CN1226319C - Viscosity highly increased water-soluble hydrophobic association copolymer and preparation method and use thereof - Google Patents
Viscosity highly increased water-soluble hydrophobic association copolymer and preparation method and use thereof Download PDFInfo
- Publication number
- CN1226319C CN1226319C CN 200310110882 CN200310110882A CN1226319C CN 1226319 C CN1226319 C CN 1226319C CN 200310110882 CN200310110882 CN 200310110882 CN 200310110882 A CN200310110882 A CN 200310110882A CN 1226319 C CN1226319 C CN 1226319C
- Authority
- CN
- China
- Prior art keywords
- water
- monomer
- tensio
- active agent
- hydrophobic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention discloses a high-viscosity hydrophobic association water soluble copolymer, a preparation method and a use, which is characterized in that 20 portions of acrylamide, 0.3 to 25 portions of anion monomers or/and cation monomers, 0.1 to 7 portions of alkylbenzene ethene, 0.3 to 205 portions of a surface active agent and 40 to 1700 portions of deionized water are added into a three-neck bottle which is provided with a stirrer, a thermometer and a nitrogen canal; the pH value is adjusted to 2.5 to 9; N2 is introduced for 30 minutes; 0.003 to 2.0 portions of an initiating agent is added to react for 6 to 30 hours at the temperature of 20 to 70 DEG C so as to obtain the hydrophobic association water soluble copolymer. The present invention has good application prospect in multiple fields, such as being as an oil displacement agent in oil extraction, being as a thickening agent in water based paint, being as a flocculating agent in water processing, etc.
Description
One, technical field
The present invention relates to a kind of high tackify hydrophobic associating water-soluble copolymer and its production and use, belong to polymeric material field.
Two, technical background
Hydrophobic associated water-soluble polymer is the multipolymer that contains a large amount of hydrophilic radicals and a small amount of hydrophobic grouping, its solution has unique tackify, anti-salt, character such as anti-shearing, and this base polymer has a good application prospect in many fields such as tertiary oil recovery, coating thickening, water treatment, mobility control, makeup, biology, printing and dyeing, mining industry.Both at home and abroad the researchist is to structure, character, the tackify mechanism of hydrophobic associated water-soluble polymer and should be used as big quantity research, exploration work, but the solvability of polymkeric substance and thermostability are two big research difficult problems of hydrophobic associated polymer, wait further solution.
At present, petroleum industry is faced with two hang-ups: (1) find is fewer and feweri; (2) also surplus in the exhausted oil reservoir have substantial oil, and conventional oil recovery technique can only stratum, extraction 30% left and right sides reserves crude oil.Therefore research and development raising petroleum recovery technology is very urgent problem.And polymer displacement of reservoir oil tech is a kind of important method that improves oil recovery, and this is proved that by domestic and international research and application the production application in oil fields such as China's grand celebration has also obtained good effect.The oil-displacing agent of present industrial use mainly is high-molecular weight partially hydrolyzed polyacrylamide (HPAM), and its molecular weight is up to 2,000 ten thousand, and degree of hydrolysis is 20%～30%.It depends on high molecular and the molecular chain-effect of the electrostatic repulsion of COO-, and molecular chain is stretched, thereby reach the tackify effect.But the anti-salt property of HPAM is poor, when in HPAM solution, adding salt, and monovalent cation such as Na
+, K
+With divalent cation Ca
2+, Mg
2+The viscosity of solution will be reduced greatly.The electrostatic repulsion between carboxylic ions is shielded in the polymkeric substance because positively charged ion makes, and molecular chain curls, and hydrodynamic volume reduces.Work as Ca
2+, Mg
2+, Sr
2+, Ba
2+When reaching finite concentration, HPAM will be precipitated out from solution, phenomenon of phase separation will take place Deng divalent cation.Another defective of the HPAM of this ultra-high molecular weight is that anti-shear performance is poor.HPAM reaches the flow process meeting tangible shear degradation of generation in the stratum and loses viscosity in stirring, dissolving, solution pumping with injection.The 3rd, the poor heat stability of HPAM, when depth of stratum during up to 2000 feet, reservoir temperature is about more than 75 ℃, and partially hydrolyzed polyacrylamide is easy to wear out in ground environment, and the viscosity of polymers soln is reduced significantly.
