CN107226886B - A kind of polymer and its preparation method and application with surface active function - Google Patents
A kind of polymer and its preparation method and application with surface active function Download PDFInfo
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- CN107226886B CN107226886B CN201610173255.7A CN201610173255A CN107226886B CN 107226886 B CN107226886 B CN 107226886B CN 201610173255 A CN201610173255 A CN 201610173255A CN 107226886 B CN107226886 B CN 107226886B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The present invention relates to oil recovering fields, disclose a kind of polymer and its preparation method and application with surface active function, the polymer contains structural unit A, structural unit B and structural unit C, wherein, the structural unit A is the structural unit with structure shown in formula (1), the structural unit B is the structural unit with structure shown in formula (2), and the structural unit C is the structural unit with structure shown in formula (3).The present invention on macromolecular chain by introducing the polymerisable monomer with surface-active, its ether chain structure determine the copolymer of synthesis have stronger hydrolytic resistance and thermal stability, the surface tension and interfacial tension of polymer solution are substantially reduced simultaneously, so that polymer has good surface-active, increase-volume emulsification and washing oil ability, and then improve oil recovery factor.
Description
Technical field
The present invention relates to oil recovering fields, and in particular, to a kind of polymer and its system with surface active function
Preparation Method and application.
Background technique
Surface active function polymer, which refers to, exists simultaneously hydrophilic radical and lipophilic group in its macromolecular structure, makes it
Solution has a kind of active new function polymer of excellent surface, oxidationreduction composite initiation system is generally used, certain
At a temperature of cause polyacrylamide and surface active monomer and carry out combined polymerization, obtain surface active function polymer.
Surface active function polymer and conventional high molecular surfactant have very big difference.High-molecular surface active
The property of agent is more likely to small molecule surface-active, and surface active function polymer mainly shows the property of polymer.High score
The relative molecular mass of sub- surfactant is not high, and generally less than 2,000,000, tackifying is not strong, and surface active function polymer
Relative molecular mass be higher than 10,000,000, even more than 15,000,000, there is stronger tackifying and viscoplasticity, while can be effective
It reduces oil water interfacial tension and with certain washing oil ability, can achieve one multi-purpose effect, thus, surface active function
Polymer has bigger application prospect as oil displacement agent, in tertiary oil recovery field.
Use surface active function polymer as oil displacement agent, is applied to tertiary oil recovery field, with polymer/surface-active
Binary combination flooding is compared and is had great advantages.Polymer/surface-active binary combination flooding is migrated in reservoir formation porous media
During chromatographic isolation phenomenon can occur, and single surface active function polymer is then not in, more can effectively play from
Body thickening, emulsification, solubilized characteristic, can not only expand swept volume, but also displacement efficiency can be improved.
Early-stage study stage, domestic and international pertinent literature report are in the surface active function polymer of the displacement of reservoir oil at present
It is very few.Such functional polymer will also promote few in chemical combined flooding oil systems use or without surfactant, Yi Jineng
The investment for reducing live filing provision, greatly reduces displacement of reservoir oil cost.
With continuing to increase for conventional oil reservoir recovery percent of reserves, the sharply reduction of recoverable reserves has employed middle and low permeable reservoir
Through extremely urgent.Such as Jiangsu oilfield proved reserves 27730.62 × 104T, wherein middle and low permeable reservoir reserves account for verifying storage
The 87.2% of amount.Polymer displacement of reservoir oil tech is carried out nearly 30 years at home, but the problem of due to injection, conventional high molecular weight
Flooding polymers are not able to satisfy the requirement of the exploitation of middle and low permeable reservoir, therefore, carry out the table for adapting to middle and low permeable reservoir condition
The research of face active function polymer oil-displacing agent has a very important significance.
The features such as polymerizable type surface active monomer has reactivity moderate, and polymer molecular weight is higher, can be used for third
The combined polymerization of acrylamide monomer, thus the Polymer Used For Oil Displacement being had excellent performance.It therefore will be with surface active function
Polymerisable monomer is introduced on the macromolecular chain of polyacrylamide, is that an effective improvement temperature-resistant and anti-salt type flooding polymers are comprehensive
It closes the important channel of performance and improves the important measures of oil recovery factor.
Summary of the invention
It is a kind of with surface active function polymer and preparation method thereof the purpose of the present invention is developing, by providing one kind
Not only with surface-active but also the function monomer that contains polymerizable styryl is to improve the tackifying and emulsification of Polymer Used For Oil Displacement
Performance reduces the performances such as surface and interface tension.
