CN106146821B - A kind of method of epoxy monomer anionic ring-opening polymerization - Google Patents
A kind of method of epoxy monomer anionic ring-opening polymerization Download PDFInfo
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- CN106146821B CN106146821B CN201510206006.9A CN201510206006A CN106146821B CN 106146821 B CN106146821 B CN 106146821B CN 201510206006 A CN201510206006 A CN 201510206006A CN 106146821 B CN106146821 B CN 106146821B
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- polyethylene glycol
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- 239000000178 monomer Substances 0.000 title claims abstract description 94
- 239000004593 Epoxy Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 71
- 238000012653 anionic ring-opening polymerization Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 58
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 10
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 54
- 239000003999 initiator Substances 0.000 claims description 53
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- -1 alkali metal alkoxide Chemical class 0.000 claims description 38
- 150000001450 anions Chemical class 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000008118 PEG 6000 Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 239000003623 enhancer Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 14
- 238000006116 polymerization reaction Methods 0.000 description 35
- 239000000047 product Substances 0.000 description 25
- 238000009826 distribution Methods 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 150000001768 cations Chemical group 0.000 description 12
- 150000003983 crown ethers Chemical group 0.000 description 11
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 10
- RDNCDNCFAGUSLT-UHFFFAOYSA-N [K].C(CCCCC)(O)O Chemical compound [K].C(CCCCC)(O)O RDNCDNCFAGUSLT-UHFFFAOYSA-N 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 239000005457 ice water Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 3
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 239000012521 purified sample Substances 0.000 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 description 2
- WIPSEISENHJQIP-UHFFFAOYSA-N C(CCC)(O)O.[K] Chemical compound C(CCC)(O)O.[K] WIPSEISENHJQIP-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004353 Polyethylene glycol 8000 Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- INNCETFUXOMLKI-UHFFFAOYSA-N [K].OCC(CO)(CO)CO Chemical compound [K].OCC(CO)(CO)CO INNCETFUXOMLKI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NDEIPVVSKGHSTL-UHFFFAOYSA-N butane-1,1,1,2-tetrol Chemical compound CCC(O)C(O)(O)O NDEIPVVSKGHSTL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WEAYWASEBDOLRG-UHFFFAOYSA-N pentane-1,2,5-triol Chemical compound OCCCC(O)CO WEAYWASEBDOLRG-UHFFFAOYSA-N 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 235000019446 polyethylene glycol 8000 Nutrition 0.000 description 1
- 229940085678 polyethylene glycol 8000 Drugs 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Abstract
The present invention provides a kind of method of epoxy monomer anionic ring-opening polymerization reaction, accelerating agent of the polyethylene glycol as reaction is used in this method, significantly improve the speed that epoxy monomer anionic ring-opening polymerization reacts, the reaction time is obviously shortened, and obtained polymer molecular weight narrowly distributing.
Description
Technical Field
The invention relates to the field of polymer preparation, in particular to a method for ring-opening polymerization of epoxy monomer anions.
Background
The ring-opening polymerization reaction of epoxy monomer is the basic method for preparing polyether rubber, polyether surfactant, polyether flocculant and other products, and is also the main method for preparing polyether polyol prepolymer in polyurethane industry.
According to the difference of initiator and catalytic system, the ring-opening polymerization of epoxy monomer can be divided into three types of coordination ring-opening polymerization, cation ring-opening polymerization and anion ring-opening polymerization.
The coordination ring-opening polymerization needs to use a transition metal catalyst, alkyl aluminum, a complexing auxiliary agent and the like, the catalytic system is complex and has high toxicity, and the process for removing the residual catalyst from the polymerization product is complex and has high energy consumption.
The cation ring-opening polymerization has more side reactions, the molecular weight of the polymer is not easy to control, and the method is rarely adopted in industry.
The anion ring-opening polymerization is generally initiated by an alkali metal compound or an alkaline earth metal compound, and these metal compounds include metal hydroxides, alkoxides, metal oxides and the like.
Since the compounds of alkali metals or alkaline earth metals have low toxicity and can be neutralized by acid, one of the advantages of anion ring-opening polymerization is high safety of the initiator and simple post-treatment process of the product. However, the anionic ring-opening polymerization has disadvantages of a slow polymerization reaction rate and a low monomer conversion rate. For example, potassium butanediol-initiated ring opening polymerization of ethylene oxide and phenyl ethylene oxide requires a duration of 3 weeks or more (Langmuir,2003,19, 943-950).
Chinese patent CN102924709A discloses a method for synthesizing block polyether, which uses the composition of crown ether and alkaline compound as catalyst to catalyze the ring-opening polymerization reaction of ethylene oxide and/or propylene oxide to obtain block polyether, wherein the ring-opening polymerization reaction time is shortened to be within several hours, thus the introduction of crown ether accelerates the ring-opening polymerization speed of epoxy monomer anion.
Chinese patent CN103788363A discloses a method for preparing high molecular weight perfluoropolyether, which uses phase transfer catalyst and anhydrous alkali metal fluoride as catalytic system, and carries out polymerization in an aprotic solvent by controlling reaction temperature to control the polymerization degree of hexafluoropropylene oxide, wherein the phase transfer catalyst can be alkyl polyethylene glycol or crown ether.
