Amine bridged bisaryloxy rare earth metal guanidinium compound and its preparation method and application

Abstract

The invention discloses an amido-bridged bisaryloxy rare-earth metal guanidyl compound. The amido-bridged bisaryloxy rare-earth metal guanidyl compound is characterized in that the general formula of the compound is [ONNO]Ln[(R1N)2C(NR2)], and the chemical structural formula of the compound is defined in the specification, wherein Ln is one of rare-earth metals ytterbium, yttrium and samarium; [ONNO]=Me2NCH2CH2N[CH2-(2-O-C6H2-R2-3-R3-5)]2, R2 and R3 are selected from one of methyl, tertiary butyl and cumenyl; and [(R1N)2C(NR2)] represents guanidyl, R1 is selected from one of isopropyl and cyclohexyl, and NR2 is selected from one of diphenylamine group, diisopropylamine group, di(trimethylsilyl) amine group, di(dimethylsilyl) amine group and piperidyl group. The compound is simple in synthesis, clear in structure and high in yield. The invention provides a preparation method for the compound aforementioned and an application method for catalyzing the ring opening polymerization of 1,4-dioxane-2-ketone by using the compound as a catalyst simultaneously. The preparation method is moderate in conditions, fast in reaction speed and high in activity; and the obtained polymer is high in molecular weight and proper in molecular weight distribution.

Description

technical field

[0001] The invention relates to the field of catalysts, in particular to an amine bridged bisaryloxy rare earth metal guanidinium compound and a preparation method and application thereof. Background technique

[0002] Poly(1,4-dioxan-2-one) [poly(p-dioxanone); PPDO)] is a biodegradable and absorbable aliphatic polyester. Because of its good toughness and knotting properties, PPDO is used to make monofilament surgical sutures and has also been applied clinically. Due to its good biocompatibility and physical properties, PPDO not only has medical applications, but also can be applied in many fields such as films, molded products, composite materials, foam materials, adhesives, non-textile materials, coatings, etc.

[0003] At present, the catalysts used to catalyze the ring-opening polymerization of PDO mainly focus on zinc (Zn), tin (Sn), aluminum (Al), titanium (Ti) and rare earth (Ln) metal complexes and biological enzymes.

[0004] Reports on Zn catalys...

Examples

Embodiment 1

[0055] Example 1: Preparation of [ONNO]Yb[Ph 2 NC(N i Pr) 2 ](R 2 =R 3 = Bu t )

[0056] Weigh 0.66 g (3.9 mmol) of diphenylamine into a reaction flask treated with dehydration and deoxygenation, add 20 ml of tetrahydrofuran (THF), place the bottle in an ice bath, add butyllithium n-BuLi (1.95 ml, 3.9 millimole, 2 mol / L hexane solution), after reacting for 2 hours; adding diisopropylcarbodiimide (0.49 g, 3.9 mmol), slowly rising to room temperature; after reacting for 1 hour, the above solution Add to [ONNO]YbCl(THF) (3.13 g, 3.9 mmol) in tetrahydrofuran (20 mL), and stir overnight at room temperature. After vacuuming the solvent, extract with toluene and centrifuge to remove lithium chloride (LiCl) precipitate; concentrate the toluene solution and let it stand at room temperature, two days later, yellow crystals (2.51 g, yield 65%) are precipitated. C 53 h 78 N 5 o 2 Theoretical value of Yb (990.26): C, 64.28; H, 7.94; N, 7.07. Elemental analysis: C, 64.69; H, 7.82...

Embodiment 2

[0057] Embodiment two: preparation [ONNO]Y[ i PR 2 NC(N i Pr) 2 ](R 2 =R 3 = Bu t )

[0058] Weigh 0.39 g (3.9 mmol) of diisopropylamine in the dehydration and deoxygenation treated reaction flask, add 20 ml of tetrahydrofuran, place the bottle in ice bath condition, add butyl lithium (1.95 ml, 3.9 mmol, 2 mole hexane solution per liter), after 2 hours of reaction, diisopropylcarbodiimide (0.49 g, 3.9 mmol) was added and slowly raised to room temperature; after 1 hour of reaction, the above solution was added to [ONNO] A solution of YCl(THF) (2.81 g, 3.9 mmol) in THF (20 mL) was stirred overnight at room temperature. After the solvent was dried in vacuum, it was extracted with toluene, and the precipitate was removed by centrifugation; the toluene solution was concentrated and allowed to stand at room temperature, and yellow crystals (1.63 g, yield 50%) were precipitated two days later. C 47 h 82 N 5 o 2 Theoretical value of Y (838.09): C, 67.36; H, 9.86; N, 8.36. ...