To achieve the goals above, in a first aspect, the present invention provides a kind of polymer with surface active function, this is poly-
It closes object and contains structural unit A, structural unit B and structural unit C, wherein the structural unit A is with structure shown in formula (1)
Structural unit, the structural unit B be the structural unit with structure shown in formula (2), the structural unit C be with formula
(3) structural unit of structure shown in；Wherein, on the basis of the weight of the polymer, the content of the structural unit A is 55-
The content of 89.9 weight %, the structural unit B is 10-40 weight %, and the content of the structural unit C is 0.1-5 weight %,
The viscosity average molecular weigh of the polymer is 22,000,000-3,200 ten thousand；
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3For the alkylidene of C1-C14；R4And R5It is respectively independent
Ground is the alkyl of H or C1-C4, and R4And R5It is not simultaneously H；M is H, Na or K；R6For the alkyl of H or C1-C4；R7For H or SO3Y,
Y is H, Na or K；M is the integer of 7-13, and n is the integer of 6-15.
Second aspect, the present invention provide a kind of preparation method of polymer with surface active function, this method comprises:
In initiator and in the presence of as the water of solvent, monomer D, monomer E and monomer F is set to carry out solution polymerization, wherein described
Monomer D is the monomer with structure shown in formula (4), and the monomer E is the monomer with structure shown in formula (5), and the monomer F is
Monomer with structure shown in formula (6), wherein the dosage of the monomer D, monomer E and monomer F make the polymer being prepared
The content of middle structural unit A is 55-89.9 weight %, and the content of structural unit B is 10-40 weight %, the content of structural unit C
For 0.1-5 weight %, and the viscosity average molecular weigh for the polymer being prepared is made to be 22,000,000-3,200 ten thousand；The structure list
First A is the structural unit with structure shown in formula (1), and the structural unit B is the structural unit with structure shown in formula (2),
The structural unit C is the structural unit with structure shown in formula (3),
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3For the alkylidene of C1-C14；R4And R5It is respectively independent
Ground is the alkyl of H or C1-C4, and R4And R5It is not simultaneously H；M is H, Na or K；R6For the alkyl of H or C1-C4；R7For H or SO3Y,
Y is H, Na or K；M is the integer of 7-13, and n is the integer of 6-15.
The third aspect, the present invention provide the polymer with surface active function that preceding method is prepared.
Fourth aspect, the present invention provide aforementioned the answering as polymer oil-displacing agent of the polymer with surface active function
With.
Polymer of the present invention with surface active function and preparation method thereof compared with prior art, in molecule
It is had the following advantages that in design and synthesis and effect:
The present invention introduces one kind not only in acrylamide copolymer to be had surface-active but also contains polymerizable styryl
Function monomer, while preferably joined defoaming agent and tetramethylethylenediamine in polymerization system, greatly facilitate polymerization system
Deaerating effect and improve copolymerization system polymerization activity etc., and then improve polymeric articles molecular weight and polyacrylamide it is molten
Surface-active, tackifying and the heat and salt resistance of liquid.The introducing of function monomer terminal long-chain saturated alkyl enhances macromolecular chain
Between interaction and copolymer heat resistance and salt tolerance, be able to maintain aqueous copolymers solution still under high temperature and high salt higher viscous
Degree；The introducing of nonionic polyoxyethylene hydrophilic chain simultaneously, greatly strengthens anti-bivalent metal ion ability, shows good
Tackifying effect and heat and salt resistance improve the swept volume of polymer flooding.
In addition, introducing the polymerisable monomer with surface-active on macromolecular chain, ether chain structure determines synthesis
Copolymer has stronger hydrolytic resistance and thermal stability, while substantially reducing surface tension and the interface of polymer solution
Power so that polymer has good surface-active, increase-volume emulsification and washing oil ability, and then improves oil recovery factor.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In the present invention, the alkyl of the C1-C4 refers to that carbon atom number is the alkyl of 1-4；The alkylidene of the C1-C14
Refer to that carbon atom number is the alkylidene of 1-14；The alkyl of the C1-C16 refers to that carbon atom number is the alkyl of 1-16.
According to the present invention, the alkyl of the C1-C4 can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, just
Butyl, sec-butyl, isobutyl group and tert-butyl.
According to the present invention, the alkylidene of the C1-C14 can be linear chain or branched chain, and the alkylidene of the C1-C14 can
To include but is not limited to: methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, sub- sec-butyl, isobutylidene, Asia
Tert-butyl, sub- n-pentyl, isoamylidene, sub- tertiary pentyl, sub- neopentyl, sub- n-hexyl, sub- n-heptyl, sub- n-octyl, sub- positive nonyl
Base, sub- positive decyl, sub- positive hendecyl, sub- positive dodecyl, sub- positive tritriacontyl and sub- positive tetradecyl, preferably methylene.The Asia
Alkyl refers to that alkane loses the residue after two hydrogen atoms, and described two hydrogen atoms can be two hydrogen on the same carbon atom
Atom can also be different two hydrogen atoms on carbon atom, can be straight chain, be also possible to branch, for example, the Asia second
Base can be-CH2CH2Or-CH (CH3)-。
According to the present invention, the alkyl of the C1-C16 can be linear chain or branched chain, and the alkyl of the C1-C16 can wrap
Include but be not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl,
Tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive hendecyl, positive dodecyl, positive tritriacontyl,
Positive tetradecyl, positive pentadecyl and positive palmityl.