On the one hand, crown ethers are a class of compounds that are expensive and toxic, and the use of crown ethers in the preparation of polyether products not only increases costs, but also increases safety risks. On the other hand, the crown ether and the polyethylene glycol have obvious effects as phase transfer catalysts, and the application of the polyethylene glycol as a promoter in a homogeneous system is not found at present.
Aiming at the problems in the prior art, the development of a method for rapidly carrying out ring-opening polymerization on epoxy monomer anions by taking an epoxy monomer as a raw material, which has low cost, no toxicity and simple manufacturing process, is urgently needed.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: when the epoxy monomer is subjected to anion ring-opening polymerization reaction, the accelerator polyethylene glycol is added into the system, the reaction speed can be obviously improved, and the prepared product has large number average molecular weight and narrow molecular weight distribution, thereby completing the invention.
The object of the present invention is to provide the following:
in a first aspect, the present invention provides a process for the anionic ring-opening polymerization of an epoxy monomer, characterised in that the process comprises the steps of:
(1) mixing and stirring an epoxy monomer, an initiator and an accelerator;
(2) the reaction system was cooled, and a terminator was added to remove volatile substances in the system.
In a second aspect, the present invention also provides the above method, wherein the epoxy monomer, the initiator and the accelerator in step 1 are mixed in a reaction vessel according to the following molar ratio:
100 parts by mole of epoxy monomer
0.1-10 mol portions of initiator
0.01 to 20 parts by mole of an accelerator,
wherein,
the number of moles of epoxy monomer is based on the number of moles of epoxy monomer molecules,
the moles of initiator are based on the moles of initiator molecules,
the moles of promoter are based on the moles of promoter molecules.
In a third aspect, the present invention also provides the method as described above,
the structural formula of the epoxy monomer is shown as the following formula I:
wherein, the substituent R is one of hydrogen, alkyl, branched alkyl, phenyl and alkyl substituted phenyl; and/or
The accelerant is polyethylene glycol, and the number of the molar mass of the accelerant is calculated by the number average molecular weight of the accelerant; and/or
The initiator is an alkali metal alkoxide.
In a fourth aspect, the present invention also provides the method as described above,
the accelerant is polyethylene glycol with the number average molecular weight of 400-30000, more preferably the polyethylene glycol with the number average molecular weight of 700-20000, and further preferably the polyethylene glycol with the number average molecular weight of 1000-10000, such as polyethylene glycol with the brands of PEG-2000, PEG-4000, PEG-6000 and PEG-8000.
In a fifth aspect, the present invention also provides the above method, wherein in step 1, a solvent is optionally added, and the solvent is an organic solvent, preferably a hydrocarbon solvent or an ether solvent, preferably one or more selected from cyclohexane, n-hexane, dioxane, tetrahydrofuran, benzene and toluene, more preferably one or more selected from cyclohexane, tetrahydrofuran and toluene, such as tetrahydrofuran.
In a sixth aspect, the present invention also provides the method as described above, characterized in that, in step 1,
before the reaction raw materials are put into the reaction container, drying and deoxidizing the reaction container; and/or
Before the reaction raw materials are put into the reactor, the epoxy monomer and the accelerator are dried and subjected to oxygen removal treatment.
In a seventh aspect, the present invention also provides the method, wherein in step 1, the reaction temperature of the ring-opening polymerization of the epoxy monomer anions is 40 ℃ to 120 ℃, preferably 50 ℃ to 90 ℃; and/or
The epoxy monomer anion ring-opening polymerization reaction time is 10 hours to 90 hours, preferably 12 hours to 80 hours, such as 12 hours, 24 hours or 80 hours.
In an eighth aspect, the present invention also provides the above method, wherein in step 2, the terminating agent is selected from an alcohol compound or water, preferably a small molecule alcohol, such as one or more of methanol, ethanol, propanol, etc., and more preferably methanol.
In a ninth aspect, the present invention also provides the above method, wherein in step 2, the number of moles of the terminator is 2 to 20 times, preferably 5 to 15 times the number of moles of the initiator, based on the number of moles of the terminator molecules, and the number of moles of the initiator is based on the number of moles of the initiator molecules.
In a tenth aspect, the present invention also provides the use of a polyethylene glycol for promoting anionic ring-opening polymerisation of epoxy monomers.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The present invention is described in detail below.
According to a first to ninth aspect of the present invention, there is provided a method for ring-opening polymerization of an epoxy monomer anion, characterized in that the method comprises the steps of:
step 1, mixing an epoxy monomer, an initiator and an accelerator, and stirring.
In the present invention, an epoxy monomer, an initiator and an accelerator are mixed in the following molar ratio in a reaction vessel.
100 parts by mole of epoxy monomer
0.1-10 mol portions of initiator
0.01 to 20 parts by mole of an accelerator,
preferably, the first and second liquid crystal materials are,
100 parts by mole of epoxy monomer
0.2-8 parts by mole of initiator
0.1 to 10 parts by mole of an accelerator,
more preferably, the first and second liquid crystal materials are,
100 parts by mole of epoxy monomer
0.5-6 parts by mole of initiator
0.5-5 parts by mole of an accelerator.
Wherein,
the structural formula of the epoxy monomer is shown as the following formula I:
wherein,
the substituent R is one of hydrogen, alkyl, phenyl and alkyl-substituted phenyl, wherein the alkyl is a straight-chain alkyl of C1-C18, a branched-chain alkyl of C1-C18, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and the like; the alkyl-substituted phenyl is phenyl with an alkyl substituent on a benzene ring, the alkyl substituent on the benzene ring can be 1,2, 3, 4 or 5, the alkyl substituent on the benzene ring is a straight-chain alkyl of C1-C5, and a branched-chain alkyl of C1-C5, such as tolyl, xylyl, trimethylphenyl, tetramethylphenyl, pentamethyl, ethylphenyl, diethylphenyl, triethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, tert-butylphenyl, n-pentylphenyl, isopentylphenyl, neopentylphenyl and the like.
In a preferred embodiment of the present invention, the epoxy monomer used is an epoxy monomer as shown below:
and/or
The present inventors have found that ethylene oxide, hydrocarbyl-substituted ethylene oxide and phenyl-substituted ethylene oxide such as propylene oxide, butylene oxide, phenyl ethylene oxide and the like can be rapidly subjected to anionic ring-opening polymerization by the method of the present invention, but halogen-containing epoxy compounds such as epichlorohydrin and the like do not give polyether polymers but give small molecular compounds, and without being bound by any theory, the present inventors believe that in anionic ring-opening polymerization, the halogen groups liberated may cause deactivation of alkali metal alkoxides as an initiator, thereby interrupting the polymerization. Therefore, the present invention selects the above epoxy monomers for anionic ring-opening polymerization.
The initiator is alkali metal alkoxide, wherein the alkali metal forming the alkali metal alkoxide is selected from lithium, sodium or potassium; the alcohol constituting the alkali metal alkoxide is selected from one of monohydric alcohol, dihydric alcohol, trihydric alcohol and tetrahydric alcohol, and preferably methanol, ethanol, propanol, tert-butanol, pentanol, hexanol, n-octanol, ethylene glycol, propylene glycol, hexylene glycol, glycerol, 1,2, 4-butanetriol, 1,2, 5-pentanetriol, butanetetraol and pentaerythritol.
In a preferred embodiment of the present invention, the preferred initiators are potassium tert-butoxide, potassium hexanediol, potassium pentaerythritol.
The initiator used in the invention can provide negative oxygen anion active groups in a reaction system of the ring-opening polymerization of the anions of the epoxy monomer, and is easy to attack active sites on the epoxy monomer, thereby initiating the ring-opening polymerization reaction of the anions of the epoxy monomer.
The inventor finds that when the amount of the initiator is 0.1-10 parts by mole based on 100 parts by mole of the epoxy monomer, the anionic ring-opening polymerization reaction of the epoxy monomer can be rapidly initiated, the polymerization reaction can be rapidly carried out, and the reaction cannot be too violent, so that the molecular weight distribution of the generated polymerization product is narrow.
The accelerant is polyethylene glycol, preferably polyethylene glycol with the number average molecular weight of 400-30000, more preferably polyethylene glycol with the number average molecular weight of 700-20000, and further preferably polyethylene glycol with the number average molecular weight of 1000-10000, such as polyethylene glycol with the brands of PEG-2000, PEG-4000, PEG-6000 and PEG-8000.
The inventor finds that the rate of ring-opening polymerization of epoxy monomer anions is remarkably increased by adding polyethylene glycol into a reaction system, and is increased to within 4 days from the original more than 3 weeks, specifically referring to experimental examples 2-4.
The present inventors have also found that polyethylene glycol having a number average molecular weight of less than 400 or more than 30000 is not excellent in the effect of accelerating the ring-opening polymerization of anions, and without being bound by any theory, the present inventors believe that the main reason is-CH in the molecular chain of low molecular weight polyethylene glycol2-CH2The unit number of the-O- (ethylene oxide structural unit) is too small, the complexing ability to metal ions is poor, and the enhancement effect on the activity of negative oxygen anions on an initiator to attack epoxy monomers is not obvious; the polyethylene glycol with the number average molecular weight of more than 30000 can reduce the dosage of the polyethylene glycol, but has the following problems that the molecular chain of the high molecular weight polyethylene glycol is seriously entangled, the complexing capability to metal cations is reduced, and the viscosity of a polymerization system is increased, so that the heat and mass transfer processes of a reaction system such as temperature rise and the like are limited, and the polymerization reaction is inhibited, so that the polyethylene glycol with the number average molecular weight of 400-30000, more preferably 700-20000, further preferably 1000-10000, more preferably the polyethylene glycol with the brands of PEG-2000, PEG-4000, PEG-6000 and PEG-8000 is selected as an accelerator.