Being everlasting for the rheological property of control water-based paint adds fluidity regulator in the coating, claims thickening material again.In water-based paint, add thickening material and can make coating have good thixotropy, prevent filler, pigment sedimentation when coating is stored, help the brushing of coating, improve the levelling property of filming, prevent the generation of sagging phenomenon.At present, the water-based paint thickening material of industrial use mainly contains derivatived cellulose such as carboxymethyl cellulose, Natvosol and polyacrylate(s).Derivatived cellulose has good hydrophilicity, forms the cubic network structure and reach the effect of thickening in water.But its existence makes the mobile variation of coating, and is easily mouldy by microbial spoilage, reduces gloss of film.And polyacrylate(s) is met the alkali facile hydrolysis to the alkali sensitivity.
Effectively handle for a large amount of trade effluents and sanitary sewage; thereby reach emission standard and utilize requirement; most important to human survival and environment protection; and in domestic and international many water treatment method, flocculent precipitation is because of its technology is simple, easy to operate, the processing efficiency advantages of higher is widely used.In all kinds of flocculation agents, consumption is few because of having, the efficient advantages of higher is widely applied for the organic synthesis polymeric flocculant.So far, the polymeric flocculant that water treatment industry is used mainly is HPAM, also have in addition a few cationic flocculant such as dimethyl diallyl ammonium chloride homopolymer or with the multipolymer of acrylamide.But the throwing out of these polymeric flocculants significantly weakens with the increase of salt concn in the rising of temperature and the water, and its flocculation efficiency is also along with the shelf-time of flocculant aqueous solution prolongs and reduces.
For above-mentioned reasons, research and development heatproof, anti-salt, hydrophobic associating water-soluble copolymer anti-shearing, high tackify become the focus of water-soluble polymers research.But, the hydrophobic monomer of most hydrophobic associated polymers of research all is acrylamide derivative or higher hydrocarbyl acrylate at present, the hydrophobic group of these multipolymers is easy to hydrolysis in high-temperature stratum, viscosity sharply descends, the solution temperature tolerance is poor, and critical association concentration is higher, very low in the following viscosity of critical polymer concentration, in addition, many hydrophobic associated copolymer stabilities of solution of report are poor at present, the postpone polymer solution viscosity reduces for a long time, and the solvability of these hydrophobic associated copolymers is also undesirable, thereby has limited application.As M.Camailet al., European Polymer Journal, the N-alkyl of 2000,36 (9): 1853～1863 reports and N-aralkyl acrylamide synthetic and with the copolymerization of AM micella.The vinylbenzene of US Pat.4528348 report and the micella copolymerization of acrylamide.Gao Baojiao etc., polymer journal, the performance of the synthetic and solution of the acrylamide-styrol copolymer of 2001 (5): 608～611 reports.In back two pieces of reported in literature, the problem that the multipolymer that vinylbenzene obtains as hydrophobic monomer and acrylamide copolymerization exists: (1) owing to be the non-ionic type multipolymer, even add small amounts of styrene, multipolymer also is difficult to dissolving; (2) because of the cinnamic hydrophobic grouping chain of hydrophobic monomer weak point has only phenyl ring, the hydrophobic association effect of copolymer solution is poor, solution critical association concentration height; (3) soltion viscosity is low, even more than critical association concentration, the solution apparent viscosity is also lower.(4) polymers soln poor stability, microgel appears in postpone meeting for a long time, even occurs being separated, and causes copolymer solution viscosity sharply to descend.
Three, summary of the invention
The objective of the invention is provides a kind of high tackify hydrophobic associated polymer and its production and use at the deficiencies in the prior art, be characterized in wide material sources, cheap acrylamide (AM) as main hydrophilic monomer, a spot of anionic monomer (ANMO) adopts C or/and cationic monomer (CAMO) is the solubilising hydrophilic monomer
2-14Ring-alkylated styrenes (AST) has synthesized copolymer p AAST as hydrophobic monomer.
The present inventor is being hydrophobic monomer to ring-alkylated styrenes, adopt free radical micella copolymerization method synthetic copolymer PAAST, ring-alkylated styrenes is contained rigid heat resistant group phenyl ring, molecular backbone chain directly links to each other with the phenyl ring that contains alkyl, make hydrophobic grouping also not hydrolysis at high temperature, this special construction of hydrophobic monomer makes the aqueous copolymers solution that synthesizes have good thermostability.On the other hand, the introducing of phenyl ring has increased the rigidity of hydrophobic chain structure, make the alkyl hydrophobic chain be difficult for curling, help intermolecular hydrophobic association effect, moreover phenyl ring itself has plane and polarizable structure, can induce reactive force between pattern ylid Chuihua molecule, therefore, the hydrophobic association effect between the alkyl phenyl hydrophobic grouping is strong, and suitable hydrophobic monomer concentration makes multipolymer easily form intermolecular association under lower concentration, solution also has higher soltion viscosity at comparatively high temps, and the solution temperature tolerance is good.