First aspect, the present invention provides a kind of polymer with surface active function, which contains structure list
First A, structural unit B and structural unit C, wherein the structural unit A is the structural unit with structure shown in formula (1), described
Structural unit B is the structural unit with structure shown in formula (2), and the structural unit C is the structure with structure shown in formula (3)
Unit；Wherein, on the basis of the weight of the polymer, the content of the structural unit A is 55-89.9 weight %, the knot
The content of structure unit B is 10-40 weight %, and the content of the structural unit C is 0.1-5 weight %, the polymer it is viscous
Molecular weight is 22,000,000-3,200 ten thousand；
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3For the alkylidene of C1-C14；R4And R5It is respectively independent
Ground is the alkyl of H or C1-C4, and R4And R5It is not simultaneously H；M is H, Na or K；R6For the alkyl of H or C1-C4；R7For H or SO3Y,
Y is H, Na or K；M is the integer of 7-13, and n is the integer of 6-15.
Preferably, on the basis of the weight of the polymer, the content of the structural unit A is 57-84.9 weight %, institute
The content for stating structural unit B is 15-40 weight %, and the content of the structural unit C is 0.1-3 weight %, the polymer
Viscosity average molecular weigh is 24,000,000-3,000 ten thousand.
In the case of, according to the invention it is preferred to, the structure list of structure shown in the structural unit of the structure shown in formula (1), formula (2)
In the structural unit of structure shown in member and formula (3), R1And R2It is each independently H, methyl, ethyl, n-propyl, isopropyl, positive fourth
Base；R3For methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl, sub- n-hexyl；R4And R5Be each independently H,
Methyl, ethyl, n-propyl, isopropyl, normal-butyl, and R4And R5It is not simultaneously H；M is H, Na or K；R6For H, methyl, ethyl, just
Propyl, isopropyl, normal-butyl.
In the case of, according to the invention it is preferred to, the structure list of structure shown in the structural unit of the structure shown in formula (1), formula (2)
In the structural unit of structure shown in member and formula (3), R1And R2It is each independently H, methyl, ethyl, n-propyl；R3For methylene,
Ethylidene, sub- n-propyl, sub- normal-butyl；R4And R5It is each independently H, methyl, ethyl, n-propyl, and R4And R5It is not simultaneously
H；M is Na or K；R6For H, methyl, ethyl, n-propyl.
In the case of, according to the invention it is preferred to, the structure list of structure shown in the structural unit of the structure shown in formula (1), formula (2)
In the structural unit of structure shown in member and formula (3), R1And R2It is each independently H, methyl；R3For methylene；R4And R5Respectively solely
It is on the spot H, methyl, ethyl, and R4And R5It is not simultaneously H；M is Na or K；R6For H, methyl, ethyl.
The present inventor has found under study for action, by following specific structural unit A, structural unit B and structural unit C
The polymer of composition can obtain preferable oil displacement efficiency when being used as oil displacement agent.The structural unit A is with structure shown in formula (7)
Structural unit, the structural unit B be structural unit with structure shown in formula (8) and the structural unit C be with
The structural unit of structure shown in formula (9), the structural unit with structure shown in formula (10), the structure with structure shown in formula (11)
At least one of unit, the structural unit with structure shown in formula (12) and structural unit with structure shown in formula (13),
Wherein, each R7It is identical or different, it is each independently H, SO3Na or SO3H。
Second aspect, the present invention provides a kind of preparation method of polymer with surface active function, this method packets
It includes: in initiator and in the presence of as the water of solvent, monomer D, monomer E and monomer F being made to carry out solution polymerization, wherein
The monomer D is the monomer with structure shown in formula (4), and the monomer E is the monomer with structure shown in formula (5), the list
Body F is the monomer with structure shown in formula (6), wherein what the dosage of the monomer D, monomer E and monomer F to be prepared
The content of structural unit A is 55-89.9 weight % in polymer, and the content of structural unit B is 10-40 weight %, structural unit C
Content be 0.1-5 weight %, and make the polymer being prepared viscosity average molecular weigh be 22,000,000-3,200 ten thousand；It is described
Structural unit A is the structural unit with structure shown in formula (1), and the structural unit B is the structure with structure shown in formula (2)
Unit, the structural unit C are the structural unit with structure shown in formula (3),
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3For the alkylidene of C1-C14；R4And R5It is respectively independent
Ground is the alkyl of H or C1-C4, and R4And R5It is not simultaneously H；M is H, Na or K；R6For the alkyl of H or C1-C4；R7For H or SO3Y,
Y is H, Na or K；M is the integer of 7-13, and n is the integer of 6-15.
In the present invention, the structural unit of structure shown in the formula (1), the structural unit of structure shown in formula (2), formula (3)
The list of structure shown in the monomer and formula (6) of structure shown in the monomer of structure shown in the structural unit of shown structure, formula (4), formula (5)
The related definition and substance classes of substituent group in body are identical as correspondence noted earlier of the invention, and the present invention is no longer superfluous herein
It states, those skilled in the art should not be construed as the limitation to technical solution of the present invention.
In the present invention, it should be noted that the one body approximation is fully converted to the polymer of tool surface active function
The corresponding structural unit contained, the corresponding knot that the dosage of the monomer contains with the polymer of the tool surface active function
The content of structure unit can be consistent.
Preferably, the dosage of the monomer D, monomer E and monomer F make structural unit A in the polymer being prepared
Content is 57-84.9 weight %, and the content of structural unit B is 15-40 weight %, and the content of structural unit C is 0.1-3 weight
% is measured, and the viscosity average molecular weigh for the polymer being prepared is made to be 24,000,000-3,000 ten thousand.
Preferably, monomer D, monomer E and monomer F are formed into aqueous solution in presence of water；It is further preferred that in the water
In solution, the total concentration of monomer D, monomer E and monomer F are 20-40 weight %.
According to the method for the present invention, the solution polymerization preferably carries out under conditions of pH value is 6-10.The pH
Value can be obtained by the way that pH adjusting agent is added into polymerization system, and the pH adjusting agent can be the various of this field routine
PH adjusting agent, such as can be at least one of sodium hydroxide, sodium carbonate, potassium carbonate and ammonium hydroxide, preferably sodium hydroxide
And/or sodium carbonate.
According to the method for the present invention, chelating agent being added can prevent metal ion from having an impact to polymerization reaction, therefore, excellent
In the case of choosing, the solution polymerization carries out in the presence of chelating agent.The chelating agent can be ethylenediamine tetra-acetic acid two
Sodium, aminotriacetic acid or ammonium citrate, preferably disodium ethylene diamine tetraacetate.The present invention is to the dosage of the chelating agent without spy
Other restriction can change in a wider scope, on the basis of the total amount of the monomer D, the monomer E and the monomer F,
The dosage of the chelating agent can be 0.01-0.1 weight %.
According to the method for the present invention, the dissolubility of polymer can be improved by auxiliary agent being added, it is therefore preferable that in the case of, it is described
Solution polymerization carries out in the presence of auxiliary agent.The auxiliary agent can be at least one of for urea, thiocarbamide and ammonium hydroxide, preferably
Urea.There is no particular limitation for dosage of the present invention to the auxiliary agent, can change in a wider scope, with the monomer D,
On the basis of the total amount of the monomer E and the monomer F, the dosage of the auxiliary agent can be 0.01-0.1 weight %.
The solution polymerization of the invention further includes carrying out in the presence of tetramethylethylenediamine, the tetramethyl second
The dosage of diamines is the 0.02-0.2 weight % of total dosage of monomer D, monomer E and monomer F.
The solution polymerization of the invention can also carry out in the presence of defoaming agent, and the dosage of the defoaming agent is
The 0.02-0.2 weight % of total dosage of monomer D, monomer E and monomer F.The defoaming agent can for example defoam for organic silicon
Agent.
The solution polymerization can also carry out in the presence of protective gas, and the protective gas preferably can be nitrogen
Gas.
It is polymeric colloid by the product mixtures obtained after the solution polymerization, it is of the present invention in order to obtain
The polymer end product with surface active function, method of the invention can also include making the polymeric colloid of acquisition
Grain, and 2-3h is hydrolyzed at 80-90 DEG C after grain alkali is added thereto；Micelle is then taken out to be granulated, dried, crushed, sieved again
The polymer end product with surface active function is obtained after point.The grain alkali can be sodium hydroxide grain alkali.
Preferably, the monomer D is the monomer with structure shown in formula (14)；The monomer E is with shown in formula (15)
The monomer of structure；The monomer F is the monomer with structure shown in formula (16), the monomer with structure shown in formula (17), has
In the monomer of structure shown in formula (18), the monomer with structure shown in formula (19) and the monomer with structure shown in formula (20) extremely
Few one kind,
Wherein, each R7It is identical or different, it is each independently H, SO3Na or SO3H。
The monomer F can be commercially available or synthesize to obtain using the method for the prior art.For example, the present invention is such as
Under illustratively provide structure shown in formula (16) monomer preparation method, prepare the method and following methods of other relevant monomers
It is similar, be only replacement raw material, in order to avoid repeating, this is no longer going to repeat them by the present invention:
In the presence of the catalytic action of solvent such as acetone and p-methyl benzenesulfonic acid, glycerine is subjected to protection reaction, so
The product after protection reaction is contacted at subzero 20 DEG C to 20 DEG C above freezing with to heptane base benzyl chloride afterwards, the contact is deposited in pyridine
In lower progress, the first intermediate is obtained；In acid condition, by first intermediate and Cl (CH2CH2O)6SO3H is mixed
It closes, obtains the second intermediate；In the presence of a catalyst, second intermediate is reacted with to bromometllylstyrene, from
And obtain the monomer of structure shown in formula (16).
