Preparation method of double-mercapto-terminal polymer

A technology of polymers and mercapto groups, which is applied in the field of preparation of double-ended mercapto polymers, can solve the problems of affecting the average functionality of polymers, affecting application performance, and increasing viscosity, and achieves good industrial application prospects and easy molecular weight.

Active Publication Date: 2013-02-13
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the steps of the double-terminated mercapto polymer prepared by the end group conversion method are simple, due to the problem of low conversion rate in the end group conversion process, there are still substances with other functional groups in the obtained terminal mercapto polymer.
On the other hand, since the viscosity of the liquid terminal functional group polymer will increase during the re-transformation of the terminal group, its application performance will be affected.
[0005] The currently reported anionic polymerization method of double-terminated mercapto polymers is mainly the polymerization of monomers initiated by organic alkali metal initiators, such as the preparation of mercapto-terminated polymers mentioned in USP3,240,844 and USP3,755,269. Double-ended mercapto polybutadiene or double-ended mercapto isoprene liquid rubber has a high apparent viscosity due to the high content of 1,2 structure in the microstructure
Moreover, pseudo-gel phenomenon is prone to occur during the end-capping process, so it affects the average functionality of the polymer.

Method used

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  • Preparation method of double-mercapto-terminal polymer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] Embodiment 1: Preparation of tert-butyldimethylsilylthiopropyl chloride

[0046] In a 250ml three-necked flask, 55.0g (0.5mol) of 3-chloro-1-propanethiol, 75.3g (0.5mol) of tert-butyldimethylsilyl chloride, and 100ml of N,N-dimethylformamide were successively added. Then 37.4g (0.55mol) of imidazole was dissolved in 40ml of N,N-dimethylformamide, dropped into the three-necked flask through a constant pressure funnel, and the dropwise addition was completed within 1 hour at 0°C, and the reaction system continued to react for 24 hours. Then wash 3 times with 10% sodium bicarbonate solution, extract with petroleum ether, separate the petroleum ether layer, evaporate the solvent petroleum ether on a rotary evaporator, and separate through a chromatographic column to obtain the intermediate tert-butyldimethylsilylsulfide Propyl chloride, yield 95%. This reagent is stored in a brown bottle filled with calcium hydride.

Embodiment 2

[0047] Embodiment 2: Preparation of tert-butyldiphenylsilylthiopropyl bromide

[0048] In a 250ml three-necked flask, 77g (0.5mol) of 3-bromo-1-propanethiol, 137.5g (0.5mol) of tert-butyldiphenylchlorosilane, and 100ml of N,N-dimethylformamide were sequentially added. Then 37.4g (0.55mol) of imidazole was dissolved in 40ml of N,N-dimethylformamide, dropped into the three-necked flask through a constant pressure funnel, and the dropwise addition was completed within 1 hour at 0°C, and the reaction system continued to react for 24 hours. Wash 3 times with 10% sodium bicarbonate solution, extract with petroleum ether, separate the petroleum ether layer, evaporate the solvent petroleum ether on a rotary device, and separate through a chromatographic column to obtain the intermediate tert-butyldiphenylsilylsulfanyl Propyl bromide, yield 90%. This reagent is stored in a brown bottle filled with calcium hydride.

Embodiment 3

[0049] Embodiment 3: the preparation of triethylsilylthiopropyl bromide

[0050]In a 250ml three-necked flask, 77g (0.5mol) of 3-bromo-1-propanethiol, 75g (0.5mol) of triethylchlorosilane, and 100ml of N,N-dimethylformamide were sequentially added. Then 37.4g (0.55mol) of imidazole was dissolved in 40ml of N,N-dimethylformamide, dropped into the three-necked flask through a constant pressure funnel, and the dropwise addition was completed within 1 hour at 0°C, and the reaction system continued to react for 24 hours. Wash 3 times with 10% sodium bicarbonate solution, extract with petroleum ether, separate the petroleum ether layer, evaporate the solvent petroleum ether on a rotary device, and separate through a chromatographic column to obtain the intermediate triethylsilylthiopropyl bromide , yield 91%. This reagent is stored in a brown bottle filled with calcium hydride.

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PUM

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Abstract

The invention relates to a preparation method of a double-mercapto-terminal polymer. The preparation method comprises the following steps: reacting a mercapto protection reagent with halomercaptan in a polar solvent according to a molar ratio of 1:1 at -5-5DEG C for 24h, extracting with a weakly-polar solvent, taking the obtained supernatant, evaporating in a rotary evaporator to remove the solvents, and carrying out column chromatography separation to obtain an initiator intermediate, wherein a catalyst used in the above reaction is imidazole, pyrimidine or pyridine; reacting the initiator intermediate with metallic lithium in a non-polar solvent at 30-70DEG C to obtain an initiator, wherein the molar ratio of the initiator intermediate to the metallic lithium is 1:6.7; sequentially adding a solvent, the initiator, a monomer and a structure adjustment agent to a reaction kettle, and reacting at 0-60DEG C to obtain an active polymer; adding a terminating reagent to the polymer, reacting, and adding methanol to terminate; and acidifying the terminated polymer by an inorganic acid to obtain the double-mercapto-terminal polymer. The obtained polymer has the advantages of narrow molecular weight distribution, controllable molecular weight, adjustable chain microstructure, and high functionalization efficiency.

Description

technical field [0001] The invention belongs to the field of polymer preparation with terminal functional groups, and relates to a preparation method of a double-ended mercapto polymer, which uses a silane-protected mercapto initiator to initiate monomer polymerization to prepare the double-ended mercapto polymer. Background technique [0002] Terminal functional group polymer is a polymer with active groups at the end of the main chain of the molecule. Low molecular weight double-ended mercapto polybutadiene or polyisoprene is a kind of liquid rubber. Due to its special active end group And the liquid performance at room temperature makes it have special uses that solid rubber can't compare with. For example, double-ended mercapto polybutadiene has been successfully used in the bonding of caulking materials, sealing materials and solid rocket propellants due to its special mercapto groups that make it cure faster than double-ended hydroxyl polybutadiene at room temperature....

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F136/06C08F136/08C08F297/02C08F297/04C08F4/48C08F2/38
Inventor 陈继明柏海见齐永新潘光勤易建军于晶张耀亨孟凡宁邓春华盛燕李红春张建平
Owner PETROCHINA CO LTD
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