CN1086709C - Water-soluble macromolecular multi-component copolymer for oil field - Google Patents
Water-soluble macromolecular multi-component copolymer for oil field Download PDFInfo
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- CN1086709C CN1086709C CN98102465A CN98102465A CN1086709C CN 1086709 C CN1086709 C CN 1086709C CN 98102465 A CN98102465 A CN 98102465A CN 98102465 A CN98102465 A CN 98102465A CN 1086709 C CN1086709 C CN 1086709C
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- component copolymer
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Abstract
The present invention relates to a macromolecule multi-element copolymer for oilfields and a polymerization method thereof. The copolymer is characterized in that the copolymer is composed of various anion monomers, cation monomers and non ion monomers; the viscosity-average molecular weight of the copolymer is higher, wherein the viscosity-average molecular weight of an anion type copolymer is from 10000000 to 20000000, and the viscosity-average molecular weight of an amphoteric ion type copolymer of vinyl monomers is from 1000000 to 15000000. The copolymer has stronger salt resistance and strong ion pollution resistant capability of Ca<2+>, Mg<2+>, etc., and the amphoteric ion copolymer synthesized by anions and cations has the performance of inhibiting shale rock dispersion, preventing collapse and protecting well walls.
Description
Oil field of the present invention is to adopt the legal preparation of aqueous solution copolymerization by multiple negatively charged ion, positively charged ion and nonionic ethylene base monomer with macromolecular multi-component copolymer.Vinyl monomer has following expression:
1. anionic monomer:
R
1, R
2And R
3: the alkyl of H or 1～3 carbon atom;
M:H, basic metal, alkaline-earth metal or NH
4
The positive integer of m:0～3.
R
4: H or methyl;
M:H, basic metal, alkaline-earth metal or NH
4
2. cationic monomer:
R
5, R
6, R
7And R
8: the alkyl of H or 1～5 carbon atom;
A
-: halogen or BF
4And PF
6
The positive integer of n:0～3.
3. non-ionic monomer:
R
9And R
10: the alkyl of H or 1～5 carbon atom
Macromolecular multi-component copolymer of the present invention is that to be the feature monomer close reaction through aqueous solution copolymerization obtains by above I～III vinyl monomer.Adjust dissimilar monomers in multipolymer ratio and synthesize with polymerization process of the present invention, can obtain molecular weight and (be equivalent to the polyacrylamide viscosity-average molecular weight, hereinafter to be referred as molecular weight.) 3,000,000～20,000,000 multipolymer.
This analog copolymer has stronger anti-salt, anti-Ca
2+, Mg
2+The ability that plasma pollutes also shows the ability that shale disperses, prevents the formation collapse and the protection borehole wall that suppresses by negatively charged ion and positively charged ion synthetic amphoteric ion copolymer.
In the macromolecular multi-component copolymer of the present invention, the composition weight percent (Wt%) of vinyl monomer I, II and III is as follows:
0.5≤I≤90.0； 0≤II≤70.0； 5.0≤III≤95.0。
The molecular weight ranges of anionic polymer of the present invention (containing the hydrophobic type monomer): 10,000,000～20,000,000.
The ampholyte copolymer molecular weight ranges of vinyl monomer of the present invention: 1,000,000～15,000,000.
The present invention adopts aqueous solution polymerization.The polymer fluid total monomer concentration is 10%～50%, monomer solution pH value 7～12, and kick off temperature is 0～35 ℃, initiator system adopts oxidation/azo class or oxidation/reduction/azo class composite initiation system.For preventing the interference of divalent-metal ion in the polymerization system, mainly be Cu
2+To the influence of polymerization rate and molecular weight, chela and agent have been used.Be the controlled polymerization reaction process, used polyreaction promotor and vinyl monomer chain-transfer agent.For improving the water-soluble of polymkeric substance, added anti-linking agent.
