacing agent.
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| CN114736381A (en) * | 2022-04-20 | 2022-07-12 | 无锡颐景丰科技有限公司 | Comb-shaped high-molecular surfactant and synthesis method thereof |
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| CN112812816A (en) * | 2020-12-26 | 2021-05-18 | 中海油天津化工研究设计院有限公司 | Oil slurry viscosity modifier and preparation method thereof |
| CN114736381A (en) * | 2022-04-20 | 2022-07-12 | 无锡颐景丰科技有限公司 | Comb-shaped high-molecular surfactant and synthesis method thereof |
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