CN113968884A - 一种新型双磷酰胺稀土金属配合物、制备方法及催化聚合应用 - Google Patents
一种新型双磷酰胺稀土金属配合物、制备方法及催化聚合应用 Download PDFInfo
- Publication number
- CN113968884A CN113968884A CN202111244772.6A CN202111244772A CN113968884A CN 113968884 A CN113968884 A CN 113968884A CN 202111244772 A CN202111244772 A CN 202111244772A CN 113968884 A CN113968884 A CN 113968884A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- earth metal
- diphosphamide
- metal complex
- novel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 41
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 7
- -1 diphosphoramide rare earth metal Chemical class 0.000 claims abstract description 25
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052773 Promethium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- DGJMPBGBHIZZHL-UHFFFAOYSA-N [amino(diaminophosphoryloxy)phosphoryl]amine Chemical compound NP(N)(=O)OP(N)(N)=O DGJMPBGBHIZZHL-UHFFFAOYSA-N 0.000 claims description 4
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 4
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 4
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 4
- 229940078552 o-xylene Drugs 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 claims description 2
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052740 iodine Chemical group 0.000 claims description 2
- 239000011630 iodine Chemical group 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen 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
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims 3
- 238000012694 Lactone Polymerization Methods 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 abstract 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 239000003356 suture material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明提供了一种新型双磷酰胺稀土金属配合物、制备方法及催化聚合应用，属于催化技术领域。该双磷酰胺稀土金属配合物将含有不同取代基的多齿磷酰胺配体与稀土金属卤化物反应，催化剂易提纯，产率良好；该双磷酰胺稀土金属催化剂可直接用于催化环内酯的聚合反应，聚合条件温和，可以制备较高分子量且聚合物的分子量分布较窄的聚合物。
Description
技术领域
本发明属于催化技术领域，具体涉及一种多齿稀土金属配合物，并提供了其制备方法和应用。
背景技术
随着废弃塑料在全球的富集，不可降解的传统塑料带来的危害越来越大，因此开发新型环保，可降解的高分子材料尤为重要。其中以聚乳酸为代表的生物质可降解塑料，通常以玉米、甘蔗等可再生的生物质为原料，其来源充分且可再生。聚乳酸的生产过程低碳环保、其制品使用后可以降解，实现在自然界中的循环。同时随着高分子材料需求的增加，合成功能化的高分子材料尤为重要。聚丙交酯(PLA)又称为聚乳酸，因其良好的生物相容性和易降解、无污染被广泛应用在各个行业，尤其是在医药行业,被用作外科缝合材料和药物缓释载体等,发挥了巨大的作用。因此，设计一种具有高活性催化环内酯的聚合的催化剂是非常有意义的。
发明内容
本发明的目的之一在于提供一种新型双磷酰胺稀土金属配合物；本发明目的之二在于提供一种新型稀土金属配合物的制备方法；本发明的目的之三在于提供一种新型双磷酰胺稀土金属配合物在催化环内酯及其衍生物聚合领域的应用。
本发明的技术方案：
一种新型双磷酰胺稀土金属配合物，其结构式如下：
其中，Ln是稀土金属，为钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱或镥；
X是胺基之间的连接取代基，为2，2-二甲基丙基、乙基或反式-1，2-环己基；
E是磷上的取代基，为氧、硫或硒；
R是磷上的烷基取代基，为异丙基、叔丁基或苯基。
