CN109053959A - One kind is based on polysaccharide-modified hyperbranched association polymer and preparation method thereof - Google Patents
One kind is based on polysaccharide-modified hyperbranched association polymer and preparation method thereof Download PDFInfo
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- polysaccharide
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- cyclodextrin
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- 229920000642 polymer Polymers 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 51
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 29
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 28
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 28
- 229960004853 betadex Drugs 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 20
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006392 deoxygenation reaction Methods 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 230000002209 hydrophobic effect Effects 0.000 claims description 18
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- -1 alkyl carbon Chemical group 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 9
- 238000006073 displacement reaction Methods 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical group CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SVEUVITYHIHZQE-UHFFFAOYSA-N n-methylpyridin-2-amine Chemical compound CNC1=CC=CC=N1 SVEUVITYHIHZQE-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003140 primary amides Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- BBDNZMUIQBRBJH-UHFFFAOYSA-N sulfurochloridic acid;toluene Chemical compound OS(Cl)(=O)=O.CC1=CC=CC=C1 BBDNZMUIQBRBJH-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses one kind to be based on polysaccharide-modified hyperbranched association polymer, and polymerization reaction occurs by reaction monomers acrylamide, acrylic acid, functional poly amide-amine hydridization beta-cyclodextrin F β-CD and N- aryl acrylamide and is made.Preparation method step includes: step S1: preparing functional poly amide-amine hydridization beta-cyclodextrin F β-CD；Step S2: acrylamide is added in distilled water and acrylic acid stirs evenly, adjusting pH value is 6-8, adds N- aromatic radical acrylamide and lauryl sodium sulfate, stirring to solution clear, functionalization beta-cyclodextrin F β-CD is added, the dissolved oxygen in nitrogen removing solution is led to；Step S3: being added photoinitiator in the solution after deoxygenation, reacts 4-6h, and reaction temperature is 15-30 DEG C to get arriving polysaccharide-modified hyperbranched association polymer.Hyperbranched association polymer of the invention has good dissolubility, temperature resistance, salt resistance and shear resistant, is the optimal selection of oil field oil displacement agent, has broad application prospects.
Description
Technical field
The invention belongs to oil field oil displacement agent technical fields, and in particular to a kind of drive for oilfield chemistry improves recovery ratio
Based on polysaccharide-modified hyperbranched association polymer and preparation method thereof.
Background technique
Polymer displacement of reservoir oil is a kind of important tertiary oil recovery technology, is obtained in the one kind in many oil fields in China, two class oil reservoirs
Apparent oil increasing precipitation effect.However, all there is the considerable three classes of reserves even four class oil reservoirs, this kind of oil reservoir in each oil field in China
Temperature, salinity, divalent ion (calcium ions and magnesium ions) content are high and Oil layer connectivity is poor, so that this kind of oil reservoir does not have progress also
The technical conditions of polymer flooding.Meanwhile polymer on ground and underground will be subjected to very strong shear action when infusing poly-, so that traditional
The increasing stick of polymer, salt-resistance, high temperature ageing stability and shear resistant etc. all suffer from stern challenge.
The line polymer oil displacement agent HPAM being widely used at present, price economy, but it is only applicable to low temperature less salt oil
Hiding, and anti-shear performance is poor.With a large amount of short chain hydrophobic grouping on comb polymer KYPAM molecular backbone, salt-resistance is bright
It is aobvious to be better than HPAM, but when the divalent ion concentrations such as calcium and magnesium are higher in solution, tackifying is relative to HPAM also without too big excellent
Gesture.Temperature resistance, salt resistance and the anti-shear performance of biopolymer xanthan gum are better than HPAM, but its antibiont degradation property is poor, water
Dissolubility is bad, and tackifying is undesirable and price is more expensive, limits the extensive use of xanthan gum.Hydrophobic associated polymer HAPAM
Containing a small amount of long chain hydrophobic group, be capable of forming network structure in the solution, anti-salt property compared with other polymers all compared with
It is good.But the molecular backbone of KYPAM and HAPAM is still linear structure, in high temperature (>=75 DEG C), (>=30000mg/ with high salt
L) under reservoir condition, strand is crimped, and is easy to happen mechanical degradation, viscosity decline is serious, and long-time stability are undesirable.
