Application of stannylenes and germylenes as catalysts of heterocyclic compound polymerization

FIELD: organic chemistry, polymers.

SUBSTANCE: invention relates to catalysts for polymerization of cyclic esters of formula , wherein M represents tin or germanium atom L and L are independently group of formula -E14(R14)(R'14)(R''14), E15(R15)(R'15) or E16(R16); E14 represents element of 14 group; E15 represents element of 15 group; and E14 represents element of 16 group; R14, R'14, R''14, R15, R'15, and R16 are independently hydrogen atom; alkyl, cycloalkyl or aryl optionally substituted with halogen atom, alkyl cycloalkyl, aryl, nitro or cyano; rest of formula -E'14RR'R''; -E'14 represents element of 14 group; R, R', R'' are independently hydrogen atom; alkyl, cycloalkyl or aryl optionally substituted with halogen atom, alkyl cycloalkyl, aryl, nitro or cyano. Also invention relates to method for production of block- or random copolymers of cyclic esters and copolymers.

EFFECT: improved catalysts for production of heterocyclic compound copolymers.

9 cl, 6 ex

 

The present invention relates to the use of stannylene and germylenes as catalysts for polymerization of heterocyclic compounds.

It was shown that each type of catalysts used for polymerization or copolymerization of heterocyclic compounds, leads respectively to receive various polymers or copolymers, in particular as a result of redistribution reactions [Jedlinski et al., Macromolecules (1990) 191, 2287; Munson et al., Macromolecules (1996) 29, 8844; Montaudo et al., Macromolecules (1996) 29, 6461]. Therefore, the problem arises survey of new catalytic systems for the purpose of obtaining new polymers or copolymers.

On the other hand, are of particular interest catalytic system, which allows to obtain block copolymers. Indeed, in this case, it is possible to adjust the sequence of the monomers with the aim of obtaining specific copolymers having characteristic properties. It is of particular interest in the case of biocompatible copolymers, biodegradation depends on the named sequence.

The object of the present invention is also the use of stannylene and germylenes General formula 1

in which

M denotes an atom of tin or germanium;

L1and L2independently denote a group of the formula

-E14(R14)(R'14)(R14), -E15(R15)(R'15or-E16(R16or together form a chain of formula-L'1-A-L'2-;

And denotes a saturated or unsaturated chain containing one, two or three element group 14, each of which may be independently substituted in one of the following substituted (by one or more identical or different substituents) or unsubstituted radicals: alkyl, cycloalkyl, aryl, in which the above-named Deputy is a halogen atom, alkyl radical, aryl, nitro or cyano;

L'1and L'2independently denote a group of the formula

-E14(R14)(R'14)-, -E15(R15)- or-S16-,

E14denotes an element of group 14;

E15denotes an element of group 15;

E16denotes an element of group 16;

E14, R'14, R14, R15, R'15and R16independently represent a hydrogen atom, one of the following substituted (by one or more identical or different substituents) or unsubstituted radicals: alkyl, cycloalkyl or aryl, where the aforementioned Deputy is a halogen atom, an alkyl radical, cycloalkyl, aryl, nitro or cyano; a radical of the formula-E'14RR'R";

E'14denotes an element of group 14;

R, R' and R" independently represent a hydrogen atom or one of the follow is their substituted (by one or more identical or different substituents) or unsubstituted radicals: alkyl, cycloalkyl or aryl, where the aforementioned Deputy is a halogen atom, alkyl radical, aryl, nitro or cyano; as catalysts for polymerization of heterocyclic compounds.

In the above definitions, the expression halogen means fluorine atom, chlorine, bromine or iodine, preferably chlorine. The expression alkyl preferably denotes a normal or branched alkyl radical having from 1 to 6 carbon atoms, in particular alkyl radical having from 1 to 4 carbon atoms, such as radicals methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

Cycloalkyl radicals selected from monocyclic saturated or unsaturated cycloalkyl. Monocyclic saturated cycloalkyl radicals can be selected from radicals having from 3 to 7 carbon atoms, such as radicals cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. Unsaturated cycloalkyl radicals can be selected from the radicals cyclobutene, cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene.

Aryl radicals can be mono - or polycyclic type. Monocyclic aryl radicals can be selected from phenyl radicals which can be substituted by one or more alkyl radicals, such as tolyl, xylyl, mesityl, kumil. The police, the " aryl radicals can be chosen from the radicals naphthyl, antril, tenantry.

The compounds of formula 1 can be in the form of monomer or dimer, the dimer may have a linear or cyclic structure [C.Glidewell, Chem.Scripta (1987) 27, 437]. Thus, the compounds of formula 1, when L1and L2are independent from one another, can be represented in the form:

and when L1and L2form together a chain-L'1-A-L'2forms:

The compounds of formula 1 contain one or more solvent molecules [complexes stannylene-tetrahydrofuran were confirmed by a spectroscope: W.P.Neumann, Chem.Rev. (1991) 91, 311]. The solvent expression denotes an aromatic hydrocarbon such as benzene, toluene; cyclic or acyclic diakidoy ether, such as diethyl ether, dioxane, tetrahydrofuran, ethyl tert-butyl ether; a chlorinated solvent, such as dichloromethane, chloroform; aliphatic or aromatic nitrile, such as acetonitrile, benzonitrile; aliphatic or aromatic, cyclic or acyclic ketone, such as acetone, acetophenone, cyclohexanone; derivatives of aliphatic or aromatic, cyclic or acyclic carboxylic acids, such as ethyl acetate, dimethylformamide.

More spiral is the principal object of the invention is the use as catalysts for the polymerization of heterocyclic compounds defined above of compounds of General formula 1, characterized in that M denotes an atom of tin.

A more specific object of the invention is also the use as catalysts for the polymerization of heterocyclic compounds defined above of compounds of General formula 1, characterized in that the L1and L2denote E14(R14)(R'14)(R14), -E15(R15)(R'l5or-E16(R16).

The above use of compounds of formula 1 is preferred for compounds in which:

E14denotes the carbon atom or silicon;

E15denotes the nitrogen atom or phosphorus;

E16denotes an oxygen atom or sulfur;

E14, R'14, R14, R15, R'15and R16independently represent a hydrogen atom, the radical: alkyl or a radical of the formula-E'14RR'R";

E'14denotes the carbon atom or silicon;

R, R' and R" independently represent a hydrogen atom or an alkyl radical.

The above use of compounds of formula 1 is also preferred for the compounds in which:

L1and L2denote independently a group of formula-E15(R15) (R'15or-E16(R16);

E15denotes a nitrogen atom;

E16denotes an oxygen atom;

R15and R'15denote independently an alkyl radical or a radical of the formula-E sub> 14RR'R";

R16denotes an alkyl radical;

E'14denotes a silicon atom;

R, R' and R" independently represent a hydrogen atom or an alkyl radical.

Preferably the compound of formula 1 meets one of the following formulas:

-[(Me3Si)2N]2Sn;

-{[(Me3Si)2N]Sn(o-t-Bu)}2

Some of the compounds of formula 1 are known products, i.e. their synthesis and characteristics previously described [M.F.Lappert et al., J. Chem. Soc., Chem. Commun. (1973) 317; J.J.Zuckerman et al., J. Am. Chem. Soc. (1974) 895; M.Veith, Angew. Chem., Int. Ed. Engl. (1975) 14, 263; M.F.Lappert et al., J. Chem. Soc., Dalton Reans. (1977) 2004; M.Veith, Z.Naturforsch (1978) 33b, 1; ibid (1978) 33b, 7; M.F.Lappert et al., J. Chem. Soc., Chem. Commun. (1983) 639; ibid (1983) 1492; ibid (1992) 1311; M.F.Lappert et al., J. Am. Chem. Soc. (1980) 102, 2088]. In this regard, the new compounds of formula 1 can be obtained by analogy with the described circuits synthesis.

However, some of the compounds of formula 1 has been used in the polymerization of heterocycles (diepoxide) [S.Kobayashi et al., Macromol. Chem., Macromol. Symp. (1992) 54/55, 225]. But in this case they fulfil the role of co monomer and initiator of polymerization (redox copolymerization) and therefore the stoichiometric part of the structure of products of polymerization. Therefore, they are not catalysts.

The invention relates to the use of the above defined compounds of formula 1 as catalysis is tori for the (co)polymerization of heterocycles, i.e. polymerization or copolymerization of heterocyclic compounds. When carrying out the (co)polymerization of the compounds according to the invention also perform the function of the initiator or growth regulator circuit, but they are not stoichiometric in the structure of (co)polymers.

Heterocyclic compounds can contain one or more heteroatoms of groups 15 and/or 16 and have a size from three to eight links. As examples of the heterocycles that meet this definition may be called epoxides, diepoxides, cyclic esters or thioesters, such as lactones, lactams and anhydrides.

The compounds of formula 1 are of particular interest for the implementation of the (co)polymerization of epoxides, in particular of propylene oxide. The compounds of formula 1 are also of particular interest for the implementation of the (co)polymerization of cyclic esters. As an example, cyclic esters can be called polymeric cyclic esters of lactic and/or glycolic acid. Getting either random copolymers or block copolymers depends on how you enter the monomers: at the same time at the beginning of the reaction or sequentially during the reaction.

The object of the invention is also a method of obtaining a block or random copolymers or polymers, which enter into contact one or more monomers in tiator growth chain, the catalyst for polymerization and possibly solvent polymerization, and this method is characterized by the fact that the initiator of the chain growth and the polymerization catalyst are the same compound which is selected from the above defined compounds of formula 1.

(Co)polymerization can be carried out either in solution or in the melt. When the (co)polymerization is conducted in solution, the solvent of the reaction can be reactive substance (or one of the reacting substances) or reactive agent that is used in a catalytic reaction. Suitable solvents that do not participate in the catalytic reaction. As examples of such solvents can be called saturated or aromatic hydrocarbons, ethers, aliphatic or aromatic halides.

The reaction is carried out at temperatures ranging from room temperature up to approximately 250°C. the Most favorable was the range of temperatures from 40 to 200°C. the Duration of the reaction is in the range from several minutes up to 300 h and is preferably from 5 min to 72 hours

Named method (co)polymerization is particularly well suited to produce (co)polymers of cyclic esters, in particular a polymer of cyclic esters of lactic and/or glycolic acid. Produced biodegradable products, such as varnish is apically copolymer, successfully used as the basis for therapeutic compositions with a slow release. The method is particularly well suited 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, as well as semi-permeable membranes.

The method of (co)polymerization of heterocycles in accordance with the present invention has many advantages, in particular:

- catalysts (co)polymerization of the easily available and cheap;

- (co)polymerization can be carried out in a homogeneous environment, this allows the mass distribution is obtained (co)polymer is narrow;

the method is very well suited for obtaining block copolymers; sequential addition of monomers allows, in particular, to obtain the copolymer blocks.

Finally, the invention relates to polymers or copolymers that can be obtained using the above method.

Unless otherwise noted, all technical and scientific terms used in this application, have a value that is easily understandable to the ordinary specialist in the field to which the invention belongs. Moreover, all publications, patent applications and other references cited in this application, is included as reference material.

The following examples are given to illustrate the following operations and in any case should not be construed as limiting the scope of the invention.

Example 1: obtaining a statistical copolymer of D,L-lactide/glycolide with the ratio of lactide/glycolide close to 75/25

In purged with argon, the tube Slinka with a magnetic bar consistently give 0,023 g (0.05 mmol) of [(Me3Si)2N]2Sn, to 5.66 g (39,3 mmol) of D,L-lactide, 1.52 g (of 13.1 mmol) glycolide and 15 ml of mesitylene. The reaction mixture is stirred for 3 hours at 160°C.1H NMR analysis shows that the conversion for each of the monomers (lactide and glycolide) is 100%. The ratio of the integrals of the signals corresponding polylactides part (5,20 ppm) and polyglycolide part (4,85 ppm), allows us to estimate the composition of the copolymer: 75% lactide and 25% of glycolide. According to gel chromatography using calibration standards-based PS with masses from 761 to 400,000 this copolymer is a mixture of macromolecules (Mw/Mn=1,67) with highest weights (Mw=77500 daltons).

Example 2: obtaining a statistical copolymer of D,L-lactide/glycolide with higher molecular masses

In purged with argon, the tube Slinka with a magnetic bar consistently give 0,023 g (0.05 mmol) of [(Me3Si)2N]2Sn, 6,03 g (a 41.9 mmol) of D,L-lactide and of 2.08 g (to 17.9 mmol) Glick is Lida. The reaction mixture was stirred 10 min at 140°C.1H NMR analysis shows that the conversion of monomers is 83% lactide and 100% for glycolide. The ratio of the integrals of the signals corresponding polylactides part (5,20 ppm) and polyglycolide part (4,85 ppm), allows us to estimate the composition of the copolymer: 70% lactide and 30% of glycolide. According to gel chromatography using calibration standards-based PS with masses from 761 to 400,000 this copolymer is a mixture of macromolecules (Mw/Mn=1,8) with higher masses (Mw=164700 daltons).

Example 3: obtaining a statistical copolymer of D,L-lactide/glycolide with the ratio of lactide/glycolide close to 50/50

In purged with argon, the tube Slinka with a magnetic bar consistently give 0.16 g (0.36 mmol) of [(Me3Si)2N]2Sn, 7.87 in (54,7 mmol) of D,L-lactide and 6,34 g (54,7 mmol) glycolide. The reaction mixture is stirred for 2 hours at 180°C.1H NMR analysis shows that the conversion for each of the monomers is 100%. The ratio of the integrals of the signals corresponding polylactides part (5,20 ppm) and polyglycolide part (4,85 ppm), allows us to estimate the composition of a copolymer of 50% lactide and 50% of glycolide. According to gel chromatography using calibration standards-based PS with masses from 761 to 400,000 this copolymer of t is made by a mixture of macromolecules (Mw/Mn=1,7) with higher masses (Mw=39000 daltons).

Example 4: other statistical copolymer of D,L-lactide/glycolide with the ratio of lactide/glycolide close to 50/50

In purged with argon, the tube Slinka with a magnetic bar consistently give 0.16 g (0.36 mmol) of [(Me3Si)2N]2Sn, 8 g (55 mmol) of D,L-lactide, 6,34 g (55 mmol) of glycolide and 25 ml of mesitylene. The reaction mixture is stirred for 2 hours at 180°C.1H NMR analysis shows that the conversion of the monomers is 100% lactide and 100% for glycolide. The ratio of the integrals of the signals corresponding polylactides part (5,20 ppm) and polyglycolide part (4,85 ppm), allows us to estimate the composition of the copolymer: 47% lactide and 53% of glycolide. According to gel chromatography using calibration standards-based PS with masses from 761 to 400,000 this copolymer is a mixture of macromolecules (Mw/Mn=1,5) with higher masses (Mw=39400 daltons).

Example 5: receiving block copolymer of D,L-lactide/glycolide

In purged with argon, the tube Slinka with a magnetic bar consistently give 2.0 g (14 mmol) of D,L-lactide, 7 ml mesitylene and 41 mg (0.09 mmol) of [(Me3Si)2N]2Sn. The reaction mixture is stirred for 2 hours at 180°C.1H NMR analysis shows that the conversion of monomer exceeds 96%. Data gel chromatography using calibration standards-based P with masses from 761 to 400,000 indicate the polymer is a mixture of macromolecules with similar masses (Mw/Mn=1,76; Mw=18940 daltons). To the resulting solution stirred at 180°add 0.2 g (1,75 mmol) glycolide. The reaction mixture is stirred for 1 hour at 180°C.1H NMR analysis of the sample suggests that the conversion of glycolide is full and that the formed copolymer. The ratio of the integrals of the signals corresponding polylactides part (5,20 ppm) and polyglycolide part (4,85 ppm) is 7.3/1. Data gel chromatography indicate that there is a noticeable lengthening of the chains (Mw/Mn=1,89; Mw=21560 daltons).

Example 6: obtaining a statistical copolymer of D,L-lactide/glycolide with the ratio of lactide/glycolide close to 50/50

In purged with argon, the tube Slinka with a magnetic bar consistently give 0.08 g (0.11 mmol) of [(Me3Si)2N]2Sn(o-t-Bu)]2}, 4.9 g (34 mmol) of D,L-lactide/ 3,9 g (34 mmol) of glycolide and 25 ml of mesitylene. The reaction mixture is stirred for 2 hours at 180°C.1NMR analysis shows that the conversion of the monomers is 100% lactide and 100% for glycolide. The ratio of the integrals of the signals corresponding polylactides part (5,20 ppm) and polyglycolide part (4,85 ppm), allows us to estimate the composition of a copolymer of 50% lactide and 50% of glycolide. According to gel chromatography using is alibabki standards-based PS with masses from 761 to 400,000 this copolymer is a mixture of macromolecules (Mw/Mn=1,71) with higher masses (Mw=33140 daltons).

1. The catalyst for the (co)polymerization complex cyclic esters, characterized in that it is stannylene and germylene General formula 1

in which M denotes an atom of tin or germanium;

L1and L2independently denote a group of the formula

-E14(R14)(R'14)(R14); -E15(R15)(R'15or-E16(R16),

E14denotes an element of group 14;

E15denotes an element of group 15;

F16denotes an element of group 16;

R14, R'14, R14, R15, R'15and R16independently represent a hydrogen atom, one of the following substituted or unsubstituted radicals: alkyl, cycloalkyl or aryl, where the aforementioned Deputy is a halogen atom, an alkyl radical, cycloalkyl, aryl, nitro or cyano; a radical of the formula-E'14RR'R";

E'14denotes an element of group 14;

R, R' and R" independently represent a hydrogen atom or one of the following substituted (by one or more identical or different substituents) or unsubstituted radicals: alkyl, cycloalkyl or aryl, where the aforementioned Deputy is a halogen atom, alkyl radical, aryl, nitro or cyano.

2. The catalyst according to claim 1, wherein M denotes and the om tin.

3. The catalyst according to claim 1 or 2, characterized in that

E14denotes the carbon atom or silicon;

E15denotes the nitrogen atom or phosphorus;

E16denotes an oxygen atom or sulfur;

R14, R'14, R14, R15, R'15and R16independently represent a hydrogen atom, an alkyl radical or a radical of the formula-E'14RR'R";

E'14denotes the carbon atom or silicon;

R, R' and R" independently represent a hydrogen atom or an alkyl radical.

4. The catalyst according to claims 1 to 3, characterized in that

L1and L2denote independently a group of formula-E15(R15)(R'15or-E16(R16);

E15denotes a nitrogen atom;

E16denotes an oxygen atom;

R15and R'15denote independently an alkyl radical or a radical of the formula-E'14RR'R";

R16denotes an alkyl radical;

E'14denotes a silicon atom;

R, R' and R" independently represent a hydrogen atom or an alkyl radical.

5. The catalyst according to claims 1 to 4, characterized in that it meets one of the following formulas:

-[(Me3Si)2N]2Sn;

-{[(Me3Si)2N]Sn(Ot-Bu)}2.

6. The catalyst according to claims 1 to 5 for the copolymerization of cyclic esters of lactic and/or glycolic acid.

7. Pic is b receiving block or random copolymers of complex cyclic ethers, which enter into contact with the monomers, the polymerization catalyst and possibly solvent polymerization at a temperature ranging from room temperature up to 250°With the passage of time from a few minutes up to 300 h, characterized in that the initiator of the chain growth and the polymerization catalyst are the same compound of General formula 1, as defined in one of claims 1 to 5.

8. The method according to claim 7, characterized in that the monomer is selected from cyclic esters of lactic and/or glycolic acid.

9. The copolymers, which are obtained using the method according to claim 7 or 8.



 

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2 cl, 1 tbl, 23 ex

Polyether-polyols // 2263684

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7 cl, 6 ex

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3 cl, 3 tbl, 6 ex

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5 cl, 1 tbl, 16 ex

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16 cl, 1 tbl, 3 ex

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4 cl, 12 ex, 3 tbl

FIELD: chemical industry; methods of production of polyester.

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22 cl, 1 tbl, 24 ex

The invention relates to the field of Bioorganic chemistry, namely to new biologically active substances and methods of production thereof

The invention relates to a new ORGANOMETALLIC catalyst to obtain a complex ester comprising the reaction product, including interaction and complex orthoevra or condensed complex orthoevra titanium, zirconium, or aluminum; b) an alcohol containing at least two hydroxyl groups; b) organophosphorus compounds containing at least one group R-HE, and g) of the Foundation by mixing the above components; in addition, the ORGANOMETALLIC catalyst comprises the reaction product with 2-hydroxycarboxylic acid

FIELD: chemical industry; production of catalytic compounds for polymerization of monomers.

SUBSTANCE: the invention is dealt with the field of polymerization of the monomers and with the methods of production of catalytic compounds and compounds, which are applied at polymerization of at least one monomer. The offered methods contain: 1) a treated solid oxide compound produced due to a contact at least of one solid oxide with at least of one compound having an electron-seeking anion; 2)a metallocenes compound of a metal from IVA group; 3) an organoaluminum compound. The technical result: production of a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

EFFECT: the invention allows to produce a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

71 cl, 99 ex, 13 tbl

The invention relates to a new ORGANOMETALLIC catalyst to obtain a complex ester comprising the reaction product, including interaction and complex orthoevra or condensed complex orthoevra titanium, zirconium, or aluminum; b) an alcohol containing at least two hydroxyl groups; b) organophosphorus compounds containing at least one group R-HE, and g) of the Foundation by mixing the above components; in addition, the ORGANOMETALLIC catalyst comprises the reaction product with 2-hydroxycarboxylic acid

The invention relates to the field of production is fixed on the carrier homogeneous catalysts that can be used for liquid-phase and gas-phase processes
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