CN115703720B - Spiro Salen ligand, salen catalyst, preparation method and application thereof in ring-opening polymerization - Google Patents
Spiro Salen ligand, salen catalyst, preparation method and application thereof in ring-opening polymerization Download PDFInfo
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- CN115703720B CN115703720B CN202110887204.1A CN202110887204A CN115703720B CN 115703720 B CN115703720 B CN 115703720B CN 202110887204 A CN202110887204 A CN 202110887204A CN 115703720 B CN115703720 B CN 115703720B
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- salen
- spiro
- catalyst
- alkyl
- cycloalkyl
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- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000003446 ligand Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000007151 ring opening polymerisation reaction Methods 0.000 title claims abstract description 19
- 125000003003 spiro group Chemical group 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 54
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 38
- 239000003999 initiator Substances 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- -1 isopropylphenyl Chemical group 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 125000003545 alkoxy group Chemical group 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000006570 (C5-C6) heteroaryl group Chemical group 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 150000002367 halogens Chemical class 0.000 claims description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims description 19
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 16
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 125000002541 furyl group Chemical group 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 7
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229920001774 Perfluoroether Polymers 0.000 claims description 5
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 5
- 125000000958 aryl methylene group Chemical group 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000004076 pyridyl group Chemical group 0.000 claims description 5
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 2
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 75
- 238000005481 NMR spectroscopy Methods 0.000 description 70
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- 239000000243 solution Substances 0.000 description 41
- 229920000642 polymer Polymers 0.000 description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- 239000000178 monomer Substances 0.000 description 29
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 16
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 14
- 101150065749 Churc1 gene Proteins 0.000 description 14
- 102100038239 Protein Churchill Human genes 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 125000001072 heteroaryl group Chemical group 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 239000005711 Benzoic acid Substances 0.000 description 8
- 235000010233 benzoic acid Nutrition 0.000 description 8
- 238000000113 differential scanning calorimetry Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
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- 150000001875 compounds Chemical class 0.000 description 5
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- 238000004519 manufacturing process Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical group CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
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- 125000005415 substituted alkoxy group Chemical group 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- 125000003107 substituted aryl group Chemical group 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
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- 229910052725 zinc Inorganic materials 0.000 description 3
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
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- 229920001576 syndiotactic polymer Polymers 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- 229910006400 μ-Cl Inorganic materials 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- ZDYNTRMQDURVDM-UHFFFAOYSA-N bis(trimethylsilyl)azanide;lanthanum(3+) Chemical compound [La+3].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C ZDYNTRMQDURVDM-UHFFFAOYSA-N 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a spiro Salen ligand, a Salen catalyst and a preparation method and application thereof in ring-opening polymerization, belongs to the technical field of catalysts, and provides a spiro Salen ligand and Salen catalyst based on a spiro skeleton for the first time, which enriches the types of Salen ligand and Salen catalyst, widens the application fields of Salen ligand and Salen catalyst, and also relates to a polymerization reaction system containing Salen catalyst.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a spiro Salen ligand, a Salen catalyst preparation method and application thereof in poly-3-hydroxybutyrate prepared by stereoselective ring-opening polymerization of beta-butyrolactone.
Background
Chiral ligands with spiro backbones have received extensive attention since the 21 st century and have evolved into distinct chiral ligand classes. The spiro backbone chiral ligands exhibit excellent catalytic activity and enantioselectivity in various types of asymmetric catalytic reactions such as asymmetric catalytic hydrogenation, asymmetric carbon-carbon bond formation, asymmetric carbon-heteroatom bond formation, and the like, and make it possible to many asymmetric catalytic reactions in which it has been difficult to control enantioselectivity previously. In the past, the spiro structure has become a dominant structure, and corresponding spiro ligands and catalysts thereof have been widely adopted by scientific researchers at home and abroad. However, this spiro-backbone compound with chiral dominant structure has not been applied to the construction of Salen ligand backbone at present, and has not been applied to organic asymmetric catalytic reactions or polymerization reactions.
Since the invention of polymer materials, plastic products have become the most widely used artificial materials with the greatest yield. The production of plastic products has increased from two million tons in 1950 to 3.11 hundred million tons in 2015. But with this, a large amount of plastic waste is brought, and now about 26.3 million tons of plastic waste has been manufactured by humans. Most plastic garbage adopts a landfill and incineration treatment mode, and the landfill and incineration treatment is harmful to the environment and causes atmospheric pollution. Even if degraded, these chemically stable plastics continue to exist in the human living environment in a form invisible to the naked eye, such as in the form of microplastic, etc., and eventually enter the human body through the food chain, jeopardizing the health.
At present, the aliphatic polyester based on biomass sources is considered as a potential green substitute for petroleum-based high polymer materials due to unique degradability, and has certain application in the fields of biological medicine, tissue engineering, packaging and the like. For example, P3HB (poly-3-hydroxybutyrate) is used as a polymer produced by natural microorganism fermentation, and has excellent performance and is considered as a powerful substitute for PP (polypropylene) materials. The performance of poly-3-hydroxybutyrate is closely related to the stereoregularity thereof, and the natural biological fermentation poly-3-hydroxybutyrate is isotactic polymer and has isotacticity P m Greater than 0.99. The method directly starts from the cheap racemized four-ring monomer beta-butyrolactone, and the preparation of the high-regularity polymer by utilizing the selective polymerization of the metal complex is a powerful way for chemically synthesizing poly-3-hydroxybutyrate, and the cost is obviously lower than that of a biological fermentation method. However, to date, the person skilled in the art has not obtained, by numerous methods and attempts, a polymer product (P) having the same degree of regularity as the natural poly-3-hydroxybutyrate m ＝0.06-0.80)。
Disclosure of Invention
Aiming at the defects, the invention aims to provide a spiro Salen ligand, a Salen catalyst, a preparation method and application thereof in ring-opening polymerization, and also relates to a polymerization reaction system containing the Salen catalyst, wherein the method for preparing poly-3-hydroxybutyrate with different regularity by using the polymerization reaction system containing the Salen catalyst to selectively ring-open polymerize racemic beta-butyrolactone can effectively solve the problem of low regularity of poly-3-hydroxybutyrate prepared by the selective ring-opening polymerization of beta-butyrolactone in the prior art, and the stereoselectivity is at most 0.99; the invention provides a spiro Salen ligand and Salen catalyst based on a spiro skeleton for the first time, enriches the types of Salen ligand and Salen catalyst, and widens the application fields of Salen ligand and Salen catalyst.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a spiro Salen ligand, which has the following structural general formula:
wherein each R 1 、R 2 、R 3 And R is 4 Independently is hydrogen, alkyl, cycloalkyl, alkoxy, aryl, halogen, heteroaryl, substituted alkyl, substituted alkoxy, substituted aryl, substituted heteroaryl, or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or adjacent carbon atoms, each independently form a cycloalkyl, heteroaryl or aryl group.
The spiro Salen ligands of the invention have C 2 Symmetry.
Further, each R 1 、R 2 、R 3 And R is 4 Independently hydrogen, C 1 ～C 10 Alkyl, C 3 ～C 6 Cycloalkyl, C 1 ～C 10 Alkoxy, C 6 ～C 14 Aryl, halogen, 5-6 membered heteroaryl, substituted C 1 ～C 10 Alkyl, substituted C 1 ～C 10 Alkoxy, substituted by one or more R 1a Substituted C 6 ～C 14 Aryl, substituted by one or more R 1a Substituted 5-6 membered heteroaryl or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or the adjacent carbon atoms each independently form C 3 ～C 7 Cycloalkyl, 5-6 membered heteroaryl or phenyl; r is R 1a Is C 1 ～C 10 Alkyl, C 1 ～C 10 Alkoxy or halogen.
Further, each R 1 、R 2 、R 3 And R is 4 Independently hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, furyl, pyridyl, biphenyl, 2-phenylbiphenyl, trityl, isopropylphenyl, benzyl, adamantyl, and,C 1 ～C 3 Perfluoroalkoxy, C 1 ～C 3 Perfluoroalkyl, arylmethylene, heteroarylmethylene, arylmethine or heteroarylmethine.
Further, the spiro Salen ligand is a racemate or an optically pure isomer.
Further, the structural formula of the spiro Salen ligand is shown as follows:
the R group may be modified, and the general formula is written:
or->
R may be of the structure:
wherein rac represents racemization, R, S represents optical purity, and Cumyl represents isopropylphenyl.
The invention also provides a preparation method of the spiro Salen ligand, which comprises the following steps: performing ketoamine condensation reaction on salicylaldehyde compounds and spirodiamine under an acidic condition, and separating and purifying reaction products after the reaction is finished to obtain the salicylaldehyde compound;
wherein, the structural general formula of the salicylaldehyde compound is shown as follows:
R 1 、R 2 、R 3 and R is 4 Independently is hydrogen, alkyl, cycloalkyl, alkoxy, aryl, halogen, heteroaryl, substituted alkyl, substituted alkoxy, substituted aryl, substituted heteroaryl, or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or adjacent carbon atoms, each independently form a cycloalkyl, heteroaryl or aryl group.
Further, R 1 、R 2 、R 3 And R is 4 Independently hydrogen, C 1 ～C 10 Alkyl, C 3 ～C 6 Cycloalkyl, C 1 ～C 10 Alkoxy, C 6 ～C 14 Aryl, halogen, 5-6 membered heteroaryl, substituted C 1 ～C 10 Alkyl, substituted C 1 ～C 10 Alkoxy, substituted by one or more R 1a Substituted C 6 ～C 14 Aryl, substituted by one or more R 1a Substituted 5-6 membered heteroaryl or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or the adjacent carbon atoms each independently form C 3 ～C 7 Cycloalkyl, 5-6 membered heteroaryl or phenyl; r is R 1a Is C 1 ～C 10 Alkyl, C 1 ～C 10 Alkoxy or halogen.
Further, R 1 、R 2 、R 3 And R is 4 Independently hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, furyl, pyridyl, biphenyl, 2-phenylbiphenyl, trityl, isopropylphenyl, benzyl, adamantyl, C 1 ～C 3 Perfluoroalkoxy, C 1 ～C 3 Perfluoroalkyl, arylmethylene, heteroarylmethylene, arylmethine or heteroarylmethine.
Further, the spirodiamine is a racemate or an optically pure isomer; the optical pure isomer is (R) -spirodiamine or (S) -spirodiamine.
Further, the preparation method of the spiro Salen ligand comprises the following specific steps: adding salicylaldehyde compound, spirodiamine and solvent into a reaction device, carrying out reflux reaction for 1-24 hours under an acidic condition, and separating and purifying a reaction product after the reaction is finished to obtain the salicylaldehyde compound; wherein the mol ratio of the spirodiamine to the salicylaldehyde compound is 1-2:2-5.
Further, the reflux reaction time is 12 hours, and the molar ratio of the spirodiamine to the salicylaldehyde compound is 1:2.
Further, the solvent is methanol, ethanol, isopropanol, toluene, acetonitrile or N, N-dimethylformamide, preferably methanol.
The spirocyclic diamines of the invention are prepared according to the prior art.
The reaction structural formula of the preparation method of the spiro Salen ligand is shown as follows:
the invention also provides a Salen catalyst which adopts the spiro Salen ligand as a ligand.
Further, the structural general formula of the Salen catalyst is as follows:
wherein each R 1 、R 2 、R 3 And R is 4 Independently is hydrogen, alkyl, cycloalkyl, alkoxy, aryl, halogen, heteroaryl, substituted alkyl, substituted alkoxy, substituted aryl, substituted heteroaryl, or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or adjacent carbon atoms, each independently form cycloalkyl, heteroaryl or aryl; m is a metal element of group IIB, IIIA, IVA, VA or VIA; m is 1 or 2; each X is independently C 1 ～C 20 Alkyl, substituted amino, C 3 ～C 6 Cycloalkyl, C 3 ～C 6 Heterocycloalkyl, C 6 ～C 14 Aryl or 5-6 membered heteroaryl.
Further, each R 1 、R 2 、R 3 And R is 4 Independently hydrogen, C 1 ～C 10 Alkyl, C 3 ～C 6 Cycloalkyl, C 1 ～C 10 Alkoxy, C 6 ～C 14 Aryl, halogen, 5-6 membered heteroaryl, substituted C 1 ～C 10 Alkyl, substituted C 1 ～C 10 Alkoxy, substituted by one or more R 1a Substituted C 6 ～C 14 Aryl, substituted by one or more R 1a Substituted 5-6 membered heteroaryl or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or the adjacent carbon atoms each independently form C 3 ～C 7 Cycloalkyl, 5-6 membered heteroaryl or phenyl; r is R 1a Is C 1 ～C 10 Alkyl, C 1 ～C 10 Alkoxy or halogen.
Further, each R 1 、R 2 、R 3 And R is 4 Independently hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, furyl, pyridyl, biphenyl, 2-phenylbiphenyl, trityl, isopropylphenyl, benzyl, adamantyl, C 1 ～C 3 Perfluoroalkoxy, C 1 ～C 3 Perfluoroalkyl, arylmethylene, heteroarylmethylene, arylmethine or heteroarylmethine.
Further, M is Zn, co, cr, cu, fe, pd, ni, mn, Y, la, ln, sc, yb, al, ru, ti or the like, preferably Zn, Y, la or Yb.
Further, X is furyl, -N (SiHMe 2 ) 2 、-N(SiMe 3 ) 2 Alkyl, alkoxy, aryl, phenolic, halogen, etc., preferably furyl, -N (SiHMe) 2 ) 2 or-N (SiMe) 3 ) 2 。
The invention also provides a preparation method of the Salen catalyst, which comprises the following steps: coordination is carried out on the spiro Salen ligand and a metal reagent MXn, so that the spiro Salen ligand is prepared;
wherein each R 1 、R 2 、R 3 And R is 4 Independently is hydrogen, alkyl, cycloalkyl, alkoxy, aryl, halogen, heteroaryl, substituted alkyl, substituted alkoxy, substituted aryl, substituted heteroaryl, or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or adjacent carbon atoms, each independently form cycloalkyl, heteroaryl or aryl; m is a metal element of group IIB, IIIA, IVA, VA or VIA; n is 1, 2,3, 4, 5 or 6; m is 1 or 2; each X is independently C 1 ～C 20 Alkyl, substituted amino, C 3 ～C 6 Cycloalkyl, C 3 ～C 6 Heterocycloalkyl, C 6 ～C 14 Aryl or 5-6 membered heteroaryl.
Further, the molar ratio of the spiro Salen ligand to the metal reagent MXn is 1-3:1-3, preferably 1.2:1.
Further, each R 1 、R 2 、R 3 And R is 4 Independently hydrogen, C 1 ～C 10 Alkyl, C 3 ～C 6 Cycloalkyl, C 1 ～C 10 Alkoxy, C 6 ～C 14 Aryl, halogen, 5-6 membered heteroaryl, substituted C 1 ～C 10 Alkyl, substituted C 1 ～C 10 Alkoxy, substituted by one or more R 1a Substituted C 6 ～C 14 Aryl, substituted by one or more R 1a Substituted 5-6 membered heteroaryl or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or the adjacent carbon atoms each independently form C 3 ～C 7 Cycloalkyl, 5-6 membered heteroaryl or phenyl; r is R 1a Is C 1 ～C 10 Alkyl, C 1 ～C 10 Alkoxy or halogen.
Further, the methodEach R is 1 、R 2 、R 3 And R is 4 Independently hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, furyl, pyridyl, biphenyl, 2-phenylbiphenyl, trityl, isopropylphenyl, benzyl, adamantyl, C 1 ～C 3 Perfluoroalkoxy, C 1 ～C 3 Perfluoroalkyl, arylmethylene, heteroarylmethylene, arylmethine or heteroarylmethine.
Further, M is Zn, co, cr, cu, fe, pd, ni, mn, Y, la, ln, sc, yb, al, ru, ti, etc.
Further, X is furyl, -N (SiHMe 2 ) 2 、-N(SiMe 3 ) 2 Alkyl, alkoxy, aryl, phenolic, halogen, and the like.
The metal reagent MXn in the present invention can be prepared according to the prior art.
The invention also provides a polymerization reaction system which comprises the Salen catalyst and an initiator.
Further, the initiator includes alkyl alcohol, alkyl mercaptan, benzyl alcohol, benzyl mercaptan, or the like.
The invention also provides an application of the polymerization reaction system in preparing poly-3-hydroxybutyrate with different regularity by selectively ring-opening polymerizing racemic beta-butyrolactone, which comprises the following steps: adding racemic beta-butyrolactone, salen catalyst, initiator and solvent into a reaction device, reacting for 5 s-2 h at 20-45 ℃, and separating and purifying the reaction product to obtain the product; wherein, the mol ratio of the racemized beta-butyrolactone, the Salen catalyst and the initiator is 100-10000:1-5:1-5.
Further, the solvent is a conventional organic solvent such as methylene chloride, dimethyl sulfoxide, tetrahydrofuran, N-methylpyrrolidone, N-dimethylformamide, toluene and the like, preferably toluene.
The reaction structural formula for preparing the poly-3-hydroxybutyrate with different regularity by adopting the polymerization reaction system to realize the selective ring-opening polymerization of the racemization beta-butyrolactone is shown as follows:
the poly-3-hydroxybutyrate obtained by the preparation method disclosed by the invention has the advantages of high regularity and good thermal property; the syndiotactic polymer P obtained r =0.99, the isotactic polymer P obtained m =0.98; wherein, P in the art r Representing intersystem Selectivity, P m Represents isotactic selectivity; regardless of the regularity of the polymer, there are definitions: p (P) r +P m Constant equal to 1; p (P) r =1 is perfect syndiotactic, P m =1 is perfect isotactic.
It is noted that the term "substituted" in the present invention means that a hydrogen atom and/or a carbon atom in the basic structure has been substituted with a radical and/or a functional group, and/or a heteroatom or heteroatom-containing group. Thus, the term trans-radical includes a heteroatom-containing group. For purposes herein, a heteroatom is defined as any atom other than carbon and hydrogen. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group (it is the basic structure), which may also be referred to as a methyl functional group, ethanol is an ethyl group substituted with an-OH functional group (it is the basic structure), and pyridine is a phenyl group in which a carbon within the basic structure of the benzene ring is substituted with a nitrogen atom.
It is to be understood that for the purposes herein, when a group is listed, it refers to the basic structure of the group (the type of group) and all other groups formed when the group is substituted as described above. The recited alkyl groups and the like include all isomers including optionally cyclic isomers such as butyl including n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl and cyclobutyl (and similarly substituted cyclopropyl); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl and neopentyl (and similarly substituted cyclobutyls and cyclopropyl). Cyclic compounds having substituents include all isomeric forms, for example methylphenyl would include o-methylphenyl, m-methylphenyl and p-methylphenyl; dimethylphenyl would include 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-diphenylmethyl, 3, 4-dimethylphenyl and 3, 5-dimethylphenyl.
In summary, the invention has the following advantages:
1. the invention provides a spiro Salen ligand and Salen catalyst based on a spiro skeleton for the first time, and the preparation method is simple and easy to operate, and enriches the species of the Salen ligand and the Salen catalyst; meanwhile, the spiro Salen ligand and Salen catalyst are used for the selective ring-opening polymerization of the quaternary ring monomer beta-butyrolactone, and the poly-3-hydroxybutyrate obtained by the preparation method disclosed by the invention has the advantages of high regularity and good thermal property. The syndiotactic polymer P obtained r =0.99, the isotactic polymer P obtained m =0.98, effectively solving the problem of low regularity of poly-3-hydroxybutyrate prepared by selective ring-opening polymerization of beta-butyrolactone.
Drawings
FIG. 1 shows the salen ligand rac-3h prepared in the present inventionSingle crystal diffraction patterns of (2);
FIG. 2 shows a salen catalyst prepared in the present inventionSingle crystal diffraction patterns of (2);
FIG. 3 is a nuclear magnetic resonance spectrum of syndiotactic poly (3-hydroxybutyrate) produced according to example 9 of the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of isotactic poly (3-hydroxybutyrate) produced from example 14 of the present invention;
FIG. 5 is a graph showing the comparison of the syndiotactic poly (3-hydroxybutyrate) core magnetic carbon spectrum obtained from example 9 with the isotactic poly (3-hydroxybutyrate) core magnetic carbon spectrum obtained from example 14 according to the present invention;
FIG. 6 is a DSC of isotactic poly (3-hydroxybutyrate) produced from example 14 of the present invention;
FIG. 7 is an enlarged comparison of the syndiotactic poly (3-hydroxybutyrate) core magnetic carbon spectrum obtained from example 9 with the isotactic poly (3-hydroxybutyrate) core magnetic carbon spectrum obtained from example 14 according to the present invention;
FIG. 8 is a DSC chart of syndiotactic poly (3-hydroxybutyrate) produced from example 9 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the particular embodiments described herein are illustrative only and are not intended to limit the invention, i.e., the embodiments described are merely some, but not all, of the embodiments of the invention.
Thus, the following detailed description of the embodiments of the invention, as provided, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
Example 1
The example provides a preparation method of key skeleton spiroindane spiro diamine, the reaction route is as follows:
the specific reaction steps in the preparation route are as follows:
1. synthesis of Compound 1b
Pyridine and trifluoromethanesulfonic anhydride were added dropwise in sequence to a dichloromethane solution (100 mL) of compound 1a (5 g,19.8 mmol) at 0deg.C, reacted overnight at room temperature, the solvent removed in vacuo, diluted with 80mL ethyl acetate, sequentially diluted with 5% hydrochloric acid solution, saturated NaHCO 3 The organic phase was washed with saturated brine, then dried over anhydrous sodium sulfate, the solution was concentrated in vacuo, and the product 1b (10 g, yield greater than 99%) was obtained by column chromatography on silica gel.
2. Synthesis of Compound 1c
Under anhydrous and anaerobic conditions, pd (OAc) 2 (1g,4.45mmol)，Cs 2 CO 3 A toluene solution (100 mL) of (16.4 g,50.3 mmol) and (. + -.) -BINAP (3.36 g,5.40 mmol) was successively added with benzylamine (20 mL,183 mmol), 1b (9.28 g,18 mmol), the above system was reacted at 100℃for 2 hours, cooled to room temperature, filtered using a funnel with celite, the filtrate was collected, the solvent was removed in vacuo, and the product 1c (yield 83%,4.5 g) was isolated by column chromatography.
3. Synthesis of Compound rac-1d
The compound 1c obtained above was added to a mixed solvent [ ethyl acetate/methanol=500 mL/200mL, v/v]In which 10% Pd (OH) was added thereto 2 and/C (1 g), then replacing the reaction system with hydrogen, reacting for 16h at 40 ℃ under normal pressure and hydrogen atmosphere, filtering the mixture obtained after the reaction, collecting filtrate, concentrating, and separating by column chromatography to obtain the product of white powder rac-1d (3.6 g, yield more than 99%).
Example 2
This example provides a process for the preparation of spiro Salen ligands, the reaction scheme of which is shown below:
wherein, the compound rac-1d was prepared as in example 1, and the compound (R) -1d and the compound (S) -1d were synthesized by the literature route;
salicylaldehyde compound 2 a-i:
2a:R 1 ＝R 2 ＝H；2b:R 1 ＝R 2 ＝Me；
2c：R 1 ＝R 2 ＝ t Bu；2d：R 1 ＝R 2 ＝Cl；
2e：R 1 ＝R 2 ＝Cumyl；2f：R 1 ＝ i Pr，R 2 ＝H；
2g：R 1 ＝ t Bu，R 2 ＝F；2h：R 1 ＝CMePh 2 ，R 2 ＝Me；
2i：R 1 ＝CPh 3 ,R 2 ＝Me；
the specific reaction steps in the preparation route are as follows: spirodiamine (2 mmol) and the corresponding salicylaldehyde (2 a-i) (4 mmol) were added to 20mL of methanol, followed by two drops of formic acid and an overnight reflux reaction. Recrystallisation from methanol gives the corresponding product.
The spiro Salen ligands 3a-i obtained in this example are arranged in the following order from left to right and then from top to bottom:
wherein,the single crystal diffraction diagram of rac-3h is shown in FIG. 1;
example 3
This example provides a method for preparing spiro Salen ligands, differing from example 2 only in: salicylaldehyde compound is
The corresponding spiro Salen ligand is +.>
The method comprises the steps of carrying out a first treatment on the surface of the The rest steps and parameters are the same.
Example 4
This example provides a metal reagent Y [ N (SiHMe 2 ) 2 ] 3 (THF) 2 The synthesis method of (2) comprises the following steps: in a glove box, liN (SiHMe 2 ) 2 (859.3 mg,6.2 mmol) and YCl were slowly added 3 (THF) 3 (970.7 mg,2.4 mmol) in N-hexane suspension (17 mL), reacted at room temperature for 12 hours, filtered to give a white solid, washed with frozen N-hexane, the solvent was dried under vacuum, and the obtained white solid was recrystallized twice in N-pentane to give metal reagent Y [ N (SiHMe) 2 ) 2 ] 3 (THF) 2 (yield: 82%,2.07 g), the nuclear magnetic hydrogen spectrum of which is shown in FIG. 2.
Other metal reagents such as ytterbium (Yb) reagent synthesis, zinc (Zn) reagent synthesis, lanthanum (La) reagent synthesis and the like in the invention can be prepared by referring to the above processes.
The specific process is as follows:
the ytterbium (Yb) reagent was synthesized as follows:
in a glove box, 1mol/L LiNSiMe 3 YbCl was added to a hexane solution (30 mL) 3 (1.95 g,10 mmol) in tetrahydrofuran (12 mL), refluxing overnight, removing the solvent in vacuo, adding 30mL toluene and dissolving the resulting solid by heating, collecting the supernatant by filtration, and recrystallizing at room temperature to give Yb [ N (SiMe 3) 2](μ-Cl)Li(THF) 3 (yield: 63%,5.21 g).
The metallic zinc (Zn) reagent was synthesized as follows:
in a glove box, 2mol/L NaNSiMe 3 ZnCl was added to a hexane solution (20 mL) 2 (1.34 g,10 mmol) tetrahydrofuran (12 mL) suspension, refluxing at 50deg.C for 5 hours, filtering to collect filtrate, removing solvent in vacuum, and distilling under reduced pressure to obtain Zn [ N (TMS) 2 ] 2 (yield: 38%,4.4 g).
The lanthanum metal (La) reagent was synthesized as follows:
in a glove box, la [ N (TMS) 2 ] 3 (3.1 g,5 mmol), tetrahydrofuran (3.6 g,50 mmol) are added into 35mL toluene in sequence, reflux is carried out for 30 minutes at 90 ℃, and the solvent is pumped out in vacuum to obtain the La [ N (SiHMe) 2 ) 2 ] 3 (THF) 2 (yield: 99%,2.65 g).
Example 5
This example provides a method for preparing a Salen catalyst by combining the spiro Salen ligand (3 a-k) L prepared in examples 2-3 with the metal reagent MXn prepared in example 4 (Y [ N (SiHMe) 2 ) 2 ] 3 (THF) 2 、Yb[N(SiMe3)2](μ-Cl)Li(THF) 3 、Zn[N(TMS) 2 ] 2 、La[N(SiHMe 2 ) 2 ] 3 (THF) 2 ) And the directly purchased metal reagent AlEt 3 Coordination is carried out, and the reaction route is as follows:
the preparation method of the Salen catalyst comprises the following specific steps:
taking yttrium (Y) metal as an example:
a toluene solution (5 mL) of salen ligand L (3 a) (0.2 mmol) was slowly added dropwise to Y [ N (SiHMe) in a glove box 2 ) 2 ] 3 (THF) 2 (0.2 mmol) in hexane (5 mL). Reacting at room temperature for 24h, removing the solvent in vacuum, washing the obtained solid with pentane preserved at-35 ℃ for three times to obtain a corresponding Salen catalyst 4a with the yield of 92%, wherein the nuclear magnetic hydrogen spectrum is shown in figure 3; the remaining Salen ligand L (3 b-k) was used to prepare the corresponding Salen catalyst 4b-k in 70-95% yield according to the procedure described above.
Example 6
This example provides a process for preparing poly-3-hydroxybutyrate of varying regularity by selective ring-opening polymerization of racemic β -butyrolactone using the Salen catalyst prepared in example 5, the reaction scheme is shown below:
wherein the Salen catalyst isThe initiator is Ph 2 CHCH 2 OH and toluene as solvent.
The specific preparation steps of the reaction route are as follows:
racemic β -butyrolactone (86 mg,1 mmol), initiator Ph 2 CHCH 2 OH (0.99 mg,0.005 mmol) was dissolved in toluene (0.4 mL) and added with Sa at a concentration of 0.05mol/L (shown by the above structure)0.1mL of toluene solution of len catalyst rac-A; the total volume of the polymerization is 0.5mL, the initial concentration of the racemic beta-butyrolactone monomer is 2mol/L, the concentration of the Salen catalyst is 0.01mol/L, the concentration of the initiator is 0.01mol/L, and the molar ratio of the racemic beta-butyrolactone monomer to the catalyst to the initiator is 200:1:1; reacting at room temperature for 10 seconds, adding chloroform solution dissolution product with mass concentration of 10mg/mL benzoic acid, taking a small amount of solution for carrying out 1 H NMR analysis to determine conversion, the remaining reaction solution was poured into methanol to precipitate the polymer, and the precipitated solid was filtered, washed three times with methanol and dried in a vacuum oven at 60 ℃ for 12H to give poly (3-hydroxybutyrate) as white.
In this example, nuclear Magnetic Resonance (NMR) detection was performed on the obtained poly (3-hydroxybutyrate), and the result showed that the conversion rate of the monomer was 99%; determination of Polymer 13 C NMR, analysis shows the syndiotactic degree P of the polymer r 0.93. The melting temperature and glass transition of poly (3-hydroxybutyrate) was examined by Differential Scanning Calorimetry (DSC) and it was found that the melting temperature of poly (3-hydroxybutyrate) produced in this example was 175 ℃.
Example 7
This example provides a method for preparing poly-3-hydroxybutyrate of different regularity by applying Salen catalyst prepared in example 5 to selective ring-opening polymerization of racemic β -butyrolactone, with reference to the preparation process in example 6, wherein Salen catalyst isThe initiator is Ph 2 CHCH 2 OH and toluene as solvent.
The specific preparation steps of the reaction route are as follows:
racemic β -butyrolactone (86 mg,1 mmol), initiator Ph 2 CHCH 2 OH (0.99 mg,0.005 mmol) was dissolved in toluene (0.4 mL), and 0.1mL of a toluene solution of catalyst (R) -A was added at a concentration of 0.05mol/L (shown by the above structure); the total volume of the polymerization was 0.5mL, the initial concentration of the monomer was 2mol/L, the concentration of the catalyst was 0.01mol/L, and the concentration of the initiator was 0.01mol/L. The molar ratio of monomer/catalyst/initiator was 200:1:1; at room temperatureReacting for 1h, adding chloroform solution dissolved product with mass concentration of 10mg/mL benzoic acid, taking a small amount of solution for carrying out 1 H NMR analysis to determine conversion, the remaining reaction solution was poured into methanol to precipitate the polymer, and the precipitated solid was filtered, washed three times with methanol and dried in a vacuum oven at 60 ℃ for 12H to give poly (3-hydroxybutyrate) as white.
In this example, nuclear Magnetic Resonance (NMR) detection was performed on the obtained poly (3-hydroxybutyrate), and it was found that the conversion of the monomer was 79%. Determination of Polymer 13 C NMR, analysis shows the syndiotactic degree P of the polymer r 0.71.
Example 8
This example provides a method for preparing poly-3-hydroxybutyrate of different regularity by using Salen catalyst prepared in example 5 in selective ring-opening polymerization of racemic β -butyrolactone, referring to the preparation procedure of example 6,
wherein the Salen catalyst isThe initiator is Ph 2 CHCH 2 OH and toluene as solvent.
The specific preparation steps of the reaction route are as follows:
racemic β -butyrolactone (86 mg,1 mmol), initiator Ph 2 CHCH 2 OH (0.99 mg,0.005 mmol) was dissolved in toluene (0.4 mL), and 0.1mL of a toluene solution of catalyst (S) -A was added at a concentration of 0.05mol/L (shown by the above structure); the total volume of the polymerization was 0.5mL, the initial concentration of the monomer was 2mol/L, the concentration of the catalyst was 0.01mol/L, and the concentration of the initiator was 0.01mol/L. The molar ratio of monomer/catalyst/initiator was 200:1:1; reacting for 1h at room temperature, adding chloroform solution dissolution product with mass concentration of 10mg/mL benzoic acid, taking a small amount of solution for carrying out 1 H NMR analysis to determine conversion, the remaining reaction solution was poured into methanol to precipitate the polymer, and the precipitated solid was filtered, washed three times with methanol and dried in a vacuum oven at 60 ℃ for 12H to give poly (3-hydroxybutyrate) as white.
In this example, the poly (3-hydroxybutyrate) produced was subjected to nuclear magnetic resonanceVibration (NMR) measurements showed a monomer conversion of 78%. Determination of Polymer 13 C NMR, analysis shows the syndiotactic degree P of the polymer r 0.70.
Example 9
This example provides a method for preparing poly-3-hydroxybutyrate of different regularity by using Salen catalyst prepared in example 5 in selective ring-opening polymerization of racemic β -butyrolactone, referring to the preparation procedure of example 6,
wherein the Salen catalyst is(the single crystal diffraction pattern is shown in FIG. 2), and the initiator is Ph 2 CHCH 2 OH and toluene as solvent.
The specific preparation steps of the reaction route are as follows:
racemic β -butyrolactone (86 mg,1 mmol), initiator Ph 2 CHCH 2 OH (0.99 mg,0.005 mmol) was dissolved in toluene (0.4 mL), and 0.1mL of a toluene solution of catalyst (rac) -B was added at a concentration of 0.05mol/L (shown by the above structure); the total volume of the polymerization was 0.5mL, the initial concentration of the monomer was 2mol/L, the concentration of the catalyst was 0.01mol/L, and the concentration of the initiator was 0.01mol/L. The molar ratio of monomer/catalyst/initiator was 200:1:1; reacting at room temperature for 20s, adding chloroform solution dissolution product of benzoic acid with mass concentration of 10mg/mL, taking a small amount of solution for carrying out 1 H NMR analysis to determine conversion, the remaining reaction solution was poured into methanol to precipitate the polymer, and the precipitated solid was filtered, washed three times with methanol and dried in a vacuum oven at 60 ℃ for 12H to give poly (3-hydroxybutyrate) as white.
Nuclear Magnetic Resonance (NMR) detection was performed on the poly (3-hydroxybutyrate) produced in this example, which showed that the conversion of the monomer was 99%. Determination of Polymer 13 C NMR, analysis shows the syndiotactic degree P of the polymer r 0.99. The poly (3-hydroxybutyrate) obtained 13 C NMR, as shown in FIG. 4, shows the split at 169.4ppm,40.85ppm,19.96ppm as follows, and it was found that the peaks were all unimodal, demonstrating that the polymer syndiotacticity was as high as 0.99. Wherein syndiotactic poly (3) was prepared in this example-hydroxybutyrate) is shown in figure 3; the DSC chart is shown in FIG. 8.
In this example, the melting temperature and glass transition of poly (3-hydroxybutyrate) was examined by Differential Scanning Calorimetry (DSC) and as shown in FIG. 5, the result showed that the melting temperature of poly (3-hydroxybutyrate) produced in this example was 184℃and 191℃and the glass transition temperature was 11.56℃and the melting enthalpy was 80.01J/g.
Example 10
This example provides a method for preparing poly-3-hydroxybutyrate of different regularity by using Salen catalyst prepared in example 5 in selective ring-opening polymerization of racemic β -butyrolactone, referring to the preparation procedure of example 6,
wherein the Salen catalyst isThe initiator is Ph 2 CHCH 2 OH and toluene as solvent.
The specific preparation steps of the reaction route are as follows:
racemic β -butyrolactone (86 mg,1 mmol), initiator Ph 2 CHCH 2 OH (0.99 mg,0.005 mmol) was dissolved in toluene (0.4 mL), and 0.1mL of a toluene solution of catalyst (rac) -B was added at a concentration of 0.05mol/L (shown by the above structure); the total volume of the polymerization was 0.5mL, the initial concentration of the monomer was 2mol/L, the concentration of the catalyst was 0.001mol/L, and the concentration of the initiator was 0.01mol/L. The molar ratio of monomer/catalyst/initiator was 2000:1:1; reacting at room temperature for 17min, adding chloroform solution dissolved product with mass concentration of 10mg/mL benzoic acid, and taking small amount of solution for carrying out 1 H NMR analysis to determine conversion, the remaining reaction solution was poured into methanol to precipitate the polymer, and the precipitated solid was filtered, washed three times with methanol and dried in a vacuum oven at 60 ℃ for 12H to give poly (3-hydroxybutyrate) as white.
Nuclear Magnetic Resonance (NMR) detection was performed on the poly (3-hydroxybutyrate) produced in this example, which showed that the conversion of the monomer was 40%. Determination of Polymer 13 C NMR, analysis shows the syndiotactic degree P of the polymer r 0.99. Differential scanning calorimetry(DSC) melting temperature and glass transition of Poly (3-hydroxybutyrate) was examined, and as a result, it was revealed that the highest melting temperature of the poly (3-hydroxybutyrate) produced in this example was 186℃and the glass transition temperature was 11.55 ℃.
Example 11
This example provides a method for preparing poly-3-hydroxybutyrate of different regularity by using Salen catalyst prepared in example 5 in selective ring-opening polymerization of racemic β -butyrolactone, referring to the preparation procedure of example 6,
wherein the Salen catalyst isThe initiator is Ph 2 CHCH 2 OH and toluene as solvent.
The specific preparation steps of the reaction route are as follows:
racemic β -butyrolactone (86 mg,1 mmol), initiator Ph 2 CHCH 2 OH (0.99 mg,0.005 mmol) was dissolved in methylene chloride (0.4 mL), and then 0.1mL of a methylene chloride solution of catalyst (rac) -B was added at a concentration of 0.05mol/L (indicated by the structure above); the total volume of the polymerization was 0.5mL, the initial concentration of the monomer was 2mol/L, the concentration of the catalyst was 0.001mol/L, and the concentration of the initiator was 0.01mol/L. The molar ratio of monomer/catalyst/initiator was 200:1:1; reacting at room temperature for 20s, adding chloroform solution dissolution product of benzoic acid with mass concentration of 10mg/mL, taking a small amount of solution for carrying out 1 H NMR analysis to determine conversion, the remaining reaction solution was poured into methanol to precipitate the polymer, and the precipitated solid was filtered, washed three times with methanol and dried in a vacuum oven at 60 ℃ for 12H to give poly (3-hydroxybutyrate) as white.
Nuclear Magnetic Resonance (NMR) detection was performed on the poly (3-hydroxybutyrate) produced in this example, which showed that the conversion of the monomer was 90%. Determination of Polymer 13 C NMR, analysis shows the syndiotactic degree P of the polymer r 0.99.
Example 12
This example provides a process for preparing poly-3-hydroxybutyrate of varying regularity using the Salen catalyst prepared in example 5 in a selective ring-opening polymerization of racemic β -butyrolactone, differing from example 11 only in: the reaction solvent is tetrahydrofuran, and the rest steps and parameters are the same.
Nuclear Magnetic Resonance (NMR) detection was performed on the poly (3-hydroxybutyrate) produced in this example, which showed that the conversion of the monomer was 99%. Determination of Polymer 13 C NMR, analysis shows the syndiotactic degree P of the polymer r 0.99.
Example 13
The example provides a method for preparing poly-3-hydroxybutyrate with different regularity by selective ring-opening polymerization of racemic beta-butyrolactone, wherein the structural formula of Salen ligand is shown as follows:
the specific process is as follows: racemic β -butyrolactone (86 mg,1 mmol), initiator Ph 2 CHCH 2 OH (0.99 mg,0.005 mmol) was dissolved in toluene (0.4 mL) and a solution containing 0.05mol/L ligand C- (sR, aS, aS) and 0.1mol/L metal reagent Y [ N (SiHMe) 2 ) 2 ] 3 (THF) 2 0.1mL of the mixed solution; the total volume of the polymerization was 0.5mL, the initial concentration of the racemic β -butyrolactone monomer was 2mol/L, the concentration of the catalyst was 0.01mol/L, and the concentration of the initiator was 0.01mol/L. The molar ratio of the monomer to the ligand to the metal reagent to the initiator is 200:1:1:1, the reaction is carried out for 2 minutes at room temperature, chloroform solution dissolution product with the mass concentration of 10mg/mL benzoic acid is added, and a small amount of solution is taken for carrying out the reaction 1 H NMR analysis to determine conversion, the remaining reaction solution was poured into methanol to precipitate the polymer, and the precipitated solid was filtered, washed three times with methanol and dried in a vacuum oven at 60 ℃ for 12H to give poly (3-hydroxybutyrate) as white.
In this example, nuclear Magnetic Resonance (NMR) detection was performed on the obtained poly (3-hydroxybutyrate), and it was found that the conversion of the monomer was 67%. Determination of Polymer 13 C NMR, analysis shows the syndiotactic degree P of the polymer r 0.94.
Example 14
The example provides a method for preparing poly-3-hydroxybutyrate with different regularity by selective ring-opening polymerization of racemic beta-butyrolactone, wherein the structural formula of Salen ligand is shown as follows:
the specific process is as follows: racemic β -butyrolactone (86 mg,1 mmol), initiator Ph 2 CHCH 2 OH (0.99 mg,0.005 mmol) was dissolved in toluene (0.4 mL) and a solution containing 0.05mol/L ligand E- (sR, aS, aS) and 0.1mol/L metal reagent Y [ N (SiHMe) 2 ) 2 ] 3 (THF) 2 0.1mL of the mixed solution; the total volume of the polymerization was 0.5mL, the initial concentration of the racemic β -butyrolactone monomer was 2mol/L, the concentration of the catalyst was 0.01mol/L, and the concentration of the initiator was 0.01mol/L. The molar ratio of the monomer to the ligand to the metal reagent to the initiator is 200:1:1:1, the reaction is carried out for 2 minutes at room temperature, chloroform solution dissolution product with the mass concentration of 10mg/mL benzoic acid is added, and a small amount of solution is taken for carrying out the reaction 1 H NMR analysis to determine conversion, the remaining reaction solution was poured into methanol to precipitate the polymer, and the precipitated solid was filtered, washed three times with methanol and dried in a vacuum oven at 60 ℃ for 12H to give poly (3-hydroxybutyrate) as white.
In this example, nuclear Magnetic Resonance (NMR) detection was performed on the obtained poly (3-hydroxybutyrate), and the result showed that the conversion of the monomer was 99%. Determination of Polymer 13 C NMR, analysis showed isotacticity P of the polymer m 0.99. The nuclear magnetic carbon spectrum of the isotactic poly (3-hydroxybutyrate) prepared by the method is shown in figure 4; the DSC spectrum is shown in figure 6; the comparison of the syndiotactic poly (3-hydroxybutyrate) nuclear magnetic carbon spectrogram prepared from this example with the isotactic poly (3-hydroxybutyrate) nuclear magnetic carbon spectrogram prepared from example 14 is shown in fig. 5 and 7, and shows that: syndiotactic poly-3-hydroxybutyrate nuclear magnetic resonance carbon spectrum: 13 C NMR(101MHz,CDCl 3 ) Delta 169.38,67.80,40.88,19.97; isotactic poly-3-hydroxybutyrate nuclear magnetic resonance carbon spectrum: 13 C NMR(101MHz,CDCl 3 )δ169.28,67.78,40.98,19.92。
as is evident from examples 6 to 14 above, the present invention is directed to the selective polymerization of racemic β -butyrolactone, the catalyst Rac-B can achieve a syndiotactic selectivity of 0.97 to 0.99 in various types of solutions, and exhibits extremely high activity, with a monomer/catalyst equivalent to 2000/1 still having high activity. In addition, the catalyst E- (sS, aR, aR) can realize the isotactic selectivity polymerization of the racemization beta-butyrolactone, and the isotacticity is 0.97-0.99.
Comparative example 1
This example provides a process for preparing poly-3-hydroxybutyrate of varying regularity from racemic β -butyrolactone, differing from example 14 only in: the following catalysts were used:
in this example, nuclear Magnetic Resonance (NMR) detection was performed on the obtained poly (3-hydroxybutyrate), and the result showed that the conversion of the monomer was 99%. Determination of Polymer 13 C NMR, analysis showed isotacticity P of the polymer m 0.70.
Comparative example 2
This example provides a process for preparing poly-3-hydroxybutyrate of varying regularity from racemic β -butyrolactone, differing from example 9 only in: the following catalysts were used:
this example is a measurement of the polymer obtained for poly (3-hydroxybutyrate) 13 C NMR, analysis showed that the polymer had a syndiotactic degree of P r ＝0.74。
The partial characterization data of the Salen ligand and Salen catalyst prepared by the invention are shown below:
1 H NMR(400MHZ,CDCl 3 ，25℃)
1 H NMR(400MHz,cdcl 3 )δ11.58(s,2H),8.19(s,2H),7.29–7.14(m,8H),6.85–6.79(m,2H),6.76(d,J＝8.3Hz,2H),6.68(dd,J＝7.2,1.4Hz,2H),3.06(dd,J＝9.2,3.6Hz,4H),2.40–2.18(m,4H).
1 H NMR(400MHZ,CDCl 3 ,25℃)
1 H NMR(400MHz,CDCl 3 )δ12.19(s,2H),8.31(s,2H),7.30(d,J＝2.4Hz,2H),7.20–7.11(m,4H),7.02(d,J＝2.4Hz,2H),6.78(dd,J＝7.0,1.8Hz,2H),3.13–2.95(m,4H),2.37–2.17(m,4H),1.32(s,18H),1.27(s,18H).
13 C NMR(101MHz,CDCl 3 )δ162.75,158.14,145.22,144.87,142.00,139.89,136.66,128.57,127.48,126.55,123.51,118.22,116.43,60.44,38.21,35.09,34.24,31.62,31.05,29.47.
1 H NMR(400MHZ，CDCl 3 ，25℃)
1 H NMR(400MHz,CDCl 3 )δ11.78(s,2H),7.90(s,2H),7.35–7.14(m,16H),7.08(dd,J＝12.2,7.3Hz,6H),7.00(t,J＝7.6Hz,2H),6.92–6.82(m,4H),6.46(d,J＝7.8Hz,2H),3.48(s,4H),3.00–2.83(m,2H),2.76(dd,J＝15.9,8.7Hz,2H),2.14(dd,J＝12.6,7.6Hz,2H),2.03(q,J＝11.4,10.8Hz,2H),1.79-1.56(m,16H),1.52(s,12H). 13 C NMR(101MHz,CDCl 3 )δ162.20,157.59,150.90,150.64,144.62,144.48,141.60,139.20,136.06,129.33,128.37,128.17,128.13,127.64,126.81,126.02,125.75,124.97,123.32,118.26,116.57,60.19,51.02,42.48,42.03,38.14,31.03,31.01,30.76,29.43,29.01.
1 H NMR(400MHZ,CDCl 3 ,25℃)
1 H NMR(400MHz,CDCl 3 )δ12.33(s,2H),8.13(s,2H),7.32(d,J＝2.5Hz,2H),7.28–7.13(m,4H),7.09(d,J＝2.5Hz,2H),6.69(d,J＝7.6Hz,2H),3.13–3.05(m,4H),2.37(dq,J＝12.8,4.4,3.9Hz,2H),2.22(dt,J＝12.7,10.1Hz,2H). 13 C NMR(101MHz,CDCl 3 )δ160.06,155.51,145.24,143.98,141.66,132.45,129.55,128.76,124.73,122.99,122.47,120.17,116.49,60.15,38.36,30.94.
1 H NMR(400MHZ,CDCl 3 ,25℃)
1 H NMR(400MHz,CDCl 3 )δ12.19(s,2H),8.19(s,2H),7.21–7.10(m,4H),6.99(dd,J＝10.7,3.1Hz,2H),6.74(dd,J＝7.3,2.9Hz,4H),3.17–2.97(m,4H),2.41–2.18(m,4H),1.30(s,18H). 13 C NMR(101MHz,CDCl 3 )δ161.30(d,J＝3.1Hz),156.56(d,J＝1.4Hz),145.05,144.63,141.98,139.64(d,J＝5.6Hz),128.68,124.02,118.33(d,J＝7.6Hz),117.78,117.54,116.29,114.51,114.28,60.37,38.27,35.08,31.01,29.16.
1 H NMR(400MHZ,CDCl 3 ,25℃)
1 H NMR(400MHz,CDCl 3 )δ11.33(s,2H),7.96(s,2H),7.30–7.10(m,30H),7.07(d,J＝2.1Hz,2H),6.84(d,J＝2.2Hz,2H),6.67(t,J＝7.6Hz,2H),6.56(d,J＝7.4Hz,2H),6.37(d,J＝7.7Hz,2H),2.75(ddd,J＝44.5,16.3,8.2Hz,4H),2.17(s,6H),2.13–1.93(m,4H).
1 HNMR(400MHZ,CDCl 3 ,25℃)
1 H NMR(400MHz,CDCl 3 )δ11.82(s,2H),8.09(s,2H),7.32–7.20(m,12H),7.10–7.00(m,8H),6.88(t,J＝7.6Hz,2H),6.84(d,J＝2.2Hz,2H),6.77–6.71(m,2H),6.49(d,J＝7.8Hz,2H),6.37(d,J＝2.2Hz,2H),2.95–2.82(m,2H),2.76(dd,J＝15.8,8.6Hz,2H),2.18–2.12(m,8H),2.08(s,8H). 13 C NMR(125MHz,cdcl 3 )δ161.97,157.46,148.70,148.38,144.69,144.38,141.48,135.77,134.50,130.88,128.64–128.09(m),127.62(d,J＝3.8Hz),125.82,125.53,123.39,118.83,116.14,60.07,51.59,38.14,30.68,27.39,20.58.
1 H NMR(400MHZ,CDCl 3 ,25℃)
1 H NMR(400MHz,CDCl 3 CDCl 3 )δ11.83(s,2H),8.09(s,2H),7.31–7.19(m,12H),7.09–7.03(m,8H),6.89(t,J＝7.6Hz,2H),6.84(d,J＝2.2Hz,2H),6.74(dd,J＝7.5,1.0Hz,2H),6.50(d,J＝7.8Hz,2H),6.38(d,J＝2.2Hz,2H),2.88(dt,J＝10.7,7.9Hz,2H),2.76(dd,J＝15.9,8.6Hz,2H),2.20–2.13(m,8H),2.08(s,8H).
1 H NMR(400MHz,CDCl 3 )δ11.83(s,2H),8.09(s,2H),7.31–7.17(m,12H),7.11–7.03(m,8H),6.89(t,J＝7.6Hz,2H),6.85(d,J＝2.2Hz,2H),6.74(d,J＝7.4Hz,2H),6.50(d,J＝7.7Hz,2H),6.38(d,J＝2.2Hz,2H),2.98–2.83(m,2H),2.76(dd,J＝15.8,8.6Hz,2H),2.17(s,8H),2.09(s,8H). 13 C NMR(125MHz,cdcl 3 )δ161.97,157.46,148.70,148.38,144.69,144.38,141.48,135.77,134.50,130.88,128.64–128.09(m),127.62(d,J＝3.8Hz),125.82,125.53,123.39,118.83,116.14,60.07,51.59,38.14,30.68,27.39,20.58.
1 H NMR(400MHz,CDCl 3 )δ11.34(s,2H),8.37(d,J＝1.3Hz,2H),8.00(dd,J＝26.1,8.3Hz,4H),7.76–7.57(m,6H),7.54–7.41(m,2H),7.31–6.94(m,20H),6.77(t,J＝7.6Hz,2H),6.63(dd,J＝12.0,7.6Hz,4H),2.87(pd,J＝14.7,13.1,7.7Hz,4H),2.32–2.10(m,4H). 13 C NMR(101MHz,CDCl 3 )δ162.01,154.81,145.03,144.67,142.29,141.71,140.42,135.64,134.11,133.17,133.09,131.54,128.86,128.61,128.43,128.28,128.02,127.32,127.25,126.99,126.38,126.17,125.70,125.01,123.97,123.15,120.58,120.01,116.67,60.10,38.24,30.88.
1 H NMR(400MHZ,CDCl 3 ,25℃)
1 H NMR(400MHz,)δ7.57(s,2H),7.45(d,J＝2.7Hz,2H),7.05(d,J＝2.0Hz,2H),6.73(t,J＝7.3Hz,2H),6.56–6.51(m,2H),6.47(d,J＝7.4Hz,2H),5.01(p,J＝3.0Hz,2H),3.81(s,5H),2.69(s,2H),2.43(s,2H),2.03(s,2H),1.85-1.12(br,38H),0.80(dt,J＝13.1,6.4Hz,4H),0.31(dd,J＝28.3,3.0Hz,12H).
1 H NMR(400MHz,C 6 D 6 )δ7.66(d,J＝45.8Hz,2H),7.54(s,1H),7.37–6.93(m,22H),6.85–6.64(m,3H),6.64–6.28(m,4H),4.68(p,J＝3.1Hz,2H),3.21(s,2H),2.99(s,2H),2.81(d,J＝58.8Hz,8H),2.60(t,J＝10.2Hz,1H),2.45(d,J＝10.0Hz,1H),2.16(d,J＝37.9Hz,2H),1.83(d,J＝4.7Hz,8H),1.14(d,J＝6.3Hz,4H),0.43(dd,J＝15.6,3.0Hz,12H).
the foregoing is merely illustrative and explanatory of the invention as it is claimed, as modifications and additions may be made to, or similar to, the particular embodiments described, without the benefit of the inventors' inventive effort, and as alternatives to those of skill in the art, which remain within the scope of this patent.
Claims (7)
1. A spiro Salen ligand, which is characterized in that the structural general formula of the spiro Salen ligand is shown as follows:
wherein each R 1 、R 2 、R 3 And R is 4 Independently hydrogen, C 1 ~C 10 Alkyl, C 3 ～C 6 Cycloalkyl, C 1 ~C 10 Alkoxy, C 6 ~C 14 Aryl, halogen, 5-6 membered heteroaryl or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or the adjacent carbon atoms each independently form C 3 ~C 7 Cycloalkyl, 5-6 membered heteroaryl or phenyl.
2. The spiro Salen ligand according to claim 1, wherein each R 1 、R 2 、R 3 And R is 4 Independently hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, furyl, pyridyl, biphenyl, 2-phenylbiphenyl, trityl, isopropylphenyl, benzyl, adamantyl, C 1 ~C 3 Perfluoroalkoxy, C 1 ~C 3 Perfluoroalkyl, arylmethylene, heteroarylmethylene, arylmethine or heteroarylmethine.
3. A process for the preparation of a spiro Salen ligand according to any one of claims 1-2, comprising the steps of: carrying out ketoamine condensation reaction on salicylaldehyde compounds and spirodiamine under an acidic condition, and separating and purifying reaction products after the reaction is finished to obtain the salicylaldehyde compound;
wherein, the structural general formula of the salicylaldehyde compound is shown as follows:
；
R 1 、R 2 、R 3 and R is 4 Independently hydrogen, C 1 ~C 10 Alkyl, C 3 ～C 6 Cycloalkyl, C 1 ~C 10 Alkoxy, C 6 ~C 14 Aryl, halogen, 5-6 membered heteroaryl or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or the adjacent carbon atoms each independently form C 3 ~C 7 Cycloalkyl, 5-6 membered heteroaryl or phenyl;
the structural formula of the spirodiamine is shown as follows:
。
4. a Salen catalyst, characterized in that it employs a spiro Salen ligand according to any one of claims 1-3 as ligand; the structural formula of the Salen catalyst is shown as follows:
wherein each R 1 、R 2 、R 3 And R is 4 Independently hydrogen, C 1 ~C 10 Alkyl, C 3 ～C 6 Cycloalkyl, C 1 ~C 10 Alkoxy, C 6 ~C 14 Aryl, halogen, 5-6 membered heteroaryl or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or the adjacent carbon atoms each independently form C 3 ~C 7 Cycloalkyl, 5-6 membered heteroaryl or phenyl;
m is Y, yb, zn, la or Al;
x is furyl, -N (SiHMe) 2 ) 2 、-N(SiMe 3 ) 2 Alkyl, alkoxy, aryl, phenolic, halogen;
m is 1 or 2.
5. The method for preparing a spiro Salen catalyst according to claim 4, comprising the steps of: coordinating the spiro Salen ligand according to any one of claims 1-3 with a metal reagent MXm;
wherein each R 1 、R 2 、R 3 And R is 4 Independently hydrogen, C 1 ~C 10 Alkyl, C 3 ～C 6 Cycloalkyl, C 1 ~C 10 Alkoxy, C 6 ~C 14 Aryl, halogen, 5-6 membered heteroaryl or R 1 、R 2 、R 3 And R is 4 The carbon atoms to which they are attached, and/or the adjacent carbon atoms each independently form C 3 ~C 7 Cycloalkyl, 5-6 membered heteroaryl or phenyl;
m is Y, yb, zn, la or Al;
x is furyl, -N (SiHMe) 2 ) 2 、-N(SiMe 3 ) 2 Alkyl, alkoxy, aryl, phenolic, halogen;
m is 1 or 2.
6. A polymerization system comprising the Salen catalyst according to claim 4 and an initiator; the initiator is alkyl alcohol, alkyl mercaptan, benzyl alcohol or benzyl mercaptan.
7. Use of the polymerization system according to claim 6 for the preparation of poly-3-hydroxybutyrate of different regularity by selective ring-opening polymerization of racemic β -butyrolactone, characterized by comprising the steps of: adding racemic beta-butyrolactone, salen catalyst, initiator and solvent into a reaction device, reacting for 5 s-2 h at 20-45 ℃, and separating and purifying the reaction product to obtain the product; wherein the molar ratio of the racemized beta-butyrolactone, the Salen catalyst and the initiator is 100-10000:1-5:1-5.
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