Preferably, it is 0-30 DEG C that the condition of the solution polymerization, which includes: temperature,；Time is 2-15h.It is highly preferred that
The condition of the solution polymerization includes: that temperature is 0-20 DEG C；Time is 5-10h.
Preferably, the initiator includes azo-initiator, peroxide type initiators and redox type initiators
At least one of；The azo-initiator is selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azo two
Formamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano formamide, azo diisopropyl imidazoline hydrochloride, azo dicyan
At least one in base valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azobisisovaleronitrile and azobisisoheptonitrile
Kind；The peroxide type initiators be selected from hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, benzoyl peroxide and
At least one of benzoyl peroxide；The redox type initiators are selected from sulfate-sulphite, persulfuric acid
At least one of salt-thiocarbamide, persulfate-organic salt and ammonium persulfate-fatty amine.
Preferably, the initiator is redox type initiators；It is further preferred that the redox type initiators are
The oxidation-reduction trigger system being made of persulfate oxidation agent and sulfite reducing agent.Under the preferable case, persulfuric acid
The dosage of salt oxidizing agent is the 0.01-0.1 weight % of total dosage of monomer D, monomer E and monomer F；The use of sulfite reducing agent
Amount is the 0.005-0.05% of total dosage of monomer D, monomer E and monomer F.For example, the oxygen in the redox type initiators
Agent can be the persulfate aqueous solution of 0.1 weight % and/or the ammonium persulfate aqueous solution of 0.1 weight %；The oxidation is also
Reducing agent in former class initiator can be the bisulfite aqueous solutions of potassium of 0.1 weight % and/or the bisulfite of 0.1 weight %
Sodium water solution.
According to a kind of preferred embodiment, the preparation method of the polymer with surface active function includes
Following steps:
Step 1: being added in polymerisation bottle by monomer D, monomer E and monomer F and be configured to aqueous solution, adjusts the water with alkali
The pH value of solution is 6-10；
Step 2: chelating agent, aqueous solution of urea, tetramethylethylenediamine and defoaming agent are added into the aqueous solution of step 1, stirs
It mixes uniformly；
Step 3: at a temperature of 0-30 DEG C, after blasting nitrogen 5-60min, initiator being added into the aqueous solution of step 2, and
And making it after mixing blasting nitrogen, sealing polymerization 2-15h obtains polymeric colloid；
Step 4: taking out colloid, and grain alkali is added after being granulated, makes it after mixing, hydrolyzes 2-3h at 80-90 DEG C；
Step 5: take out micelle be granulated, dried again, being crushed, sieve after obtain the polymer with surface active function
Finished product.
The third aspect, the present invention provides the polymer with surface active function that preceding method is prepared.
Fourth aspect, the present invention provides aforementioned the answering as polymer oil-displacing agent of the polymer with surface active function
With.
In application of the above-mentioned polymer with surface active function as polymer oil-displacing agent, specific application method
The technology being well known to those skilled in the art.
The polymer with surface active function of the invention may be used as polymer oil-displacing agent, can be suitably used for it is high,
Low-mid permeability pools and high-temperature oil reservoir and high temperature and high salt oil deposit, further increase oil recovery factor in tertiary oil recovery.
The present invention will be described in detail by way of examples below.
In following embodiment, the test method being related to is as follows:
The viscosity average molecular weigh of polymer is tested using one point method using Ubbelohde viscometer.
It is in salinity with Brookfield viscosimeter measurement polymer solution under nominative testing temperature (85 DEG C)
30000mg/L, wherein calcium ions and magnesium ions are the apparent viscosity under 800mg/L (with high salt).
Aqueous solution table under nominative testing temperature (25 DEG C) with DCAT-21 surface tension instrument measurement polymer under pure water
Face tension.
Embodiment 1-5 is for illustrating the polymer and preparation method thereof with surface active function of the invention.
Embodiment 1
1, by 15.8g acrylamide (the 79 weight % for accounting for monomer total amount), the 2- acrylamido -2- methyl-prop sulphur of 4.0g
Function monomer (m=7, n=6, R shown in sour (the 20 weight % for accounting for monomer total amount) and 0.2g formula (16)7For SO3It is total to account for monomer by H
1 weight % of amount) it is added in heat preservation polymerisation bottle (i.e. polymerization bottle), deionized water 60.0g dissolution is added and is made into aqueous solution,
Adding sodium hydroxide and adjusting pH value is 6.0；
2, the EDTA-2Na aqueous solution 1.0g of 1 weight %, the aqueous solution of urea 0.5g of 1 weight %, tetramethyl are sequentially added
Ethylenediamine 10.0mg, dimethyl polysiloxane 15.0mg, stirs evenly；
3, the temperature of aqueous solution is controlled at 10 DEG C, is led to nitrogen flooding oxygen after 30 minutes, is added the potassium peroxydisulfate of 0.1 weight %
The aqueous solution of sodium bisulfite 1.0g of aqueous solution 2.0g and 0.1 weight %, initiation reaction stop after continuing logical nitrogen 5min, close
Polymerization reaction of being honored as a queen 6 hours；
4, blob of viscose is taken out, 0.3g sodium hydroxide grain alkali is added after granulation and is hydrolyzed at 80 DEG C after mixing 3 hours；
5, taking-up micelle is granulated again, drying to constant weight, crushing, sieving obtains white granular surface-active at 60 DEG C
Polymer samples.
Test result: the molecular weight of polymer samples is 26,000,000, apparent viscosity 50.6mPas, and surface tension is
32.56mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 2
1, by 15.8g acrylamide (the 79 weight % for accounting for monomer total amount), the 2- acrylamido -2- methyl-prop sulphur of 4.0g
Function monomer (m=9, n=10, R shown in sour (the 20 weight % for accounting for monomer total amount) and 0.2g formula (17)7For SO3H, Zhan Danti
1 weight % of total amount) it is added in heat preservation polymerisation bottle (i.e. polymerization bottle), addition deionized water 80.0g dissolution is made into water-soluble
Liquid, adding sodium hydroxide and adjusting pH value is 7.2；
2, the EDTA-2Na aqueous solution 1.0g of 1 weight %, the aqueous solution of urea 0.5g of 1 weight %, tetramethyl are sequentially added
Ethylenediamine 10.0mg, dimethyl polysiloxane 15.0mg, stirs evenly；
3, the temperature of aqueous solution is controlled at 15 DEG C, is led to nitrogen flooding oxygen after 30 minutes, is added the potassium peroxydisulfate of 0.1 weight %
The aqueous solution of sodium bisulfite 1.0g of aqueous solution 2.0g and 0.1 weight %, initiation reaction stop after continuing logical nitrogen 5min, close
Polymerization reaction of being honored as a queen 8 hours；
4, blob of viscose is taken out, 0.3g sodium hydroxide grain alkali is added after granulation and is hydrolyzed at 90 DEG C after mixing 2 hours；
5, taking-up micelle is granulated again, drying to constant weight, crushing, sieving obtains white granular surface-active at 60 DEG C
Polymer samples.
Test result: the molecular weight of polymer samples is 29,000,000, apparent viscosity 65.8mPas, and surface tension is
27.65mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 3
1, by 17.95g acrylamide (the 89.75 weight % for accounting for monomer total amount), the 2- acrylamido -2- methyl of 2.0g
Function monomer (m=13, n=15, R shown in propane sulfonic acid (the 10 weight % for accounting for monomer total amount) and 0.05g formula (18)7For H, account for
0.25 weight % of monomer total amount) it is added in heat preservation polymerisation bottle (i.e. polymerization bottle), deionized water 60.0g dissolution is added and matches
At aqueous solution, adding sodium hydroxide and adjusting pH value is 9.0；
2, the EDTA-2Na aqueous solution 1.0g of 1 weight %, the aqueous solution of urea 0.5g of 1 weight %, tetramethyl are sequentially added
Ethylenediamine 10.0mg, dimethyl polysiloxane 15.0mg, stirs evenly；
3, the temperature of aqueous solution is controlled at 20 DEG C, is led to nitrogen flooding oxygen after 30 minutes, is added the potassium peroxydisulfate of 0.1 weight %
The aqueous solution of sodium bisulfite 5.0g of aqueous solution 10.0g and 0.1 weight %, initiation reaction stop after continuing logical nitrogen 5min, close
Polymerization reaction of being honored as a queen 7 hours；
4, blob of viscose is taken out, 0.5g sodium hydroxide grain alkali is added after granulation and is hydrolyzed 2.5 hours at 85 DEG C after mixing；
5, taking-up micelle is granulated again, drying to constant weight, crushing, sieving obtains white granular surface-active at 60 DEG C
Polymer samples.
Test result: the molecular weight of polymer samples is 25,500,000, apparent viscosity 48.6mPas, and surface tension is
26.25mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 4
1, by 15.98g acrylamide (the 79.9 weight % for accounting for monomer total amount), the 2- acrylamido -2- methyl of 4.0g
Function monomer (m=9, n=6, R shown in propane sulfonic acid (the 20 weight % for accounting for monomer total amount) and 0.02g formula (19)7For H, Zhan Dan
0.1 weight % of body total amount) it is added in heat preservation polymerisation bottle (i.e. polymerization bottle), deionized water 80.0g dissolution is added and is made into
Aqueous solution, adding sodium hydroxide and adjusting pH value is 7.0；
2, the EDTA-2Na aqueous solution 1.0g of 1 weight %, the aqueous solution of urea 0.5g of 1 weight %, tetramethyl are sequentially added
Ethylenediamine 4.0mg, dimethyl polysiloxane 15.0mg, stirs evenly；
3, the temperature of aqueous solution is controlled at 15 DEG C, is led to nitrogen flooding oxygen after 30 minutes, is added the potassium peroxydisulfate of 0.1 weight %
The aqueous solution of sodium bisulfite 2.5g of aqueous solution 5.0g and 0.1 weight %, initiation reaction stop after continuing logical nitrogen 5min, close
Polymerization reaction of being honored as a queen 6 hours；
4, blob of viscose is taken out, it is small to be hydrolyzed 2.5 at 85 DEG C after mixing for addition 0.3g sodium hydroxide grain alkali after granulation
When；
5, taking-up micelle is granulated again, drying to constant weight, crushing, sieving obtains white granular surface-active at 60 DEG C
Polymer samples.