Dissaving polymer is a kind of polymer with special nature newly to emerge, with hyperbranched three-dimensional structure,
The properties such as a large amount of end group, highly dissoluble, high chemical reactivity are generally considered poly- after linear, branching, crosslinking at present
Close the 4th class high molecular material after object.Using the architectural characteristic of hyperbranched macromolecular, the anti-shearing of polymer can be improved
Performance.For cyclodextrin as a kind of natural reproducible raw material, source is wide, pollution-free.Its spy hydrophilic with the hydrophobic outer wall in inner cavity
Property, the aqueous solution polymerization of hydrophobic monomer can be realized with the hydrophobic class molecule of inclusion.A large amount of literature survey the result shows that, utilize
The architectural characteristic of hyperbranched macromolecular can significantly improve the anti-shear performance of polymer.Polysaccharide is as a kind of natural reproducible
Raw material, source is wide, pollution-free, and itself has comparable resistance to mild anti-shear performance.Based on polysaccharide-modified hyperbranched
Macromolecular, intramolecule there are many cavitys, it is peripheral then have largely can be carried out functionalization end group (- OH ,-COOH or-
NH2Deng), they can further be reacted with functionalized reagent, or be interacted with its ambient substance, according to practical need
The macromolecule of different structure performance is designed, is considered using polysaccharide or modification of polysaccharides as the basic bone of synthesis of super branched polymer
Frame unit shows special potentiality and advantage.Therefore, the dissaving polymer based on cyclo-dextrin-modified not only has certain
Heat-resistant salt-resistant also has anti-shear performance, shows special structure and advantage.
Summary of the invention
It is excellent it is an object of the invention to solve at least the above problems and/or defect, and provide at least to will be described later
Point.
A further object of the invention is for Polymer Used For Oil Displacement heat and salt resistance and shear restoration in the prior art
The disadvantage of difference provides a kind of based on polysaccharide-modified hyperbranched association polymer.The dissaving polymer is with polysaccharide-modified macromolecular
Centered on, hydrophilic radical, rigid hydrophobic grouping are introduced by the way of free-radical polymerized, being formed has the super of spacial framework
Branched polymer is the optimal selection of oil field oil displacement agent to meet good dissolubility, heat and salinity tolerance shear resistant, tool
Have broad application prospects.
It is a still further object of the present invention to provide a kind of preparation method based on polysaccharide-modified hyperbranched association polymer, works
Skill step is simple, and thoroughly, yield is high for reaction.
In order to realize these purposes and other advantages according to the present invention, provides and a kind of hyperbranched formed based on polysaccharide-modified
Polymer is closed, by reaction monomers acrylamide, acrylic acid, functional poly amide-amine hydridization beta-cyclodextrin F β-CD and N- aryl
Acrylamide occurs polymerization reaction and is made；The structural formula of the hyperbranched association polymer is as follows:
X in formula, y, a are structural unit number, and m is alkyl carbon chain-CH2Length, the concrete structure formula of F β-CD are as follows:
Preferably, the x is 75%-85%, y 15%-25%, a=1-x-y.
Preferably, the hyperbranched association polymer viscosity average molecular weigh is 150-500 ten thousand.
Preferably, the concrete structure formula of the hyperbranched association polymer are as follows:
A kind of preparation method based on polysaccharide-modified hyperbranched association polymer comprising following steps:
Step S1: functional poly amide-amine hydridization beta-cyclodextrin F β-CD, concrete operations are prepared are as follows:
S11: under the condition of ice salt bath, beta-cyclodextrin and paratoluensulfonyl chloride being reacted, and obtain 6-OTs- β-CD；
S12: obtained 6-OTs- β-CD reacts to obtain BEA- β-CD with butanediamine BEA under the action of catalyst；S13: by what is obtained
BEA- β-CD reacts to obtain intermediate 1 with methyl acrylate MA；S14: intermediate 1 reacts to obtain intermediate with butanediamine BEA again
2；S15: intermediate 2 is dissolved in N, in N- dimethyl sulfoxide, dicyclohexylcarbodiimide is then added, obtains solution A, by acrylic acid
It is dissolved in N, obtains solution B in N- dimethyl sulfoxide, solution B is slowly dropped in solution A under ice salt bath and logical condition of nitrogen gas, is dripped
8h is reacted at 25 DEG C after adding, becomes sticky to reaction solution, obtains sticky two generation of the shape function monomer F β-CD of pale yellow transparent, use
The washing of acetone repeated precipitation, obtains white product, and vacuum drying obtains target product functionalization beta-cyclodextrin F β-CD；
Step S2: acrylamide and acrylic acid being added in distilled water, stirred evenly, and adjusting pH value with NaOH is 6-8, so
Hydrophobic monomer N- aromatic radical acrylamide and Surfactant SDS are added afterwards, stirs to solution clear,
Functionalization beta-cyclodextrin F β-CD is added, the dissolved oxygen in nitrogen 30min removing solution is then led to；
Step S3: being added photoinitiator, Photoinitiated reactions 4-6h in the solution after deoxygenation, reaction temperature is 15-30 DEG C, obtains
To white polymer colloid, as polysaccharide-modified hyperbranched association polymer.
Preferably, the photoinitiator is 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone.
Preferably, in the step S2, reaction monomers total mass fraction is 20%, wherein acrylamide 14-
16.5%, acrylic acid 2.5-5%, N- aromatic radical-Methacrylamide is 0.1-0.25%, functionalization beta-cyclodextrin F β-CD
For 0.1%-0.25%, lauryl sodium sulfate 0.4-1.0%.
Preferably, the step S12 specifically: 6-OTs- β-CD is mixed with butanediamine BEA, catalyst 4- bis- is added
Methylamino pyridine is stirred to react 7h at 70 DEG C under dry nitrogen protection；Revolving removes unreacted butanediamine BEA, institute
It obtains after light yellow liquid is cooled to room temperature and is slowly dropped in excessive cold acetone, stir and simultaneously crystallized at 4 DEG C, be precipitated faint yellow glutinous
Thick object, the mixed solvent of filter cake deionized water and methanol dissolves after filtering, then is added dropwise to crystalline deposit in cold acetone, mistake
Filter, and use acetone washing, repeat purify 3 times；It is dried in vacuo for 24 hours at 40 DEG C of the sticky sediment of gained, obtains fluffy white powder shape
Substance, as BEA- β-CD.
Preferably, the step S14 specifically: intermediate 1 is dissolved in methanol, under the conditions of ice-water bath, is added dropwise to fourth
Diamines BEA is gradually increased to 25 DEG C of reaction 48h after being stirred to react 1h, and vacuum distillation removes excessive butanediamine BEA and methanol, then
Concentrate is added drop-wise in acetone, precipitation white solid is stirred continuously, repeats to purify through methanol dissolution, acetone precipitation after suction filtration,
Vacuum drying, obtains Tan solid；Intermediate 1 is replaced with gained Tan solid, the operation of step S14 is repeated, obtains centre
Body 2.
The synthetic reaction principle that functional poly amide-amine hydridization beta-cyclodextrin F β-CD is prepared in the present invention is as follows:
Compared with existing hydrophobic monomer, the present invention uses the hydrophobic monomer of acrylamide class formation, has the advantage that
(1) hydrophobic monomer is similar with the structure of main monomer acrylamide, is easy to be copolymerized with water-soluble monomers such as acrylamides；(2)
Contain benzene ring structure in the hydrophobic chain of hydrophobic monomer, the hydrolysis of amide groups can be inhibited, while molecule chain rigidity can be increased,
Improve temperature tolerance；(3) using polysaccharide-modified functionalization beta-cyclodextrin as core, N- is introduced on the macromolecular chain based on acrylamide
The temperature-resistant anti-salt dissaving polymer of aromatic radical-N- alkyl acrylamide is with heatproof, salt resistance, shear resistant and diffluent
Comprehensive performance.Therefore polysaccharide-modified hyperbranched association polymer of the invention improves oil recovery factor for being used as in oil field development
Oil displacement agent, have broad application prospects.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention
Fig. 1 is the infrared spectrum of polysaccharide-modified hyperbranched association polymer；
Fig. 2 is viscosity-concentration relationship curve of polysaccharide-modified hyperbranched association polymer；
Fig. 3 is viscosity-temperature curve of polysaccharide-modified hyperbranched association polymer；
Fig. 4 is viscosity-salinity relation curve of polysaccharide-modified hyperbranched association polymer；
Fig. 5 is the viscoelasticity curve of polysaccharide-modified hyperbranched association polymer.
