CN103788295B - A kind of two-step method prepares the method for acrylamide based copolymer - Google Patents
A kind of two-step method prepares the method for acrylamide based copolymer Download PDFInfo
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Abstract
The present invention relates to a kind of method preparing acrylamide copolymer, the method uses new type low temperature oxidoreduction composite initiation system acrylamide triggered (AM), 2 acrylamidos 2 methyl propane sulfonic acid (AMPS) and allylthiourea to carry out aqueous solution adiabatic polymerisation, hydrolyze after pelletize of blob of viscose, be dried after secondary granulation after hydrolysis, pulverize, sieve and obtain acrylamide copolymer.The acrylamide copolymer of the present invention has good high-temperature oxidation resistance.The invention discloses a kind of antioxidant POLYACRYLAMIDE FLOODING agent and preparation method thereof.
Description
Technical field
The present invention relates to a kind of acrylamide copolymer preparation method.
Background technology
Petroleum works and the development of technology, it is desirable to farthest improve the recovery ratio in existing oil field.As
Main polymer oil-displacing agent, partially hydrolyzed polyacrylamide (PHPA) (HPAM) is in conventional oil reservoir tertiary oil recovery
(EOB) in technology, obtained large-scale promotion and application, played important for oilfield stable production and volume increase
Effect.Along with the minimizing of conventional reservoir reserve, it is all that high temperature and high salt oil deposit makes the application of HPAM be faced with
Many difficult problems, dissolved oxygen conditions in high temperature, high salt and solution when being mainly reflected in exploitation high temperature and high salt oil deposit
The compound action produced makes HPAM solution viscosity be greatly reduced, and causes HPAM oil displacement efficiency not show
Write.Research shows, when temperature is higher than 70 DEG C, the reaction that the amide groups hydrolysis of HPAM generates carboxyl is notable
Aggravation, when degree of hydrolysis reaches more than 40%, carboxyl is just easy to and Ca in solution2+、Mg2+Ion generates
Precipitation, makes solution viscosity lose.Additionally, at high temperature, dissolve present in oxygen in air and solution
Oxygen can cause main polymer chain fracture to make solution viscosity be remarkably decreased.
With acrylamide (AM) and heat-resistant salt-resistant monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS)
Copolymerization bipolymer relatively HPAM in heat-resistant salt-resistant performance increases really.As entitled
" the low temperature synthesis of AMPS/AM copolymer and performance " (Chang Zhiying, polymer material science and engineering,
1997,13,16) report the low temperature using oxidation-reduction trigger system to carry out AMPS/AM to be total to
Aggregating into, the viscosity-average molecular weight obtaining copolymer is 106～107.It is entitled that " partial hydrolysis method prepares high score
Son amount water solublity (acrylamide/acrylic acid/2-acrylamide-2-methylpro panesulfonic acid) terpolymer "
(Zhu Linyong, macromolecule journal, 2000,3,315), use low temperature hydrolysis reaction, by AM and AMPS
Copolymer synthetic molecular weight is 106Terpolymer.Above two method, either copolymerization method is still
Polymer molecular weight (the ＜ 10 the most on the low side that copolymerization co-hydrolysis obtains7), it is difficult to be applicable to high temperature and high salt
Oil reservoir.Additionally, how to ensure that copolymer has stronger heat resistanceheat resistant oxygen degradation property in oil recovery process, it is
Can this base polymer be applied to the key of three class oil reservoir tertiary oil recoveries.
From the point of view of thermal-oxidative degradation formation mechenism, the residual initiators of polymerization process, the dissolved oxygen of process for preparation,
The metal ion that preparation container and feed-line etc. introduce all may produce with the sulfide in on-the-spot sewage
Living radical makes HPAM main polymer chain that chain fracture to occur, and makes molecular weight and molecular weight.And with temperature
Raising, this free radical cracking effect aggravates all the more, makes polymer solution viscosity damage the most in a large number
Lose, thus lose use value.For weakening the negative shadow that this free radical cracking effect brings to solution viscosity
Ring, generally in synthesis or process for preparation, add various stabilizer.Wherein, in order to improve the anti-of HPAM
Oxygen performance, conventional method is to add little molecule, such as Thiourea antioxygen in the course of processing or during using
Stabilizer etc..Owing to little stabilizer molecule and macromolecule oil-displacing agent physicochemical properties exist very big difference,
In blowhole flow event, chromatographic fractionation effect occurs, cause stabilizer to add in actual use
Greatly and service efficiency is low to add consumption.JP74-27660 discloses and adds two sulfur before HPAM micelle is dried
For the little stabilizer molecule of slaine of amido class, it is possible to prevent product crosslinking and degraded.In this invention, by
It is physical blending between the little stabilizer molecule of slaine and the HPAM of dithio amido class, makes actual
There will be during with and chromatographic fractionation effect between little stabilizer molecule and macromolecule oil-displacing agent, can be produced, cause
Stabilizing agent dosage is big and service efficiency is low.
Therefore, improve oil displacement agent antioxygen property under the high temperature conditions the most further to be still one and need badly and change
Kind problem.