Test result: the molecular weight of polymer samples is 24,000,000, apparent viscosity 44.6mPas, and surface tension is
28.26mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 5
1, by 15.8g acrylamide (the 79 weight % for accounting for monomer total amount), the 2- acrylamido -2- methyl-prop sulphur of 4.0g
Function monomer (m=7, n=15, R shown in sour (the 20 weight % for accounting for monomer total amount) and 0.2g formula (20)7For SO3H, Zhan Danti
1 weight % of total amount) it is added in heat preservation polymerisation bottle (i.e. polymerization bottle), addition deionized water 47.0g dissolution is made into water-soluble
Liquid, adding sodium hydroxide and adjusting pH value is 10.0；
2, the EDTA-2Na aqueous solution 1.0g of 1 weight %, the aqueous solution of urea 0.5g of 1 weight %, tetramethyl are sequentially added
Ethylenediamine 20.0mg, dimethyl polysiloxane 20.0mg, stirs evenly；
3, the temperature of aqueous solution is controlled at 20 DEG C, is led to nitrogen flooding oxygen after 30 minutes, is added the potassium peroxydisulfate of 0.1 weight %
The aqueous solution of sodium bisulfite 2.5g of aqueous solution 5.0g and 0.1 weight %, initiation reaction stop after continuing logical nitrogen 5min, close
Polymerization reaction of being honored as a queen 6 hours；
4, blob of viscose is taken out, it is small to be hydrolyzed 2.5 at 85 DEG C after mixing for addition 0.3g sodium hydroxide grain alkali after granulation
When；
5, taking-up micelle is granulated again, drying to constant weight, crushing, sieving obtains white granular surface-active at 60 DEG C
Polymer samples.
Test result: the molecular weight of polymer samples is 25,000,000, apparent viscosity 46.2mPas, and surface tension is
29.55mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Comparative example 1
1, by 16.0g acrylamide (the 80 weight % for accounting for monomer total amount), the 2- acrylamido -2- methyl-prop sulphur of 4.0g
Sour (the 20 weight % for accounting for monomer total amount) are added in heat preservation polymerisation bottle (i.e. polymerization bottle), and it is molten that deionized water 47.0g is added
Solution is made into aqueous solution, and adding sodium hydroxide and adjusting pH value is 10.0；
2, the EDTA-2Na aqueous solution 1.0g of 1 weight %, the aqueous solution of urea 0.5g of 1 weight %, tetramethyl are sequentially added
Ethylenediamine 20.0mg, dimethyl polysiloxane 20.0mg, stirs evenly；
3, the temperature of aqueous solution is controlled at 20 DEG C, is led to nitrogen flooding oxygen after 30 minutes, is added the potassium peroxydisulfate of 0.1 weight %
The aqueous solution of sodium bisulfite 2.0g of aqueous solution 4.0g and 0.1 weight %, initiation reaction stop after continuing logical nitrogen 5min, close
Polymerization reaction of being honored as a queen 6 hours；
4, blob of viscose is taken out, it is small to be hydrolyzed 2.5 at 85 DEG C after mixing for addition 0.3g sodium hydroxide grain alkali after granulation
When；
5, taking-up micelle is granulated again, drying to constant weight, crushing, sieving obtains white granular polymer-like at 60 DEG C
Product.
Test result: the molecular weight of polymer samples is 21,000,000, apparent viscosity 20.5mPas, and surface tension is
68.24mN/m。
There is surface using what method of the invention was prepared it can be seen from the result of above-described embodiment and comparative example
The polymer molecular weight of active function is big and has excellent surface-active and resisting high temperature, high salt performance.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of polymer with surface active function, which is characterized in that the polymer contains structural unit A, structural unit B
With structural unit C, wherein the structural unit A is the structural unit with structure shown in formula (1), and the structural unit B is tool
There is the structural unit of structure shown in formula (2), the structural unit C is the structural unit with structure shown in formula (3)；Wherein, with
On the basis of the weight of the polymer, the content of the structural unit A is 55-89.9 weight %, the content of the structural unit B
For 10-40 weight %, the content of the structural unit C is 0.1-5 weight %, and the viscosity average molecular weigh of the polymer is 2200
Ten thousand -3,200 ten thousand；
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3For the alkylidene of C1-C14；R4And R5It is each independently
The alkyl of H or C1-C4, and R4And R5It is not simultaneously H；M is H, Na or K；R6For the alkyl of H or C1-C4；R7For H or SO3Y, Y are
H, Na or K；M is the integer of 7-13, and n is the integer of 6-15.
2. polymer according to claim 1, wherein on the basis of the weight of the polymer, the structural unit A's
Content is 57-84.9 weight %, and the content of the structural unit B is 15-40 weight %, and the content of the structural unit C is
0.1-3 weight %, the viscosity average molecular weigh of the polymer are 24,000,000-3,000 ten thousand.
3. polymer according to claim 1, wherein the structural unit A is the structure list with structure shown in formula (7)
Member, the structural unit B are structural unit with structure shown in formula (8) and the structural unit C for formula (9) institute
Show structural unit, the structural unit with structure shown in formula (10), the structural unit with structure shown in formula (11), the tool of structure
There are the structural unit of structure shown in formula (12) and at least one of the structural unit with structure shown in formula (13),
Wherein, each R7It is identical or different, it is each independently H, SO3Na or SO3H。
4. a kind of preparation method of the polymer with surface active function, this method comprises: in initiator and as solvent
In the presence of water, monomer D, monomer E and monomer F is made to carry out solution polymerization, wherein the monomer D is with shown in formula (4)
The monomer of structure, the monomer E are the monomer with structure shown in formula (5), and the monomer F is with structure shown in formula (6)
Monomer, wherein the dosage of the monomer D, monomer E and monomer F make the content of structural unit A in the polymer being prepared to be
The content of 55-89.9 weight %, structural unit B are 10-40 weight %, and the content of structural unit C is 0.1-5 weight %, and
So that the viscosity average molecular weigh for the polymer being prepared is 22,000,000-3,200 ten thousand；The structural unit A is with shown in formula (1)
The structural unit of structure, the structural unit B be the structural unit with structure shown in formula (2), the structural unit C be with
The structural unit of structure shown in formula (3),
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3For the alkylidene of C1-C14；R4And R5It is each independently
The alkyl of H or C1-C4, and R4And R5It is not simultaneously H；M is H, Na or K；R6For the alkyl of H or C1-C4；R7For H or SO3Y, Y are
H, Na or K；M is the integer of 7-13, and n is the integer of 6-15.
5. according to the method described in claim 4, wherein, what the dosage of the monomer D, monomer E and monomer F to be prepared
The content of structural unit A is 57-84.9 weight % in polymer, and the content of structural unit B is 15-40 weight %, structural unit C
Content be 0.1-3 weight %, and make the polymer being prepared viscosity average molecular weigh be 24,000,000-3,000 ten thousand.
6. according to the method described in claim 4, wherein, the monomer D is the monomer with structure shown in formula (14)；The list
Body E is the monomer with structure shown in formula (15)；The monomer F is monomer with structure shown in formula (16), has formula (17)
The monomer of shown structure, the monomer with structure shown in formula (18), the monomer with structure shown in formula (19) and have formula (20)
At least one of the monomer of shown structure,
Wherein, each R7It is identical or different, it is each independently H, SO3Na or SO3H。
7. method according to any one of claims 4 to 6, wherein the condition of the solution polymerization includes: temperature
Degree is 0-30 DEG C, preferably 0-20 DEG C；Time is 2-15h, preferably 5-10h.
8. method according to any one of claims 4 to 6, wherein the initiator includes azo-initiator, mistake
At least one of oxide-based initiator and redox type initiators；The azo-initiator is selected from two isobutyric acid of azo
Dimethyl ester, azo-bis-isobutyrate hydrochloride, azodicarbonamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano
Formamide, azo diisopropyl imidazoline hydrochloride, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azo two
At least one of isobutyl cyanide and azobisisoheptonitrile；The peroxide type initiators are selected from hydrogen peroxide, ammonium persulfate, mistake
At least one of sodium sulphate, potassium peroxydisulfate, benzoyl peroxide and benzoyl peroxide；The redox class is drawn
Send out agent in sulfate-sulphite, persulfate-thiocarbamide, persulfate-organic salt and ammonium persulfate-fatty amine extremely
Few one kind.
9. the polymer with surface active function that method described in any one of claim 4-8 is prepared.
10. the polymer described in any one of claim 1-3 and 9 with surface active function is as polymer oil-displacing agent
Application.
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| CN103665260A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Heat resistance and salt tolerance polymer for oil displacement and preparation method thereof |
| CN104650301A (en) * | 2013-11-15 | 2015-05-27 | 中国石油化工股份有限公司 | Acrylamide copolymer and its preparation method and use |
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| CN103665260A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Heat resistance and salt tolerance polymer for oil displacement and preparation method thereof |
| CN104650301A (en) * | 2013-11-15 | 2015-05-27 | 中国石油化工股份有限公司 | Acrylamide copolymer and its preparation method and use |
Non-Patent Citations (1)
| Title |
|---|
| "Preparation and Properties of Polystyrene Model Colloids I. Preparation of Surface-Active Monomer and Model Colloids Derived Therefrom";Sheng-Liang Tsaur et al;《Journal of Colloid and Interface Science》;19870228 |
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