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Production method of polymers by using living anionic polymerization method

a technology of anionic polymerization and production method, which is applied in the field of producing polymers by using a living anionic polymerization method, can solve the problems of increasing the relative effect of polymerization inhibiting substances, difficult control of anionic polymerization under the presence of these materials, and prone to deactivation of growing terminal anion, etc., and achieves high yield.

Inactive Publication Date: 2008-02-21
NIPPON SODA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0025] By using the production method of the present invention, it is possible to produce high molecular weight polymers while controlling the molecular weights thereof even if anionic polymerizable monomers or solvents which contain trace amounts of polymerization inhibiting substances are used. In other words, it is possible to produce targeted living anionic polymers in which the molecular weights are controlled with a high yield even if living anionic polymers are produced on an industrial scale or when anionic polymerizable monomers or solvents to be used contain trace amounts of polymerization inhibiting substances.
[0026] Living anionic polymers obtained by the production method of the present invention, especially high molecular weight block anionic copolymers have microstructures which are controlled to a higher order and are useful as materials for nanopattern formation.

Problems solved by technology

In anionic polymerization systems, since active hydrogen compounds such as water and alcohol, oxygen, or the like become polymerization inhibiting substances, which deactivate the growing terminal anions or initiators, the control of anionic polymerization under the presence of these materials is known to be difficult.
On the other hand, when producing a polymer having a high molecular weight of, for example, several tens of thousands or more by an anionic polymerization method, since the more attempts are made to obtain polymers having high molecular weights, the more the concentration of the growing terminal anion in the polymerization solution reduces, relative effects of polymerization inhibiting substances increase greatly and the growing terminal anion becomes prone to deactivation.
For this reason, there has been a problem in that the production of polymers having a desired molecular weight is difficult and yields of targeted polymers are reduced.
In this method, there is a need to add an excessive amount of benzylmagnesium bromide, butyllithium, or the like in order to completely remove the polymerization inhibiting substances.
For this reason, there was a practically problem when carrying out anionic polymerization on an industrial scale, since there were some cases where the purification process or the like became complex, and moreover, monomers partially polymerized at the time of purifying the monomers by a distillation method or the like caused a reduction of the purification recovery factor of the monomers.
However, even in these examples using dibutylmagnesium, precise control of the molecular weight of a high molecular weight polymer has not been achieved (see Non-patent documents 1 to 4).

Method used

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  • Production method of polymers by using living anionic polymerization method
  • Production method of polymers by using living anionic polymerization method
  • Production method of polymers by using living anionic polymerization method

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0096] After adding 2.56 g (3.67 mmol) of a dibutyl magnesium solution (DBuMg) to 570 g of THF under a nitrogen atmosphere at −40° C., 29.8 g (286.1 mmol) of styrene was added thereto and the resulting mixture was stirred for 10 minutes. 1.15 g (2.76 mmol) of n-BuLi solution was added to the resulting solution and the entire mixture was stirred at −40° C. for 30 minutes. 11.2 g (63.7 mmol) of p-t-butoxystyrene (PTBST) was then added to this reaction solution and further stirred at −40° C. for 90 minutes. After stopping the reaction by adding methanol to the obtained reaction mixture, the resulting mixture was subjected to a reprecipitation process using a methanol solvent to obtain a reprecipitate, then the reprecipitate was filtered to obtain the retained matter, and the retained matter was air-dried to obtain styrene-PTBST copolymer A (yield 99%). The Mw of the copolymer A was 219,500 and the ratio Mw / Mn was 1.15.

[0097] The GPC curve of copolymer A is shown in FIG. 1. The horizon...

example 2

[0100] After adding 2.46 g (3.46 mmol) of a dibutyl magnesium solution (DBuMg) to 570 g of THF under a nitrogen atmosphere at −40° C., 32.7 g (314.0 mmol) of styrene was added thereto and the resulting solution was stirred for 15 minutes. 1.01 g (2.42 mmol) of n-BuLi solution was added to this solution and the resultant solution was stirred at −40° C. for 30 minutes. A mixed solution of 0.40 g (0.56 mmol) of DBuMg and 12.7 g (72.1 mmol) of p-t-butoxystyrene (PTBST) was then added to this reaction solution and the resulting solution was further stirred at −40° C. for 90 minutes. After stopping the reaction by adding methanol to the obtained reaction mixture, the resulting mixture was subjected to a reprecipitation process using a methanol solvent to obtain a reprecipitate, then the reprecipitate was filtered to obtain the retained matter, and the retained matter was air-dried to obtain styrene-PTBST copolymer C (yield 99%). The Mw of the copolymer C was 335,550 and the ratio Mw / Mn wa...

example 3

[0102] After adding 3.80 g (5.35 mmol) of a dibutyl magnesium solution (DBuMg) to 570 g of THF under a nitrogen atmosphere at −40° C., 30.8 g (297.6 mmol) of styrene was added thereto and the resulting solution was stirred for 10 minutes. 1.02 g (2.45 mmol) of n-BuLi solution was added to the solution and the resultant solution was stirred at −40° C. for 30 minutes. 6.43 g (33.4 mmol) of 4-(2-ethoxy-ethoxystyrene) (PEES) was then added to this reaction solution and the resulting solution was further stirred at −40° C. for 3 hours. After stopping the reaction by adding methanol to the obtained reaction mixture, the resulting mixture was subjected to a reprecipitation process using a methanol solvent to obtain a reprecipitate, then the reprecipitate was filtered to obtain the retained matter, and the retained matter was air-dried to obtain St-PEES copolymer D (yield 99%). The Mw of the copolymer D was 282,000 and the ratio Mw / Mn was 1.19.

[0103] The GPC curve of this copolymer D is sh...

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Abstract

An anionic polymerizable monomer is added to a reaction system in which an anion species which is incapable of initiating polymerization but may react with polymerization inhibiting substances to convert them into compounds that do not inhibit polymerization is present, and then an anion species capable of initiating polymerization is added thereto. It becomes possible to produce high molecular weight polymers and to precisely control the molecular weight thereof even if polymerization inhibiting substances are present in the system or when polymerization inhibiting substances enter from outside.

Description

CROSS-REFERENCE TO PRIOR APPLICATION [0001] This is a U.S. National Phase Application under 35 U.S.C. §371 of International Patent Application No. PCT / JP2005 / 010485 filed Jun. 8, 2005, and claims the benefit of Japanese Patent Application Nos. 2004-170963, filed Jun. 9, 2004 and 2004-290963, filed Oct. 4, 2004, all of which are incorporated by reference herein. The International Application was published in Japanese on Dec. 22, 2005 as WO 2005 / 121189 A1 under PCT Article 21(2).TECHNICAL FIELD [0002] The present invention relates to a method for producing polymers by using a living anionic polymerization method, and more specifically, relates to a production method of polymers by using a living anionic polymerization method which make it possible to produce polymers having high molecular weights without performing stringent raw-material purification and also to precisely control the molecular weight of the obtained polymers. BACKGROUND ART [0003] In anionic polymerization systems, si...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C08F4/00C08F2/38C08F4/44C08F12/22
CPCC08F4/44C08F12/22C08F212/08C08F220/14C08F2/38
Inventor TAKAHASHI, EIJIYAMAGUCHI, SHOJI
Owner NIPPON SODA CO LTD
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