Summary of the invention
It is an object of the invention to overcome the defect of above-mentioned prior art, it is provided that a kind of super high molecular weight, high temperature
Acrylamide copolymer that lower antioxygen property is good and its preparation method and application.
In flooding polymers field, introducing on macromolecular chain by antioxidant group by copolymerization mode, raising is driven
The antioxygen property of oil polymer, there is not yet relevant report, does not more report and applies it to acrylamide
And the copolymerization of heat-resistant salt-resistant monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) copolymerization (AM)
Thing.The present inventor finds through numerous studies, by allylthiourea, acrylamide and 2-acrylamido
-2-methyl propane sulfonic acid salt carries out copolymerization, makes the group with antioxygen function be connected on main polymer chain,
Keep high molecular same of existing acrylamide-2-acrylamide-2-methylpro panesulfonic acid copolymer
Time, improve the service efficiency of antioxidant group, copolymer antioxidant under the high temperature conditions is greatly improved
Energy.In actual use, owing to passing through covalent bonding between antioxidant group and main polymer chain,
Do not have the chromatographic fractionation effect used between the little stabilizer molecule of physical blending and macromolecule oil-displacing agent.
Find based on above, complete the present invention.
First aspect present invention provides a kind of acrylamide copolymer, and this acrylamide copolymer contains formula
(11) the construction unit E of structure shown in, the construction unit F of structure shown in formula (12), formula (13)
The construction unit H of structure shown in the construction unit G of shown structure and formula (14), in each structural formula,
R1For C1～C4Alkylidene；R2For C1～C4Alkyl, R3For C1～C4Alkyl, R2With R3
Identical or different；M1For sodium or potassium.
Formula (11),
Formula (12)
Formula (13)Formula (14)
Second aspect present invention provides the preparation method of a kind of acrylamide copolymer,
Comprise the following steps:
The first step, prepares the first monomer mixture solution, regulates pH to 5-10 with inorganic alkaline compound,
Obtain second comonomer mixture solution, under the conditions of solution polymerization, in the presence of initiator, make
Two monomer mixtures carry out polyreaction, obtain acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt
/ allylthiourea copolymer colloid；
Described first monomer mixture contains monomer A, monomer B and monomer C, and described monomer A is tool
Having the monomer of structure shown in formula (1), described monomer B is for having the monomer of structure, institute shown in formula (2)
State monomer C for having the monomer of structure shown in formula (3), described second comonomer mixture contain monomer A,
Monomer D and monomer C, described monomer A are for having the monomer of structure shown in formula (1), described monomer D
For having the monomer of structure shown in formula (4), described monomer C for having the monomer of structure shown in formula (3),
In each structural formula, R1For C1～C4Alkylidene；R2For C1～C4Alkyl, R3For C1～C4's
Alkyl, R2With R3Identical or different；M1For sodium or potassium；
Formula (1),
Formula (2),
Formula (3),
Formula (4),
Second step, the acrylamide that the first step is obtained/2-acrylamide-2-methylpro panesulfonic acid salt/alkene
After propylthio urea copolymer granulating from colloid becomes micelle, contact with alkali metal hydroxide, then through granulating and drying
Crush and screen and obtain acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/acrylates/allyl
Base thiourea quadripolymer.
The viscosity-average molecular weight more than 20,000,000 of the described acrylamide quadripolymer obtained, each structural formula
In, R1For C1～C4Alkylidene；R2For C1～C4Alkyl, R3For C1～C4Alkyl, R2
With R3Identical or different；M1For sodium or potassium.
In described first monomer mixture, the molar content of described monomer A is 1～99 part, described list
The molar content of body B is 0.1～98 part, and the molar content of described monomer C is 0.001～5 part；Excellent
Selection of land, the molar content of described monomer A is 60～97.5 parts, the molar content of described monomer B be 1～
39 parts, the molar content of described monomer C is 0.01～1.5 part；The condition of described solution polymerization makes
After polyreaction resulting polymers viscosity-average molecular weight 30,000,000～35,000,000, preferably 32,000,000～
33500000.
Third aspect present invention provides the above-mentioned acrylamide copolymer of the present invention answering as oil displacement agent
With.
The acrylamide copolymer of the present invention has high viscosity-average molecular weight, prepares acryloyl in embodiment 1
The viscosity-average molecular weight of amine copolymer thing all can reach more than 30,000,000；The apparent viscosity of 95 DEG C is 20.1mPa s,
Apparent viscosity retention rate (the O of 3 months2Content is 8mg/L) it is 88.3%, and identical in other conditions
In the case of, monomer mixture there is no the acrylamide that the comparative example 1 of allylthiourea prepares altogether
Polymers viscosity-average molecular weight be the apparent viscosity of 28,500,000,95 DEG C be 16.2mPa s, 3 months apparent viscosities
Retention rate (O2Content is 8mg/L) it is only 16.7%.Illustrate that the acrylamide copolymer of the present invention has concurrently
Good antioxygen property and high apparent viscosity, it is possible to realize good oil displacement efficiency.