The present inventor finds in the polyreaction that various reaction conditionss such as ion monomer concentration, surfactant concentration, temperature of reaction, hydrophobic monomer concentration etc. have a significant impact resulting polymers structure and solution behavior.Add an amount of ionic comonomer and can increase considerably the collaborative thickening property of polymer dissolution and performance and hydrophobic monomer, and hydrophobic association concentration is reduced significantly, critical hydrophobic association apparent viscosity increases substantially.This is because add an amount of anionic monomer or/and cationic monomer in non-ionic hydrophobic association copolymer reaction, on the one hand, multipolymer polarity improves, increased the water-soluble of multipolymer, on the other hand, help to make molecular chain to stretch, help being cross-linked to form supramolecular structure, system viscosity is sharply risen by intermolecular dynamic physical.When the dosage of ionic comonomer surpassed a certain extreme value, interionic electrostatic repulsion forces can weaken the association between hydrophobic grouping, and more soluble in water, and the associating effect of hydrophobic grouping is weakened, and soltion viscosity is descended, and salt resistance reduces.In polymerization reaction system, add an amount of tensio-active agent, can obtain to have the hydrophobic associated polymer of the segment of certain hydrophobic block length, strong hydrophobic association effect and good aqueous solubility.Suitable initiator concentration, total reaction monomer concentration and temperature of reaction can obtain to have the copolymer p AAST of certain molecular weight and high hydrophobic monomer content.Suitable pH value in reaction can obtain full-bodied PAAST, and the pH value is low excessively, and imidization and hydrolysis can take place acrylamide; The pH value is too high, and the amide group in the acrylamide can be hydrolyzed to carboxyl.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
1. the recipe ingredient of high tackify hydrophobic associating water-soluble copolymer is:
20 parts of acrylic amine
Anionic monomer is or/and 0.3～20 part of cationic monomer
To 0.1～6 part of ring-alkylated styrenes
2～120 parts in tensio-active agent
150～1100 parts of deionized waters
Wherein anionic monomer is at least a in vinylformic acid, methacrylic acid, methylene-succinic acid, vinylbenzenesulfonic acid and/or the 2-acrylamido-2-methyl propane sulfonic acid etc.; Cationic monomer is at least a in dimethyl diallyl ammonium chloride, Jia Jibingxisuanyizhi base trimethyl ammonium chloride, ethyl propenoate base trimethyl ammonium chloride and/or 2-acrylamido-quaternary ammonium salt unsaturated monomers such as 2-trimethoxysilyl propyl methacrylate ammonium chloride; When hydrophilic monomer was anionic monomer, tensio-active agent was a sodium lauryl sulphate; When hydrophilic monomer was cationic monomer, tensio-active agent was a trimethylammonium hexadecyl brometo de amonio; When hydrophilic monomer was anionic monomer and cationic monomer mixing use, tensio-active agent was the octyl group Soxylat A 25-7.
2. the preparation of high tackify hydrophobic associating water-soluble copolymer PAAST
With 20 parts of acrylamides, 0.3～20 part of anionic monomer or cationic monomer, to 0.1～6 part of ring-alkylated styrenes, 2～120 parts in tensio-active agent, deionized water adds in the three neck reaction flasks for 150～1100 parts, regulator solution pH=2.5～9, logical N
2Behind the 30min, add 0.002～0.3 part of initiator persulphate down for 20～70 ℃ in temperature, reacted 6～30 hours, make PAAST, dilute with water obtains the PAAST strong solution again.
Wherein anionic monomer is a kind of in vinylformic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid, methylene-succinic acid and/or the vinylbenzenesulfonic acid etc.; Cationic monomer is a kind of in dimethyl diallyl ammonium chloride, Jia Jibingxisuanyizhi base trimethyl ammonium chloride, ethyl propenoate base trimethyl ammonium chloride and/or 2-acrylamido-quaternary ammonium salt unsaturated monomers such as 2-trimethoxysilyl propyl methacrylate ammonium chloride; When hydrophilic monomer was anionic monomer, tensio-active agent was a sodium lauryl sulphate; When hydrophilic monomer was cationic monomer, tensio-active agent was a trimethylammonium hexadecyl brometo de amonio; When hydrophilic monomer was anionic monomer and cationic monomer mixing use, tensio-active agent was the octyl group Soxylat A 25-7.
To ring-alkylated styrenes is C
2-14Ring-alkylated styrenes.
3. the performance of high tackify hydrophobic associating water-soluble copolymer PAAST
Remove specified otherwise, all do not add tensio-active agent in the following copolymer p AAST solution.
(1) relation of the solution apparent viscosity of copolymer p AAST and concentration is as shown in table 1.The result shows that the PAAST aqueous solution of lower concentration also has very high apparent viscosity.
(2) package stability of PAAST is shown in table 2 and table 3.The result show the fresh water solution of PAAST and salts solution under 45 ℃ through 120 days its viscosity no changes, all show excellent in storage stability.
(3) relation of the temperature of PAAST and soltion viscosity is as shown in table 4, and in certain temperature range, polymers soln is after heating for the first time, and the soltion viscosity under relevant temperature also slightly increases, and illustrates that polymkeric substance has good heat resistance.
(4) shearing action is as shown in table 5 to the influence of the soltion viscosity of PAAST.As seen from the table, under shearing action, the hydrophobic association structure is destroyed gradually, and soltion viscosity descends; In eliminating the process of shearing action, intermolecular association forms again, and soltion viscosity recovers again gradually, even viscosity that can be when not shearing.The chemical structure that multipolymer is described is not damaged and degrades, and the effect of shearing force when testing for the first time also has been described simultaneously, and molecular chain is more stretched, and causes intermolecular association to be strengthened.
(5) solvability of copolymer p AAST is as shown in table 6.As seen from the table, copolymer p AAST dissolves substantially at 0.5h, dissolves fully during 1h, shows fabulous solvability.
(6) Sodium dodecylbenzene sulfonate is as shown in table 7 to the influence of copolymer p AAST solution apparent viscosity.The result shows that anion surfactant has considerable influence to the tackifying of copolymer p AAST, and near the tensio-active agent micelle-forming concentration, polymeric system reaches ultimate viscosity number.
(7) copolymer p AAST and tensio-active agent are compound, by the interaction of copolymer molecule with surfactant molecule, produce polymolecular accumulative physical cross-linked network, in addition, surfactant molecule has solublization to the supramolecule that hydrophobic associated polymer forms, thereby the solution apparent viscosity is increased considerably.When copolymer p AAST concentration is 0.1wt% and surfactant-free, 25 ℃ and 6s
-1The time, its apparent viscosity is up to 1180mPas; When polymer concentration is 0.2wt%, its viscosity is up to 2900.4mPas.Under suitable surfactant concentration, when polymer concentration is that 0.2wt%, NaCl concentration are 1.5wt%, 25 ℃ and 6s
-1The time, its viscosity is up to 926mPas.Compare with the result of study (＜250mPas is under the same test condition) of reported in literature, the polymkeric substance that the present invention developed all has good tackifying in fresh water or salt solution.
(8) copolymer p AST concentration is 0.1wt%, and after room temperature was placed 7 months, its viscosity still kept 99.98%, 45 ℃ place 4 months after, its viscosity still keeps 99.1%, illustrates that polymers soln is in that to be lower than 45 ℃ of following package stabilities fabulous.
Add an amount of copolymer p AAST in the emulsion paint that concrete surface is used, this emulsion paint was placed after 6 months, and filler, pigment still are uniformly dispersed, and sedimentation phenomenon do not occur.During the emulsion paint brushing, coating does not produce the sagging phenomenon, and after the emulsion paint drying, film coated surface is smooth, no groove, streak and wrinkle, and also paint film has good gloss.
4. the purposes of hydrophobic associating water-soluble copolymer PAAST
Hydrophobic associating water-soluble copolymer PAAST can be used as the flocculation agent in oil-displacing agent, water-based paint thickening material, the water treatment.
(1) copolymer p AAST being made into concentration is 0.05～0.3wt%, surfactant concentration is the aqueous solution of 0.01～4mmol/l, adding has in the mixing tank of whipping appts, at room temperature stirs, and promptly obtains high tackify, salt tolerant, anti-shearing hydrophobic associated water-soluble polymer oil-displacing agent.
Wherein tensio-active agent contains: anion surfactant C
8-16Sodium alkyl benzene sulfonate, C
8-16Sodium alkyl sulfate; Cats product is C
8-16Alkyl trimethyl bromine (chlorine) is changed quaternary ammonium salts such as ammonium; Nonionogenic tenside is C
8-16Alkyl dimethyl ammonium oxide and C
8-16At least a in the alkyl polyoxyethylene ether.
(2) preparation of hydrophobic associated copolymer water-based paint thickening material.
Copolymer p AAST is made into the aqueous solution that concentration is 0.05～0.3wt%, obtains to have the water-based paint thickening material of excellent package stability.The consumption of PAAST in coating is 0.01～0.1wt%.
(3) the hydrophobic associated copolymer water treatment preparation of flocculation agent
Copolymer p AAST is made into the aqueous solution that concentration is 0.05-0.3wt%, obtains to have the water treatment flocculation agent of excellent package stability.PAAST is 10mg/L～100mg/L as water treatment with the consumption of flocculation agent in sewage.
Four, embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the researchist in this field can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.
Embodiment 1
Acrylamide 20.000 grams, vinylformic acid 16.073 are restrained, t-butyl styrene 3.780 grams and sodium lauryl sulphate 108.912 grams are dissolved in 1099 ml distilled waters, add in three mouthfuls of reaction flasks, with NaOH regulator solution pH=8,50 ℃ of temperature of reaction, logical N
230min adds 0.05mol/l Potassium Persulphate initiator solution 1.21ml, reaction 16h, and the polymkeric substance dilute with water makes the PAAST strong solution.
Embodiment 2
Acrylamide 20.000 grams, 2-acrylamido-2-methyl propane sulfonic acid 0.630 gram, n-butylbenzene ethene 0.455 gram and sodium lauryl sulphate 3.875 grams are dissolved in 155 ml deionized water, regulate pH=3 with NaOH, 50 ℃ of temperature of reaction, logical N
2Add 0.05mol/l ammonium persulfate initiator solution 0.65ml behind the 30min, reaction 6h.The polymkeric substance water dissolution makes the PAAST strong solution.
Embodiment 3
Acrylamide 20.000 grams, dimethyl diallyl ammonium chloride 4.620 grams, positive hexyl phenenyl ethene 0.561 gram and trimethylammonium hexadecyl brometo de amonio 10.750 grams are dissolved in 250 ml deionized water, regulate pH=7,50 ℃ of temperature of reaction, logical N with hydrochloric acid
2Add 0.05mol/l Potassium Persulphate initiator solution 5.51ml behind the 30min, reaction 20h.The polymkeric substance water dissolution makes the PAAST strong solution.
Embodiment 4
Acrylamide 20.000 grams, ethyl propenoate base trimethyl ammonium chloride 18.073 grams, n-dodecane vinylbenzene 5.160 grams and trimethylammonium n-Hexadecane brometo de amonio 59.220 grams are dissolved in 658 ml deionized water, regulate pH=9,55 ℃ of temperature of reaction, logical N with NaOH
2Add 0.05mol/L Sodium Persulfate initiator solution 15.55ml behind the 30min, reaction 30h, the polymkeric substance water dissolution makes the PAAST strong solution.
Embodiment 5
Acrylamide 20.000 grams, vinylformic acid 6.170 grams, dimethyl diallyl ammonium chloride 3.326 are restrained, t-butyl styrene 1.863 grams and octyl group Soxylat A 25-7 12.915 grams are dissolved in 235 ml deionized water, regulate pH=5 with NaOH, 55 ℃ of temperature of reaction, logical N
2Add 0.05mol/L Potassium Persulphate initiator solution 3.27ml behind the 30min, reaction 12h, the polymkeric substance water dissolution makes the PAAST strong solution.
Application example 1
Get a certain amount of PAAST hydrophobic associated polymer preparation oil-displacing agent aqueous sample, sample is the water white transparency shape.Polymer concentration is 0.10wt%, and Sodium dodecylbenzene sulfonate 0.3mmol/l adds in the mixing tank of band stirring, stirs under room temperature, obtains the hydrophobic associated water-soluble polymer oil-displacing agent.
Application example 2
With 3wt% diatomite suspension as simulated sewage, add the 100ml simulated sewage in tool plug graduated cylinder, the concentration that adds embodiment 3 preparations again is the flocculation agent PAAST solution 3ml of 0.05wt%, come and go and shake up for several times, static 2h, getting supernatant liquor, is 99.97% with its transmittance of spectrophotometric determination.
Application example 3
Get a certain amount of PAAST hydrophobic associated polymer preparation oil-displacing agent aqueous sample, sample is the water white transparency shape.Polymer concentration is 0.10wt%, C
12Alkyl dimethyl ammonium oxide 0.2mmol/l adds in the mixing tank of band stirring, stirs under room temperature, obtains the hydrophobic associated water-soluble polymer oil-displacing agent.
The relation of table 1 copolymer concentration and solution apparent viscosity
| Polymer concentration, g/dl | 0.05 | 0.1 | 0.15 | 0.2 | 0.3 | 0.45 |
| Apparent viscosity, MPas | 283 | 1180 | 1863 | 2900 | 4817 | 9844 |
45 ℃ of fresh water solution of table 2 apparent viscosity is with the variation of period of storage
| Time (my god) | 0 | 1 | 5 | 15 | 30 | 60 | 120 |
| Apparent viscosity, MPas | 1180 | 1190 | 1188 | 1179 | 1181 | 1173 | 1169 |
Annotate: copolymer solution concentration 0.1g/dl
45 ℃ of saline solution apparent viscosities of table 3 are with the variation of period of storage
| Time (my god) | 0 | 1 | 5 | 15 | 30 | 60 | 120 |
| Apparent viscosity, MPas | 926 | 928 | 923 | 921 | 915 | 920 | 924 |
Annotate: copolymer solution concentration 0.20g/dl, NaCl concentration 0.256mol/L, surfactant concentration are 0.2mmol/L.
Table 4 temperature is to the impact of solution apparent viscosity
| Temperature (℃) | 20℃ | 25℃ | 30℃ | 35℃ | 45℃ | 55℃ | 65℃ |
| Apparent viscosity (MPas) | 967 | 1180 | 1210 | 1039 | 859 | 521 | 397 |
| Apparent viscosity (MPas) | |||||||
| (place after the test for the first time and surveyed again in two days) | 983 | 1237 | 1284 | 1064 | 891 | 536 | 412 |
Annotate: copolymer solution concentration 0.1g/dl
Table 5 shear rate is to the impact of solution apparent viscosity
| Shear rate (s-1) | 6.01 | 10.0 | 20.0 | 30.0 | 40.0 | 50.0 |
| Apparent viscosity (MPas) | 1180 | 901 | 440 | 370 | 305 | 301 |
| Apparent viscosity (MPas) | ||||||
| (placing 30min after surveying for the first time surveys again) | 1253 | 946 | 458 | 373 | 306 | 304 |
Annotate: copolymer solution concentration 0.1g/dl
Table 6 copolymer solution viscosity is with the variation of PAAST dissolution time
| Dissolution time (hr) | 0.5 | 1 | 3 | 5 | 7 | 10 | 15 | 20 |
| Apparent viscosity | 1149 | 1180 | 1182 | 1179 | 1180 | 1181 | 1185 | 1180 |
Annotate: copolymer solution concentration 0.1g/dl
Table 7 neopelex concentration is to the impact of apparent viscosity
| Surfactant concentration, mmol/l | 0 | 0.2 | 0.4 | 0.6 | 0.8 | 1.0 |
| Apparent viscosity | 1180 | 1536 | 1986 | 2674 | 2870 | 615 |
Annotate: copolymer solution concentration 0.1g/dl
More than the apparent viscosity in the table is except specifying, test condition is 25 ℃, 6s-1.
Claims (5)
1. high tackify hydrophobic associating water-soluble copolymer is characterized in that the recipe ingredient of this multipolymer is by weight:
20 parts of acrylamides
0.3～20 part of anionic monomer and/or cationic monomer
To 0.1～6 part of ring-alkylated styrenes
2～120 parts in tensio-active agent
150～1100 parts of deionized waters
Wherein anionic monomer is at least a in vinylformic acid, methacrylic acid, methylene-succinic acid, vinylbenzenesulfonic acid and/or the 2-acrylamido-2-methyl propane sulfonic acid; Cationic monomer is at least a in dimethyl diallyl ammonium chloride, Jia Jibingxisuanyizhi base trimethyl ammonium chloride, ethyl propenoate base trimethyl ammonium chloride and/or 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride; When hydrophilic monomer was anionic monomer, tensio-active agent was a sodium lauryl sulphate; When hydrophilic monomer was cationic monomer, tensio-active agent was a trimethylammonium hexadecyl brometo de amonio; When hydrophilic monomer was anionic monomer and cationic monomer mixing use, tensio-active agent was the octyl group Soxylat A 25-7.
2. high according to claim 1 tackify hydrophobic associating water-soluble copolymer is characterized in that to ring-alkylated styrenes be to C
2-14At least a in the ring-alkylated styrenes.
3. the preparation method of high as claimed in claim 1 or 2 tackify hydrophobic associating water-soluble copolymer is characterized in that:
With acrylamide 20 weight parts, anionic monomer or/and cationic monomer 0.3～20 weight part, ring-alkylated styrenes 0.1～6 weight part, tensio-active agent 2～120 weight parts and deionized water 150～1100 weight parts added have agitator, thermometer and N
2In the three-necked bottle of tracheae, regulate pH=2.5～9, logical N
230 minutes, add initiator persulphate 0.002～0.3 weight part, reaction 6～30 hours in 20～70 ℃ of temperature, make high tackify hydrophobic associating water-soluble copolymer.
4. the purposes of high according to claim 1 tackify hydrophobic associating water-soluble copolymer, it is characterized in that it is that 0.05～0.3wt% and tensio-active agent are that the water-soluble mixed solution of 0.01～4mmol/L is as oil-displacing agent that this multipolymer is made into concentration, multipolymer is made into the solution that concentration is 0.05～0.3wt%, as the water-based paint thickening material, consumption in coating is 0.01-0.1wt%, and consumption is that 10～100mg/L is as the flocculation agent in the water treatment.
5. as the purposes of high tackify hydrophobic associating water-soluble copolymer as described in the claim 4, it is characterized in that the tensio-active agent in multipolymer and the tensio-active agent blended oil-displacing agent is anion surfactant: C
8-16Sodium alkyl benzene sulfonate or C
8-16Sodium alkyl sulfate; Cats product: C
8-16Alkyl trimethyl ammonium bromide or C
8-16Alkyl trimethyl ammonium chloride; Nonionogenic tenside: C
8-16Alkyl dimethyl ammonium oxide or C
8-16At least a in the alkyl polyoxyethylene ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310110882 CN1226319C (en) | 2003-11-07 | 2003-11-07 | Viscosity highly increased water-soluble hydrophobic association copolymer and preparation method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310110882 CN1226319C (en) | 2003-11-07 | 2003-11-07 | Viscosity highly increased water-soluble hydrophobic association copolymer and preparation method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1542031A CN1542031A (en) | 2004-11-03 |
| CN1226319C true CN1226319C (en) | 2005-11-09 |
Family
ID=34335792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310110882 Expired - Fee Related CN1226319C (en) | 2003-11-07 | 2003-11-07 | Viscosity highly increased water-soluble hydrophobic association copolymer and preparation method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1226319C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100418990C (en) * | 2006-01-11 | 2008-09-17 | 丹东恒星精细化工有限公司 | Acrylate emulsifying thickening agent and production process thereof |
| CN101412906B (en) * | 2008-12-05 | 2012-01-25 | 河南省科学院高新技术研究中心 | Acid fracturing thickening agent and preparation thereof |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402563C (en) * | 2005-01-31 | 2008-07-16 | 大连广汇化学有限公司 | Method for preparing temperature-resistant and anti-salt type polyacrylamide |
| CN100391990C (en) * | 2005-12-08 | 2008-06-04 | 西南石油学院 | Water-solubility molecule associatad three-construction units hydrophobic associated polymer and synthesizing process thereof |
| CN100402564C (en) * | 2006-02-20 | 2008-07-16 | 四川大学 | Water soluble organic amphoteric high molecule copolymer and its preparation method |
| EP1967545A1 (en) * | 2007-03-09 | 2008-09-10 | Rohm and Haas France SAS | Cationic polymer latex |
| FR2920818B1 (en) * | 2007-09-11 | 2013-03-22 | Snf Sas | IMPROVED PROCESS FOR ASSISTED OIL RECOVERY. |
| CN101260171B (en) * | 2008-04-22 | 2010-08-04 | 山东大学 | Comb-type structure activity polymer and its preparation technique and application |
| RU2495053C2 (en) | 2008-08-22 | 2013-10-10 | Акцо Нобель Н.В. | Polymer dispersion |
| CN102585094A (en) * | 2011-12-23 | 2012-07-18 | 山东宝莫生物化工股份有限公司 | Preparation method of deoiling flocculant |
| CN104119472B (en) * | 2014-06-30 | 2017-01-11 | 大庆高新区华龙祥化工有限公司 | Active pre-crosslinking gel particle |
| CN104085971B (en) * | 2014-07-10 | 2019-09-27 | 中昊(大连)化工研究设计院有限公司 | Compound cationic flocculant and preparation method thereof |
| CN105440206B (en) * | 2014-08-13 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of polymer with surface active function and preparation method thereof |
| CN105440205B (en) * | 2014-08-13 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of polymer with surface active function and preparation method thereof |
| CN104761678A (en) * | 2015-04-11 | 2015-07-08 | 烟台润星环保科技发展有限公司 | Method for preparing flocculating agent for dry discharge of tailings |
| CN106279523B (en) * | 2015-06-25 | 2019-03-15 | 中国石油天然气股份有限公司 | Thickening agent and preparation method and application thereof |
| CN105013390B (en) * | 2015-06-29 | 2017-06-06 | 中国海洋石油总公司 | A kind of application of cationic surfactant |
| CN106608974B (en) * | 2015-10-21 | 2019-05-17 | 中国石油化工股份有限公司 | A kind of tackifier for drilling fluid copolymerization associated matter and preparation method thereof |
| CN106608975B (en) * | 2015-10-21 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of graft starch tackifier copolymerization associated matter and preparation method thereof |
| CN106608976B (en) * | 2015-10-21 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of starch-containing tackifier copolymerization associated matter and preparation method thereof |
| CN106608972B (en) * | 2015-10-21 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of preparation method of tackifier copolymerization associated matter |
| CN106608973B (en) * | 2015-10-21 | 2019-05-17 | 中国石油化工股份有限公司 | A method of preparing tackifier copolymerization associated matter |
| CN106609129B (en) * | 2015-10-21 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of tackifier copolymerization associated matter and preparation method thereof |
| CN108047378B (en) * | 2017-12-21 | 2021-03-02 | 山东诺尔生物科技有限公司 | Hydrophobic association oil displacement polymer and preparation method thereof |
| CN110204025A (en) * | 2019-05-28 | 2019-09-06 | 中国海洋石油集团有限公司 | A kind of interfacial activity water cleaning agent and the preparation method and application thereof |
| CN112375177B (en) * | 2020-10-20 | 2022-06-14 | 爱森（中国）絮凝剂有限公司 | Novel hydrophobically associating polymer and preparation method and application thereof |
| CN115785334B (en) * | 2022-12-16 | 2024-07-16 | 化学与精细化工广东省实验室 | Hydrophobic association type anionic polyacrylamide and preparation method and application thereof |
| CN116622356A (en) * | 2023-04-28 | 2023-08-22 | 成都赛璐石油科技有限公司 | Surface-aggregation binary compound oil displacement agent suitable for fracture-cavity oil reservoir and preparation method thereof |
-
2003
- 2003-11-07 CN CN 200310110882 patent/CN1226319C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100418990C (en) * | 2006-01-11 | 2008-09-17 | 丹东恒星精细化工有限公司 | Acrylate emulsifying thickening agent and production process thereof |
| CN101412906B (en) * | 2008-12-05 | 2012-01-25 | 河南省科学院高新技术研究中心 | Acid fracturing thickening agent and preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1542031A (en) | 2004-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1226319C (en) | Viscosity highly increased water-soluble hydrophobic association copolymer and preparation method and use thereof | |
| CN101293944B (en) | High adhesion-promotion salt resistant water-soluble copolymer, preparation method and application thereof | |
| CN101492515B (en) | Acrylic amide modified graft copolymer, preparation method and application thereof | |
| CN101463116B (en) | Non-linear associating water-soluble quadripolymer, and preparation and use thereof | |
| CN1042037C (en) | Process for the preparation of dispersion of water-soluble cationic polymer | |
| CN100528918C (en) | Novel high molecular weight associative amphoteric polymers and uses thereof | |
| CN104448125B (en) | Amphoteric hydrophobically-associating polymer and preparation method thereof | |
| AU604359B2 (en) | Water dispersible hydrophobic thickening agent | |
| CN106866878B (en) | Polymer-type profile control agent and preparation method thereof suitable for high temperature and high salt harshness oil reservoir | |
| KR101322386B1 (en) | Polyelectrolyte complexes as thickeners for high ionic strength salt solutions | |
| CN105566565B (en) | A kind of side chain contains the hydrophobic associated polymer of double bond, preparation method and the usage | |
| CN1125094C (en) | Heat-resistant salt-resistant thickening agent of copolymer | |
| CN101284893A (en) | Comb-typed amphiphilic water-soluble co-polymer, method for preparing same and use | |
| CN107556423A (en) | Double physical crosslinking polyacrylic acid high intensity, the preparation method of high tenacity hydrogel | |
| CN101302266A (en) | Water-soluble micro-crosslinked copolymer, preparation and use thereof | |
| CN101280038A (en) | High molecular weight anionic polymer fluid dispersion, preparation and application thereof | |
| CN1148432C (en) | Method for preparing oil-displacing agent of high-tack-producing hydrophobic association polymer | |
| CN104327215A (en) | Ultra-high molecular weight anion biological polysaccharide grafted copolymer and preparation method thereof | |
| CN102660250A (en) | Cation hydrophobic associating polymer oil displacement agent and preparation method thereof | |
| CN114262412B (en) | Anti-shearing modified polyacrylamide and application thereof | |
| CN1118532C (en) | High-temp. high-pressure hypersalinity drilling fluid rheological property stabilizing agent | |
| CN103421137A (en) | Preparation method of high temperature resistance polyacrylamide for oil displacement | |
| CN105646776A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN103333672A (en) | Salt-resistant resistance-reducing agent applied to shale gas reservoir | |
| CN105037644A (en) | Polymer cationic surfactant, preparation method and applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |