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Acyclic lithium alkylide evocating agent with hydroxylic protected by silane, preparation thereof and application thereof

A silane-protected, aliphatic technology, used in the synthesis of aliphatic alkyllithium initiators, high-performance hydroxyl-terminated polybutadiene, and heterofunctionalized polybutadiene, can solve the problem of reducing the average functionality of polymers , incomplete hydrolysis of protecting groups, many preparation steps, etc., to achieve high yield, good storage stability, and simple process

Inactive Publication Date: 2008-10-01
SINOPEC LANZHOU GASOLINEEUM CHEM IND CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But at present this kind of protective group initiator has many preparation steps, complex process, low yield, incomplete hydrolysis of protective group, which reduces the average functionality of the polymer, etc.

Method used

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  • Acyclic lithium alkylide evocating agent with hydroxylic protected by silane, preparation thereof and application thereof
  • Acyclic lithium alkylide evocating agent with hydroxylic protected by silane, preparation thereof and application thereof
  • Acyclic lithium alkylide evocating agent with hydroxylic protected by silane, preparation thereof and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] In a 250ml three-necked flask, 38g (0.4mol) of 3-chloro-1-propanol, 61g (0.4mol) of triethylchlorosilane, and 80ml of N,N-dimethylformamide were sequentially added. Then the N, N-dimethylformamide (30ml) solution containing 38g (0.44mol) imidazole was added dropwise to the reaction system within 30min at 5°C. 2 Stir at room temperature under protection for 6 hours. 350ml of cyclohexane was added, and then washed three times with 5% aqueous sodium bicarbonate solution, and the cyclohexane layer was separated. After drying with calcium hydride, the solvent was evaporated by rotary evaporation, and the colorless liquid was obtained by chromatographic column separation—namely, triethyl-(3-chloropropoxy)-silane, with a yield of 90%.

[0036] Under Ar atmosphere, add 8g (1.01mol) lithium, 100ml cyclohexane and 22.3g (0.107mol) triethyl-(3- Chloropropoxy)-silane was added into the reaction flask, the temperature was raised to 60°C, and stirred for 2h. The crude product was ...

Embodiment 2

[0040] In a 250ml three-necked flask, add 38g (0.4mol) 1-chloro-2-propanol, 77g (0.4mol) triisopropylchlorosilane, 100ml N, N-dimethylformamide and 35.2g (0.44 mol) pyrimidine, reacted at 5°C for 30 minutes, under N 2 Stir at room temperature under protection for 6 hours. Add 350ml of n-hexane, then wash with 5% NaHCO3 aqueous solution three times, and separate the n-hexane layer. After drying with calcium hydride, the solvent was evaporated by rotary evaporation, and the colorless liquid was obtained by separation through chromatographic column—that is, triisopropyl-(3-chloropropoxy)silane, with a yield of 83%.

[0041]Under Ar atmosphere, add 8g (1.01mol) lithium, 100ml cyclohexane and 22.3g (0.107mol) triisopropyl-(3 -Chloropropoxy)silane was added into the reaction flask, the temperature was raised to 60°C, and stirred for 2h. Crude product is filtered under Ar environment, obtains expected initiator, and its structural formula is as follows:

[0042] (CH...

Embodiment 3

[0045] In a 250ml three-necked flask, add 38g (0.4mol) 3-chloro-1-propanol, 60g (0.4mol) tert-butyldimethylsilyl chloride, 100ml N, N-dimethylformamide and 38g ( 0.44mol) of imidazole, reacted at 5°C for 30 minutes, and stirred at room temperature for 6 hours under nitrogen protection. Add 350ml of n-hexane, then wash with 5% aqueous sodium bicarbonate solution three times, and separate the n-hexane layer. After drying with calcium hydride, the solvent was evaporated by rotary evaporation, and the colorless liquid—tert-butyl-(3-chloropropoxy)dimethylsilane was obtained by chromatographic column separation, with a yield of 90%.

[0046] Under Ar atmosphere, add 8g (1.01mol) of lithium and 50ml of cyclohexane into the reaction flask into a 250ml three-necked flask equipped with a condenser, a constant pressure dropping funnel, and magnetic stirring, and then add 22.3g (0.107mol) of t 50 ml of a cyclohexane solution of butyl-(3-chloropropoxy)dimethylsilane was dropped into the r...

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Abstract

The invention provides an evocating agent for lithium alkylide of aliphatic series for silane protecting hydroxyl and a preparation method thereof. In a polar solvent, imidazole or pyridine is used as a catalyst, and halogenosilane is used for protecting the hydroxyl of haloalcohol and producing halogenoalkoxylsilaneaether; then in a non-polar solvent, halogenoalkoxylsilanea ether reacts with lithium metal or butyl lithium and produces the evocating agent for lithium alkylide of aliphatic series for silane protecting hydroxyl. The lithium aliphatic alkylide for protecting hydroxyl of silane in the invention has high activity, is easy to be dissolved in a non-polar organic solvent; protecting groups are easily hydrolyzed and an epoxy is extremely easy to be used for end capping and forming a polymer of which one end is provided with hydroxyl. When the evocating agent is used for evocating a polymer of hydroxyl-terminated polybutadiene liquor, the polymer with narrow molecular distribution (Mw / Mn is less than 1.2) is obtained; the polymer does not encounter with a fake gel phenomenon in the processes of end capping and removing the protecting groups and the average functionality thereof is close to 2.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and relates to an initiator for anionic polymerization, in particular to an aliphatic alkyllithium initiator with silane-protected hydroxyl groups, which is mainly used for the synthesis of high-performance hydroxyl-terminated polybutadiene, and can also be used for Synthesis of heterofunctionalized polybutadiene. Background technique [0002] Anionic initiator is one of the important links of anionic polymerization. According to different studies on anionic polymerization, initiators for anionic polymerization are divided into monofunctional, difunctional and multifunctional initiators. Compared with sodium-based and potassium-based initiators, lithium-based initiators are widely used in anionic polymerization because of their small radius, easy solubility in non-polar solvents, and good storage stability. [0003] The preparation of lithium-based initiators for the synthesis of hydroxyl-term...

Claims

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Application Information

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IPC IPC(8): C08F4/58C08F136/06
Inventor 潘广勤陈继明鲁在君于晶易建军齐永新张耀亨柏海见黄英
Owner SINOPEC LANZHOU GASOLINEEUM CHEM IND CORP
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