Further, the present inventors have also found that when the amount of the epoxy monomer added is greater than 20 parts by mole based on 100 parts by mole of the polyethylene glycol, the proportion of the epoxy monomer in the reaction system decreases, resulting in a slow rate of polymerization; when the addition amount of the polyethylene glycol is less than 0.01 mole part, the promotion effect of the polyethylene glycol on the polymerization reaction is not obvious, so the addition amount of the selective promoter polyethylene glycol is 0.01 to 20 mole parts, preferably 0.1 to 10 mole parts, more preferably 0.5 to 5 mole parts, wherein the mole number of the polyethylene glycol is calculated by the mole number of polyethylene glycol molecules, and the number value of the mole mass of the polyethylene glycol is calculated by the number average molecular weight of the polyethylene glycol molecules.
Without being bound by any theory, the present inventors believe that the principle that polyethylene glycol is capable of promoting the ring-opening polymerization of epoxy monomer anions is as follows:
the reaction system is a homogeneous polymerization reaction system, negative oxygen anions generated by the initiator can attack carbon-oxygen bonds in epoxy ternary rings in epoxy monomers to initiate ring opening of the epoxy monomers to further perform chain growth reaction, the polyethylene glycol has a flexible chain structure, the chain structure can be complexed with metal cations in the initiator, and the metal cations in the initiator can be nested in a cavity formed by a tortuous chain structure of the polyethylene glycol, so that the distance between the negative oxygen anions and the metal cations in the initiator is increased, the exposure degree of the negative oxygen anions is increased, the steric hindrance caused by the attack of the negative oxygen anions in the epoxy monomers by the initiator is reduced, and the initiator has stronger initiating effect. Meanwhile, the distance between a new terminal group negative oxygen anion formed by initiating ring-opening polymerization of the epoxy monomer by the initiator and a metal cation in the initiator can be increased by the complexation of the polyethylene glycol, so that the exposure degree and the ring-opening polymerization activity of the terminal group negative oxygen anion are improved, and the effect of continuously promoting the ring-opening polymerization is realized.
In addition, the polymerization system of the present invention is a homogeneous phase system, and thus, the function of polyethylene glycol in the reaction system is different from that of a phase transfer catalyst, i.e., polyethylene glycol does not rely on its solubility in two immiscible phases to increase the degree of dissolution of the initiator in the two phases to promote the reaction.
The polyethylene glycol has a flexible chain structure, so that the size of a cavity formed by the polyethylene glycol can be changed along with the size of the radius of a metal cation in an initiator, therefore, the polyethylene glycol can be complexed with metal ions with different radii in the invention, and the ring-opening polymerization reaction of anions initiated by the initiators containing different metal cations is promoted, for example, the initiator with the metal cation being lithium ion, the initiator with the metal cation being sodium ion or the initiator with the metal cation being potassium ion, namely, the adaptability of the polyethylene glycol is strong, and the application range is wide.
Crown ether is high in toxicity and price, so that compared with crown ether, polyethylene glycol cannot cause environmental pollution in the process of promoting the anionic polymerization reaction of epoxy monomers, the risk that operators are poisoned due to the use of the accelerator is avoided, if the crown ether remains in products, users are poisoned, and therefore the crown ether is used as the accelerator, and the operation of removing and recycling the crown ether is required after the polymerization reaction is finished.
The method provided by the invention has the advantages that after the polymerization reaction is finished, the prepared polymer has no toxicity even if polyethylene glycol residues in a system are not removed during the post-treatment of the prepared product, so that the method provided by the invention is a green and environment-friendly method for carrying out the anionic polymerization of the epoxy monomer.
In addition, the polyethylene glycol is used as an accelerant, so that the production cost can be reduced by over 80 percent.
The order of addition of the epoxy monomer, initiator and accelerator is not particularly limited in the present invention.
Before the reaction raw materials are put into the reaction vessel, the reaction vessel is dried and oxygen is removed.
The present inventors have found that trace amounts of water, moisture, carbon dioxide, air, etc. cause termination of the ring-opening polymerization of the epoxy monomer anions, and thus it is necessary to remove water or air which may remain in the reaction vessel before the raw materials are added to the reaction vessel, thereby ensuring smooth progress of the ring-opening polymerization of the epoxy monomer anions.
The manner of drying the reaction vessel is not particularly limited in the present invention, and any method of drying the reaction vessel that is feasible in the prior art, such as drying at 120 ℃ to 150 ℃ for 3 hours to 5 hours, may be used.
The method for removing oxygen in the reaction vessel is not particularly limited, and any method that is feasible in the prior art, such as introducing a chemically inert gas, vacuumizing, and the like, may be used, wherein the chemically inert gas is selected from nitrogen and argon, and preferably nitrogen.
In a preferred embodiment of the present invention, after the raw materials are added to the reaction vessel, the reaction vessel is sealed so as not to cause the termination of the polymerization reaction by the mixing of air and other impurity gases carried by the air into the reaction system.
In a more preferred embodiment of the present invention, the raw materials, such as epoxy monomers and accelerators, are subjected to a water and oxygen removal treatment prior to being added to the reaction vessel.
The method for removing water and oxygen from the raw material is not particularly limited in the present invention, and any method capable of removing trace water and trace oxygen from the raw material in the art, such as freeze drying, high vacuum drying, and molecular sieve water and oxygen removal, may be used.
In the invention, the reaction temperature of the ring-opening polymerization of the anions of the epoxy monomers is 40-120 ℃, the reaction temperature can be selected in a targeted manner to be slightly higher than the boiling point of the epoxy monomers aiming at each different epoxy monomers, so that the reaction system is kept in a slightly boiling state, and particularly for the epoxy monomers with lower boiling points, the rapid proceeding of the ring-opening polymerization of the anions can be ensured, the excessive internal pressure of a reaction container can be prevented, and the leakage of the reaction container is avoided; the present inventors have found that even for epoxy monomers having a relatively high boiling point, when the reaction temperature exceeds 120 ℃, the molecular weight distribution of the resulting polymerization product becomes broad, and therefore, the present invention selects the reaction temperature for the anion ring-opening polymerization of the epoxy monomer to be 40 ℃ to 120 ℃, preferably 50 ℃ to 90 ℃.
In a preferred embodiment of the present invention, the temperature in the reaction vessel is kept constant during the anionic ring-opening polymerization of the epoxy monomer.
The inventor finds that the molecular weight and the molecular weight distribution of the prepared epoxy monomer anion ring-opening polymerization product are closely related to the reaction time, and the shorter the reaction time is, the smaller the molecular weight of the polymerization product is, and the narrower the molecular weight distribution is; the longer the reaction time, the larger the molecular weight of the polymer product, but the broader the molecular weight distribution; therefore, the present invention selects the epoxy monomer anion ring-opening polymerization reaction time to be 10 hours to 90 hours, preferably 12 hours to 80 hours, such as 12 hours, 24 hours or 80 hours, and prepares the epoxy monomer anion ring-opening polymerization product with large molecular weight and narrow molecular weight distribution.
Optionally, a solvent may also be added in step 1.
The present inventors have found that in the present invention, a halogenated hydrocarbon solvent, an ester solvent, or the like causes deactivation of a polymerization active chain, and thus conversion rate of anion ring-opening polymerization of an epoxy monomer is low.
In the present invention, the solvent is an organic solvent, preferably a hydrocarbon solvent or an ether solvent, preferably one or more selected from cyclohexane, n-hexane, dioxane, tetrahydrofuran, benzene and toluene, more preferably one or more selected from cyclohexane, tetrahydrofuran and toluene, such as tetrahydrofuran.
In the present invention, the weight ratio of the solvent to the epoxy monomer is (0 to 5):1, preferably (0.05 to 3):1, for example, 1: 1.
And 2, cooling the reaction system, adding a terminator, and removing volatile substances in the system.
After the reaction is finished, the reaction system is cooled, and can be cooled to room temperature or other predetermined temperature, preferably to room temperature, so as to facilitate subsequent operation.
The cooling method in the present invention is not particularly limited, and any method capable of cooling the reaction system in the prior art, such as natural cooling or ice-bath cooling, may be used.
The present inventors have found that when a terminator is added to the reaction system at the end of the polymerization reaction, the molecular weight distribution of the obtained epoxy monomer anion ring-opening polymerization product is narrower than that when no terminator is added, that is, the molecules of the obtained epoxy monomer anion ring-opening polymerization product are more uniform, and therefore, the present invention has selected to add the terminator to the reaction system at the end of the polymerization reaction.
In the invention, the terminating agent is selected from alcohol compounds or water, preferably small molecular alcohol compounds, such as one or more of methanol, ethanol, propanol and the like, and more preferably methanol.
The inventor finds that when the addition amount of the terminating agent is too small, for example, less than 2 times of the mole number of the initiator, the effect of completely terminating the reaction cannot be achieved, and in the post-treatment process of the polymerization product, partial molecular chains still keep activity to continue the polymerization reaction, so that the molecular weight distribution of the polymerization product is widened; on the other hand, if the amount of the terminator to be added is too large, and if the number of moles of the terminator is more than 20 times the number of moles of the initiator, the devolatilization load at the time of the post-treatment of the polymerization product increases, and the post-treatment efficiency decreases. Therefore, the amount of the terminator to be used is selected so that the number of moles of the terminator is 2 to 20 times, preferably 5 to 15 times, the number of moles of the initiator is the number of moles of the terminator and the number of moles of the initiator is the number of moles of the initiator.
When a terminator is added into a polymerization reaction system, the terminator is fully contacted with the reaction system to completely terminate the polymerization reaction, and volatile substances in the system are removed to obtain the epoxy monomer anion ring-opening polymerization product.
The method for removing volatile substances in the system is not particularly limited, and examples include distillation under reduced pressure.
The volatile substances comprise unreacted reaction raw materials, a terminator, small molecular weight byproducts and the like.
According to a tenth aspect of the present invention there is provided the use of polyethylene glycol to facilitate anionic ring-opening polymerisation of epoxy monomers.
Wherein the polyethylene glycol is as described in the first to ninth aspects above;
the epoxy monomer is as described in the above first to ninth aspects.
The method for using the polyethylene glycol in promoting the ring-opening polymerization reaction of the epoxy monomer anions is as described in the first to ninth aspects.
According to the method for ring-opening polymerization of the epoxy monomer anions provided by the invention, the following beneficial effects are achieved:
(1) the used accelerant polyethylene glycol obviously improves the ring-opening polymerization reaction rate and the polymerization conversion rate of the epoxy monomer anions, shortens the preparation time of a polymerization product, improves the utilization efficiency of the epoxy monomer, and the prepared polymerization product has narrow molecular weight distribution;
(2) the used accelerant polyethylene glycol has low cost, is non-toxic and harmless, is environment-friendly, does not need to be removed, simplifies the post-treatment process of the polyether product and reduces the product cost;
(3) the method provided by the invention has mild conditions, easy realization and strong operability;
(4) the method provided by the invention can be used for ring-opening polymerization of various types of epoxy monomer anions and has a wide application range.
Examples
The commercial information for the reagents used in this example is as follows:
phenyl oxirane: shanghai Taiton chemical Co., Ltd;
butylene oxide: shanghai spectral vibration Biotechnology, Inc.;
potassium tert-butoxide: ziboxing Hao chemical Co., Ltd;
polyethylene glycol-400: new treasures chemical company, south china;
polyethylene glycol-2000: new treasures chemical company, south china;
polyethylene glycol-4000: new treasures chemical company, south china;
polyethylene glycol-6000: new treasures chemical company, south china;
polyethylene glycol-8000: new treasures chemical company, south china;
polyethylene glycol-20000: shanghai Jinjinle industries, Ltd;
tetrahydrofuran: xiong chemical corporation;
hexanediol: tianjin Guangfu Fine chemical research institute;
metal potassium: shanghai Aladdin Co.
Example 1 preparation of initiator potassium hexanediol
(1) Putting 110g (0.93mol) of hexanediol and 100g (1.39mol) of tetrahydrofuran dried by a molecular sieve into a reactor which is dried in advance and filled with high-purity nitrogen;
(2) slowly putting a metal potassium sheet (78g, 2.0mol) which is cut into small pieces with the size of about 2-4 mm in advance into a reactor, and stirring for 12 hours at room temperature under the protection of high-purity nitrogen flow;
(3) and after the reaction is finished, filtering in a nitrogen atmosphere to remove excessive metal potassium, and heating the filtrate at 70-80 ℃ to evaporate tetrahydrofuran to obtain the hexanediol potassium.
Example 2
(1) 150g (1.25mol) of phenyloxirane, 0.67g (0.006mol) of potassium tert-butoxide and 24g (0.012mol) of polyethylene glycol-2000 were added to a reactor previously dried and filled with high-purity nitrogen, and after sealing, the mixture was stirred at a constant temperature of 80 ℃ for 12 hours;
(2) after the reaction, the reactor was placed in an ice-water bath to cool to room temperature, 1.0g (0.031mol) of methanol was added to terminate the reaction, and the volatile matter was removed by distillation under reduced pressure to obtain a polymer.
Example 3
(1) 150g (1.25mol) of phenyloxirane, 0.67g (0.006mol) of potassium tert-butoxide and 36g (0.009mol) of polyethylene glycol-4000 were charged into a reactor which had been dried beforehand and filled with high-purity nitrogen gas, sealed and stirred at a constant temperature of 80 ℃ for 24 hours;
(2) after the reaction, the reactor was placed in an ice-water bath to cool to room temperature, 1.9g (0.059mol) of methanol was added to terminate the reaction, and the volatile matter was removed by distillation under reduced pressure to obtain a polymer.
Example 4
(1) 150g (2.08mol) of tetrahydrofuran, 150g (2.08mol) of butylene oxide, 1.36g (0.007mol) of potassium hexanediol and 21g (0.0035mol) of polyethylene glycol-6000 are added into a reactor which is dried in advance and filled with high-purity nitrogen, and after sealing, the reactor is stirred at a constant temperature of 70 ℃ for 80 hours;
(2) after the reaction, the reactor was placed in an ice-water bath to cool to room temperature, 1.1g (0.034mol) of methanol was added to terminate the reaction, and the volatile matter was removed by distillation under reduced pressure to obtain a polymer.
Of these, potassium hexanediol was prepared as in example 1.
Example 5
(1) 150g (2.08mol) of tetrahydrofuran, 150g (2.08mol) of butylene oxide, 1.36g (0.007mol) of potassium hexanediol and 21g (0.0007mol) of polyethylene glycol-30000 are added to a reactor which is dried in advance and filled with high-purity nitrogen gas, and after sealing, the reactor is stirred at a constant temperature of 70 ℃ for 80 hours;
(2) after the reaction, the reactor was placed in an ice-water bath to cool to room temperature, 1.1g (0.034mol) of methanol was added to terminate the reaction, and the volatile matter was removed by distillation under reduced pressure to obtain a polymer.
Of these, potassium hexanediol was prepared as in example 1.
In this example, [ BO ]: [ OK ]: [ PEG-30000]: [ THF ] (molar ratio) was 300:1:0.1:300, and the monomer conversion was 46%, the number average molecular weight Mn (g/mol) was 6500, and the molecular weight distribution Mw/Mn was 1.26, where BO represents butylene oxide, as measured by the method of (one) in experimental example; OK represents potassium hexanediol; THF represents tetrahydrofuran.
Example 6
(1) 150g (1.25mol) of phenyl oxirane, 11.1g (0.1mol) of potassium tert-butoxide and 70g (0.175mol) of polyethylene glycol-400 are added to a reactor which is dried in advance and filled with high-purity nitrogen, and the mixture is stirred for 36 hours at a constant temperature of 50 ℃ after being sealed;
(2) after the reaction was completed, the reactor was placed in an ice-water bath to cool to room temperature, 15.5g (0.48mol) of methanol was added to terminate the reaction, and the volatile matter was removed by distillation under reduced pressure to obtain a polymer.
In this example, [ STO ]: [ OK ]: [ PEG-400] (molar ratio): 100:8:14, monomer conversion was 92%, number average molecular weight Mn (g/mol) was 1310, molecular weight distribution Mw/Mn was 1.24 as measured by the method of (one) in experimental example, where STO represents phenyl ethylene oxide; OK represents potassium tert-butoxide.
Example 7
(1) 150g (1.25mol) of phenyl oxirane, 8.38g (0.075mol) of potassium tert-butoxide and 30g (0.0015mol) of polyethylene glycol-20000 are introduced into a reactor which has been previously dried and filled with high-purity nitrogen, and after sealing, the mixture is stirred at a constant temperature of 90 ℃ for 90 hours;
(2) after the reaction was completed, the reactor was placed in an ice-water bath to cool to room temperature, 12.1g (0.378mol) of methanol was added to terminate the reaction, and the volatile matter was removed by distillation under reduced pressure to obtain a polymer.
In this example, [ STO ]: [ OK ]: [ PEG-20000] (molar ratio): 100:6:0.12, the monomer conversion was 98%, the number average molecular weight Mn (g/mol) was 1890, and the molecular weight distribution Mw/Mn was 1.30 as measured by the method (one) in the experimental example, wherein STO represents phenyl ethylene oxide; OK represents potassium tert-butoxide.
Comparative example
Comparative example 1
The procedure in example 2 was repeated except that polyethylene glycol-2000 was not added.
Comparative example 2
The procedure in example 3 was repeated except that polyethylene glycol-4000 was not added.
Comparative example 3
The procedure in example 4 was repeated except that polyethylene glycol-6000 was not added.
Examples of the experiments
(I) determination of the molecular weight and molecular weight distribution of the sample
Sample preparation: 0.1g of the polymerization products prepared in the examples 2 to 4 and the comparative examples 1 to 3 is taken, soaked and dissolved in 10 times of deionized water by weight for 24 hours, centrifuged at 4000rpm for 30 minutes, the clear solution is poured out, fresh deionized water is added for washing and centrifuging for 2 times, and reduced pressure drying is carried out to obtain a purified sample, and the purified sample is prepared into a tetrahydrofuran solution of 4 mg/mL.
The instruments and experimental conditions used were:
HLC-8230 GPC full-automatic gel permeation chromatograph of Japan TOSOH company;
a chromatographic column: TSKgel SuperMultipore HZM-M, two in series;
and (3) testing temperature: 40 ℃;
mobile phase: tetrahydrofuran;
flow rate: 0.35 ml/min;
standard sample preparation: monodisperse polystyrene.
Experimental example 1
The molecular weight and molecular weight distribution of the samples prepared in example 2 and comparative example 1 were measured by the method of (a), and the results are shown in the following table 1,
TABLE 1 results of anionic Ring opening polymerization of phenyloxirane STO with PEG-2000 as an accelerator
Wherein STO represents phenyl oxirane; OK represents potassium tert-butoxide; PEG-2000 refers to polyethylene glycol with the trade name PEG-2000; mn represents a number average molecular weight; Mw/Mn represents a molecular weight distribution.
As can be seen from the experimental results of Table 1, the addition of PEG-2000 improves the polymerization rate and monomer conversion of phenyl ethylene oxide, and the resulting polymer product has a narrow molecular weight distribution (1.17), indicating that PEG-2000 can promote the polymerization of phenyl ethylene oxide.
Experimental example 2
The molecular weight and molecular weight distribution measurements were carried out on the samples prepared in example 3 and comparative example 2 by the method (a) and the results are shown in the following table 2:
TABLE 2 result of anionic ring-opening polymerization of phenyloxirane STO using PEG-4000 as accelerator
Wherein STO represents phenyl oxirane; OK represents potassium tert-butoxide; PEG-4000 refers to polyethylene glycol with the trade name PEG-4000; mn represents a number average molecular weight; Mw/Mn represents a molecular weight distribution.
As can be seen from the experimental results in Table 2, the addition of PEG-4000 improves the polymerization rate and monomer conversion rate of phenyl oxirane, and the resulting polymer has a narrow molecular weight distribution (1.24), indicating that PEG-4000 can promote the ring-opening polymerization of phenyl oxirane anion.
Experimental example 3
The molecular weight and molecular weight distribution measurements were carried out on the samples prepared in example 4 and comparative example 3 by the method (a) and the results are shown in the following table 3:
TABLE 3 Ring opening polymerization results for butylene oxide BO anion
Wherein BO represents butylene oxide; OK represents potassium hexanediol; PEG-6000 refers to polyethylene glycol with the trade name of PEG-6000; THF represents tetrahydrofuran; mn represents a number average molecular weight; Mw/Mn represents a molecular weight distribution.
From the experimental results of table 3, it can be seen that although the reaction time is prolonged by the decrease of the temperature and the addition of the solvent, the addition of PEG-6000 still increases the polymerization rate and monomer conversion rate of butylene oxide, and the obtained polymer still has a narrow molecular weight distribution (1.28), indicating that PEG-6000 can promote the ring-opening polymerization of butylene oxide anion.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (19)
1. A process for the anionic ring-opening polymerization of an epoxy monomer, comprising the steps of:
(1) mixing and stirring an epoxy monomer, an initiator and an accelerator;
(2) cooling the reaction system, adding a terminator, removing volatile substances in the system,
the structural formula of the epoxy monomer is shown as the following formula I:
wherein, the substituent R is one of hydrogen, alkyl, phenyl and alkyl substituted phenyl;
the accelerant is polyethylene glycol, and the number of the molar mass of the accelerant is calculated by the number average molecular weight of the accelerant; and
the initiator is an alkali metal alkoxide.
2. The method of claim 1, wherein the epoxy monomer, the initiator and the accelerator in step 1 are mixed in a reaction vessel according to the following molar ratio:
100 parts by mole of epoxy monomer
0.1-10 mol portions of initiator
0.01 to 20 parts by mole of an accelerator,
wherein,
the number of moles of epoxy monomer is based on the number of moles of epoxy monomer molecules,
the moles of initiator are based on the moles of initiator molecules,
the moles of promoter are based on the moles of promoter molecules.
3. The method of claim 1,
the accelerant is polyethylene glycol with the number average molecular weight of 400-30000.
4. The method according to claim 3, wherein the accelerator is polyethylene glycol having a number average molecular weight of 700 to 20000.
5. The method according to claim 4, wherein the accelerator is polyethylene glycol having a number average molecular weight of 1000 to 10000.
6. The method of claim 5, wherein the enhancer is polyethylene glycol PEG-2000, PEG-4000, PEG-6000, PEG-8000.
7. The method according to claim 1, wherein in step 1, a solvent is added, and the solvent is a hydrocarbon solvent or an ether solvent.
8. The method according to claim 7, wherein in step 1, the solvent is selected from one or more of cyclohexane, n-hexane, dioxane, tetrahydrofuran, benzene and toluene.
9. The method according to claim 8, wherein in step 1, the solvent is selected from one or more of cyclohexane, tetrahydrofuran and toluene.
10. The method according to claim 9, wherein in step 1, the solvent is tetrahydrofuran.
11. The method according to claim 1, wherein, in step 1,
before the reaction raw materials are put into the reaction container, drying and deoxidizing the reaction container; and/or
Before the reaction raw materials are put into the reactor, the epoxy monomer and the accelerator are dried and subjected to oxygen removal treatment.
12. The method according to claim 1, wherein in step 1, the reaction temperature of the anionic ring-opening polymerization of the epoxy monomer is 40 ℃ to 120 ℃; and/or
The ring-opening polymerization reaction time of the epoxy monomer anions is 10 to 90 hours.
13. The method according to claim 12, wherein in step 1, the reaction temperature of the ring-opening polymerization of the epoxy monomer anion is 50 ℃ to 90 ℃; and/or
The ring-opening polymerization reaction time of the epoxy monomer anions is 12 to 80 hours.
14. The method of claim 1, wherein in step 2, the terminating agent is selected from an alcohol compound or water.
15. The method of claim 14, wherein in step 2, the terminating agent is one or more of methanol, ethanol and propanol.
16. The method of claim 15, wherein in step 2, the terminating agent is methanol.
17. The method according to claim 1, wherein in step 2, the number of moles of the terminating agent is 2 to 20 times the number of moles of the terminating agent based on the number of moles of the molecules of the terminating agent, and the number of moles of the initiator is based on the number of moles of the molecules of the initiating agent.
18. The method of claim 17, wherein in step 2, the number of moles of the terminating agent is based on the number of moles of the terminating agent molecules, the number of moles of the initiator is based on the number of moles of the initiator molecules, and the number of moles of the terminating agent is 5 to 15 times the number of moles of the initiator.
19. Use of polyethylene glycol to promote the ring-opening polymerisation of an epoxy monomer anion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510206006.9A CN106146821B (en) | 2015-04-27 | 2015-04-27 | A kind of method of epoxy monomer anionic ring-opening polymerization |
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| CN109734904B (en) * | 2018-12-28 | 2021-03-12 | 中国科学院青岛生物能源与过程研究所 | Metal-free catalytic system for organic concerted catalysis of ring-opening polymerization of three-way heterocyclic ring |
| CN114605374B (en) * | 2022-04-01 | 2023-06-09 | 浙江肯特催化材料科技有限公司 | Method for continuously oligomerizing ethylene oxide into aliphatic crown ether |
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