CN104262602B - A kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer and its preparation method and application - Google Patents
A kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer and its preparation method and application Download PDFInfo
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- CN104262602B CN104262602B CN201410466418.1A CN201410466418A CN104262602B CN 104262602 B CN104262602 B CN 104262602B CN 201410466418 A CN201410466418 A CN 201410466418A CN 104262602 B CN104262602 B CN 104262602B
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- acid
- carboxylic acids
- arylalkyl
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- arylalkyl carboxylic
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- -1 arylalkyl carboxylic acids Chemical class 0.000 title claims abstract description 82
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 23
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003921 oil Substances 0.000 claims abstract description 27
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 17
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 8
- 239000001294 propane Substances 0.000 claims abstract description 7
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 7
- 238000011084 recovery Methods 0.000 claims abstract description 6
- 238000007046 ethoxylation reaction Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000000295 fuel oil Substances 0.000 claims abstract 2
- 239000007908 nanoemulsion Substances 0.000 claims abstract 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011964 heteropoly acid Chemical class 0.000 claims description 4
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 3
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001553 barium compounds Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Chemical class 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004945 emulsification Methods 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 23
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000010779 crude oil Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 239000004530 micro-emulsion Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 229960003237 betaine Drugs 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 239000003027 oil sand Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000006200 ethylation reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- VPGSXIKVUASQIY-UHFFFAOYSA-N 1,2-dibutylnaphthalene Chemical compound C1=CC=CC2=C(CCCC)C(CCCC)=CC=C21 VPGSXIKVUASQIY-UHFFFAOYSA-N 0.000 description 1
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- SPLKSRDVCTUAGF-UHFFFAOYSA-N 3-(1-adamantyl)-4-methyl-5-phenyl-1,2,4-triazole Chemical compound N=1N=C(C23CC4CC(CC(C4)C2)C3)N(C)C=1C1=CC=CC=C1 SPLKSRDVCTUAGF-UHFFFAOYSA-N 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer and there is logical structure shown in formula I, preparation method is alkene-carboxylic acid to be alkylated with aromatic hydrocarbon, obtain arylalkyl carboxylic acids, arylalkyl carboxylic acids is carried out ring-opening reaction with expoxy propane, obtain arylalkyl carboxylic acids's polyoxypropylene ester, arylalkyl carboxylic acids's polyoxypropylene ester carries out ethoxylation with oxirane again, obtains arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer.Arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer, can be used for residual oil emulsification, the field such as prepared by reducing thick oil viscosity, heavy oil pour point depression, nanoemulsions, tertiary oil recovery, daily-use chemical industry.
Description
Technical field
The present invention relates to a kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer and preparation method thereof and answer
With.
Background technology
Fatty acid polyglycol oxypropylene polyoxyethylene block copolymer is the nonionic surfactant that a class is novel, owing to using
Polyoxyethylene polyoxypropylene block copolymeric structure so that it is use as emulsifying agent and have solely in fields such as oil exploitations
Special application performance.
The direct-connected alkyl structure of fatty acid polyglycol oxypropylene polyoxyethylene block copolymer with have alkane, aromatic hydrocarbons, colloid with
The performance of crude oils difference of asphalitine component is relatively big, and therefore, some performance indications is the most unsatisfactory.
Generally the chemical constituent of crude oil is alkane, aromatic hydrocarbon, resin and asphalt.Daqing crude oil and China are listed below
The fractional composition of some crude oil, is shown in Tables 1 and 2.
Table 1 Daqing oil field crude oil forms
Some crude oil fractional compositions of table 2 China
There is the carboxylic acid polyoxyethylene polyoxypropylene block copolymer of aryl alkyl structure, at crude oil, viscous crude, residual oil
The aspect performances such as emulsification, viscosity reduction, pour point depression can be more outstanding, simultaneously in fields such as tertiary oil recovery, low permeability oil field exploitations
Also it is with a wide range of applications.
Summary of the invention
The purpose of the present invention aims to provide a kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer, has logical
Structure shown in formula I:
Wherein: m+n is 0,1,2 ... 28,29,30 positive integers；
P is 1,2 ... 4998,4999,5000 positive integers；
Q is 0,1,2 ... 4998,4999,5000 positive integers；
R is phenyl, tolyl, meta-xylene base, paraxylene base, ortho-xylene base, ethylbenzene, n-propylbenzene
Base, isopropyl phenyl, n-butylphenyl, isobutyl phenenyl, tert-butyl-phenyl, naphthyl, methyl naphthyl, dimethyl
Naphthyl, ethyl naphthyl, propyl group naphthyl, butyl naphthyl, xenyl, the one in phenylol.
Further, in technique scheme, m+n is preferably the positive integer of 8,15,19, and more preferably 15,
Further, in technique scheme, p is preferably 5,6 ... 49,50 positive integers,
Further, in technique scheme, q is preferably 5,6 ... 49,50 positive integers,
Further, in technique scheme, R is preferably meta-xylene.
Another object of the present invention is to provide the preparation of above-mentioned arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer
Method, technical scheme is:
Under acidic catalyst effect, alkene-carboxylic acid is alkylated with aromatic hydrocarbon, obtains arylalkyl carboxylic acids；
Again arylalkyl carboxylic acids is carried out ring-opening reaction with expoxy propane under acidity or base catalyst effect, obtain virtue
Base alkyl carboxylic acid polyoxypropylene ester, arylalkyl carboxylic acids's polyoxypropylene ester again with oxirane at acid or base catalyst
Carry out ethoxylation under effect, obtain arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer；
Further, in technique scheme, the preparation of present invention acidic catalyst used by arylalkyl carboxylic acids,
For sulfuric acid, hydrofluoric acid, pyrovinic acid, TFMS, metal salts of trifluoromethane sulphonic acid or load TFMS root,
Any one or a few mixture in heteropoly acid, solid super-strong acid, acid zeolite, perfluorinated resin, ionic liquid,
The preferably TFMS root of pyrovinic acid, metal salts of trifluoromethane sulphonic acid or load, more preferably pyrovinic acid.
Further, in technique scheme, acidic catalyst used by ring-opening reaction or ethylation reaction is selected from BF3、
SbCI5、SnCI4, solid acid, heteropoly acid, one in carried molecular sieve catalyst, base catalyst used selects
From potassium hydroxide, NaOH, sodium methoxide, caustic alcohol, Mg/AI composite oxides (MAO), the oxide of barium
Compound with phosphoric acid with hydroxide, aluminum alkoxide sulfonate, rare metal alcoxyl sulfate, alkaline earth oxide
One in thing, preferably potassium hydroxide, sodium methoxide, Mg/AI composite oxides (MAO).
Further, in technique scheme, alkene-carboxylic acid of the present invention, for undecenoic acid:
CH2=CH (CH2)8COOH, oleic acid: CH3(CH2)7CH=CH (CH2)7COOH, erucic acid: cis
-13-docosenoic acid, preferably oleic acid.
Further, in technique scheme, aromatic hydrocarbon of the present invention, for benzene, toluene, meta-xylene,
Paraxylene, ortho-xylene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, isobutyl-benzene, tert-butyl benzene,
Naphthalene, methyl naphthalene, dimethylnaphthalene, ethylnaphthalene, propyl group naphthalene, dibutyl naphthalene, biphenyl, the one in phenol, preferably between two
Toluene.
Further, in technique scheme, pyrovinic acid as catalyst, alkene-carboxylic acid and aromatic hydrocarbon mole
Ratio is 1:1.5-3.5, reaction temperature 100-135 DEG C, drips alkene-carboxylic acid, and then reaction 5 hours, are washed to pH value
Neutrality, short-path distillation removes unreacted raw material and saturated acid therein, obtains arylalkyl carboxylic acids.Described alkene-carboxylic acid
It is 1:1.15-2.0 with the mol ratio of pyrovinic acid.
Further, in technique scheme, arylalkyl carboxylic acids of the present invention and opening that expoxy propane is carried out
Ring reacts, and preferred aryl groups alkyl carboxylic acid and expoxy propane mol ratio are the reaction of 1:5～50.
Further, arylalkyl carboxylic acids's polyoxypropylene ester of the present invention is anti-with the ethoxylation that oxirane is carried out
Should, preferred aryl groups alkyl carboxylic acid polyoxypropylene ester with molar than the reaction for 1:5～50.
The beneficial outcomes of the present invention is:
1. arylalkyl carboxylic acids's group of the present invention and oxypropylene block are oil-soluble, have the strongest with former
The energy that mixes of oil, viscous crude, residual oil etc., by controlling to access the size of ethylene oxide block, can control aryl alkyl carboxylic
The hydrophil lyophil balance of acid polyoxyethylene polyoxypropylene block, is widely used in residual oil emulsification, reducing thick oil viscosity, crude oil breast
The fields such as change；
2. arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer of the present invention, for the nonionic that molecular weight is bigger
Type surfactant, has the effect of thickening under finite concentration, can be used for improving oil recovery factor, especially weak
Use under alkali and alkali-free system, have thickening, solubilising, emulsify, the effect such as wetting；
3. arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer preparation method conversion ratio of the present invention is high, is suitable for
Industrialization produces.
Accompanying drawing explanation
Accompanying drawing 3 width of the present invention,
Fig. 1 is the infrared spectrogram of the meta-xylene base octadecane carboxylic acid that embodiment 1 prepares；
Fig. 2 is meta-xylene base octadecane carboxylic acid polyoxypropylene (15) the ester flight time mass spectrum that embodiment 1 prepares
Figure；
Fig. 3 is that meta-xylene base octadecane carboxylic acid polyoxypropylene (15) polyoxyethylene (15) that embodiment 1 prepares is embedding
Section copolymer flight time mass spectrum figure.
Detailed description of the invention
The present invention is further illustrated below in conjunction with embodiment, but not as a limitation of the invention.
Embodiment 1:
Friedel-Crafts alkylation:
Equipped with agitator, thermometer, constant voltage dropper, condenser 1000ml reaction bulb in, between putting into 248 grams two
Toluene (AR), 112 grams of pyrovinic acids (AR), be warming up to 125～130 DEG C, and (oleic acid contains to drip high-purity oleic acid
Amount >=75%) 220 grams, time for adding is 5 hours, continues reaction 2 hours.Cooling, is washed to pH value neutral,
The meta-xylene of Rotary Evaporators removing excess, molecular clock decolours, obtains meta-xylene base octadecane carboxylic acid.Liquid phase look
Analysis of spectrum oleic acid conversion >=90%.
Meta-xylene base octadecane carboxylic acid infrared spectrogram is shown in Fig. 1.
1412cm in FIG-1(carboxylic acid O-H flexural vibrations), 1710cm-1(carboxylic acid C=O stretching vibration)；725cm-1
(a disubstituted C-H out-of-plane bending vibration), 1047cm-1(aromatic hydrocarbons C-H in-plane bending vibration), 1459cm-1
(aromatic hydrocarbons C=C stretching vibration)；2853cm-1(CH2 alkane symmetrical stretching vibration), 2925cm-1(CH2 alkane
Antisymmetric stretching vibration).
Ring-opening reaction:
Weigh 116 grams of meta-xylene base octadecane carboxylic acids and 1.5 grams of Mg/AI composite oxides (MAO) put into 1 liter
In synthesis reactor, synthesis reactor is sealed, replace 3 times with nitrogen.Start stirring, be warming up to 140 DEG C, start vavuum pump
Vacuumize, stop when being warming up to 170 DEG C vacuumizing.Open inlet valve, with nitrogen by storage tank 261.36 grams of epoxies third
Alkane is gradually pressed in reactor, control reaction temperature at 140 DEG C～180 DEG C, pressure≤0.15MPa, react 5 hours.
Cooling, discharging, filter, remove catalyst, obtain meta-xylene base octadecane carboxylic acid polyoxypropylene (15) ester.
Meta-xylene base octadecane carboxylic acid polyoxypropylene (15) ester flight time mass spectrum figure is shown in Fig. 2.
It is the normal distribution of polyoxypropylene structure distribution in fig. 2, owing to this experiment used catalyst is that Mg/AI is multiple
Close oxide (MAO), embody the feature of narrow ditribution.
Ethylation reaction:
Weigh 252 grams of meta-xylene base octadecane carboxylic acid polyoxypropylene (15) esters and 1.5 grams of sodium methoxides put into 1 liter of conjunction
Become in still, synthesis reactor is sealed, replace 3 times with nitrogen.Start stirring, be warming up to 130 DEG C, start vacuum pumping
Vacuum, stops when being warming up to 160 DEG C vacuumizing.Open inlet valve, with nitrogen by storage tank 133 grams of oxirane by
Gradually press-in reactor in, control reaction temperature at 130 DEG C～170 DEG C, pressure≤0.15MPa, react 6 hours.Fall
Temperature, discharging, obtain meta-xylene base octadecane carboxylic acid polyoxypropylene (15) polyoxyethylene (15) block copolymer.
Meta-xylene base octadecane carboxylic acid polyoxypropylene (15) polyoxyethylene (15) block copolymer flight time mass spectrum
Figure is shown in Fig. 3.
We have seen that on the basis of meta-xylene base octadecane carboxylic acid polyoxypropylene (15) ester at Fig. 3, add ring
Oxidative ethane (15EO), obtains extremely complex flight time mass spectrum figure, this is because in gathering in normal distribution state
In oxypropylene structure, each structure all may result in extremely complex structure divide plus the oxirane of normal distribution
Cloth form.
Application examples 1
The application in tertiary oil recovery of the arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer of the present invention:
Composition components and content:
Erucyl amide propyl group carboxybetaine (from synthesis) 0.20%
Meta-xylene base octadecane carboxylic acid polyoxypropylene (15) polyoxyethylene (15) ester 0.15%
Remaining is water.
Erucyl amide propyl group carboxybetaine therein is with erucyl amide propyl group tertiary amine and sodium chloroacetate proportioning as 1:1.1
(mol ratio), 100 DEG C of methyl alcohol make solvent, carry out quaternary ammonium reaction 8 hours, and separating methanol obtains product.
Using grand celebration to recover the oil ten factory's crude oil and simulate water, the interfacial tension of test system is 5.63x10-3MN/m, system
Viscosity is 18.6mPa.s.
Meta-xylene base octadecane carboxylic acid polyoxypropylene (15) polyoxyethylene (15) ester solubilising erucyl amide propyl group carboxyl
Glycine betaine, interfacial tension reaches ultralow；Thickening binary system, has certain viscosity in the case of being not added with polymer；
And play emulsification.
Natural core oil displacement experiment enters according to People's Republic of China's oil and gas industry standard SY/T6424-2000
OK.Experiment oil is grand celebration ten factory simulated oil, and experimental water is that water is simulated by grand celebration ten factory.When water drive to aqueous 100%
Time inject the formula system of above-mentioned composition of 0.7 times of pore volume (PV), then when carrying out water drive to aqueous 100%
Terminate.
Natural core parameter is as shown in table 3:
The natural core parameter of table 3. composite formula system
Composite formula system is utilized to carry out natural core oil displacement experiment result as shown in table 4:
The oil displacement experiment result of table 4. composite formula system
Conclusion: erucyl amide propyl group carboxybetaine reaches ultralow with the interfacial tension of profit, but only with surfactant
Uncontrollable mobility itself, simultaneously because the beet alkali surface activator dissolubility of big molecule bad, its effect is also difficult
To play.Meta-xylene base octadecyl carboxylic acid polyoxyethylene polyoxypropylene block copolymer, can solubilising glycine betaine table
Face activating agent, can viscosify again the aqueous phase with glycine betaine activating agent, plays the purpose controlling mobility, has reached raising former
The purpose of oil recovery.
Application examples 2
The application in prepared by microemulsion of the arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer of the present invention:
Oil-sand is a kind of sand shape mineral reserve containing crude oil, and main component is pitch, water, clay and gravel, its stock number
Huge, account for the 30% of world oil reserves.
Being used in by microemulsion in oil-sand washing oil and will have highly important application prospect, microemulsion directly acts on oil-sand,
Normal temperature, it is not necessary to more heat energy, it is possible to decrease cost of winning.
Cetyl hydroxypropyl sulfobetaines therein is
1:1.1 (mol ratio), 125 DEG C of methyl alcohol make solvent, carry out quaternary ammonium reaction 8 hours, and separating methanol obtains product.
Form middle microemulsion phase when profit volume ratio is 1, displacement efficiency is up to 89.6%.
Claims (8)
1. arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer, it is characterised in that there is formula I knot
Structure:
Wherein, m+n is 0-30 positive integer；
P is 1-5000 positive integer；
Q is 0 or 1-5000 positive integer；
R is phenyl, tolyl, meta-xylene base, paraxylene base, ortho-xylene base, ethylbenzene, n-propylbenzene
Base, isopropyl phenyl, n-butylphenyl, isobutyl phenenyl, tert-butyl-phenyl, the one in phenylol.
The preparation side of a kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer the most as claimed in claim 1
Method, it is characterised in that comprise the following steps:
1.. the alkylated reaction that alkene-carboxylic acid and aromatic hydrocarbon are carried out under acidic catalyst effect, obtain aryl alkyl carboxylic
Acid；
2.. arylalkyl carboxylic acids step 1. obtained again is carried out under acidity or base catalyst effect with expoxy propane
Ring-opening reaction, then under acidity or base catalyst effect, carry out ethoxylation with oxirane, obtain aryl alkane
Yl carboxylic acid polyoxyethylene polyoxypropylene block copolymer.
Preparation method the most according to claim 2, it is characterised in that: described step 1. middle acidic catalyst is sulphur
Acid, hydrofluoric acid, pyrovinic acid, TFMS, metal salts of trifluoromethane sulphonic acid or heteropoly acid, solid super-strong acid, acid
Any one or a few in property zeolite, perfluorinated resin, ionic liquid.
Preparation method the most according to claim 2, it is characterised in that described step 2. middle ring-opening reaction or ethyl
Change the acidic catalyst of reaction selected from BF3、SbCl5、SnCl4, solid acid, heteropoly acid, carried molecular sieve catalysis
One in agent；Base catalyst is selected from potassium hydroxide, NaOH, sodium methoxide, caustic alcohol, Mg/Al composite oxygen
Compound, oxide and hydroxide, aluminum alkoxide sulfonate, rare metal alcoxyl sulfate, the alkaline-earth metal oxygen of barium
Compound and the one in the compound of phosphoric acid.
Preparation method the most according to claim 2, it is characterised in that: described step 1. middle alkene-carboxylic acid is 11
One or more in olefin(e) acid, oleic acid, erucic acid.
Preparation method the most according to claim 2, it is characterised in that: described step 2. in arylalkyl carboxylic acids with
The ring-opening reaction that expoxy propane is carried out, arylalkyl carboxylic acids and expoxy propane mol ratio are the reaction of 1:5～50.
Preparation method the most according to claim 2, it is characterised in that: described step 2. middle arylalkyl carboxylic acids gather
The ethoxylation that oxypropylene ester is carried out with oxirane, arylalkyl carboxylic acids's polyoxypropylene ester and molar
Ratio is 1:5～50.
8. arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer as claimed in claim 1 emulsify at residual oil,
Prepared by reducing thick oil viscosity, heavy oil pour point depression, nanoemulsions, tertiary oil recovery, application in daily-use chemical industry.
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| CN103641750A (en) * | 2013-11-28 | 2014-03-19 | 中国石油天然气股份有限公司 | Surfactant containing aralkyl hydrophobic chain and amido bond connecting group |
| CN103865053A (en) * | 2012-12-10 | 2014-06-18 | 辽宁奥克化学股份有限公司 | Terminal alkenyl unsaturated acid/ester polyoxyalkyl ether, and preparation method and use thereof |
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| CN103320110A (en) * | 2013-06-26 | 2013-09-25 | 工合聚能(天津)石油精化科技发展有限公司 | Nano composite high-temperature-resistant extraction aid for thickened oil and super-thickened oil recovery and preparation method thereof |
| CN103641750A (en) * | 2013-11-28 | 2014-03-19 | 中国石油天然气股份有限公司 | Surfactant containing aralkyl hydrophobic chain and amido bond connecting group |
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