Metal complexes with tridentate ligand as polymerization catalysts

 

(57) Abstract:

Describes metal complexes with tridentate ligand of General formula 1 in which M is an atom of tin or zinc, a and b independently is a carbon chain containing 2 to 4 carbon atoms, L1- L3independently a group of formula-E15(R15)-, in which E15the nitrogen atom, R15is a hydrogen atom, alkyl radical, a radical of the formula RR'R"E14-, in which E14- carbon or silicon and R, R', R" independently is a hydrogen atom or alkyl radical. Also described is a method of obtaining compounds of formula 1, a method of obtaining random copolymers or block copolymers or polymers using as the polymerization catalyst and the initiator of the chain of the compounds of formula 1 and the polymers or copolymers resulting from the implementation of this method. 4 C. and 3 h.p. f-crystals, 2 ill., table 2.

The invention relates to new compounds containing the element 11, 12 or 14 groups and tridentate ligand, the method of their derivation. their use, in particular, as a catalyst of polymerization.

It was shown that each type of catalysts used for the polymerization or copolymerization gives a relatively early centers (Jedlinski et all., Macromolecules, (1990) 191, 2287; Munson et. coll., Macromolecules, (1996) 29, 8844; Montaudo et coll., Macromolecules, (1990) 29, 6461).

Therefore, the problem was to find a new catalytic system for new polymers or copolymers and, more specifically, the copolymers. The use of catalytic systems to obtain copolymers, enables regulation of education in the polymer chain of the monomers with the aim of obtaining specific copolymers having appropriate properties. This is especially interesting for biocompatible copolymers, biodegradation which is under the influence of such education in the polymer chain.

Thus, the subject invention are compounds of General formula 1

< / BR>
in which

M denotes the element 11, 12 or 14 groups;

A and b independently represent a carbon chain containing from 2 to 4 carbon atoms, possibly substituted by one of the following radicals, substituted (by one or more identical or different substituents) or unsubstituted: alkyl, cycloalkyl or aryl, where the aforementioned Deputy represents a halogen atom, an alkyl radical, a nitro-group, or cyano;

L1, L2and L3designation>denotes a hydrogen atom; one of the following radicals, substituted (by one or more identical or different substituents) or unsubstituted: cycloalkyl or aryl, where the aforementioned Deputy represents a halogen atom, an alkyl radical, a nitro-group or a cyano; a radical of the formula RR'R"E14-, in which E14denotes the element 14 group and R, R' and R" represent independently a hydrogen atom or one of the following radicals, substituted (by one or more identical or different substituents) or unsubstituted: alkyl, cycloalkyl, aryl, alkoxy, cycloalkane, aryloxy, alkylthio, cycloalkyl or aaltio, in which the above-mentioned Deputy represents a halogen atom, an alkyl radical, a nitro-group, or cyano; or a radical of the formula SO2R'15in which R'15denotes a halogen atom, alkyl, allogeneically or aryl radical, possibly substituted by one or more substituents selected among alkyl radicals, halogenating radicals and halogen atoms.

In the definitions above, the term halogen means fluorine atom, chlorine, bromine or iodine, preferably chlorine. The term alkyl denotes predpochtitaemye, containing from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl.

The term halogenated preferably denotes a radical in which the alkyl radical is as defined above, such as bromacil, trifluoromethyl, triptorelin or more pentaverate. Alkoxylation can correspond to the radicals in which the alkyl radical is as defined above. Preferred radicals methoxy, ethoxy, isopropoxy or tert-butoxy. Alkylthiomethyl are preferably radicals in which the alkyl is as defined above, for example radicals methylthio or ethylthio.

Cycloalkyl radicals chosen among saturated or unsaturated monocyclic cycloalkyl radicals. Saturated monocyclic cycloalkyl radicals can be selected from among radicals containing from 3 to 7 carbon atoms, such as radicals cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. Unsaturated cycloalkyl radicals can be selected among cyclobutenones, cyclopentenone, cyclohexenone, cyclopentadienones, cyclohexadiene radicals. Cycloalkenyl will radicalfashion radicals, cyclopropane, cyclopentane or cyclohexyloxy. Cycloalkylcarbonyl can correspond to the radicals, in which cycloalkenyl radical is as defined above, as, for example, cyclohexyldiamine.

Aryl radicals can be mono or polycyclic. Monocyclic aryl radicals can be selected from among a phenyl radical, possibly substituted by one or more alkyl radicals, such as tolyl, xylyl, mesityl, cumenyl. Polycyclic aryl radicals can be selected among naftiliaki, antilego, phenanthroline radicals. Aryloxyalkyl can correspond to the radicals in which the aryl radical is as defined above. Preferred radicals of phenoxy, 2,4,6-tri-tert-butylphenoxy, tolyloxy or mesityloxy. Keltiradigan preferably denote radicals in which the aryl radical is as defined above, as, for example, in phenylthiazole.

The compounds of formula 1 can be in the form of a monomer or dimer, and more specifically the compounds of formula 1 in which M denotes an atom of Zn, are usually in the form of a dimer.

More specifically, the subject invention are the products of General formula 1, are independently a carbon chain, containing from 2 to 4 carbon atoms and, in particular, a carbon chain of 2 carbon atoms;

L1, L2and L3denote independently a radical of the formula-E15(R15)-, in which E15denotes the nitrogen atom or phosphorus and R15denotes a radical of the formula RR'R"E14-, in which E14denotes the carbon atom or silicon and R, R' and R" represent independently a hydrogen atom or an alkyl or aryl radical, preferably a hydrogen atom or alkyl radical.

Preferably M represents an atom of tin or zinc; a and b independently represent a carbon chain of 2 carbon atoms; L1, L2and L3denote independently a radical of the formula-E15(R15)-, in which E15denotes a nitrogen atom and R15denotes a radical of the formula RR'R"E14-, in which E14denotes the carbon atom or silicon and R, R' and R" represent independently a hydrogen atom or a metal, ethyl, sawn or isopropyl radical.

More specifically, the subject invention are compounds described below in the examples, in particular of the compounds corresponding to the following formula:

- [(Me2CHNCH2CH2)2NMe]Sn;

- [(Me3SiNCH2CH2
(L1-A-L3-B-L2)2-, 2Y+(I)

in which L1AND L3, And L2have the meanings indicated above and Y denotes an ORGANOMETALLIC group, a metal or a hydrogen atom, is introduced into reaction with the compound of the formula (II)

MZ1Z2(II)

in which M has the meaning indicated above, and Z1and Z2denote independently tsepliaeva group, to obtain the product of formula 1, as defined above.

The compound of formula I similarly can be written in the following non-ionic form: Y-L1-A-L3-B-L2-Y (I'). When Y represents a hydrogen atom, the compounds of formula I are usually in the form of I'.

The reaction of compounds of General formula I with a compound of General formula II with obtaining compounds of General formula 1 can be carried out in an inert atmosphere such as an atmosphere of freon or argon, in an aprotic solvent at a temperature of from -90 to +50oC. Connections 1, thus obtained, purified by usual purification methods.

As the aprotic solvent can be used aromatic hydrocarbons such as benzene, toluene; aliphati yoksan, tetrahydrofuran, ethyl tert-butyl ether; chlorinated solvents such as dichloromethane or chloroform.

In compounds I, Y denotes an ORGANOMETALLIC group, a metal or a hydrogen atom. ORGANOMETALLIC group may be a compound of the formula R"'M1or R"'3M2in which R"' represents alkyl, cycloalkyl, aryl, alkoxygroup, cycloalkanes or alloctype defined above, M1denotes the atom of zinc or mercury, and M2denotes the atom of tin or lead; preferably ORGANOMETALLIC group chosen among groups ZnMe, Sn3, Snu3or b3. The metal may be an alkali metal selected among lithium, sodium or potassium, or alkaline earth metal such as magnesium.

In the compounds II Z1and Z2denote independently tsepliaeva group such as a hydrogen atom, alkyl, cycloalkyl, alkoxygroup, aryl or alloctype defined above, or methysulfonylmethane, benzolsulfonate, p-toluensulfonate.

The initial compounds of the formula I are known compounds or can be obtained from the known compounds. For SinTe the

The compounds of formula II are commercial or can be obtained by methods known to the expert.

The subject of the invention is also the use of compounds of formula 1, as defined above, as catalysts for the implementation of the (co)polymerization, i.e., polymerization or copolymerization. When implementing (co)polymerization of the compounds according to the invention likewise play the role of initiator or growth regulator polymer chain.

The compounds of formula 1 are of special interest for the implementation of polymerization of heterocycles. Heterocycles may contain one or more heteroatoms 15 and/or 16 groups and having in its structure from three to eight links. As examples of the heterocycles that meet the previous formulation can be called epoxides, diepoxides, cyclic esters or thioesters, such as lactones, lactams and anhydrides.

The compounds of formula 1 are equally particularly interesting for the implementation of the (co)polymerization of cyclic esters. As an example, cyclic esters can be called dimeric cyclic esters of lactic acid and/or glycolic acid (lactide and glycolide). Statisticly or sequentially during the reaction.

The subject of the invention is also a method of obtaining random copolymers, or block copolymers, or polymers, which lies in the interaction of one or more monomers, initiator growth chains, polymerization catalyst and, if necessary, solvent polymerization, characterized in that the initiator of the growth of the chains and the polymerization catalyst represented by one and the same connection, which is chosen among the compounds of formula 1, as defined above.

(Co)polymerization can be carried out either in solution or in a supercooled state. When the (co)polymerization is carried out in solution, the solvent of the reaction may be the substrate or one of the substrates used in catalytic reactions. Solvents that have no effect on the catalytic reaction, is also suitable. As examples of such solvents can be called saturated or aromatic hydrocarbons, ethers, aliphatic or aromatic halides.

The reaction is carried out at temperatures of prisoners between room temperature and approximately 250oC; temperature range 40 - 200oWith turns out to be the most favorable. Times but is well suited to produce (co)polymers of cyclic esters, in particular dimeric cyclic esters of lactic and/or glycolic acids. The resulting products, such as biodegradable copolymer of lactic and glycolic acids, is used favorably as a carrier for therapeutic compositions with prolonged selection. The method is also particularly suitable for the polymerization of epoxides, in particular of propylene oxide. The resulting polymers are compounds that can be used for the synthesis of organic liquid crystals, or even as a semi-permeable membranes.

Likewise the invention concerns polymers or copolymers that can be obtained by implementing the method described above. The polydispersity (Mw/Mn) (co)polymers thus obtained can be changed by keeping the reaction mixture at the reaction temperature after complete conversion of the monomer or monomers. Weight (co)polymers little affected during this process. These phenomena occur due to reactions of intramolecular or intermolecular pereeterifikacii (Kiecheldorf et all., Macromolecules, (1988) 21, 286).

The following examples are provided to illustrate the invention, and by no means slicer 1. [(Me2CHNCH2CH2)2NMe]Sn;

M=Sn; A=B=-CH2CH2-; L1=L2=NCHMe2; L3=NMe

In the vessel Slanka, equipped with a rod magnet and purged with argon, consistently give of 1.00 g (4.7 mmol) of [(Me2CHNCH2CH2)2NMe]2-, 2Li+and 20 ml of diethyl ether. The reaction mixture was cooled to -78oWith, then enter suspension of 0.89 g (4.7 mmol) SnCl2in diethyl ether. The reaction mixture was returned to room temperature and maintained at room temperature while stirring for 18 hours the Solution is filtered and the solvent evaporated. The desired compound is isolated in the form of a yellow oil (yield 74%). This connection is characterized by means of NMR spectroscopy on protons and carbon nuclei and tin.

NMR1N (C6D6; 250 MHz): 1,49 (l, JNN=6.2 Hz, 6N, ); and 1.54 (d, JNN= 6.2 Hz, 6N, ); 2,11 (s, 3H, J119SnC=20.2 Hz, J117SnC=17.5 Hz, ); is 2.37 (m, 4H, ); 3,11 (m, 2H, ); 3,67 (Sept, JNN=6.2 Hz, 2H, ).

NMR13C6D6; 62,896 MHz): 26,64 (C ); 26,93 (C ); 49,05 (s, JSnC=53,5 Hz, N3); 54,64 (s, CH2); 55,04 (C ); 63,32 (C ).

NMR119Sn (C6D6; 32,248 MHz): 121,13 (v1/2=600 Hz).

Example 2. [(Me3SiNCH2CHvessel Slanka, equipped with the core magnet and purged with argon, consistently give 1.22 g (4.7 mmol) of [(Me3SiNCH2CH2)2The N]2-, 2L1+and 20 ml of diethyl ether. The reaction mixture was cooled to -78oWith, then enter suspension of 0.89 g (4.7 mmol) SnCl2in diethyl ether. The reaction mixture was returned to room temperature and maintained at room temperature under stirring for 2 hours. The solution is filtered, the solvent evaporated and the residue is treated with pentane. After evaporation of the solvent receive an orange oil. The desired compound is isolated in the form of white crystals by crystallization from toluene (5 ml) at -20oWith (yield 80%). This connection is characterized by NMR spectroscopy at various nuclei and x-ray (Fig. 1 and table. 1, see below). The melting point of 20oC.

Example 3. [(Me3SiNCH2CH2)2NMe]Zn; (see tab. 2)

M=Zn; a=b=-CH2CH2-; L1=L2=NSi3; L3=NMe

In the vessel Slanka, equipped with a rod magnet and purged with argon, is injected 1.1 g (4.2 mmol) (Me3SiNCH2CH2)2NMe and 20 ml of toluene. The reaction mixture was cooled to -78oWith, then injected a suspension of 2.1 ml ZnM for 3 hours. The solvent is then evaporated. Get the oil deep yellow color. This oil is warm again at 110oC for 4 hours. The desired compound was washed with 5 ml of pentane (3 times) and emit in the form of white crystals (yield 75%). This connection is characterized by NMR spectroscopy and x-ray (Fig. 2 and table. 2, see below).

NMR1N (C6D6; 250 MHz): 0,25 (, N, ); 0,30 (s, N, ); 2,11 (s, 6N, ); 2,24 (m, 8H, ); 3,05 (m, 8H, ).

NMR13WITH (C6D6; 50,323 MHz): 3,22 (s, Si); or 3.28 (s, ); 44,49 (C ); 47,66 (C ); 47,72 (C ); 60,31 (C ); 65,91 (C ).

Example 4. Obtaining poly(D,L-lactide)

In the vessel Slanka, equipped with a rod magnet and purged with argon, consistently give 0.08 g (0.21 mmol) of [(Me3SiNCH2CH2)2NMe]Sn, to 6.67 g (46,3 mmol) of D,L-lactide and 70 ml of toluene. The reaction mixture was kept under stirring at 75oC for 2.5 hours, the Polymer was characterized by NMR on the carbon nuclei and protons: conversion of monomer is 60%. According to the analysis by GPC method (gel chromatography) using a calibration performed using standard samples of polystyrene (PS) with molecular masses from 761 to 400,000, the sample consists of polymers with close (Mw/M3
SiN2CH2)2NMe]Zn, 0,621 g (to 43.1 mmol) of D,L-lactide and 50 ml of toluene. The reaction mixture was kept under stirring at 30oC for 36 hours the Polymer was characterized by NMR on the carbon nuclei and protons: conversion of monomer is 92%. According to the analysis by GPC method (gel chromatography) using a calibration performed using standard samples of polystyrene (PS) with molecular masses from 761 to 400,000, the sample consists of polymers with large molecular mass (Mw=34654).

Example 6. Getting blockcopolymer D,L-lactide and glycolide

In the vessel Slanka, equipped with a rod magnet and purged with argon, consistently give 0.08 g (0.21 mmol) of [(Me3SiNCH2CH2)2NMe]Sn, 5,00 g (34,72 mmol) of D,L-lactide and 70 ml of toluene. The reaction mixture was kept under stirring at 75oC for 4 h Analysis method TMR allows you to confirm that the conversion of the monomer is more than 95%. The previous solution was added to 1.00 g (8.6 mmol) of glycolide. The reaction mixture was kept under stirring at 75oC for 1 h Anal is stuudy polylactides part (5,20 m D.) and polyglycolide part (4,85 M. D.), equal to 8/1. According to the analysis by GPC method using a calibration performed using standard samples of PS with molecular masses from 761 to 400,000, this copolymer is a mixture of macromolecules (Mw/Mn=2,35) with large (Mw=68950) molecular masses.

Example 7. Changing polydispersity copolymer of D,L-lactide and glycolide

The copolymer obtained according to example 6 (Mw/Mn=2,35), incubated at 75oWith over 20 hours analysis of the aliquot of sample by GPC method shows that the dispersion is increased, and the mass remained constant (Mw/Mn=69; Mw=68850). The mixture is again incubated 20 h at 75oC. analysis of the aliquot of sample by GPC method shows that the dispersion begins to decrease, and the weight remains almost constant (Mw/Mn= 2,02; Mw=65659). After 40 hours of additional heating at 75oWith a polydispersity equal 1,53 when the mass-average molecular mass 62906.

Example 8. Obtaining a statistical copolymer of D,L-lactide and glycolide

In the vessel Slanka, equipped with a rod magnet and purged with argon, consistently give 0.08 g (0.21 mmol) of [(Me3SiNCH2CH2)NMe]Sn, 4, the EP is characterized by NMR on the carbon nuclei and protons; the conversion of the monomers is complete. According to the analysis by GPC method using a calibration performed using standard samples of PS with molecular masses from 761 to 400,000, the sample consists of polymers having a polydispersity (Mw/Mn)=2,24 and mass-average molecular mass (Mw)=21650.

Example 9. Obtaining a statistical copolymer of D,L-lactide and glycolide having the composition of lactide/glycolide close to 50/50

In the vessel Slanka, equipped with a rod magnet and purged with argon, consistently give 0.01 g (0,031 mmol) of [(Me3SiNCH2CH2)2NMe]Zn, of 5.55 g (a 38.5 mmol) of D,L-lactide and at 1.91 g (16.5 mmol) of glycolide. The reaction mixture was kept under stirring at 100oWith over 144 minutes Analysis by NMR on protons allows to confirm that the conversion of monomers is 76% for lactide and 100% for glycolide. The ratio of the integrals of the signals corresponding polylactides part (5,20 M. D.) and polyglycolide part (4,85 M. D.), allows us to estimate the composition of the copolymer as 46/54. According to the analysis by GPC method using a calibration performed using standard samples of PS with molecular masses from 761 to 400,000, this copolymer is a mixture of makromolekulare statistical copolymer of D, L-lactide and glycolide having the composition of lactide/glycolide close to 70/30

In the vessel Slanka, equipped with a rod magnet and purged with argon, consistently give 0.015 g (0.046 mmol) of [(Me3SiNCH2CH2)2NMe]Zn, 13.3 g (with 92.4 mmol) of D,L-lactide and 3.1 g (26,4 mmol) glycolide. The reaction mixture was kept under stirring at 180oC for 5 hours. Analysis by NMR on protons allows to confirm that the conversion of monomers is 66% lactide and 100% for glycolide. The ratio of the integrals of the signals corresponding polylactides part (5,20 M. D.) and polyglycolide part (4,85 M. D. ), allows us to estimate the composition of the copolymer as 68% lactide and 32% of glycolide. According to the analysis by GPC method using a calibration performed using standard samples of PS with molecular masses from 761 to 400,000, this copolymer is a mixture of macromolecules (Mw/Mn=2,30) with large molecular masses (Mw=71281).

1. Metal complexes with tridentate ligand of General formula 1

< / BR>
in which M is an atom of tin or zinc;

A and b independently is a carbon chain containing 2 to 4 carbon atoms;

L1- L3independently is a group of formula-E1514-, in which E14- carbon or silicon and R, R' and R" independently is a hydrogen atom or alkyl radical.

2. Connection on p. 1, wherein M is an atom of tin or zinc; a and b independently is a carbon chain of 2 carbon atoms; L1- L3independently is a radical of the formula-E15(R15)-, in which E15is a nitrogen atom and R15is a radical of the formula RR'R"E14-, in which E14the atom is carbon or silicon and R, R' and R" independently is a hydrogen atom or a methyl, ethyl, sawn or isopropyl radical.

3. Connection under item 1 or 2, characterized in that they correspond to the following formulas:

-[(Me2CHNCH2CH2)2NMe] Sn;

-[(Me3SiNCH2CH2)2NMe] Sn;

-[(Me3SiN2CH2)2NMe] Zn.

4. Compounds according to any one of paragraphs. 1-3, characterized in that they are catalysts for the polymerization or copolymerization of cyclic ethers, in particular dimeric cyclic esters of lactic acid and/or glycolic acid.

5. The method of obtaining compounds of General formula 1, characterized in that compounds of the formula I

(L1-A-L3IN L2)2-, 2Y+(I)

in which L1
enter into reaction with the compound of the formula (II)

MZ1Z2(II)

in which M has the values specified in paragraph 1;

Z1and Z2independently - tsepliaeva group,

in an inert atmosphere, such as freon or argon, in an aprotic solvent at a temperature of from -90 to +50oC.

6. The way to obtain random copolymers, or block copolymers, or polymers involving the interaction of one or more monomers selected from the group consisting of a complex of cyclic ethers, in particular dimeric complex of cyclic esters of lactic acid and/or glycolic acid catalyst polymerization and possibly solvent polymerization, at a temperature from room temperature up to 250oC for 1 to 300 hours, characterized in that the initiator of the growth of the chains and the polymerization catalyst represented by one and the same connection, which is chosen among the compounds according to paragraphs. 1-3.

7. Polymers or copolymers resulting from the implementation of the method according to p. 6.

 

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