DE4001158A1 - Macrocyclic polymer contg. phthalocyanine or porphyrin gps. - with high heat and dimensional stability, hardness and heat conductivity - Google Patents

Abstract

Polymeric macrocyclic cpds. of formula (I) are claimed. In (I) X = -CN, -CC-, -O-CH2-CH2-O-, -O-, NH, -S-, or gp. of formulae (i)-(vii). Y = -CH=CH-CH=CH-, -CH=CH-, -N=N-, or -CCCC-; Porph(Me) = gp. with phthalocyanine or porphyrin structure, opt. with a central Me metal atom, with Porph arranged so that the normal principal plane is parallel to the direction of the chain; n = at least 10; m pref. = 2. (I) are prepd. by reacting stoichiometric amts. of a substd. metal phthalocyanine or porphyrin of formula Porph(Me)(Y')m and a cpd. yielding the residue (X), and the inner linkage of the prod. through the Y' substits. Y' = gp. convertible to Y. USE/ADVANTAGE - The polymers have a tubular structure, with conjugation forming through peripheral cross-linking, making charge transport possible and giving a conductivity of more than 10 power(+3) s/cm. They have high heat stability (less than 0.1% wt. loss at up to 300 deg.C), and high dimensional stability, hardness and heat conductivity. The polymers are suitable as electrical conductors, for electrodes and battery units, as whiskers for blends and for reinforcement, with introduction of specific functionality, as probe and sensor materials, as components for membranes and ion-exchangers, and as macromolecular units for grafting purposes.

Description

It is already known polymer-bridged macrocyclic metal complexes (H. Hanack et al. in Handbook of Conducting Polymers, T. A. Skotheim ed. Vol. I p. 133 [1986], Marcel Dekker Inc., N.Y.); Macrocycles which can be used according to the invention are described in this publication e.g. B. referred to as ethinyl- or pyrazinylbridged compounds.

These metal complexes have a central axis and are free to rotate the individual macro cycles; their electrical conductivity reaches approx. 10 ^-1 Siemens.

It has now been found that new polymers emerge when the individual Macrocycles can be networked via peripheral functional groups. Subject of the invention is therefore a polymeric macrocyclic compound of the general Structure I

in which X denotes a divalent and / or divalent residue, selected from

-O-CH₂-CH₂-O-, -O-, -NH- or -S- and Y at least one further divalent bridge member selected from -C≡CC≡C-, -CH = CH-CH = CH-, - CH = CH- and -N = N- and in the porph (Me) each means a residue which may have a central metal atom Me with a phthalocyanine or porpyhrin structure, this residue being essentially arranged in such a way that its main plane normal is parallel runs to the chain direction, the degree of polymerization n being at least 10 and the number m of bridge members preferably being 2, as is obtained by reacting an essentially stoichiometric amount of a substituted metal phthalocyanine or porphyrin of the general formula porph (Me) (Y ′) _m , in which Y 'is a substituent which is convertible to the divalent radical Y, with a compound which provides the radical X and internal linkage of the reaction product via the substituents Y'. The polymers according to the invention have a tubular structure, with conjugation being formed via peripheral crosslinking, which enables charge transport and leads to a conductivity of more than 10 ⁺³ s / cm.

They are obtained by inserting an appropriate spacer (X) between the respective central atoms Me and peripheral ones functional groups (Y) that form bridging members and in addition to that serve targeted cargo transport.

For example, the following macro cycles are used as starting compounds in question:

Me preferably means Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Pd ²⁺ , Ru ²⁺ , Mn ²⁺ , Mn ³⁺ , Cr ³⁺ , but also Si, Ce, Sn.

The following groups come into question as axial spacers X. Me either purely coordinatively, such as B. in the case of pyrazine or by covalent or otherwise defined bonds are connected:  

The peripheral networking that leads to the peripheral bridge members Y takes place predominantly by condensation reactions, e.g. B. according to one of the following principles:

The bridge members Y obtained are peripherally fixed to the macrocycle, they contribute to the charge transport by their conjugation, cause the lifting free rotation around the axis of rotation - cf. Scheme I - see above that tubular polymers are formed.

The polymers according to the invention are notable for: high thermal stability (up to 300 ° C; weight loss <0.1%), high dimensional stability, Hardness and thermal conductivity.

The new materials are suitable as electrical conductors for electrodes and storage elements, as polymeric whiskers for blends and for reinforcement with incorporation of specific functionality, as probe and sensor material, as a membrane and ion exchange component as well as a macromolecular Building block for grafting processes.

The parts mentioned in the examples are parts by weight.  

Example 1

6.18 parts of tetravinyl phthalocyanine (No. XI) are dissolved in 100 parts of carbon tetrachloride suspended with 6.4 parts of bromine at room temperature Reacted and stirred for 30 min, then the precipitate suction filtered, washed with CCl₄ (3 times with 15 ml each) and dried (50 ° C, 3 h, 0.1 Torr).

The elemental analysis shows a bromine value of 49.2% (theoretically 50.87%), the melting point is 270 ° C with decomposition.

10 parts of the octabromotetraethane phthalocyanine shown above are added Given room temperature in a methanolic solution of potassium tert-butoxide (10 parts in 200 parts of methanol) and 2 hours at room temperature stirred, then suction filtered and dried - as described above. It 5.2 parts of product are isolated, which have no melting point at 300 ° C. show and decompose spontaneously from approx. 310 ° C.

The product obtained shows the typical IR bands at 3280 and 2150 cm and H-NMR at 3.2 to 3.3 ppm.

The introduction of spacer group X was carried out according to the instructions from O. Schneider and M. Hanack, Chem. Ber., 116, 2088 [1983] Pyrazin built-in.

The elementary analysis shows

18.2% N (theoretically 18.76%) and
7.0% Fe (theoretically 7.5%).

The compound begins to decompose at 290 ° C, in the IR the sharp alkyne bands at 3275 and 2130 cm ^{-1 are} slightly shifted to the short-wave compared to the starting product.

The product is subjected to the conditions of the Glaser coupling; therefor 1 part are suspended in 1000 parts of acetone, 0.8 parts of Cu₂Cl₂ are fed and 1.0 part of NH₄Cl over 1 hour and stirring at room temperature and passing oxygen (0.5 l / h) for 10 hours 1 part of a deep black, insoluble product is isolated.

The elementary analysis for this product shows:

18.1% N (theoretically 18.76%) and
7.0% Fe (theoretically 7.5%).

The H-NMR analysis reveals significant changes: instead of 3.2 to 3.3 maxima are now found at 2.2 ppm, which is for -C≡C-C≡E units speaks, also the H-C≡C proton signal is missing at about 1.80 ppm.

Now the triple bonds are reduced: 1 part of the connection becomes suspended in 100 parts of benzene and at room temperature in an autoclave with 0.2 parts of PdBd on CaCO₃ (7 wt .-% Pd) at 50 bar hydrogen pressure reduced. Working up takes place as described above, the resultant Product is contaminated by the insoluble catalyst.

Example 2

• a) Preparation of 1,3-diiminoisoindoline: according to Lit. MK Lovery et al. Inorganic Chemistry 4, 128 [1965] and YA Elvidge et al., J. Chem. Soc. 5000 [1952]
  Ammonia is passed in a slow stream for 40 minutes through a mixture of 320 g of o-phthalonitrile, 4 g of Na methylate and 1 liter of methanol, then the mixture is refluxed for 3.2 hours with continued stirring and passing through ammonia.
  After cooling, a greenish precipitate separates, which is filtered off and washed with ether.
  Yield 101 g, leaving to stand and cooling the filtrate leads to a new precipitate of 54 g; corresponding to a total yield of 43%.
  Recrystallization with methanol and ether gives colorless crystals with a melting point of 195 to 196 ° C. (with partial decomposition).
• b) Preparation of methyl-substituted diiminoisoindoline 365 g of 3-methyl-o-phthalonitrile are reacted in accordance with the above instructions. 162 g corresponding to 44% methyldiiminoisoindoline are obtained. The melting point is 178 ° C.
• c) Preparation of alkyne-substituted diiminoisoindoline 350 g of 3-alkynyl-o-phthalonitrile are reacted in accordance with the instructions of Example 1. 155 g, corresponding to 40% alkynyldiiminoisoindolines, are obtained. The melting point is 165 ° C with partial decomposition.
• d) Preparation of chlorine-substituted diiminoisoindoline 355 g of 3-chloro-o-phthalonitrile are reacted in accordance with the above instructions. 124 g corresponding to 35% chlorodiiminoisoindoline are obtained. The melting point is 201 ° C with partial decomposition.
• e) dichloro (phthalocyanino) silicone (PcSiCl₂):
  41.5 ml of silicon tetrachloride are slowly added to 36.5 g of diiminoisoindoline dissolved in quinoline (415 ml) with stirring at room temperature; then heated to 219 ° C (reflux) (30 min), then cooled to 184 ° C and filtered. After washing the purple precipitate with benzene, methanol and acetone, 2.4 g, corresponding to 71%, based on the diiminoisoindoline used, is obtained.
• f) Are analogous to that described under d) methyl, chlorine, alkynyl derivative 24.2 g or 19.4 g or 18.3 g are substituted Get PcSiCl₂.  
• g) Introduction of the spacer X in PcSiCl₂ for the production of the poly (phthalocyanino) silicone poly (Si D).
• h) Introduction of the spacer X in substituted PcSiCl₂ for the preparation of the peripherally substituted poly (phthalocanino) silicones.
  If the polycondensation described under g (g₁-g₂) is carried out with substituted dichloro (phthalocyanino) silicones, e.g. B. with derivatives of the type f₁, f₂ and / or f₃, the polymer structures listed under h are obtained.
  • h₁) Are accordingly g₁ z. B. 20 g of tetramethyl PcSiCl₂ used, the analog tetramethyl polysilicon is obtained with an -O bridge in about 95% yield.
  • h₂) Are accordingly g₁ z. B. 20 g of tetraalkine PcSiCl₂, the tetraalky silicone (IR: 3305 and 1244 cm ^-1 ≡CH vibration) is obtained with an -O bridge in about 95% yield.
  • h₃) If, according to g₂, 20 g tetraalkine PcSiCl₂ is used, the tetraalkyne polysilicon is obtained in about 80% yield.
    In the cases (h₁-h₃) the decomposition temperatures are <350 ° C, no melting was observed.
    The characterization is done by IR spectroscopy g₁.
  • h₄) Introduction of -CHO groups into the unsubstituted polysilicon g₁ by means of the Vilsmeier reaction:
    1.0 g of the polysilicon g₁ (with X = -O- as a spacer group) are added at room temperature in 100 ml of hexane over the course of 15 minutes with 27.0 g of N-methylformanilide and 30.6 g of phosphorus oxychloride and for 30 hours 40 ° C stirred, during the reaction time at intervals of 15 'for 1 min the reaction mixture in an ultrasonic bath, then the reaction mixture is carried in 750 ml of ice water, the precipitate is suctioned off and washed 3 times with 50 ml of acetone and then with 1 mol 50 ml of n-hexane. The resulting product shows the typical [= CO] vibration in the IR (KBr) at 1670 cm ^-1 .
    1 H-NMR 8 CDCl₃) δ = 10.29 (s 1H, aldehyde CH)
    The melting point of the derivative is 380 ° C (partial decomposition). Characterization of the aldehyde group additionally by formation of a tetradinitrophenylhydrazone.
  • i₁) Preparation of the peripheral bridge Y -C≡CC≡C- linking the macrocycles (intramolecular)
    2 g of tetraalkine polysilicon h₂ (with the spacer group X = O) are suspended in 1000 ml of dimethylformamide (DMF) and mixed with 2.5 g of Cu₂Cl₂ and 3 g of NH₄Cl at room temperature and with intensive stirring (500 rpm) with 200 liters O₂ fumigated (12 h at 55 ° C).
    The precipitate is then suctioned off.
    IR analysis no longer finds any ≡CH vibration at 2200 and 1245 cm ^-1 .
  • i₂) Production of the peripheral bridge Y -CH = CH-CH = CH-
    1.2 g of the product obtained according to i₁) are suspended in 200 ml of n-hexane and reduced with 1 g of Pd to CaCO₃ with H₂O at 50 atm and 50 ° C.
    The filtered reaction product no longer shows any -C≡CC≡C bands, but only olefinic CH vibrations.
    IR: 3080 cm ^-1 and -C = C vibrations 895 cm ^-1 .
    The product has after washing with HCl 1% in methanol and then doping with SbCl₅ (1% in nitromethane) an electr. Conductivity of 500 s / cm. Sb content in the polymer 11.2%.

Claims (1)

Polymeric macrocyclic compound of general structure I in which X denotes a divalent and / or divalent radical, selected from -O-CH₂-CH₂-O-, -O-, -NH- or -S- and Y at least one further divalent bridge member selected from -C≡CC≡C-, -CH = CH-CH = CH-, - CH = CH- and -N = N- and in the porph (Me) each means a residue which may have a central metal atom Me and has a phthalocyanine or porphyrin structure, this residue being arranged essentially in such a way that its main plane normal is parallel runs to the chain direction, the degree of polymerization n being at least 10 and the number m of bridge members preferably being 2, as is obtained by reacting an essentially stoichiometric amount of a substituted metal phthalocyanine or porphyrin of the general formula porph (Me) (Y ′) _m , in which Y 'is a substituent which is convertible to the divalent radical Y, with a compound which provides the radical X and internal linkage of the reaction product via the substituents Y'.