CN114989364B - Polyurethane dendritic polymer and preparation method and application thereof - Google Patents
Polyurethane dendritic polymer and preparation method and application thereof Download PDFInfo
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- CN114989364B CN114989364B CN202110226208.5A CN202110226208A CN114989364B CN 114989364 B CN114989364 B CN 114989364B CN 202110226208 A CN202110226208 A CN 202110226208A CN 114989364 B CN114989364 B CN 114989364B
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 103
- 239000004814 polyurethane Substances 0.000 title claims abstract description 103
- 239000000412 dendrimer Substances 0.000 title claims abstract description 52
- 229920000736 dendritic polymer Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 15
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 13
- 230000001603 reducing effect Effects 0.000 claims abstract description 13
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 11
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- -1 N-dimethylacrylamide Chemical compound 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000000977 initiatory effect Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- PDFIEHRTRXPBNH-UHFFFAOYSA-N 2-methyl-2-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)OC(=O)C=C PDFIEHRTRXPBNH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 150000000703 Cerium Chemical class 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 claims description 2
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 claims description 2
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 claims description 2
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 20
- 238000005886 esterification reaction Methods 0.000 abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 7
- 230000035699 permeability Effects 0.000 abstract description 5
- 230000009977 dual effect Effects 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000005553 drilling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000000440 bentonite Substances 0.000 description 5
- 229910000278 bentonite Inorganic materials 0.000 description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- TURGQUUEAIELPU-UHFFFAOYSA-N methyl 2-[(dihydroxyamino)methyl]butanoate Chemical compound COC(C(CN(O)O)CC)=O TURGQUUEAIELPU-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- RDFJGUVEUBDQSI-UHFFFAOYSA-N ON(CC(C(=O)OCCCC)CC)O Chemical compound ON(CC(C(=O)OCCCC)CC)O RDFJGUVEUBDQSI-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FDYSSWYQRTVFIS-UHFFFAOYSA-N buta-1,3-diene 3-phenylprop-2-enoic acid Chemical compound C=CC=C.C(=O)(O)C=CC1=CC=CC=C1 FDYSSWYQRTVFIS-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane dendritic polymer, a preparation method and application thereof, wherein the polyurethane dendritic polymer takes hydroxyl-terminated dendritic polyurethane as a core and is obtained by polymerizing hydroxyl-terminated dendritic polyurethane and an alkenyl monomer; the hydroxyl-terminated dendritic polyurethane is obtained by carrying out esterification reaction on a compound containing more than two hydroxyl ends and carboxylic acid containing more than two hydroxyl ends, or is obtained by carrying out transesterification reaction on a compound containing more than two hydroxyl ends and carboxylic acid ester containing more than two hydroxyl ends; the carboxylic acid or carboxylic acid ester containing more than two terminal hydroxyl groups contains tertiary amino groups. The polyurethane dendritic polymer disclosed by the invention has excellent plugging and fluid loss reducing agent performances, can effectively reduce mud cake permeability while obviously reducing fluid loss, can effectively plug microcracks of a well wall, and has the dual effects of plugging and fluid loss reducing.
Description
Technical Field
The invention belongs to the field of petroleum engineering, and particularly relates to a polyurethane dendritic polymer and a preparation method and application thereof.
Background
Dendritic polymers are novel polymers with a dendritic structure, the surfaces of the dendritic polymers are enriched with a large number of functional groups, the molecules have nanometer sizes and cavities exist inside the dendritic polymers, and the dendritic molecules have compact structures similar to spheres in three-dimensional space due to the highly branched topological morphology of the dendritic polymers. At present, the research of dendritic polymers in the field of petroleum engineering is just started, and the research is mainly focused on utilizing the special rheological property and the reactivity of active end groups of the dendritic polymers, namely, shearing resistant polymers for improving the recovery ratio of oil fields and amine inhibitors for drilling fluid. Chinese patent document CN 106519254B discloses a dendritic quaternary ammonium salt shale inhibitor, which can effectively inhibit hydration dispersion of active shale (high montmorillonite); chinese patent document CN 106520085A discloses a dendritic polyether shale inhibition, which has excellent shale inhibition performance and can significantly inhibit hydration expansion and dispersion of shale.
The polymer filtrate reducer is a key auxiliary agent for guaranteeing the performance of drilling fluid, and the field consumption is large. High temperature and salt resistant polymeric fluid loss additives have been the focus and difficulty of research. Chain polymer filtrate reducer molecules break, fold or intertwine molecular chains in high-valence salt and the like at high temperature, so that the chain polymer filtrate reducer weakens or even loses the filtrate reducing effect. The plugging agent can also reduce the permeability of mud cakes while plugging the microcracks of the well wall, thereby assisting in reducing the fluid loss. At present, the organic nanometer plugging agent mainly takes polymer nanometer composite materials at home and abroad, such as deformable nanometer plugging polymer MAX-SHIELD developed by Bekkes corporation, is carboxyl styrene-butadiene latex or sulfonated styrene-butadiene latex with average granularity smaller than 0.2 mu m, and can form a layer of compact membrane structure on the surface of a well wall when the addition amount is 3%, so as to prevent water molecules from passing, thereby achieving the plugging effect and the well wall stabilizing effect.
The dendritic polymer is introduced into the field of petroleum engineering, so that a new means can be provided for solving some complex technical problems, but the research on the plugging filtrate reducer of the dendritic polymer drilling fluid is less at present.
Disclosure of Invention
The invention aims to solve the technical problems that in the research of drilling fluid plugging filtrate reducer, the research related to dendritic polymers is less, and the available dendritic polymers are few; the plugging and filtrate reducing agent effect is to be improved.
Aiming at the technical problems, the invention provides a preparation method of a polyurethane dendritic polymer, wherein the polyurethane dendritic polymer takes hydroxyl-terminated dendritic polyurethane as a core and is obtained by polymerizing hydroxyl-terminated dendritic polyurethane and an alkenyl monomer;
the hydroxyl-terminated dendritic polyurethane is obtained by carrying out esterification reaction on a compound containing more than two hydroxyl-terminated groups and carboxylic acid containing more than two hydroxyl-terminated groups, wherein the carboxylic acid containing more than two hydroxyl-terminated groups contains tertiary amino groups; or,
the hydroxyl-terminated dendritic polyurethane is obtained by performing transesterification on a compound containing more than two hydroxyl-terminated groups and carboxylic acid ester containing more than two hydroxyl-terminated groups; the carboxylic acid ester containing more than two terminal hydroxyl groups contains tertiary amino groups.
The hydroxyl-terminated dendritic polyurethane is an oligomer, a compound containing more than two hydroxyl-terminated groups is taken as a core, and the hydroxyl-terminated groups of the compound serving as the core are esterified with a carboxyl compound to obtain the first generation hydroxyl-terminated dendritic polyurethane, and the carboxyl compound also contains more than two hydroxyl-terminated groups, so that the carboxyl compound can be subjected to esterification reaction with the first generation hydroxyl-terminated dendritic polyurethane to obtain the second generation hydroxyl-terminated dendritic polyurethane; and by analogy, the hydroxyl-terminated dendritic polyurethane of the third generation, the fourth generation, the fifth generation and the like can be obtained.
The hydroxyl-terminated groups of the present invention mean that the hydroxyl groups are located at the ends of the compound, including both the ends of the compound backbone and the ends of the compound branches. The carboxyl groups of the compounds are also necessarily at the ends. The hydroxyl and carboxyl at the end have larger reactivity in esterification reaction, and hydroxyl-terminated dendritic polyurethane is easy to form. Since hydroxyl-terminated dendritic polyurethane is obtained by polycondensation of hydroxyl and carboxyl and contains tertiary amine groups, the dendritic polymer finally obtained by the invention is called polyurethane dendritic polymer for the sake of description accuracy and convenience because the structure of the hydroxyl-terminated dendritic polyurethane is not completely matched with that of 'urethane'.
Similarly, when the hydroxyl-terminated dendritic polyurethane is obtained by transesterification of a compound having two or more hydroxyl groups with a carboxylic acid ester having two or more hydroxyl groups, the same effect as in the esterification can be achieved by the transesterification although the ester group is not at the terminal end in the carboxylic acid ester having two or more hydroxyl groups. The esterification reaction is polycondensation to generate ester and water, while the transesterification of the invention is to generate ester and alcohol, the generated alcohol is generally micromolecular substance (such as methanol, ethanol, propanol and butanol), and the micromolecular compound generated by reduced pressure distillation can not influence the subsequent reaction.
Preferably, the hydroxyl-terminated dendritic polyurethane of the present invention consists of C, H, O, N elements only, ensuring the structural stability of the center. The hydroxyl-terminated dendritic polyurethane is synthesized by a one-step method with a core, so that the preparation of the hydroxyl-terminated dendritic polyurethane is very convenient.
Preferably, the alkenyl monomer is selected from anionic monomers, cationic monomers and nonionic monomers; preferably, the nonionic monomers include acrylamide, N-dimethylacrylamide, N-ethylacrylamide, N-diethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, and N-vinyl-2-pyrrolidone; preferably, the anionic monomers include acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and 2-acryloyloxy-2-methylpropanesulfonic acid; preferably, the cationic monomers include dimethyldiallylammonium chloride, acryloyloxyethyl trimethylammonium chloride, and methacryloyloxyethyl trimethylammonium chloride.
Preferably, two or more alkenyl monomers are selected for polymerization with the hydroxyl-terminated dendritic polyurethane; and/or the mass ratio of the hydroxyl-terminated dendritic polyurethane to the alkenyl monomer is 1:10 to 1:100. the invention discovers that the polyurethane dendritic polymer obtained by polymerizing more than two alkenyl monomers has larger molecular weight and can achieve better plugging and fluid loss reducing effects.
Preferably, the compound containing more than two hydroxyl ends is taken as a core, and the hydroxyl-terminated dendritic polyurethane with the algebraic number of 1-5 generation is obtained after esterification or transesterification; preferably, the compound containing two or more terminal hydroxyl groups is an alcohol, wherein the number of terminal hydroxyl groups is three, four or six; preferably, the carboxylic acid having two or more terminal hydroxyl groups is a monocarboxylic acid having two or more terminal hydroxyl groups; preferably, the carboxylic acid having two or more terminal hydroxyl groups is a monocarboxylic acid having two terminal hydroxyl groups, wherein the two terminal hydroxyl groups and one carboxyl group are respectively bonded to the ends of three substituted hydrocarbon groups of the tertiary amine group; preferably, the carboxylic acid ester containing two or more terminal hydroxyl groups is a monocarboxylic acid ester containing two or more terminal hydroxyl groups; preferably, the carboxylic acid ester having two or more terminal hydroxyl groups is a monocarboxylic acid ester having two terminal hydroxyl groups, wherein two terminal hydroxyl groups and one ester group are each bonded to three substituted hydrocarbon groups of the tertiary amine group.
Preferably, the compound containing a plurality of terminal hydroxyl groups is one of pentaerythritol, dipentaerythritol and trimethylolpropane; and/or the carboxylic acid containing a plurality of terminal hydroxyl groups is one of N, N-dihydroxyethyl-3-aminopropionic acid, N-dihydroxyethyl-3-aminopropionic acid and N, N-dihydroxyethyl-3-aminopropionic acid; the carboxylic acid ester containing a plurality of terminal hydroxyl groups is one of N, N-dihydroxyethyl-3-aminopropionic acid methyl ester, N-dihydroxyethyl-3-aminopropionic acid ethyl ester and N, N-dihydroxyethyl-3-aminopropionic acid butyl ester.
Preferably, in the preparation method of the hydroxyl-terminated dendritic polyurethane, trifluoro methane sulfonic acid or p-toluenesulfonic acid is used as a catalyst, and the hydroxyl-terminated dendritic polyurethane is obtained after the reaction for 2 to 5 hours at the temperature of between 120 and 140 ℃ under the protective atmosphere.
Preferably, the polymerization of the hydroxyl-terminated dendritic polyurethane with the alkenyl monomer is carried out in an aqueous solution; the mode of initiating polymerization comprises initiating polymerization, ultraviolet initiating polymerization and microwave initiating polymerization; preferably, in the initiator initiated polymerization, the initiator is a tetravalent cerium salt, including ceric ammonium nitrate, ceric ammonium sulfate, ceric ammonium phosphate or ceric sulfate.
Preferably, in the preparation method of the polyurethane dendritic polymer, deionized water, hydroxyl-terminated dendritic polyurethane and alkenyl monomers are added into a reactor, the pH value is regulated to 5-9 by alkali liquor, under the anaerobic condition, the temperature is raised to 30-60 ℃ for initiation, the reaction is stopped after the temperature in the reactor is reduced to room temperature, a viscous solution is obtained, and the viscous solution is dried and crushed to obtain the polyurethane dendritic polymer.
The invention also provides the polyurethane dendritic polymer obtained by the preparation method.
The preparation method of the present invention will be described below by taking a second-generation hydroxyl-terminated dendritic polyurethane as an example. The structural formula of the second-generation hydroxyl-terminated dendritic polyurethane is shown as follows, the second-generation hydroxyl-terminated dendritic polyurethane takes trimethylolpropane as a core, three hydroxyl groups in the trimethylolpropane are all positioned at the terminal position, and the three hydroxyl groups are subjected to transesterification reaction with N, N-dihydroxyethyl-3-aminopropionate methyl ester; the first generation hydroxyl-terminated dendritic polyurethane is obtained after transesterification, and because the N, N-dihydroxyethyl-3-amino methyl propionate contains two hydroxyl-terminated groups, the hydroxyl-terminated groups are introduced while the first generation hydroxyl-terminated dendritic polyurethane is synthesized, and the hydroxyl-terminated groups can be subjected to transesterification with other N, N-dihydroxyethyl-3-amino methyl propionate to obtain the second generation hydroxyl-terminated dendritic polyurethane with the following structure.
For ease of description, the second-generation hydroxyl-terminated dendritic polyurethane may be represented by HPAE-G2, HPAE representing the hydroxyl-terminated dendritic polyurethane and G2 representing the second generation.
Similarly, the inventors also described the preparation method of the present invention using a second-generation hydroxyl-terminated dendritic polyester as an example. The structural formula of the second-generation hydroxyl-terminated dendritic polyester is shown as follows, the second-generation hydroxyl-terminated dendritic polyurethane takes trimethylolpropane as a core, three hydroxyl groups in the trimethylolpropane are all positioned at the terminal position, and the three hydroxyl groups are esterified with carboxyl groups of 2, 2-dimethylolpropionic acid; the first generation hydroxyl-terminated dendritic polyurethane is obtained after esterification, and as the 2, 2-dimethylolpropionic acid contains two hydroxyl-terminated groups, the hydroxyl-terminated groups are introduced while the first generation hydroxyl-terminated dendritic polyurethane is synthesized, and the hydroxyl-terminated groups can be polymerized with other 2, 2-dimethylolpropionic acid to obtain the second generation hydroxyl-terminated dendritic polyester with the following structure.
The invention also provides application of the polyurethane dendritic polymer in blocking and fluid loss reducing.
Aiming at the requirements of the drilling fluid on the filtration reducing and plugging effects, the invention develops a novel polyurethane dendritic polymer which takes dendritic polyurethane as a core and grafts a large number of molecular chains with the filtration reducing effect on the surface, the polyurethane dendritic polymer weakens or eliminates the influence of the high Wen Duanlian of the chain polymer filtration reducing agent, and the novel polyurethane dendritic polymer has a hydrophobic polyurethane dendritic polymer core and has the filtration reducing and plugging effects. The polyurethane dendritic polymer prepared by the invention has the advantages of space three-dimensional configuration, self-micelle effect, strong temperature resistance and salt resistance and excellent plugging property.
The polyurethane dendritic polymer is used as a plugging filtrate reducer in drilling fluid, the mass concentration of the polyurethane dendritic polymer is 0.5-5wt%, the mud cake permeability can be effectively reduced, microcracks can be plugged, and the filtrate loss is reduced.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polyurethane dendritic polymer disclosed by the invention has excellent plugging and fluid loss reducing agent performances, can effectively reduce mud cake permeability while obviously reducing fluid loss, can effectively plug microcracks of a well wall, and has the dual effects of plugging and fluid loss reducing.
(2) The polyurethane dendritic polymer plugging filtrate reducer is prepared by grafting a plurality of long chains containing different functional groups on dendritic polyurethane containing a large number of terminal hydroxyl groups, grafting long-chain branched chains polymerized by monomers on dendritic polyurethane molecules with a central core, wherein the long-chain branched chains are not collapsed in conformation at high temperature, and the local high Wen Duanlian has small influence on performance, so that the heat resistance is improved.
(3) The dendritic polyurethane of different generations can be synthesized through one-step reaction, and is simple and easy to implement. The preparation method of the polyurethane dendritic polymer plugging filtrate reducer has the advantages of mild polymerization reaction conditions, easiness in control, readily available raw materials and convenience in industrialization.
Drawings
FIG. 1 is a schematic illustration of the polymerization reaction of a polyurethane dendrimer prepared in example 1 of the present invention.
FIG. 2 is an infrared spectrum of dendritic polyurethane HPAE-G2 prepared in an embodiment of the present invention.
FIG. 3 is an infrared spectrum of the polyurethane dendrimer plugging filtrate reducer prepared in example 3.
Detailed Description
The invention will be further illustrated with reference to specific examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials, unless otherwise specified, are all commercially available; % w/w means mass percent, and unless otherwise specified,% means mass percent. Because the polyurethane dendritic polymer synthesized by the invention is mainly used for plugging and reducing the fluid loss, the polyurethane dendritic polymer synthesized in the embodiment is also called a polyurethane dendritic polymer plugging fluid loss additive.
Synthesis of hydroxyl-terminated dendritic polyurethane of different algebra (HPAE-Gn, HPAE means hydroxyl-terminated dendritic polyurethane, G means "algebraic" and n means algebraic).
Taking HPAE-G1 as an example, the preparation process is: 1.34g of trimethylolpropane and 5.73g of N, N-dihydroxyethyl-3-aminopropionic acid methyl ester are added into a 100mL three-necked flask, 0.05g of p-toluenesulfonic acid is added, nitrogen is introduced, the temperature is raised to 120 ℃ under stirring, the reaction is carried out for 2 hours under the protection of the nitrogen, the middle is vacuumized twice, the reaction is vacuumized for more than 30min after the reaction is finished, and the temperature is reduced, so that light yellow transparent viscous liquid is obtained, and the hydroxyl-terminated dendritic polyurethane of 1 generation is obtained. The hydroxyl-terminated dendritic polyurethane with the algebraic number of 2 to 5 can be obtained by changing the feeding ratio. The result of infrared spectrum test of HPAE-G2 obtained in the present invention is shown in FIG. 2.
Example 1
300mL of deionized water is added into a 500mL reactor, 1.0G of hydroxyl-terminated dendritic polyurethane HPAE-G2 is added, stirring and dissolving are carried out uniformly, 5.0G of acrylamide, 10.0G of 2-acrylamide-2-methylpropanesulfonic acid and 2.0G of N, N-dimethylacrylamide are added, after stirring and dissolving uniformly, the pH value is regulated to 7.5 by using 30% NaOH solution, nitrogen is introduced for deoxidization, the temperature is raised to 35 ℃, and ultraviolet light is used for initiating polymerization reaction. And (3) after the temperature in the reactor is reduced to room temperature, stopping the reaction to obtain a viscous solution, and drying and crushing to obtain the polyurethane dendritic polymer plugging filtrate reducer which is marked as a product (1). The chemical reaction formula of the above polymerization reaction is shown with reference to fig. 1. The product in fig. 1 is a polyurethane dendritic polymer, the right side structure of the polymer is a chemical structure schematic diagram of a polymer molecular chain segment containing alkenyl monomers, and the polymer molecular chain segments containing other alkenyl monomers in the polymer are represented by wavy line bars.
Example 2
300mL of deionized water is added into a 500mL reactor, 1.0G of hydroxyl-terminated dendritic polyurethane HPAE-G3 is added, stirring and dissolving are carried out uniformly, 3.0G N-vinylformamide, 10.0G of 2-acrylamide-2-methylpropanesulfonic acid and 2.0G N-vinyl-2-pyrrolidone are added, after stirring and dissolving uniformly, 30% NaOH solution is used for adjusting the pH value to 6.5, nitrogen is introduced for deoxidization, the temperature is raised to 40 ℃, and 5mL of aqueous solution dissolved with 0.05G of ceric ammonium nitrate is added for initiating polymerization reaction. And (3) after the temperature in the reactor is reduced to room temperature, stopping the reaction to obtain a viscous solution, and drying and crushing to obtain the polyurethane dendritic polymer plugging filtrate reducer which is marked as a product (2).
Example 3
300mL of deionized water is added into a 500mL reactor, 0.5G of hydroxyl-terminated dendritic polyurethane HPAE-G3 is added, stirring and dissolving are carried out uniformly, 3.0G of acrylamide, 10.0G of 2-acrylamido-2-methylpropanesulfonic acid and 4.0G of acrylic acid are added, after stirring and dissolving uniformly, 30% NaOH solution is used for regulating the pH value to 7.0, nitrogen is introduced for deoxidization, the temperature is raised to 40 ℃, and 5mL of aqueous solution dissolved with 0.05G of ammonium cerium nitrate is added for initiating polymerization reaction. And (3) after the temperature in the reactor is reduced to room temperature, stopping the reaction to obtain a viscous solution, treating the viscous solution with ethanol, and drying and crushing the viscous solution to obtain the polyurethane dendritic polymer plugging filtrate reducer which is marked as a product (3). The infrared spectrum of the product (3) is shown in fig. 3.
Example 4
300mL of deionized water is added into a 500mL reactor, 2.0G of hydroxyl-terminated dendritic polyurethane HPAE-G1 is added, stirring and dissolving are carried out uniformly, 4.0G of G N-vinylformamide, 5.0G of 2-acryloyloxy-2-methylpropanesulfonic acid and 4.0G of acryloyl are added, after stirring and dissolving uniformly, 30% NaOH solution is used for regulating the pH value to 6.0, nitrogen is introduced for deoxidization, the temperature is raised to 50 ℃, and 5mL of aqueous solution with 0.08G of ammonium cerium sulfate is added for initiating polymerization reaction. And (3) after the temperature in the reactor is reduced to room temperature, stopping the reaction to obtain a viscous solution, treating the viscous solution with ethanol, and drying and crushing the viscous solution to obtain the polyurethane dendritic polymer plugging filtrate reducer which is marked as a product (4).
Example 5
300mL of deionized water is added into a 500mL reactor, 1.0G of hydroxyl-terminated dendritic polyurethane HPAE-G2 is added, stirring and dissolving are carried out uniformly, 3.0G of acrylamide, 10.0G of 2-acryloyloxy-2-methylpropanesulfonic acid and 2.0G of acryloyloxy ethyl trimethyl ammonium chloride are added, after stirring and dissolving uniformly, the pH value is regulated to 8.0 by using 30% NaOH solution, nitrogen is introduced for deoxidization, the temperature is raised to 50 ℃, and ultraviolet light is used for initiating polymerization reaction. And (5) after the temperature in the reactor is reduced to room temperature, stopping the reaction to obtain a viscous solution, treating the viscous solution with ethanol, and drying and crushing the viscous solution to obtain the polyurethane dendritic polymer plugging filtrate reducer which is marked as a product (5).
Comparative example
Essentially the same as in example 3, except that hydroxyl-terminated dendritic polyurethane HPAE-G3 was not added. 300mL of deionized water, 3.0g of acrylamide, 10.0g of 2-acrylamido-2-methylpropanesulfonic acid and 4.0g of acrylic acid are added into a 500mL reactor, the mixture is stirred and dissolved uniformly, the pH value is regulated to 7.0 by using 30% NaOH solution, nitrogen is introduced for deoxidization, the temperature is raised to 40 ℃, 3mL of aqueous solution containing 0.03g of ammonium persulfate and 3mL of aqueous solution containing 0.03g of sodium bisulfite are added, and polymerization reaction is initiated. And (3) after the temperature in the reactor is reduced to room temperature, stopping the reaction to obtain a viscous solution, treating the viscous solution with ethanol, and drying and crushing the viscous solution to obtain a polymer product, namely a product (6).
The polyurethane dendrimer plugged fluid loss additive products (1) to (5) prepared in examples 1 to 5 and the polymer product (6) prepared in comparative example were subjected to performance evaluation.
(1) 300mL of water was added to the high-stirring cup, and 0.6g of anhydrous sodium carbonate and 12.0g of bentonite were added under stirring, and the mixture was left to hydrate for 24 hours to obtain 4% bentonite-based slurry. 30g of sodium chloride is added, and after high stirring, the mixture is aged for 16 hours at 180 ℃, the medium-pressure water loss is 178mL in the test, and the permeation plugging performance (the filter medium is a FANN ceramic sand disc, and the test pressure is 3.5MPa and the test temperature is 150 ℃) is tested by using a high-temperature high-pressure filtration plugging tester. 152mL of filtrate was collected for 30 min.
(2) 30g of sodium chloride is added into 300mL of 4% bentonite-based slurry, 9.0g of the prepared product is added after high stirring for 30min, the mixture is stirred at a high speed for 20min to be uniformly dissolved, the mixture is put into a high-temperature aging tank, and is aged for 16 hours at 180 ℃ by hot rolling, the medium-pressure water loss is tested, and the permeability blocking performance (FANN ceramic sand disc as a filter medium) is tested by a high-temperature high-pressure filtration blocking property tester. The blocking rate was calculated as follows.
Middle FL 0 The filtrate was taken up for 30min for the base slurry (4% bentonite+10% sodium chloride), FL was 3 when 3% synthetic sample was addedThe amount of the filtrate was 0 min.
Table 1 performance index of each of examples and comparative examples
It can be seen that the filtrate reducer prepared by taking hydroxyl-terminated dendritic polyurethane as a core, in bentonite slurry containing 10% sodium chloride, after hot rolling for 16 hours at 180 ℃, not only significantly reduces the filtrate loss, but also has better plugging performance on micro holes of a ceramic sand disc, and the plugging rate of the ceramic filter disc is more than 85%, which is far higher than that of the polymer filtrate reducer without dendritic polyurethane core of the comparative example.
Claims (9)
1. The application of the polyurethane dendritic polymer in blocking and fluid loss reducing is characterized in that the polyurethane dendritic polymer is prepared by the following method: the polyurethane dendritic polymer takes hydroxyl-terminated dendritic polyurethane as a core and is obtained by polymerizing hydroxyl-terminated dendritic polyurethane and an alkenyl monomer;
the hydroxyl-terminated dendritic polyurethane is obtained by performing transesterification on a compound containing more than two hydroxyl-terminated groups and carboxylic acid ester containing more than two hydroxyl-terminated groups; the carboxylic acid ester containing more than two terminal hydroxyl groups contains tertiary amino groups;
the alkenyl monomers include anionic monomers and nonionic monomers;
the nonionic monomers include acrylamide, N-dimethylacrylamide, N-ethylacrylamide, N-diethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide and N-vinyl-2-pyrrolidone;
the anionic monomers include acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and 2-acryloyloxy-2-methylpropanesulfonic acid;
the mass ratio of the hydroxyl-terminated dendritic polyurethane to the alkenyl monomer is 1:10 to 1:100;
in the preparation method of the polyurethane dendritic polymer, deionized water, hydroxyl-terminated dendritic polyurethane and alkenyl monomer are added into a reactor, the pH value is regulated to 5-9 by alkali liquor, under the anaerobic condition, the temperature is raised to 30-60 ℃ for initiation, the reaction is stopped when the temperature in the reactor is reduced to room temperature, a viscous solution is obtained, and the polyurethane dendritic polymer is obtained after drying and crushing.
2. The use according to claim 1, wherein the hydroxyl-terminated dendritic polyurethane having an algebraic number of 1 to 5 is obtained by transesterification with the compound containing two or more hydroxyl-terminated groups as a core.
3. The use according to claim 2, wherein the number of terminal hydroxyl groups in the compound containing two or more terminal hydroxyl groups is three, four or six.
4. The use according to claim 3, wherein the carboxylic acid ester containing two or more terminal hydroxyl groups is a monocarboxylic acid ester containing two or more terminal hydroxyl groups.
5. The use according to claim 4, wherein the carboxylic acid ester containing more than two terminal hydroxyl groups is a monocarboxylic acid ester containing two terminal hydroxyl groups, wherein two terminal hydroxyl groups and one ester group are each attached to three substituted hydrocarbon groups of a tertiary amine group.
6. The use according to any one of claims 1 to 5, wherein the compound containing a plurality of terminal hydroxyl groups is one of pentaerythritol, dipentaerythritol and trimethylolpropane.
7. The method according to claim 6, wherein the hydroxyl-terminated dendritic polyurethane is obtained by reacting with trifluoromethanesulfonic acid as a catalyst at 120-140 ℃ in a protective atmosphere for 2-5 hours.
8. The use according to claim 7, wherein the polymerization of the hydroxyl-terminated dendritic polyurethane with the alkenyl monomer is carried out in aqueous solution; the mode of initiating polymerization includes initiating polymerization, ultraviolet light initiated polymerization and microwave initiated polymerization.
9. The use according to claim 8, wherein in the initiator-initiated polymerization, the initiator is a tetravalent cerium salt, comprising ceric ammonium nitrate, ceric ammonium sulfate, ceric ammonium phosphate or ceric sulfate.
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| PCT/CN2022/078349 WO2022184023A1 (en) | 2021-03-01 | 2022-02-28 | Dendritic polymer, and preparation method therefor and application thereof |
| US18/548,460 US20240174793A1 (en) | 2021-03-01 | 2022-02-28 | Dendritic polymer, and preparation method therefor and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999000440A1 (en) * | 1997-06-26 | 1999-01-07 | Perstorp Ab | Synthesis of a dendritic polyalcohol |
| CN1502646A (en) * | 2002-11-21 | 2004-06-09 | 清华大学 | Dendritic polyurethane macromole and synthesis method |
| CN101993532A (en) * | 2010-11-02 | 2011-03-30 | 东南大学 | Acrylate containing carboxyl hyperbranched poly(amine-ester) and preparation method thereof |
| TWI572670B (en) * | 2015-12-25 | 2017-03-01 | 國立臺北科技大學 | Dendritic waterborne polyurethane composition and film formed by dendritic waterborne polyurethane composition |
| CN107674189A (en) * | 2017-09-30 | 2018-02-09 | 合众（佛山）化工有限公司 | A kind of height divides hyperbranched Si modification unsaturated polyester resin and preparation method thereof admittedly |
| CN109134839A (en) * | 2018-09-04 | 2019-01-04 | 济南大学 | A kind of preparation of hyperbranched type paraffin and its application in wood-based plate |
-
2021
- 2021-03-01 CN CN202110226208.5A patent/CN114989364B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999000440A1 (en) * | 1997-06-26 | 1999-01-07 | Perstorp Ab | Synthesis of a dendritic polyalcohol |
| CN1502646A (en) * | 2002-11-21 | 2004-06-09 | 清华大学 | Dendritic polyurethane macromole and synthesis method |
| CN101993532A (en) * | 2010-11-02 | 2011-03-30 | 东南大学 | Acrylate containing carboxyl hyperbranched poly(amine-ester) and preparation method thereof |
| TWI572670B (en) * | 2015-12-25 | 2017-03-01 | 國立臺北科技大學 | Dendritic waterborne polyurethane composition and film formed by dendritic waterborne polyurethane composition |
| CN107674189A (en) * | 2017-09-30 | 2018-02-09 | 合众（佛山）化工有限公司 | A kind of height divides hyperbranched Si modification unsaturated polyester resin and preparation method thereof admittedly |
| CN109134839A (en) * | 2018-09-04 | 2019-01-04 | 济南大学 | A kind of preparation of hyperbranched type paraffin and its application in wood-based plate |
Non-Patent Citations (1)
| Title |
|---|
| 超支化聚丙烯酰胺的合成与双重交联凝胶堵水剂的研究;张昊;《硕士电子期刊》;20180116(第02期);12-13,26页 * |
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