JP2539767B2 - Polycarbonate polymer complex and method for producing the same - Google Patents

Description

The present invention relates to a polycarbonate-based polymer complex and a method for producing the same, and more particularly to a polycarbonate-based polymer complex containing a porphyrin nucleus residue and a method for producing the same.

[Problems to be Solved by Prior Art and Invention] It is known that a porphyrin complex can be used as a model compound of cytochromes as an oxygen-immobilized catalyst, an oxygen carrier or an oxygen carrier capable of reversibly adsorbing and desorbing oxygen. Has been. Further, application to a proton transfer type photoisomerization memory material is expected.

By the way, since this porphyrin complex easily aggregates, measures have been taken to make it easier to handle by binding it to a polymer substance. For example, in JP-A-52-141882, a copolymer of a porphyrin having a vinyl group and styrene is obtained, but this is complicated in the manufacturing process and it is difficult to introduce the porphyrin nucleus at a high density. There is a point.

[Means for Solving the Problems] The present invention provides a novel polycarbonate-based polymer complex containing a porphyrin nucleus residue, particularly a porphyrin nucleus residue at both ends, and a complex process for producing the same. The purpose is to provide a method of doing so.

That is, the present invention is firstly the formula [A] Or the formula [B] (However, Ar represents the following group, and n represents an integer of 1 or more.

In addition, M represents the following metal atom.

Cu, Ag, Au, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Al, Ga, In, Tl, Sc, Y, La,
Si, Ge, Sn, Pb, Ti, Zr, Hf, As, Sb, Bi, V, Nb, Ta, Cr, Mo, W, Mn, T
c, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Pr, Eu, Yb, Th Further, R ^{1 to} R ⁵ are hydrogen atom, halogen atom, carbon number 1 to 1
6 alkyl groups, phenyl groups, lower alkyl group-substituted phenyl groups, halogen-substituted phenyl groups, and alkoxy groups having 1 to 6 carbon atoms are shown. ), And a reduced viscosity [η _{sp / c} ] of a solution of 0.5 g / dl in methylene chloride at 20 ° C. is 0.59 dl / g
The present invention relates to the above-mentioned polycarbonate-based polymer complex. Secondly, the reaction product of a dihydric phenol and a carbonic acid ester-forming compound is reacted with a porphyrin having a monovalent phenolic hydroxyl group or a metal complex thereof. And a solution of the above formula [A] or [B] and having a concentration of 0.5 g / dl in methylene chloride as a solvent at 20 ° C.
Relates to a method for producing a polycarbonate-based polymer complex having a reduced viscosity [η _{sp / c} ] of 0.59 dl / g or more.

The polycarbonate-based polymer complex of the present invention is a compound represented by the above formula [A] or [B]. Among these, as a preferable example, Ar in these formulas is Or It is preferable that R ^{1 to} R ⁵ are hydrogen, a lower alkyl group or a phenyl group. Further, preferred as M in the formula [B] are Mn, Fe, Co, Ni,
Metal atoms such as Mg, Zn and Al.

The polycarbonate polymer complex of the present invention represented by the above formula [A] or [B] can be produced by the following method.

First, After dissolving dihydric phenol such as the above in an aqueous solution of an alkali metal salt such as sodium salt or potassium salt, phosgene gas, which is a carbonic acid ester forming compound, is added to 2 moles per mol of the raw material dihydric phenol while stirring and adding methylene chloride. Blow in at a ratio of ~ 5 mol, and stop blowing phosgene gas at the time of pH 7-10. When the obtained reaction product is statically separated, a methylene chloride solution of the polycarbonate oligomer is obtained in the organic layer. Alternatively, in addition to the above-mentioned phosgene method, a transesterification method using diphenyl carbonate as a carbonic acid ester-forming compound can be adopted. In that case, the reaction may be carried out by a conventional method.

Next, to the methylene chloride solution of the polycarbonate oligomer having a chloroformate group at the molecular end obtained above, the porphyrin having the monovalent phenolic hydroxyl group or a metal complex thereof is added, and a divalent phenol is further added with an alkali. Add a solution dissolved in an aqueous metal salt solution, triethylamine, etc. as a polymerization catalyst to 0.5 at 10 to 50 ℃.
The polymerization reaction is carried out under stirring for ~ 3 hours. After the reaction is completed, the product is diluted with methylene chloride, washed with, for example, water, an aqueous solution of sodium hydroxide, water, hydrochloric acid, and water in this order, and this is poured into methanol for reprecipitation to obtain a polymer, It is the polycarbonate polymer complex of the present invention.

[Examples] Next, the present invention will be described with reference to Examples.

Example 1 A mixture of 67 g of 2,2-bis (4-hydroxyphenyl) propane dissolved in 450 ml of a 6% strength by weight aqueous sodium hydroxide solution and 200 ml of methylene chloride was vigorously stirred under ice cooling. Phosgene gas was blown at a rate of 1000 ml / minute, and when the pH of the reaction system dropped to 9, the blowing of phosgene gas was stopped. Next, the obtained reaction product was allowed to stand and separate to obtain a methylene chloride solution of a polycarbonate oligomer having a degree of polymerization of 2-3 in the organic layer and having a chloroformate group at the molecular end.

Next, 50 ml of methylene chloride was added to the methylene chloride solution of the above polycarbonate oligomer to dilute it. 5- (4-hydroxyphenyl) -1 as porphyrin
0.2 g of 0,15,20-tritolylporphyrin was added, and
A solution prepared by dissolving 5.9 g of 2,2-bis (4-hydroxyphenyl) propane in 50 ml of a 2 N aqueous sodium hydroxide solution was added, and 0.5 ml of a 0.5 mol / l aqueous triethylamine solution was added as a catalyst while stirring, The reaction was carried out at 28 ° C for 1 hour. After completion of the reaction, the product was diluted with 500 ml of methylene chloride, and water, 0.01N aqueous sodium hydroxide solution, water, 0.1 ml.
It was washed in the order of 01 normal hydrochloric acid and water. Further, this was poured into methanol and reprecipitated to recover 35 g of a polymer.

This polymer has a reduced viscosity [η _{sp / c} ] of 0.70 dl / g at 20 ° C in a solution of 0.5 g / dl in methylene chloride.
And the glass transition temperature was 157 ° C.

Furthermore, the visible absorption spectrum (solvent: chloroform) of this polymer was measured and found to be 421nm, 485nm, 516nm, 552n.
Absorption was observed at the positions of m, 593 nm and 649 nm, and it was revealed that the porphyrin was bound to the polycarbonate.

Example 2 The same operation as in Example 1 was carried out except that 0.3 g of 5- (4-hydroxyphenyl) -10,15,20-tritolylporphinatomanganese chloride was used as the porphyrin, and 38 g A polymer of The reduced viscosity [η _{sp / c} ] of this polymer was 0.62 dl / g, and the glass transition temperature was 147 ° C.

Furthermore, the visible absorption spectrum (solvent: chloroform) of this polymer was measured and found to be 474nm, 528nm, 578nm, 616n.
Absorption was observed at the m position, confirming that the porphyrin was bound to the polycarbonate.

Example 3 Example 3 was repeated except that 0.3 g of 5- (4-hydroxyphenyl) -2,3,7,8,12,13,17,18-octaethylporphinato iron chloride was used as the porphyrin. The same operation as in Example 1 was carried out to obtain 37 g of a polymer. The polymer had a reduced viscosity [η _{sp / c} ] of 0.59 dl / g and a glass transition temperature of 146 ° C.

Furthermore, it was confirmed from the result of measuring the visible absorption spectrum (solvent: chloroform) of this polymer that porphyrin was bound to the polycarbonate.

[Effect of the Invention] According to the method of the present invention, a novel polycarbonate-based polymer complex containing a porphyrin nucleus residue can be produced in a simple process. Further, the novel polycarbonate polymer complex of the present invention can be utilized as a material for organic synthesis catalysts and electronics.

Claims (3)

(57) [Claims] 1. A formula [A] Or the formula [B] (However, Ar represents the following group, and n represents an integer of 1 or more. In addition, M represents the following metal atom. Cu, Ag, Au, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Al, Ga, In, Tl, Sc, Y, La,
Si, Ge, Sn, Pb, Ti, Zr, Hf, As, Sb, Bi, V, Nb, Ta, Cr, Mo, W, Mn, T
c, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Pr, Eu, Yb, Th Further, R ^{1 to} R ⁵ are hydrogen atom, halogen atom, carbon number 1 to 1
6 alkyl groups, phenyl groups, lower alkyl group-substituted phenyl groups, halogen-substituted phenyl groups, and alkoxy groups having 1 to 6 carbon atoms are shown. ), And a reduced viscosity [η _{sp / c} ] of a solution of 0.5 g / dl in methylene chloride at 20 ° C. is 0.59 dl / g
The above is a polycarbonate-based polymer complex. 2. A formula [A] characterized in that a reaction product of a dihydric phenol and a carbonic acid ester-forming compound is reacted with a porphyrin having a monohydric phenolic hydroxyl group or a metal complex thereof. Or the formula [B] (However, Ar represents the following group, and n represents an integer of 1 or more. In addition, M represents the following metal atom. Cu, Ag, Au, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Al, Ga, In, Tl, Sc, Y, La,
Si, Ge, Sn, Pb, Ti, Zr, Hf, As, Sb, Bi, V, Nb, Ta, Cr, Mo, W, Mn, T
c, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Pr, Eu, Yb, Th Further, R ^{1 to} R ⁵ are hydrogen atom, halogen atom, carbon number 1 to 1
6 alkyl groups, phenyl groups, lower alkyl group-substituted phenyl groups, halogen-substituted phenyl groups, and alkoxy groups having 1 to 6 carbon atoms are shown. ), And a reduced viscosity [η _{sp / c} ] of a solution of 0.5 g / dl in methylene chloride at 20 ° C. is 0.59 dl / g
The method for producing a polycarbonate-based polymer complex as described above. 3. The method according to claim 2, wherein the carbonic acid ester forming compound is phosgene or diphenyl carbonate.