Embodiment 3

[0059] Embodiment three: preparation [ONNO]Y[ i PR 2 NC(NCy) 2 ](R 2 =R 3 = Bu t )

[0060] Weigh 0.38 g (3.8 mmol) of diisopropylamine in the reaction flask that has been dehydrated and deoxygenated, add 20 ml of tetrahydrofuran, place the bottle in an ice bath, add butyllithium (1.9 ml, 3.8 mmol, 2 mole hexane solution per liter), after 2 hours of reaction, dicyclohexylcarbodiimide (0.78 g, 3.8 mmol) was added, and slowly raised to room temperature; after 1 hour of reaction, the above solution was added to [ONNO]YCl (THF) (2.73 g, 3.8 mmol) in tetrahydrofuran (20 mL), stirred overnight at room temperature. After the solvent was dried in vacuum, it was extracted with toluene, and the precipitate was removed by centrifugation; the toluene solution was concentrated and allowed to stand at room temperature, and yellow crystals (1.92 g, yield 55%) were precipitated two days later. C 53 h 90 N 5 o 2 Theoretical value of Y (918.22): C, 69.33; H, 9.88; N, 7.63. Elemental...

technical field

[0001] The invention relates to the field of catalysts, in particular to an amine bridged bisaryloxy rare earth metal guanidinium compound and a preparation method and application thereof. Background technique

[0002] Poly(1,4-dioxan-2-one) [poly(p-dioxanone); PPDO)] is a biodegradable and absorbable aliphatic polyester. Because of its good toughness and knotting properties, PPDO is used to make monofilament surgical sutures and has also been applied clinically. Due to its good biocompatibility and physical properties, PPDO not only has medical applications, but also can be applied in many fields such as films, molded products, composite materials, foam materials, adhesives, non-textile materials, coatings, etc.

[0003] At present, the catalysts used to catalyze the ring-opening polymerization of PDO mainly focus on zinc (Zn), tin (Sn), aluminum (Al), titanium (Ti) and rare earth (Ln) metal complexes and biological enzymes.

[0004] Reports on Zn catalys...

Examples

Embodiment 1

[0055] Example 1: Preparation of [ONNO]Yb[Ph 2 NC(N i Pr) 2 ](R 2 =R 3 = Bu t )

[0056] Weigh 0.66 g (3.9 mmol) of diphenylamine into a reaction flask treated with dehydration and deoxygenation, add 20 ml of tetrahydrofuran (THF), place the bottle in an ice bath, add butyllithium n-BuLi (1.95 ml, 3.9 millimole, 2 mol / L hexane solution), after reacting for 2 hours; adding diisopropylcarbodiimide (0.49 g, 3.9 mmol), slowly rising to room temperature; after reacting for 1 hour, the above solution Add to [ONNO]YbCl(THF) (3.13 g, 3.9 mmol) in tetrahydrofuran (20 mL), and stir overnight at room temperature. After vacuuming the solvent, extract with toluene and centrifuge to remove lithium chloride (LiCl) precipitate; concentrate the toluene solution and let it stand at room temperature, two days later, yellow crystals (2.51 g, yield 65%) are precipitated. C 53 h 78 N 5 o 2 Theoretical value of Yb (990.26): C, 64.28; H, 7.94; N, 7.07. Elemental analysis: C, 64.69; H, 7.82...

Embodiment 2

[0057] Embodiment two: preparation [ONNO]Y[ i PR 2 NC(N i Pr) 2 ](R 2 =R 3 = Bu t )

[0058] Weigh 0.39 g (3.9 mmol) of diisopropylamine in the dehydration and deoxygenation treated reaction flask, add 20 ml of tetrahydrofuran, place the bottle in ice bath condition, add butyl lithium (1.95 ml, 3.9 mmol, 2 mole hexane solution per liter), after 2 hours of reaction, diisopropylcarbodiimide (0.49 g, 3.9 mmol) was added and slowly raised to room temperature; after 1 hour of reaction, the above solution was added to [ONNO] A solution of YCl(THF) (2.81 g, 3.9 mmol) in THF (20 mL) was stirred overnight at room temperature. After the solvent was dried in vacuum, it was extracted with toluene, and the precipitate was removed by centrifugation; the toluene solution was concentrated and allowed to stand at room temperature, and yellow crystals (1.63 g, yield 50%) were precipitated two days later. C 47 h 82 N 5 o 2 Theoretical value of Y (838.09): C, 67.36; H, 9.86; N, 8.36. ...

Embodiment 3

[0059] Embodiment three: preparation [ONNO]Y[ i PR 2 NC(NCy) 2 ](R 2 =R 3 = Bu t )

[0060] Weigh 0.38 g (3.8 mmol) of diisopropylamine in the reaction flask that has been dehydrated and deoxygenated, add 20 ml of tetrahydrofuran, place the bottle in an ice bath, add butyllithium (1.9 ml, 3.8 mmol, 2 mole hexane solution per liter), after 2 hours of reaction, dicyclohexylcarbodiimide (0.78 g, 3.8 mmol) was added, and slowly raised to room temperature; after 1 hour of reaction, the above solution was added to [ONNO]YCl (THF) (2.73 g, 3.8 mmol) in tetrahydrofuran (20 mL), stirred overnight at room temperature. After the solvent was dried in vacuum, it was extracted with toluene, and the precipitate was removed by centrifugation; the toluene solution was concentrated and allowed to stand at room temperature, and yellow crystals (1.92 g, yield 55%) were precipitated two days later. C 53 h 90 N 5 o 2 Theoretical value of Y (918.22): C, 69.33; H, 9.88; N, 7.63. Elemental...

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