一种新型双磷酰胺稀土金属配合物的制备方法，步骤如下：
(1)制备新型双磷酰胺稀土金属配合物
在氮气氛围下，将氢化钾加入到0.07～0.1M的双磷酰胺配体的四氢呋喃溶液中，氢化钾与双磷酰胺配体的摩尔比为2.05～2.1，室温反应4小时；然后将上述混合液加入到与三卤化稀土(LnX3，其中Ln是稀土金属，为钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱或镥，X是卤素，为氯、溴、碘中的一种)的四氢呋喃悬浊液中，在85℃反应12小时，得到新型双磷酰胺稀土金属配合物；其中，双磷酰胺配体与三卤化稀土的摩尔比为2.05～2.1。
一种新型双磷酰胺稀土金属配合物的应用，新型双磷酰胺稀土金属配合物可直接用于催化环内酯及其衍生物的聚合反应。
催化聚合反应的步骤如下：
在氮气氛围下，称取一定比例的环内酯和双磷酰胺稀土金属配合物有机良溶剂中进行聚合反应；反应1min～24h后，加入链终止剂，使反应中止；将反应液用析出液进行沉降，析出聚合物，并在40℃～70℃下真空干燥至恒重。
其中，所述的环内酯与双磷酰胺稀土金属配合物的摩尔比为100～1500:1；反应体系中四齿稀土金属配合物的浓度为1×10-3～5×10-2mol/L。
所述的环内酯类型为L-丙交酯、ε-己内酯、rac-丙交酯、meso-丙交酯、γ- 戊内酯及其衍生物的一种或两种。
所述的有机良溶剂为石油醚、正戊烷、正己烷、正辛烷、苯、甲苯、间二甲苯、邻二甲苯、对二甲苯、溴苯、氯苯、二氯甲烷或四氢呋喃中的一种或两种以上混合；优选四氢呋喃、二氯甲烷、甲苯。
所述的链终止剂为甲醇、乙醇、正丁醇、异丁醇、异丙醇，以及含HCl的上述醇溶液；其中含HCl的体积比为5％～10％。
本发明的有益效果：(1)本发明所述的双磷酰胺配体，反应操作简便易行，原料易得且易于修饰；(2)本发明所述的新型双磷酰胺稀土金属配合物可直接用于催化环内酯的聚合反应。
附图说明
图1为配合物(L1-Ce)K的31PNMR谱图；
图2为配合物(L2-Ce)K的31PNMR谱图；
图3为配合物(L3-Ce)K的31PNMR谱图；
图4为所制备聚丙交酯的凝胶色谱图；
图5为所制备聚己内酯的凝胶色谱图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下将结合实施例进行阐述本发明。
实施例1
(L1-Ce)K催化剂的制备
氮气氛围下，将氢化钾(0.03g,0.7481mmol)加入到双磷酰胺配体(1.005g，2mmol)的四氢呋喃(4ml)中，室温反应4小时。然后将其加入到与四氢呋喃配位的溴化铈(0.3798g，1mmol)的四氢呋喃溶液中，在85℃反应12小时。过滤，得到双磷酰胺铈配合物L1-Ce，产量0.5g，产率72％。配合物(L1-Ce)K 核磁磷谱如附图1所示。
实施例2
(L2-Ce)K催化剂的制备
催化剂的制备过程和实施例1中的制备方法相同，催化剂的制备方法如下：
具体步骤与实施例1中方法类似，不同的是采用配体H2L2替代了上文中的配体H2L1,得到配合物(L2-Ce)K，产量0.6g，产率为70％。配合物(L2-Ce) K核磁磷谱如附图2所示。
实施例3
(L3-Ce)K催化剂的制备
催化剂的制备过程和实施例1中的制备方法相同，催化剂的制备方法如下：
具体步骤与实施例1中方法类似，不同的是采用配体H2L3替代了上文中的配体H2L1，得到配合物(L3-Ce)K产量0.5g，产率为72％。配合物(L3-Ce) K核磁磷谱如附图3所示。
实施例4
手套箱中，将双磷酰胺稀土金属催化剂L1-Ce(10μmol)催化剂和rac-丙交酯依次加入到10mL反应瓶中，rac-丙交酯与双磷酰胺稀土金属配合物的摩尔比为200:1，加入2mL的THF，在室温下搅拌反应60min；聚合终止过程为：加入乙醇作为链终止剂，使反应中止；将反应液用无水乙醇进行沉降，析出固体聚合物，最后，将聚合物在45℃下真空干燥至恒重，得到聚丙交酯0.288g，产率 100％。聚丙交酯GPC图如附图4所示。
实施例5
手套箱中，将双磷酰胺稀土金属催化剂L1-Ce(15μmol)催化剂和ε-己内酯依次加入到20mL反应瓶中，ε-己内酯与双磷酰胺稀土金属配合物的摩尔比为 500:1，加入适量的THF溶剂，在室温下搅拌反应12h；聚合终止过程为：加入甲醇作为链终止剂，使反应中止；将反应液用无水甲醇进行沉降，析出固体聚合物，最后，将聚合物在45℃下真空干燥至恒重，得到聚己内酯0.82g，产率 96％。聚己内酯GPC图如附图5所示。
Claims (10)
1.一种新型双磷酰胺稀土金属配合物，其特征在于，该新型双磷酰胺稀土金属配合物的结构式如下：
其中，Ln是稀土金属，为钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱或镥；
X是胺基之间的连接取代基，为2，2-二甲基丙基，乙基或反式-1，2-环己基；
E是磷上的取代基，为氧、硫或硒；
R是磷上的烷基取代基，为异丙基、叔丁基或苯基。
2.一种新型双磷酰胺稀土金属配合物的制备方法，其特征在于，步骤如下：
在氮气氛围下，将氢化钾加入到0.07～0.1M的双磷酰胺配体的四氢呋喃溶液中，氢化钾与双磷酰胺配体的摩尔比为2.05～2.1，室温反应4小时；然后将上述混合液加入到与三卤化稀土LnX3的四氢呋喃悬浊液中，在85℃反应12小时，得到新型双磷酰胺稀土金属配合物；其中，双磷酰胺配体与三卤化稀土的摩尔比为2.05～2.1；
其中，Ln是稀土金属，为钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱或镥，X为氯、溴或碘。
3.将权利要求1所述的新型双磷酰胺稀土金属配合物直接用于催化环内酯及其衍生物的开环聚合反应，得到环境友好的高分子材料。
4.根据权利要求3所述的新型双磷酰胺稀土金属配合物直接用于催化环内酯及其衍生物的开环聚合反应，其特征在于，催化聚合反应的步骤如下：
在氮气氛围下，新型双磷酰胺稀土金属配合物催化环内酯在有机良溶剂条件下进行聚合；反应1min～24h后，加入链终止剂，使反应中止；将反应液用析出液进行沉降，析出聚合物，并在40℃～70℃下真空干燥至恒重。
5.根据权利要求4所述的开环聚合反应，其特征在于，所述的环内酯与新型双磷酰胺稀土金属配合物的摩尔比为100～5000:1；反应体系中新型双磷酰胺稀土金属配合物的浓度为1×10-3～5×10-2mol/L。
6.根据权利要求3或4所述的双磷酰胺稀土金属配合物用于催化环内酯聚合反应，其特征在于，所述的环内酯为L-丙交酯、ε-己内酯、rac-丙交酯、meso-丙交酯、γ-戊内酯及其衍生物的一种或两种以上组合。
7.根据权利要求3、4或5所述的催化的环内酯的聚合反应，其特征在于，所述的有机良溶剂为石油醚、正戊烷、正己烷、正辛烷、苯、甲苯、间二甲苯、邻二甲苯、对二甲苯、溴苯、氯苯、二氯甲烷或四氢呋喃中的一种或两种以上混合。
8.根据权利要求6所述的催化的环内酯的聚合反应，其特征在于，所述的有机良溶剂为石油醚、正戊烷、正己烷、正辛烷、苯、甲苯、间二甲苯、邻二甲苯、对二甲苯、溴苯、氯苯、二氯甲烷或四氢呋喃中的一种或两种以上混合。
9.根据权利要求4、5或8所述的聚合反应，其特征在于，所述的链终止剂为甲醇、乙醇、正丁醇、异丁醇、异丙醇，以及含HCl的上述醇溶液；其中含HCl的体积比为5％～10％。
10.根据权利要求7所述的聚合反应，其特征在于，所述的链终止剂为甲醇、乙醇、正丁醇、异丁醇、异丙醇，以及含HCl的上述醇溶液；其中含HCl的体积比为5％～10％。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111244772.6A CN113968884B (zh) | 2021-10-26 | 2021-10-26 | 一种新型双磷酰胺稀土金属配合物、制备方法及催化聚合应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111244772.6A CN113968884B (zh) | 2021-10-26 | 2021-10-26 | 一种新型双磷酰胺稀土金属配合物、制备方法及催化聚合应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113968884A true CN113968884A (zh) | 2022-01-25 |
| CN113968884B CN113968884B (zh) | 2022-07-19 |
Family
ID=79588518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111244772.6A Active CN113968884B (zh) | 2021-10-26 | 2021-10-26 | 一种新型双磷酰胺稀土金属配合物、制备方法及催化聚合应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113968884B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114835755A (zh) * | 2022-06-08 | 2022-08-02 | 常州德能新材料有限公司 | 催化聚合的双次膦酰胺金属配合物催化剂及其制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2248463A1 (en) * | 1998-09-28 | 2000-03-28 | Scott Collins | Iminophosphonamide complexes for olefin polymerization |
| CN101490069A (zh) * | 2006-07-07 | 2009-07-22 | 住友化学株式会社 | 稀土类金属配合物、聚合用催化剂和聚合物的制备方法 |
| US20110112273A1 (en) * | 2008-02-25 | 2011-05-12 | Total Petrochemicals Research Feluy | Group 3 Post-Metallocene Complexes Based on Bis(Naphthoxy)Pyridine and Bis(Naphthoxy)ThioPhene Ligands for the Ring-Opening Polymerisation of Polar Cyclic Monomers |
| US20210188878A1 (en) * | 2019-12-19 | 2021-06-24 | Brown University | Catalyst and process for ring opening polymerization |
-
2021
- 2021-10-26 CN CN202111244772.6A patent/CN113968884B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2248463A1 (en) * | 1998-09-28 | 2000-03-28 | Scott Collins | Iminophosphonamide complexes for olefin polymerization |
| CN101490069A (zh) * | 2006-07-07 | 2009-07-22 | 住友化学株式会社 | 稀土类金属配合物、聚合用催化剂和聚合物的制备方法 |
| US20110112273A1 (en) * | 2008-02-25 | 2011-05-12 | Total Petrochemicals Research Feluy | Group 3 Post-Metallocene Complexes Based on Bis(Naphthoxy)Pyridine and Bis(Naphthoxy)ThioPhene Ligands for the Ring-Opening Polymerisation of Polar Cyclic Monomers |