Detailed description of the invention
The invention provides a kind of acrylamide copolymer, this acrylamide copolymer contains formula (1) institute
Show the construction unit E of structure, the construction unit F of structure shown in formula (2), structure shown in formula (3)
The construction unit H of structure shown in construction unit G and formula (4), gluing all of described acrylamide copolymer
Molecular weight is more than 20,000,000；
The viscosity-average molecular weight of described acrylamide copolymer is more than 20,000,000；
Formula (1),
Formula (2)
Formula (3)Formula (4)
In each structural formula, R1For C1～C4Alkylidene；R2For C1～C4Alkyl, R3For C1~
C4Alkyl, R2With R3Identical or different；M1For sodium or potassium.
In the present invention, described C1～C4The example of alkylidene can include but not limited to: methylene,
Ethylidene, sub-n-pro-pyl, isopropylidene, sub-normal-butyl, sub-sec-butyl, isobutylidene and the sub-tert-butyl group,
It is preferably methylene.Described alkylidene refer to alkane lose two hydrogen atoms after residue, said two hydrogen
Atom can be two hydrogen atoms on same carbon atom, it is also possible to two hydrogen on different carbon atoms are former
Son, can be straight chain, it is also possible to be side chain, and such as, described ethylidene can be-CH2CH2-
Or-CH (CH3)-。
In the present invention, described alkyl can be straight chain, it is also possible to be side chain.Described C1～C4's
The example of alkyl can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, secondary
Butyl, isobutyl group, the tert-butyl group.
According to the present invention, wherein, E, F, G, the content of H structure unit are not important to by the present invention
Ask, it is preferable that in described acrylamide copolymer, the molal quantity ratio in construction unit is, described knot
Structure unit E is 1～99 part, and described construction unit F is 0.1～98 part, and described construction unit G is
0.001～5 part；Described construction unit H is 0.1～40 part；Preferably, described construction unit E is
50～92.5 parts, described construction unit F is 1～39 part, and described construction unit G is 0.01～1.5 part；
Described construction unit H is 5～30 parts；The viscosity-average molecular weight of described acrylamide copolymer be 30,000,000～
35000000, preferably 32,000,000～33,500,000.
The present inventor finds under study for action, by specific construction unit E, construction unit F, knot
The quadripolymer of structure unit G and construction unit H composition can obtain the preferable displacement of reservoir oil when oil displacement agent
Effective.Work as R1For methylene；R2And R3Identical, for methyl；M1、M2It is identical, for sodium, i.e.
Construction unit B is that 2-acrylamide-2-methylpro panesulfonic acid sodium polymerization obtains, and construction unit D is propylene
When acid sodium polymerization obtains, oil displacement efficiency is good.
Present invention also offers the preparation method of a kind of acrylamide copolymer,
Comprise the following steps:
The first step, prepares the first monomer mixture solution, regulates pH to 5-10 with inorganic alkaline compound,
Obtain second comonomer mixture solution, under the conditions of solution polymerization, in the presence of initiator, make
Two monomer mixtures carry out polyreaction, obtain acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt
/ allylthiourea copolymer colloid；
Described first monomer mixture contains monomer A, monomer B and monomer C, and described monomer A is tool
Having the monomer of structure shown in formula (1), described monomer B is for having the monomer of structure, institute shown in formula (2)
State monomer C for having the monomer of structure shown in formula (3), described second comonomer mixture contain monomer A,
Monomer D and monomer C, described monomer A are for having the monomer of structure shown in formula (1), described monomer D
For having the monomer of structure shown in formula (4), described monomer C for having the monomer of structure shown in formula (3),
In each structural formula, R1For C1～C4Alkylidene；R2For C1～C4Alkyl, R3For C1～C4's
Alkyl, R2With R3Identical or different；M1For sodium or potassium；
Formula (1),
Formula (2),
Formula (3),Formula (4),
Second step, the acrylamide that the first step is obtained/2-acrylamide-2-methylpro panesulfonic acid salt/alkene
After propylthio urea copolymer granulating from colloid becomes micelle, contact with alkali metal hydroxide, then through granulating and drying
Crush and screen and obtain acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/acrylates/allyl
Base thiourea quadripolymer.
The viscosity-average molecular weight more than 20,000,000 of the described acrylamide quadripolymer obtained, each structural formula
In, R1For C1～C4Alkylidene；R2For C1～C4Alkyl, R3For C1～C4Alkyl, R2
With R3Identical or different；M1For sodium or potassium.Preferably, R1For methylene；R2And R3It is methyl；
M1For sodium.That is, monomer B is 2-acrylamide-2-methylpro panesulfonic acid sodium.
According to the present invention, although the present invention does not has special wanting to the consumption of described monomer A, B, C and D
Asking, it is preferable that in described first monomer mixture, the molar content of described monomer A is 1～99
Part, the molar content of described monomer B is 0.1～98 part, the molar content of described monomer C be 0.001～
5 parts；Preferably, the molar content of described monomer A is 60～97.5 parts, described monomer B mole
Content is 1～39 part, and the molar content of described monomer C is 0.01～1.5 part；Described polymerisation in solution is anti-
The condition answered makes the viscosity-average molecular weight 30,000,000～35,000,000 of resulting polymers after polyreaction, preferably
It is 32,000,000～33,500,000.
According to the present invention, the condition of described polyreaction can be the condition that this area is conventional.Such as, institute
Stating polyreaction to carry out in the presence of an inert gas, described polymeric reaction condition may include that temperature is-10
DEG C to 20 DEG C, the time is 1～20 hour, and pH value is 4～12；Under preferable case, temperature is-7 DEG C
To 15 DEG C, the time is 2～10 hours, and pH value is 6～9.
In the present invention, the B in described monomer mixture can be by sulfonic acid corresponding for monomer B and inorganic alkaline
Compound reaction obtains.Described alkali inorganic alkaline compound can be selected from sodium hydroxide, potassium hydroxide, carbon
At least one in acid sodium, preferably sodium hydroxide.
According to the present invention, described initiator can be the various initiator in this area.Such as, selected from azo
Initiator and/or oxidoreduction body class initiator, preferably azo-initiator and oxidoreduction body class draw
Send out agent.On the basis of described 100 weight portion the first monomer mixtures, the consumption of described azo initiator is
0.0001～0.1 weight portion, preferably 0.001～0.05 weight portion.
In the present invention, it is preferable that described azo-initiator selected from azodiisobutyronitrile, 4,4 '-azo is double
(4-cyanopentanoic acid), 2,2 '-azo diisobutyl amidine hydrochlorate and azo diimidazole quinoline base propane dihydrochloride
In at least one, more preferably 4,4 '-azo double (4-cyanopentanoic acid), 2,2 '-azo diisobutyl
At least one in amidine hydrochlorate and azo diimidazole quinoline base propane dihydrochloride.
Described redox type initiators includes Oxidizing and Reducing Agents, single with described 100 weight portions first
On the basis of body mixture, consumption 0.0001～0.1 weight portion of described oxidant, more preferably
0.001～0.05 weight portion；Under preferable case, described oxidant is selected from Ammonium persulfate., potassium peroxydisulfate, mistake
At least one in sodium sulfate and hydrogen peroxide, more preferably Ammonium persulfate., potassium peroxydisulfate and over cure
At least one in acid sodium；Described reducing agent can be inorganic reducing agent (helping reducing agent) and/or organic also
Former dose (chain extender), preferably inorganic reducing agent (helping reducing agent) and organic reducing agent (chain extender)
Mixing reducing agent, on the basis of described 100 weight portion the first monomer mixtures, wherein, described inorganic
The consumption of reducing agent is 0.0001～0.1 weight portion, preferably 0.001～0.05 weight portion；Described inorganic
Reducing agent can be selected from sodium sulfite, sodium sulfite, rongalite, sodium thiosulfate, ferrous sulfate,
At least one in sodium hydrosulfite, ascorbic acid and urea, more preferably sodium sulfite and/or sulfurous acid
Sodium；
On the basis of described 100 weight portion the first monomer mixtures, the consumption of described organic reducing agent is
0.0001～0.1 weight portion, preferably 0.001～0.05 weight portion；The concrete reality of described organic reducing agent
Example can be, but not limited to as N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, N-dimethyl piperazine
Piperazine, N, N '-dimethyl piperazine, tetramethylurea element, N, N-dimethyl urea element, N, N, N ', N '-tetramethyl second
Diamidogen, N, N '-dimethyl ethylenediamine, N, N '-dimethyl-1,3-propane diamine, 3-methylamino propylamine and N, N-
At least one in dimethyl-ethylenediamine；More preferably N, N '-dimethyl-1,3-propane diamine and
N, N, N ', at least one in N '-tetramethylethylenediamine, more preferably N, N, N ', N '-tetramethylethylenediamine；
Described inorganic alkaline compound is sodium hydroxide or potassium hydroxide.
In the preferred embodiment of the present invention, described initiator is 2,2 '-azo diisobutyl amidine salt
Hydrochlorate, sodium peroxydisulfate, sodium sulfite and N, N, N ', N '-tetramethylethylenediamine.
According to the present invention, when described polyreaction starts, the weight of described first monomer mixture and water and
The ratio of the gross weight of described first monomer mixture is preferably 0.15～0.4:1, more preferably
0.2～0.3:1.
According to the present invention, the present invention may also include the acrylamide copolymer prepared is hydrolyzed,
Pelletize, it is dried, crushes and screens and packs.Wherein said pelletize, it is dried, pulverizes, sieves and packs
It is the ordinary skill in the art.
According to the present invention, described hydrolysising condition includes: hydrolysis temperature is 50～110 DEG C, and hydrolysis time is
0.5～6h, more preferably hydrolysis temperature is 55～105 DEG C, and hydrolysis time is 1～5.5h；More enter
One step selective hydrolysis temperature is 70～90 DEG C；Hydrolysis time is 1～4 hour.
According to the present invention, the present invention to dry method and condition without particular/special requirement, under preferable case, can
To use hot-air seasoning, described hot air drying temperature is 40～110 DEG C, preferably 70～90 DEG C；Heat
The air-dried dry time is 0.2～4 hour, preferably 0.5～2 hour.
The present invention one preferred embodiment in, the preparation method bag of described acrylamide copolymer
Include following steps:
(1) by acrylamide, 2-acrylamide-2-methylpro panesulfonic acid and allylthiourea and deionization
Water mixes, and being made into acrylamide, 2-acrylamide-2-methylpro panesulfonic acid and allylthiourea total concentration is
The solution (that is, the first monomer mixture solution) of 20～30 weight %, control solution temperature-10～20 DEG C,
It is preferably 6～9 with inorganic alkaline compound regulation pH to 4～12(), obtain acrylamide, 2-propylene
Amide groups-2-methyl propane sulfonic acid salt and allylthiourea monomer solution (that is, second comonomer mixture solution)；
(2) acrylamide, 2-acrylamide-2-methylpro panesulfonic acid salt and alkene step (1) obtained
Propyl group thiourea monomer solution pumps in polymeric kettle, adds water-soluble azo initiator and amine reduction auxiliary agent,
Logical high pure nitrogen deoxygenation (time of being passed through is 0.5～2 hour), adds sulphite and persulfate, continues
Continue logical nitrogen until thermocouple starts to warm up in polymeric kettle, be-10 DEG C to 20 DEG C (preferably-7 DEG C in temperature
To 15 DEG C) response time 1～20 hours (preferably 2～10 hours), obtain acrylamide copolymer；
(3) by comminutor, the acrylamide copolymer granulating from colloid that step (2) obtains is become 4～6
The little micelle of millimeter, under hydrolysising condition, obtains acrylamide copolymer and inorganic alkaline chemical combination by polymerization
Thing contacts, and hydrolysis temperature is 50～110 DEG C, and hydrolysis time is 0.5～6 hour.
(4) copolymer colloid that step (3) is obtained under the conditions of 40～110 DEG C of hot blasts be dried 0.2～
4 hours, by crushing and screening and be packaged to be powdery acrylamide copolymer.
Present invention also offers the acrylamide copolymer prepared according to said method.
Additionally, present invention also offers the application in oil displacement agent of the described acrylamide copolymer.
Below, by following example, the present invention will be described in more detail
In following example, the performance test of product uses following methods to carry out:
Solid content is measured according to the method for regulation in GB12005.2-89；
Dissolution time is measured according to the method for regulation in GB12005.8-89；
Intrinsic viscosity is measured according to the method for regulation in GB12005.1-89；
Formula M=([η]/K) is used according to the method for regulation in GB12005.10-921/αCalculate polymer
Viscosity-average molecular weight, wherein, K=4.75 × 10-3, α=0.80, [η] is intrinsic viscosity；
Degree of hydrolysis is measured according to the method for regulation in GB12005.6-89；
The apparent viscosity of aqueous solutions of polymers is to measure with Brookfield viscometer at a temperature of 95 DEG C；
Measure according to Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard Q/SH1020 1572-2006
The filtration ratio of the aqueous solution of polymer, insolubles content and acrylamide residual monomer content；
Polymer solution antioxygen thermal ageing test method includes: will be poly-with the saline of salinity 32000mg/L
Compound is made into the solution of 1500mg/L, by oxygen content in solution except to required value, the polymer that will obtain
Solution is at a temperature of 95 DEG C, after aging 3 months, measures polymer solution with Brookfield viscometer and exists
The apparent viscosity of 95 DEG C, with below equation calculate apparent viscosity retention ratio:
Apparent viscosity retention rate %=aging post-consumer polymer solution apparent viscosity/aging prepolymer solution table
See viscosity × 100%；
In following example, acrylamide is commercially available from Bao Mo biochemical industry limited company, 2-acryloyl
Amido-2-methyl propane sulfonic acid commercially available from Xiamen Changtian Enterprise Co., Ltd., 2,2 '-azo (2-amidine propane) two
Hydrochlorate is commercially available from Aldrich, and allylthiourea is commercially available from Aldrich company limited.
Embodiment 1
The present embodiment is used for acrylamide copolymer according to the present invention and preparation method thereof is described.
Batching kettle adds 869.56 kilograms of (12.233kmol) acrylamides, 1647.86 kilogram (7.951
Kmol) 2-acrylamide-2-methylpro panesulfonic acid and 23.68 kilograms of (2.038mol) allylthioureas,
5929 kilograms of deionized waters, under stirring, control solution temperature-7 DEG C with chilled brine, add hydrogen-oxygen
Change sodium regulation pH to 6.Monomer solution is pumped in polymeric kettle, add water-soluble azo initiator 2,2 '-
Azo (2-amidine propane) dihydrochloride 12.706 grams and reduction auxiliary agent N, N, N ', N '-tetramethylethylenediamine
12.706 grams, logical high pure nitrogen deoxygenation 0.5h, add sodium sulfite 12.706 grams and Ammonium persulfate. 12.706
Gram, continue logical nitrogen until thermocouple starts to warm up in polymeric kettle, response time 10h, obtain acrylamide
Copolymer (that is, acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/allylthiourea ternary polymerization
Thing).Open Polycondensation Reactor and Esterification Reactor ball valve, by 0.3MPa compressed air, the acrylamide copolymer obtained extruded,
The little micelle of 4～6 millimeters is become by granulator granulation.The little micelle obtained and 81.55 kg of hydrogen are aoxidized
Sodium grain alkali mediates contact, hydrolyzes 1h, after secondary granulation, 70 DEG C of hot blast conditions under temperature 70 C
Under be dried 2h, by crushing and screening and be packaged to be the acrylamide/2-acrylamido of 20～80 mesh
-2-methyl propane sulfonic acid sodium/sodium acrylate/allylthiourea quadripolymer.Properties of product are as follows: admittedly contain
Amount >=89%, dissolution time is less than 2h, in salinity 32000mg/L, temperature 95 DEG C, concentration 1500mg/L,
Apparent viscosity 20.1mPa s, filtration ratio 1.1, insolubles content 0.05%, acrylamide residual monomer
0.01%.Wherein viscosity-average molecular weight, apparent viscosity, the data of monomer remnants amount are shown in Table 1, different
Under oxygen content, Heat Aging Viscosity apparent viscosity retention rate is shown in Table 2.
Comparative example 1
Use method same as in Example 1 to prepare acrylamide copolymer, except for the difference that, do not add alkene
Propyl group thiourea, obtains acrylamide copolymer (that is, acrylamide/2-acrylamide-2-methylpro panesulfonic acid
Sodium/sodium acrylate terpolymer) properties of product as follows: solid content >=89%, dissolution time be less than 2h,
Apparent viscous in the saline that salinity 32000mg/L, temperature are 95 DEG C and when concentration is 1500mg/L
Degree 16.0mPa s, filtration ratio 1.0, insolubles content 0.15%, acrylamide residual monomer 0.06%.
Wherein viscosity-average molecular weight, apparent viscosity, the data of monomer remnants amount are shown in Table 1, under different oxygen
Apparent viscosity retention rate is shown in Table 2.
Embodiment 2
The present embodiment is used for acrylamide copolymer according to the present invention and preparation method thereof is described.
1530 kilograms of acrylamides, 45.752 kilograms of 2-acrylamido-2-methyl are added in batching kettle
Propane sulfonic acid and 6457 kilograms of deionized waters of 38.477 kilograms of allyl sulfides, under stirring, with freezing salt
Water management solution temperature 15 DEG C, adds sodium hydroxide regulation pH to 9.Monomer solution is pumped into polymeric kettle
In, add water-soluble azo initiator 2,2 '-azo (2-amidine propane) dihydrochloride 807.11 grams and reduction
Auxiliary agent N, N, N ', N '-tetramethylethylenediamine 807.11 grams, logical high pure nitrogen deoxygenation 0.5h, add sulfurous acid
807.11 grams of hydrogen sodium and Ammonium persulfate. 807.11 grams, continue logical nitrogen until thermocouple starts to rise in polymeric kettle
Temperature, response time 2h, obtain acrylamide copolymer.Open Polycondensation Reactor and Esterification Reactor ball valve, press with 0.3MPa
The acrylamide copolymer obtained is extruded by contracting air, is become the little glue of 4～6 millimeters by granulator granulation
Grain.The little micelle obtained and 44.15 kilogram sodium hydroxide grain alkali are mediated contact, water under temperature 70 C
Solve 1h, after secondary granulation, under the conditions of 70 DEG C of hot blasts, be dried 2h, by crushing and screening and packing
Acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate/allyl to 20～80 mesh
Base thiourea quadripolymer.Properties of product are as follows: solid content >=89%, and dissolution time is less than 2h, in ore deposit
Change degree 32000mg/L, temperature 95 DEG C, concentration 1500mg/L, apparent viscosity 21.0mPa s, filtration ratio
1.1, insolubles content 0.05%, acrylamide residual monomer 0.02%.Wherein viscosity-average molecular weight, apparent
Viscosity, the data of monomer remnants amount are shown in Table 1, and under different oxygen, Heat Aging Viscosity apparent viscosity is protected
Rate is stayed to be shown in Table 2.
Embodiment 3
The present embodiment is used for acrylamide copolymer according to the present invention and preparation method thereof is described.
1200 kilograms of acrylamides, 874.21 kilograms of 2-acrylamido-2-methyl are added in batching kettle
Propane sulfonic acid and 0.245 kilogram of allylthiourea, 5186.13 kilograms of deionized waters, under stirring, with cold
Freeze salt water management solution temperature 0 DEG C, add sodium hydroxide regulation pH to 7.Monomer solution is pumped into polymerization
In still, add water-soluble azo initiator 2,2 '-azo (2-amidine propane) dihydrochloride 188.9 grams and also
Former auxiliary agent N, N, N ', N '-tetramethylethylenediamine 188.9 grams, logical high pure nitrogen deoxygenation 0.5h, add sulfurous
188.9 grams of hydrogen sodium of acid and Ammonium persulfate. 188.9 grams, continue logical nitrogen until thermocouple starts to rise in polymeric kettle
Temperature, response time 4h, obtain acrylamide copolymer.Open Polycondensation Reactor and Esterification Reactor ball valve, press with 0.6MPa
The acrylamide copolymer obtained is extruded by contracting air, is become the little glue of 4～6 millimeters by granulator granulation
Grain.The little micelle obtained and 253.24 kilogram sodium hydroxide grain alkali are mediated contact, at temperature 85 DEG C
Hydrolysis 1.5h, after secondary granulation, is dried 2h, by crushing and screening and wrapping under the conditions of 70 DEG C of hot blasts
Dress obtain the acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate of 20～80 mesh/
Allylthiourea quadripolymer.Properties of product are as follows: solid content >=89%, and dissolution time is less than 2h,
In salinity 32000mg/L, temperature 95 DEG C, concentration 1500mg/L, apparent viscosity 21.8mPa s, filter
Cross ratio 1.1, insolubles content 0.02%, acrylamide residual monomer 0.03%.Wherein viscosity-average molecular weight,
Apparent viscosity, the data of monomer remnants amount are shown in Table 1, apparent viscosity retention ratio row under different oxygen
In table 2.
Embodiment 4
The present embodiment is used for acrylamide copolymer according to the present invention and preparation method thereof is described.
Using method same as in Example 1 to prepare, except for the difference that, initiator uses 2,2 '-azo (2-
Amidine propane) dihydrochloride 12.706 grams, sodium sulfite 12.706 grams and Ammonium persulfate. 12.706 grams,
Wherein, the properties of product of the acrylamide copolymer granule obtained are as follows: solid content >=89%, during dissolving
Between less than 2h, in the saline that salinity 32000mg/L, temperature are 95 DEG C and concentration is 1500mg/L
Time apparent viscosity 15.8mPa s, filtration ratio 1.0, insolubles content 0.06%, acrylamide remnants are mono-
Body 0.06%.Wherein viscosity-average molecular weight, apparent viscosity, the data of monomer remnants amount are shown in Table 1, no
It is shown in Table 2 with viscosity retention ratio apparent under oxygen content.
Embodiment 5
The present embodiment is used for acrylamide copolymer according to the present invention and preparation method thereof is described.
Method same as in Example 1 is used to prepare acrylamide copolymer, except for the difference that, without water
Solve, the most do not carry out the little micelle obtained and 81.55 kilogram sodium hydroxide grain alkali being pinched in embodiment 1
Splice grafting touches, and hydrolyzes the step of 1h, obtain acrylamide copolymer (that is, acryloyl under temperature 70 C
Amine/2-acrylamide-2-methylpro panesulfonic acid sodium/allylthiourea terpolymer) properties of product such as
Under: solid content >=89%, dissolution time is less than 2h, is 95 DEG C in salinity 32000mg/L, temperature
In saline and concentration is apparent viscosity 15.3mPa s during 1500mg/L, filtration ratio 1.0, insoluble matter contains
Amount 0.08%, acrylamide residual monomer 0.05%.Wherein viscosity-average molecular weight, apparent viscosity, monomer are residual
The data of surplus are shown in Table 1, and under different oxygen, apparent viscosity retention ratio is shown in Table 2.
Table 1
Table 2
In conjunction with the data of Tables 1 and 2, embodiment 1 is contrasted with embodiment 4, due to initiator
The change of kind, the viscosity-average molecular weight of the product that embodiment 1 obtains is by 28,000,000 increases of embodiment 4
To 32,500,000,95 DEG C of apparent viscosities are increased to 20.1mPa s by 16.0mPa s, and acrylamide remnants are mono-
Body burden is also reduced to 0.01 weight % by 0.06 weight %.
By embodiment 1 compared with Example 5, owing to embodiment 1 having carried out rear hydrolysis operation, altogether
Polymer configurations unit introduces sodium acrylate construction unit, and after not carrying out in embodiment 5, hydrolysis is grasped
Make, copolymer structure unit does not has sodium acrylate construction unit, gluing of the product that embodiment 1 obtains
Average molecular weight is increased to 32,500,000 by the 27500000 of embodiment 5, and 95 DEG C of apparent viscosities are by 15.3mPa s
Increasing to 20.1mPa s, acrylamide residual monomer content is also reduced to 0.01 weight by 0.18 weight %
%。
By embodiment 1 compared with comparative example 1, the present invention is used the acrylamide quaternary prepared to be total to
Polymers is compared with the acrylamide copolymer that traditional method prepares, and the viscous of the product obtained is divided equally
Son amount is increased to 32,500,000 by 28,500,000, and 95 DEG C of apparent viscosities are increased to 19.2mPa s by 16.0mPa s,
Antioxygenic property is greatly improved, such as, along with the increase of oxygen content, the acrylamide in comparative example 1/
2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate terpolymer apparent viscosity retention rate is significantly
Reduce, O2When content is 4mg/L, its apparent viscosity retention rate is 40.5%, and third in embodiment 1
Acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate/allylthiourea is quarternary copolymerized
Thing apparent viscosity retention rate is 90.2%, works as O2When content reaches saturated oxygen content 8mg/L, acryloyl
Amine/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate terpolymer apparent viscosity retention rate
It is 16.7%, and acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate/pi-allyl
Thiourea quadripolymer apparent viscosity retention rate is 88.3%.Result above shows, the third of present invention offer
Acrylamide copolymer has high apparent viscosity and non-oxidizability concurrently.
Claims (9)
1. a preparation method for acrylamide copolymer, comprises the following steps:
The first step, prepares the first monomer mixture solution, with inorganic alkaline compound regulation pH to 5～
10, obtain second comonomer mixture solution, under the conditions of solution polymerization, in the presence of initiator,
Make second comonomer mixture carry out polyreaction, obtain acrylamide/2-acrylamido-2-methyl-prop sulphur
Hydrochlorate/allylthiourea copolymer colloid；
Described first monomer mixture contains monomer A, monomer B and monomer C, and described monomer A is tool
Having the monomer of structure shown in formula (1), described monomer B is for having the monomer of structure, institute shown in formula (2)
State monomer C for having the monomer of structure shown in formula (3)；
Described second comonomer mixture contains described monomer A, monomer D and described monomer C, described monomer
D is for having the monomer of structure shown in formula (4)；
Second step, the acrylamide that the first step is obtained/2-acrylamide-2-methylpro panesulfonic acid salt/alkene
After propylthio urea copolymer granulating from colloid becomes micelle, contact with alkali metal hydroxide, then through granulating and drying
Crush and screen, obtain acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/acrylates/allyl
Base thiourea quadripolymer；
The acrylamide obtained/2-acrylamide-2-methylpro panesulfonic acid salt/acrylates/pi-allyl
Thiourea quadripolymer contains structure shown in the construction unit E of structure shown in formula (11), formula (12)
The structure list of structure shown in the construction unit G of structure shown in construction unit F, formula (13) and formula (14)
Unit H, the viscosity-average molecular weight of described acrylamide copolymer is more than 20,000,000；
In described each structural formula, R1For methylene；R2And R3It is methyl；M1For sodium；
In described first monomer mixture, the molar content of described monomer A is 60～97.5 parts, institute
The molar content stating monomer B is 1～39 part, and the molar content of described monomer C is 0.01～1.5 part；
Described initiator is azo-initiator and/or redox type initiators, with described 100 weight
On the basis of part the first monomer mixture, the consumption of described azo-initiator is 0.001～0.05 weight portion；
The consumption of the oxidant of described redox type initiators is 0.001～0.05 weight portion；Described oxidation is also
The consumption of the inorganic reducing agent of former class is 0.001～0.05 weight portion；The organic of described oxidoreduction class goes back
The consumption of former agent is 0.0001～0.05 weight portion；
At least one in following of described azo-initiator: 4,4 '-azo double (4-cyanopentanoic acid),
2,2 '-azo diisobutyl amidine hydrochlorate and azo diimidazole quinoline base propane dihydrochloride；
At least one in following of described oxidant: Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate and
Hydrogen peroxide；
At least one in following of described inorganic reducing agent: sodium sulfite, sodium sulfite, carving are white
Powder, sodium thiosulfate, ferrous sulfate and sodium hydrosulfite；
At least one in following of described organic reducing agent: N, N-dimethylethanolamine, N, N-diformazan
Base Propanolamine, N, N '-dimethyl piperazine, 4-methyl urea, N, N-dimethyl carbamide, N, N, N ', N '-
Tetramethylethylenediamine, N, N '-dimethyl ethylenediamine, N, N '-dimethyl-1,3-propane diamine, 3-methylamino third
Amine, N, N-dimethyl-ethylenediamine, ascorbic acid and urea；
Described inorganic alkaline compound is sodium hydroxide.
Preparation method the most according to claim 1, is characterized in that:
Described first step polyreaction is carried out in the presence of an inert gas, described solution polymerization condition bag
Including: temperature is-10 DEG C to 20 DEG C, the time is 1～20 hour.
Preparation method the most according to claim 1, is characterized in that:
Described first step polyreaction is carried out in the presence of an inert gas, described solution polymerization condition bag
Include: temperature is-7 DEG C to 15 DEG C；Time is 2～10 hours；PH value is 6～9.
Preparation method the most according to claim 1, is characterized in that:
Described polyreaction is carried out in water, the weight of described first monomer mixture and water and the first monomer
The ratio of the gross weight of mixture is 0.15～0.4:1.
Preparation method the most according to claim 1, is characterized in that:
Described polyreaction is carried out in water, and the weight of described first monomer mixture mixes with water and the first monomer
The ratio of the gross weight of thing is 0.2～0.3:1.
Preparation method the most according to claim 1, is characterized in that:
In second step, the temperature contacted with alkali metal hydroxide is 50～110 DEG C, the time of contact
Being 0.5～6 hour, described alkali metal hydroxide is sodium hydroxide.
Preparation method the most according to claim 1, is characterized in that:
In second step, the temperature contacted with alkali metal hydroxide is 70～90 DEG C, and the time of contact is
1～4 hour, described alkali metal hydroxide was sodium hydroxide.
8. the acrylamide copolymer that in claim 1～7, preparation method described in any one prepares.
9. the acrylamide copolymer described in claim 8 is as the application of oil displacement agent.
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