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Polysilyl ether and method for synthesizing polysilyl ether through selective dehydrogenation coupling of prochiral silane and diol under catalysis of cobalt

A technology of dehydrogenation coupling and polysilicon ether, which is applied in the field of silicon-containing polymer synthesis, can solve the problems of undeveloped, unfavorable property adjustment of polysilicon ether, etc., and achieves simple and practical reaction operation, novel structure and convenient preparation. Effect

Active Publication Date: 2021-12-07
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, cobalt-catalyzed dehydrocoupling polymerization of alcohols and silanes has not been developed.
In addition, another problem affecting the development of polysiloxanes is that the structures of polysiloxanes currently synthesized are relatively similar, which is not conducive to the adjustment of the properties of polysiloxanes.

Method used

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  • Polysilyl ether and method for synthesizing polysilyl ether through selective dehydrogenation coupling of prochiral silane and diol under catalysis of cobalt
  • Polysilyl ether and method for synthesizing polysilyl ether through selective dehydrogenation coupling of prochiral silane and diol under catalysis of cobalt
  • Polysilyl ether and method for synthesizing polysilyl ether through selective dehydrogenation coupling of prochiral silane and diol under catalysis of cobalt

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Synthesis of monomer 3a

[0050]

[0051] 1,6-bis(phenylsilyl)hexyl Alkane (3a). Under nitrogen protection, add Co(acac) in the reaction flask 2 (15.6 mg, 0.06 mmol), 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene xantphos (34.8 mg, 0.06 mmol) and THF (10 mL). The solution was stirred at room temperature for 10 minutes. Then, phenylsilane 1 (4.544 g, 42 mmol) and 1,5-hexadiene (1.574 g, 19 mmol) were added to the bottle under nitrogen. The reaction vial was stirred at room temperature for 12 hours. Then, the resulting solution was concentrated in vacuo. The crude product was dissolved in petroleum ether, and the solution was quickly filtered through a short column of silica gel. The filtrate was collected and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (petroleum ether) to obtain a colorless oily liquid. In order to improve the polymerization performance of the monomer, a dehydration process must be perfo...

Embodiment 2

[0053] Synthesis of Monomer 6

[0054]

[0055] 11-(phenylsilyl)undecane- 14,5-Bis(diphenylphosphine)-9,9-dimethylxanthene-ol (6). Under nitrogen protection, add Co(acac) in the reaction flask 2 (7.7 mg, 0.03 mmol), xantphos (17.4 mg, 0.03 mmol) and THF (5 mL). The solution was stirred at room temperature for 10 minutes. Then, phenylsilane 1 (0.893 g, 8.3 mmol) and methyl 10-undecenoate 4 (1.486 g, 7.5 mmol) were added to the bottle under nitrogen. The reaction vial was stirred at room temperature for 24 hours. Then, the resulting solution was concentrated in vacuo. The crude product was dissolved in petroleum ether, and the solution was quickly filtered through a short column of silica gel. The filtrate was collected and concentrated under reduced pressure. Et was added to the crude product 2 O (30 mL). The mixture was cooled on an ice bath, and LiAlH was added carefully 4 (300 mg, 7.5 mmol). The reaction mixture was allowed to warm to room temperature and stirr...

Embodiment 3-18

[0057]Optimization of Dehydrocoupling Polymerization Conditions

[0058] In the glove box, put Co(acac) in the reaction bottle 2 (1 mol% of the amount of substrate used) and bisphosphine ligand (1 mol% of the amount of substrate used), tetrahydrofuran (1.0 mL) was added, stirred at room temperature for 5 min, and the tetrahydrofuran was dried under vacuum. Silane 3a (0.4mmol), diol 7a (0.4mmol) and reaction solvent (2.0mL) were added in a reaction vial. React at 60–80°C for 24 hours; then add 2 ml of dichloromethane to dissolve the product, add dropwise 15 ml of cold methanol to precipitate the product, remove the upper solvent, and drain to obtain the polymer product. The reaction formula and ligand structure are as follows:

[0059]

[0060] The number average molecular weight of the polymer (M n ) and molecular weight distribution (PDI) are measured by gel chromatography (GPC), and the productive rate is the separation yield, changing the reaction temperature and solve...

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Abstract

The invention discloses a polysilyl ether and a method for synthesizing the polysilyl ether, and a series of polysilyl ethers with novel structures are obtained by catalyzing selective dehydrogenation coupling of prochiral silane and diol by taking a diphosphine ligand complex of cheap metal cobalt as a catalyst. The molar ratio of the cobalt complex to the monomer containing the hydroxyl silane is (0.005-0.020): 1. The reaction activity is high, and the maximum number-average molecular weight of the polysilyl ether can reach 3.23 * 10 < 4 >. The catalyst is convenient to prepare, simple and practical in reaction operation and mild in reaction condition; the synthesized polysilyl ether is derived from different types of monomers. In addition, the catalyst can be used for synthesizing polysilyl ether by a hydrosilylation / dehydrogenation coupling two-step one-pot method. When the chiral diphosphine ligand is used, chiral polysilyl ether can be obtained through the reaction. The synthesized chiral polysilyl ether has potential practical application value in the field of chiral separation.

Description

technical field [0001] The invention belongs to the technical field of silicon-containing polymer synthesis, and specifically relates to a polysilicon ether and a method for catalytically synthesizing the polysilicon ether with a novel structure using cobalt bisphosphine ligand complexes. Background technique [0002] Due to the diverse properties and the abundant reserves of silicon and oxygen in the earth's crust, polymers containing silicon-oxygen bonds in the main chain have always been a research hotspot (reference 1: W.M.Haynes, Abundance of Elements in the Earth's Crustandin the Sea, CRC Handbook of Chemistry and Physics, 96th ed.; CRCPress, 2015-2016; sections14-18.). So far, some polymers containing silicon-oxygen bonds in the main chain have been gradually developed and applied, including polysiloxane, polysiloxane, and polysilicone. Due to the similarity of the main chain structure, these polymers often exhibit similar properties, such as lower glass transition t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G77/50C08G77/52
CPCC08G77/50C08G77/52
Inventor 周永贵翟小勇孙蕾
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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