In the initiator that the present invention adopts, inorganic peroxide mainly is selected from ammonium persulphate ((NH
4)
2S
2O
8), Sodium Persulfate (Na
2S
2O
8), Potassium Persulphate (K
2S
2O
8) and hydrogen peroxide (H
2O
2); Organo-peroxide mainly is selected from di-cyclohexylperoxy dicarbonate (DCPD), tertbutyl peroxide (BHP), di-isopropyl Peracetic Acid (DIPC), cyclohexanone peroxide (CHP) and methylethyl ketone peroxide (MEPK) etc.; Azo-initiator mainly is Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ADVN).When hydrophobic monomer existed, inorganic and organic oxidizing agent used simultaneously.Reductive agent is sodium bisulfite (NaHSO
3), Sulfothiorine (Na
2S
2O
35H
2O), Sodium Pyrosulfite (Na
2S
2O
5) etc.Oxygenant account for the vinyl monomer gross weight (Wt/Wt, as follows.) ratio be 0.5 * 10
-4～5.0 * 10
-3The reductive agent dosage accounts for 0.5 * 10 of total monomer weight
-5～5.0 * 10
-3The weight ratio of oxygenant and reductive agent is 10: 1～1: 1.
The used anionic monomer aqueous solution of the present invention is acid, needs to neutralize with alkali before polymerization.Generally select NH for use
4OH, LiOH, NaOH, KOH, Na
2CO
3, K
2CO
3And Ca (OH)
2All can.
The sequestrant that the present invention adopts is ethylenediamine tetraacetic acid (EDTA) (EDTA) disodium salt, and the ratio that its dosage accounts for total monomer weight is 1.0 * 10
-5～2.0 * 10
-3
The polyreaction promotor that the present invention adopts is selected from following compound:
1. organic amine:
The expression formula of the organic amine that the present invention uses:
①NH(CH
2CH
2NH)
pCH
2CH
2NH， p≥2
R, R ': the alkyl that is respectively carbonatoms 1～3;
R ": the alkyl of carbonatoms 1～3, alkylamino; Carboxyl, hydroxyl, amido,
Itrile group and sulfonic group;
The positive integer of q:1～5.
2. thiazoles:
X is H or basic metal.
The ratio that the polyreaction accelerator level accounts for total monomer weight is 0.5 * 10
-4～5.0 * 10
-31. and 2. need be used in the organic amine with certain proportion, 1.: ratio range 2.: 1: 10～10: 1.
The vinyl monomer chain-transfer agent that the present invention uses mainly is alcohol or polyvalent alcohol, for example Virahol, ethylene glycol or glycerol, and the ratio that its consumption accounts for total monomer weight is 0.5 * 10
-4～5.0 * 10
-4
The anti-linking agent that the present invention uses is urea or thiocarbamide, and the ratio that its dosage accounts for total monomer weight is 1.0 * 10
-4～5.0 * 10
-3
The following stated example in detail the present invention.In these examples, unless otherwise indicated, the umber of all vinyl monomers all by weight, percentage ratio or thousand marks of auxiliary material to account for total monomer weight.
Embodiment 1.
Add 1000 parts of deionized waters, 112 parts of acrylamides, 94 parts of 2-acrylamido-2-methyl propane sulfonic acids, 6 parts of N--isopentyl acrylamides in normal temperature condition downhill reaction still successively, fully stirring makes it to dissolve fully.Use Na
2CO
3Regulation system pH value equals 10, adds 0.02% EDTA, 0.2% urea, 0.05 ‰ Virahol, 0.8 ‰ polyethylene polyamine and N, the mixing solutions of N-dimethylaminopropylamine then in reaction solution.To the logical nitrogen of reaction solution 40 minutes, add 0.2 ‰ ammonium persulphate, 0.05 ‰ Diisopropyl azodicarboxylate and 0.03 ‰ sodium bisulfite with high purity nitrogen (nitrogen gas purity is more than 99.99%) again.Through about 10 hours, polyreaction was finished substantially.Then colloid is carried out granulation, drying, pulverizing, obtain molecular weight and be 13,200,000 anionic copolymer.
Embodiment 2.
Add 1000 parts of deionized waters, 197 parts of acrylamides, 35 parts of 2-acrylamido-2-methyl propane sulfonic acids, 10 parts of N--isopentyl acrylamides in normal temperature condition downhill reaction still successively, fully stirring makes it to dissolve fully.Use Na
2CO
3Regulation system pH value equals 10, adds 0.03% EDTA, 0.2% urea, 0.05 ‰ Virahol, 1.0 ‰ polyethylene polyamine and N, the mixed solution of N-dimethylaminopropylamine, 0.1 ‰ 2-benzothiazolyl mercaptans then in reaction solution.To the logical nitrogen of reaction solution 40 minutes, add 0.2 ‰ ammonium persulphate and 0.1 ‰ Diisopropyl azodicarboxylate with high purity nitrogen (nitrogen gas purity is more than 99.99%) again, through about 10 hours, polyreaction was finished substantially.At last colloid is carried out granulation, drying, pulverizing, obtain molecular weight and be 19,500,000 anionic copolymer.
Embodiment 3.
Add 1200 parts of deionized waters, 130 parts of acrylamides, 85 parts of 2-acrylamido-2-methyl propane sulfonic acids, 15 parts of N-isobutyl-acrylamides in normal temperature condition downhill reaction still successively, fully stirring makes it to dissolve fully.Use Na
2CO
3And NH
4OH regulation system pH value equals 10, adds 0.08% EDTA, 0.1% urea then in reaction solution successively, 0.03 ‰ glycerol, 0.7 ‰ polyethylene polyamine and N, the mixed solution of N-dimethylamino propionic acid.With the logical nitrogen of high purity nitrogen (nitrogen gas purity is more than 99.99%) 40 minutes, add 0.2 ‰ Potassium Persulphate, 0.05 ‰ Diisopropyl azodicarboxylate and 0.02 ‰ sodium bisulfite again.Through about 12 hours, polyreaction was finished substantially.Then colloid is carried out granulation, drying, pulverizing, obtain molecular weight and be 16,400,000 anionic copolymer.
Embodiment 4.
In reactor, add 1400 parts of deionized waters, 320 parts of acrylamides, 168 parts of 2-acrylamido-2-methyl propane sulfonic acids, 114 parts of N successively, N-diethyl diallyl ammonium chloride, fully stirring makes it to dissolve fully.Use Na
2CO
3Regulation system pH value equals 8, adds 0.05% EDTA, 0.1% urea, 0.7 ‰ polyethylene polyamine and N then in reaction solution successively, the mixed solution of N-dimethylamino propionic acid, conditioned reaction temperature to 20 ℃.With high purity nitrogen (nitrogen gas purity is more than 99.99%) reaction solution is led to nitrogen 40 minutes, add 0.4 ‰ ammonium persulphate again.Through about 7 hours, polyreaction was finished substantially.Then colloid is carried out granulation, drying, pulverizing, obtain molecular weight at last and be 8,110,000 amphoteric ion copolymer.
Claims (8)
1. be applicable to the macromolecular multi-component copolymer that use in the oil field, it is characterized in that by anionic monomer I-1 or I-2, cationic monomer II-1 or II-2 and non-ionic monomer III preparation, obtain molecular weight (being equivalent to the polyacrylamide viscosity-average molecular weight) 3,000,000～20,000,000 multipolymer, three class monomers have following chemical expression:
R
1, R
2And R
3: the alkyl of H or 1～3 carbon atom
M:H, basic metal, alkaline-earth metal or NH
4
The positive integer of m:0～3
R
4: H or methyl
M:H, basic metal, alkaline-earth metal or NH
4 
R
5, R
6, R
7And R
8: the alkyl of H or 1～5 carbon atom
A
-: halogen or BF
4And PF
6
The positive integer of n:0～3
R
9And R
10: the alkyl of H or 1～5 carbon atom
In macromolecular multi-component copolymer, it is as follows that each monomer is formed weight percent:
0.5≤I-1 or I-2≤90.0
0≤II-1 or II-2≤70.0
5.0≤III≤95.0
2. by the macromolecular multi-component copolymer of claim 1., the viscosity-average molecular weight when it is anionic polymer should meet following requirement: 10,000,000～20,000,000; Viscosity-average molecular weight when it is amphoteric ion polymer should meet following requirement: 1,000,000～15,000,000.
3. press the preparation method of the macromolecular multi-component copolymer of claim 1. or 2., adopt water solution polymerization process.The polymer fluid total monomer concentration is 10%～50%; Monomer solution pH value 7～12; 0～35 ℃ of kick off temperature; Adopt oxygenant/azo class or oxygenant/reductive agent/azo class to do initiator system; Adopt disodium EDTA to do chela and agent; Adopt organic amine or thiazole compound to do polyreaction promotor; Adopt alcohol to do polymerization chain transfer agents; Adopt urea or thiocarbamide to make anti-linking agent.
4. press the preparation method of the macromolecular multi-component copolymer of claim 3., oxygenant is ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide, di-cyclohexylperoxy dicarbonate, tertbutyl peroxide, di-isopropyl Peracetic Acid, cyclohexanone peroxide or methylethyl ketone peroxide, and azo-initiator is Diisopropyl azodicarboxylate and 2,2'-Azobis(2,4-dimethylvaleronitrile); Reductive agent is sodium bisulfite, Sulfothiorine or Sodium Pyrosulfite.
5. press the preparation method of the macromolecular multi-component copolymer of claim 3., the ratio that chela and agent consumption account for total monomer weight is: 1.0 * 10
-5～2.0 * 10
-3
6. press the preparation method of the macromolecular multi-component copolymer of claim 3., organic amine compound is:
(1)NH(CH
2CH
2NH)
pCH
2CH
2NH P≥2
R or R ': the alkyl that is 1～3 carbon atom
R ": the alkyl of 1～3 carbon atom, alkylamino, carboxyl, amido, itrile group and sulfonic group
The weight ratio of the positive integer of q:1～5 its (1) and (2) is that 1: 10～10: 1 thiazole compounds are:
X is H or basic metal
7. press the preparation method of the macromolecular multi-component copolymer of claim 3., the alcohols chain-transfer agent is Virahol, ethylene glycol or glycerol, and its consumption accounts for 0.5 * 10 of total monomer weight
-4～5.0 * 10
-4
8. press the preparation method of the macromolecular multi-component copolymer of claim 3., anti-dosage of crosslinking agent accounts for 1.0 * 10 of total monomer weight
-4～5.0 * 10
-3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102465A CN1086709C (en) | 1998-06-30 | 1998-06-30 | Water-soluble macromolecular multi-component copolymer for oil field |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102465A CN1086709C (en) | 1998-06-30 | 1998-06-30 | Water-soluble macromolecular multi-component copolymer for oil field |
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| Publication Number | Publication Date |
|---|---|
| CN1204652A CN1204652A (en) | 1999-01-13 |
| CN1086709C true CN1086709C (en) | 2002-06-26 |
Family
ID=5217366
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98102465A Expired - Fee Related CN1086709C (en) | 1998-06-30 | 1998-06-30 | Water-soluble macromolecular multi-component copolymer for oil field |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153999B (en) * | 2011-01-21 | 2012-11-21 | 西安石油大学 | Profile modification agent for amphion jelly |
| CN102875729B (en) * | 2012-09-27 | 2014-08-27 | 北京奥凯立科技发展股份有限公司 | Preparation method of inhibitors for drilling fluid |
| EP2933271B1 (en) * | 2014-04-15 | 2016-03-23 | Basf Se | Method for the preparation of (meth) acrylamide comprising water-soluble homo- or copolymers |
| CN106520084A (en) * | 2016-10-25 | 2017-03-22 | 中国石油化工股份有限公司 | Stabilizer of delayed cross-linked polymer for plugging and profile control and preparation method thereof |
| CN108641686B (en) * | 2018-05-25 | 2021-01-01 | 成都理工大学 | Flow pattern regulator for ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074692A (en) * | 1992-01-24 | 1993-07-28 | 金日辉 | Dispersed suspension type polyacrylamide for adjustment analysis use |
| CN1088184A (en) * | 1992-10-30 | 1994-06-22 | 诺尔科化学公司 | The dispersed polymeres that is used for oil field water clarification |
-
1998
- 1998-06-30 CN CN98102465A patent/CN1086709C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074692A (en) * | 1992-01-24 | 1993-07-28 | 金日辉 | Dispersed suspension type polyacrylamide for adjustment analysis use |
| CN1088184A (en) * | 1992-10-30 | 1994-06-22 | 诺尔科化学公司 | The dispersed polymeres that is used for oil field water clarification |
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|---|---|
| CN1204652A (en) | 1999-01-13 |
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