Specific embodiment
Combined with specific embodiments below, it elaborates to the present invention.
Embodiment 1
A kind of preparation method based on polysaccharide-modified hyperbranched association polymer comprising following steps:
Step S1: functional poly amide-amine hydridization beta-cyclodextrin F β-CD, concrete operations are prepared are as follows:
S11: under the condition of ice salt bath, 50g beta-cyclodextrin is suspended in 100mL distilled water, magnetic agitation, by 16.7mL
Concentration is that the sodium hydroxide solution of 8.5mol/L is slowly dropped into beta-cyclodextrin suspension, until suspension becomes clarification；Then will
The acetonitrile solution (concentration of toluene sulfochloride is 2.0mol/L) of 34mL paratoluensulfonyl chloride p-TsCl is placed in constant pressure funnel
It is interior, it is added dropwise in the sodium hydroxide solution of beta-cyclodextrin, reacts 2h under the conditions of 22 DEG C of constant temperature after dripping；After reaction will
Unreacted p-TsCl is filtered to remove, and filtrate is neutralized to the pH=8.0 of solution with the dilute hydrochloric acid of concentration 2.6mol/L, quiet at 4 DEG C
It filters after setting overnight to get 6-OTs- β-CD crude product；After crude product is cleaned three times with acetone, 150mL distilled water is added, 80
It recrystallizes 3 times at DEG C, is dried in vacuo for 24 hours under the conditions of 40 DEG C in vacuum drying oven, obtaining white crystals sprills is to purify
6-OTs-β-CD；
S12: the 6-OTs- β-CD for taking 16.0g to purify is added 40mL butanediamine BEA and 0.032g catalyst 4- dimethylamino
Pyridine DMAP is stirred to react 7h for 70 DEG C of constant temperature under dry nitrogen protection；Revolving removes unreacted BEA, and gained is light yellow
Liquid is slowly dropped in excessive cold acetone after being cooled to room temperature, is stirred and is crystallized at 4 DEG C, has faint yellow dope to be precipitated,
The mixed solvent (volume ratio 3:1) of filter cake appropriate amount of deionized water and methanol dissolves after filtering, then is added dropwise in cold acetone
Precipitating, filtering, and use acetone washing, repeat purify 3 times；The sticky sediment of gained is placed in a vacuum drying oven 40 DEG C of dryings of constant temperature
For 24 hours, fluffy white powder shape substance is obtained, the BEA- β-CD as purified；
S13: under the conditions of ice-water bath, 4.0g BEA- β-CD being dissolved in 80mL methanol, and 40.0g acrylic acid first is added dropwise
Ester MA is gradually heated to 25 DEG C of reactions for 24 hours after stirring 30min in ice-water bath, with removed in rotary evaporator unreacted MA and
Concentrate is added drop-wise in acetone by methanol, and white solid is precipitated, and is filtered, is added drop-wise to third after obtained solid is dissolved with methanol again
In ketone, dissolved, precipitate purification repeatedly after be dried in vacuo, obtaining pale solid is intermediate 1, for half for product
G0.5CP；
S14: 2.0g intermediate 1 is dissolved in 70mL methanol, and 24g butanediamine is added dropwise under ice-water bath, is stirred to react 1h,
It is gradually heated to 25 DEG C of reaction 48h later, vacuum distillation removes excessive BEA and methanol, then concentrate is added drop-wise in acetone,
It is stirred continuously precipitation white solid, repeats to purify through methanol dissolution, acetone precipitation after suction filtration, vacuum drying obtains Tan solid,
As generation product G 1.0CP；It replaces intermediate 1 to repeat the operation of S14 with G1.0CP, finally obtains intermediate 2, be two generations
Product G 2.0CP；
S15: taking the 25g N of 20g intermediate 2, and N- dimethyl sulfoxide DMF dissolution is placed in three-necked flask, adds 0.3g bis-
Cyclohexyl carbodiimide, obtains solution A；6g acrylic acid is dissolved in 35g DMF, solution B is obtained, leads to nitrogen item in ice salt bath
Solution B is slowly dropped in solution A under part, reacts 8h after dripping at 25 DEG C, reaction solution becomes sticky, obtains faint yellow
Transparent two generation of sticky shape function monomer F β-CD；It is washed with acetone repeated precipitation, obtaining white product is the polysaccharide-modified of functionalization
Hyperbranched macromolecular is placed in a vacuum drying oven and is dried to obtain target product functional modification beta-cyclodextrin F β-CD.
Step S2: 16.5g acrylamide and 2.5g acrylic acid being added in distilled water, stirred evenly, and adjust pH with NaOH
Value is 6, adds 0.1g hydrophobic monomer N- aromatic radical acrylamide and 0.7g Surfactant SDS, addition one
Quantitative distilled water, makes liquor capacity reach 80mL, stirs to solution clear, adds 0.2g functionalization beta-cyclodextrin F β-
CD；Then lead to the dissolved oxygen in nitrogen 30min removing solution.
Step S3: being added photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone in the solution after deoxygenation,
It is placed under light-initiated device and reacts 4h, reaction temperature is 30 DEG C, obtains white polymer colloid, as polysaccharide-modified hyperbranched to form
Close polymer.Preferred photoinitiator is Irgacure 2959.
Embodiment 2
A kind of preparation method based on polysaccharide-modified hyperbranched association polymer comprising following steps:
Step S1: functional poly amide-amine hydridization beta-cyclodextrin F β-CD, the step S1 of specific method and embodiment 1 are prepared
It is identical.
Step S2: 14g acrylamide and 5g acrylic acid being added in distilled water, stirred evenly, and are adjusted pH value with NaOH and are
7,0.25g hydrophobic monomer N- aromatic radical acrylamide and 0.5g Surfactant SDS are added, addition is certain
Distilled water is measured, liquor capacity is made to reach 80mL, stirs to solution clear, adds 0.25g functionalization beta-cyclodextrin F β-
CD；Then lead to the dissolved oxygen in nitrogen 30min removing solution.
Step S3: being added photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone in the solution after deoxygenation,
It is placed under light-initiated device and reacts 5h, reaction temperature is 20 DEG C, obtains white polymer colloid, as polysaccharide-modified hyperbranched to form
Close polymer.Preferred photoinitiator is Irgacure 2959.
Embodiment 3
A kind of preparation method based on polysaccharide-modified hyperbranched association polymer comprising following steps:
Step S1: functional poly amide-amine hydridization beta-cyclodextrin F β-CD, the step S1 of specific method and embodiment 1 are prepared
It is identical.
Step S2: 15.2g acrylamide and 3.7g acrylic acid being added in distilled water, stirred evenly, and adjust pH with NaOH
Value is 8, adds 0.1g hydrophobic monomer N- aromatic radical acrylamide and 0.9g Surfactant SDS, addition one
Quantitative distilled water, makes liquor capacity reach 80mL, stirs to solution clear, adds 0.1g functionalization beta-cyclodextrin F β-
CD；Then lead to the dissolved oxygen in nitrogen 30min removing solution.
Step S3: being added photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone in the solution after deoxygenation,
It is placed under light-initiated device and reacts 6h, reaction temperature is 15 DEG C, obtains white polymer colloid, as polysaccharide-modified hyperbranched to form
Close polymer.Preferred photoinitiator is Irgacure 2959.
Performance characterization
(1) structural characterization of polysaccharide-modified hyperbranched association polymer
Fig. 1 is the infrared spectrum of polysaccharide-modified hyperbranched association polymer synthesized by embodiment 1.It can from figure
It arrives: 3413cm-1、3226cm-1Place is primary amide N-H stretching vibration absworption peak, 1622cm-1Place is the characteristic absorption peak of carbonyl,
3552cm-1And 3466cm-1It is the stretching vibration absworption peak of-OH in beta-cyclodextrin, 3126cm-1And 3016cm-1It is C-H on phenyl ring
Stretching vibration absworption peak；1456cm-1And 1509cm-1It is the stretching vibration absworption peak of C=C double bond in phenyl ring, 2992cm-1With
2859cm-1It is the stretching vibration absworption peak of C-H in chain, 1540cm-1Place is the absorption vibration peak of C=O, 1112cm-1It is C-N
Absorb vibration peak.
(2) the increasing stick effect analysis of polysaccharide-modified hyperbranched association polymer
The polymer that embodiment 1 is obtained is configured to the polymer solution of various concentration.It is in room temperature, shear velocity
7.34s-1Under conditions of, measure viscosity-concentration curve (as shown in Figure 2) of hydrophobic associated polymer.When polymer concentration is lower than
When critical association concentration, polymer molecular chain curling, polymer water power small volume, polymer viscosity increasess slowly；When poly-
When closing object concentration higher than critical association concentration, the heat resistance and salt tolerance between hydrophobic grouping to form space networks between strand
Network structure, polymer viscosity quickly increase.
(3) heat-resisting property of polysaccharide-modified hyperbranched association polymer
The polymer that embodiment 1 is obtained is configured to the solution of concentration 2000mg/L, is 7.34s in shear rate-1Condition
The apparent viscosity (as shown in Figure 3) of lower measurement polymer at different temperatures.The viscosity of polymer first is slowly increased, at 50 DEG C
Reach maximum value, then reduces as the temperature increases.When temperature reaches 95 DEG C, viscosity retention rate is 87.56%, temperature resistance
It is functional.
(4) salt-resistance of polysaccharide-modified hyperbranched association polymer
The quick Journal of Sex Research of salt is carried out to the polymer that embodiment 1 is prepared.Polymer is configured under different salinities
Concentration is the polymer solution of 2000mg/L.In room temperature, shear velocity 7.34s-1Under conditions of, measure the table of polymer solution
Viscosity is seen with the variation relation of salinity (see Fig. 4).Figure 4, it is seen that the apparent of polymer sticks with the raising of salinity
Degree, which shows, first reduces the trend for increasing reduce again afterwards, shows good salt resistance effect.
(5) viscoelasticity of polysaccharide-modified hyperbranched association polymer
Viscoelasticity research is carried out to the polymer that embodiment 1 obtains.In low frequency area, loss moduli is greater than elasticity modulus；
Subsequent loss moduli and elasticity modulus increase simultaneously, and last elasticity modulus is greater than loss moduli, the table in tertiary oil recovery and pressure break
Reveal huge application potential.
Above embodiment, which is intended to illustrate the present invention, to be realized or use for professional and technical personnel in the field, to above-mentioned
Embodiment, which is modified, will be readily apparent to those skilled in the art, therefore the present invention includes but is not limited to
Above embodiment, it is any to meet the claims or specification description, meet with principles disclosed herein and novelty,
The method of inventive features, technique, product, fall within the scope of protection of the present invention.
Claims (9)
1. one kind be based on polysaccharide-modified hyperbranched association polymer, which is characterized in that by reaction monomers acrylamide, acrylic acid,
Functional poly amide-amine hydridization beta-cyclodextrin F β-CD and N- aryl acrylamide occurs polymerization reaction and is made；It is described hyperbranched to form
The structural formula for closing polymer is as follows:
X in formula, y, a are structural unit number, and m is alkyl carbon chain-CH2Length, the concrete structure formula of F β-CD are as follows:
2. being based on polysaccharide-modified hyperbranched association polymer as described in claim 1, which is characterized in that the x is 75%-
85%, y 15%-25%, a=1-x-y.
3. being based on polysaccharide-modified hyperbranched association polymer as claimed in claim 2, which is characterized in that the hyperbranched association
Polymer viscosity average molecular weigh is 150-500 ten thousand.
4. being based on polysaccharide-modified hyperbranched association polymer as claimed in claim 3, which is characterized in that the hyperbranched association
The concrete structure formula of polymer are as follows:
5. a kind of preparation method based on polysaccharide-modified hyperbranched association polymer, which comprises the steps of:
Step S1: functional poly amide-amine hydridization beta-cyclodextrin F β-CD, concrete operations are prepared are as follows:
S11: under the condition of ice salt bath, beta-cyclodextrin and paratoluensulfonyl chloride being reacted, and obtain 6-OTs- β-CD；S12:
To 6-OTs- β-CD react to obtain BEA- β-CD under the action of catalyst with butanediamine BEA；S13: the BEA- β-CD that will be obtained
It reacts to obtain intermediate 1 with methyl acrylate MA；S14: intermediate 1 reacts to obtain intermediate 2 again with butanediamine BEA；S15: will
Intermediate 2 is dissolved in N, in N- dimethyl sulfoxide, dicyclohexylcarbodiimide is then added, obtains solution A, acrylic acid is dissolved in N, N-
Obtain solution B in dimethyl sulfoxide, solution B be slowly dropped in solution A under ice salt bath and logical condition of nitrogen gas, after dripping
8h is reacted at 25 DEG C, becomes sticky to reaction solution, obtains sticky two generation of the shape function monomer F β-CD of pale yellow transparent, repeatedly with acetone
Washing of precipitate, obtains white product, and vacuum drying obtains target product functionalization beta-cyclodextrin F β-CD；
Step S2: acrylamide and acrylic acid being added in distilled water, stirred evenly, and adjusting pH value with NaOH is 6-8, then plus
Enter hydrophobic monomer N- aromatic radical acrylamide and Surfactant SDS, stirs to solution clear, then plus
Enter functionalization beta-cyclodextrin F β-CD, then leads to the dissolved oxygen in nitrogen 30min removing solution；
Step S3: being added photoinitiator, Photoinitiated reactions 4-6h in the solution after deoxygenation, reaction temperature is 15-30 DEG C, obtains white
Color polymeric colloid, as polysaccharide-modified hyperbranched association polymer.
6. the preparation method as claimed in claim 5 based on polysaccharide-modified hyperbranched association polymer, which is characterized in that described
Photoinitiator is 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone.
7. the preparation method as claimed in claim 5 based on polysaccharide-modified hyperbranched association polymer, which is characterized in that described
In step S2, reaction monomers total mass fraction is 20%, wherein acrylamide 14-16.5%, acrylic acid 2.5-5%, N-
Aromatic radical-Methacrylamide is 0.1-0.25%, and functionalization beta-cyclodextrin F β-CD is 0.1%-0.25%, dodecyl sulphur
Sour sodium is 0.4-1.0%.
8. the preparation method as claimed in claim 5 based on polysaccharide-modified hyperbranched association polymer, which is characterized in that described
Step S12 specifically: 6-OTs- β-CD is mixed with butanediamine BEA, catalyst 4-dimethylaminopyridine is added, in dry nitrogen
7h is stirred to react for 70 DEG C of constant temperature under gas shielded；Revolving removes unreacted butanediamine BEA, and gained light yellow liquid is cooled to room temperature
After be slowly dropped in excessive cold acetone, stir, crystallized at 4 DEG C, faint yellow dope be precipitated, filter cake deionization after filtering
The dissolution of the mixed solvent of water and methanol, then is added dropwise to crystalline deposit in cold acetone, filters, and uses acetone washing, repeatedly mentions
Pure 3 times；It is dried in vacuo for 24 hours at 40 DEG C of the sticky sediment of gained, obtains fluffy white powder shape substance, as BEA- β-CD.
9. the preparation method as claimed in claim 8 based on polysaccharide-modified hyperbranched association polymer, which is characterized in that described
Step S14 specifically: intermediate 1 is dissolved in methanol, under the conditions of ice-water bath, is added dropwise to butanediamine BEA, be stirred to react after 1h by
It edges up to 25 DEG C of reaction 48h, vacuum distillation removes excessive butanediamine BEA and methanol, then concentrate is added drop-wise in acetone, no
White solid is precipitated in disconnected stirring, repeats to purify through methanol dissolution, acetone precipitation after suction filtration, vacuum drying obtains Tan solid；With
Gained Tan solid replaces intermediate 1, repeats the operation of step S14, obtains intermediate 2.
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| CN111393865A (en) * | 2020-05-27 | 2020-07-10 | 吴碧玉 | High-viscosity modified asphalt and preparation method thereof |
| CN114106249A (en) * | 2021-12-21 | 2022-03-01 | 西南石油大学 | Supermolecule star polymer taking beta-CD as core and preparation method thereof |
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| CN114539476A (en) * | 2022-04-27 | 2022-05-27 | 东营市大用石油助剂有限责任公司 | Graft copolymerization high polymer material with viscoelasticity and preparation method thereof |
| CN117264141A (en) * | 2023-11-16 | 2023-12-22 | 克拉玛依市新聚工贸有限责任公司 | Temperature-resistant salt-resistant acrylamide polymer for fracturing and preparation process thereof |
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