| US20210188878A1 (en) * | 2019-12-19 | 2021-06-24 | Brown University | Catalyst and process for ring opening polymerization |
Non-Patent Citations (2)
| Title |
|---|
| RACHEL H. PLATEL ET AL.: "A Series of Bis(phosphinic)diamido Yttrium Complexes As Initiators for Lactide Polymerization", 《INORGANIC CHEMISTRY》 * |
| 潘昱等: "共轭双烯高顺式聚合用稀土金属催化体系研究进展", 《稀土》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114835755A (zh) * | 2022-06-08 | 2022-08-02 | 常州德能新材料有限公司 | 催化聚合的双次膦酰胺金属配合物催化剂及其制备方法 |
| CN114835755B (zh) * | 2022-06-08 | 2023-08-18 | 常州德能新材料有限公司 | 催化聚合的双次膦酰胺金属配合物催化剂及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113968884B (zh) | 2022-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112076790B (zh) | 一种应用聚酯材料可控解聚的锌催化剂及其催化方法 | |
| JP5385390B2 (ja) | カルベン誘導体によって触媒される環状化合物の制御可能な開環重合の方法 | |
| CN112079999B (zh) | 一种锌催化剂催化环酯开环聚合的方法 | |
| CN109694471B (zh) | 一种吡啶基脲催化剂及其在开环聚合中的应用 | |
| WO2008128548A2 (en) | Catalyst and method for polymerization and copolymerization of lactide | |
| CN113968884B (zh) | 一种新型双磷酰胺稀土金属配合物、制备方法及催化聚合应用 | |
| CN112079790A (zh) | 一种绿色荧光的双胺-噁唑啉锌配合物、制备方法和应用 | |
| EP1485422A1 (en) | Catalytic systems | |
| CN113698584A (zh) | 一种镁催化体系催化丙交酯及其类似物开环聚合的方法 | |
| CN109705328B (zh) | 苯酚-噁唑啉稀土金属催化剂、制备方法及应用 | |
| CN115584018B (zh) | 一种聚酯i-聚酯ii-聚碳酸酯三嵌段共聚物的制备方法 | |
| CN111995633B (zh) | 一种三齿稀土金属配合物、制备方法和应用 | |
| CN113527650B (zh) | 一种酸碱对催化剂催化乙交酯丙交酯共聚的方法 | |
| JP6120856B2 (ja) | 環式エステルおよびカーボネートのイモータル開環重合用のフェノレート錯体をベースにした触媒系 | |
| CN111704714B (zh) | 一种苯并五元、六元环(硫)脲催化剂及其在开环聚合中的应用 | |
| CN111548480B (zh) | 一种含呋喃环的聚合物的合成方法 | |
| CN111269402B (zh) | 利用不对称双核胺亚胺铝配合物催化丙交酯聚合的方法 | |
| Munzeiwa et al. | A perspective into ring-opening polymerization of ε-caprolactone and lactides: effect of, ligand, catalyst structure and system dynamics, on catalytic activity and polymer properties | |
| CN113861234B (zh) | 一种络合物催化剂及其制备方法和在制备聚碳酸酯中的应用 | |
| Suo et al. | Novel epoxide-promoted polymerization of lactides mediated by a zinc guanidine complex: a potential strategy for the tin-free PLA industry | |
| Sinenkov et al. | Bulk polymerization of rac-lactide initiated by guanidinate alkoxide complexes of rare earth metals. The molecular structure of the cluster [{(Me 3 Si) 2 NC (NPr i) 2} Nd] 4 (μ 3-OPr i) 8 Li 7 (μ 2-Cl) 3 (μ 3-Cl) 2 (μ 4-Cl) 2 | |
| CN115260217B (zh) | 一类桥连双噁唑啉稀土金属催化剂、制备方法及应用 | |
| CN111423564A (zh) | 一种聚己内酯的聚合方法 | |
| CN115536823B (zh) | 一种用于开环聚合制备聚酯的催化剂及其制备聚酯的方法 | |
| CN115322231B (zh) | 一种噁唑啉基n,n-二齿铁配合物、制备方法和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |