Compounds having an element of group iii of the periodic system of elements of d. i. mendeleev associated with mono - or dianions tridentate ligand, the method of their production and their use as polymerization catalysts

 

(57) Abstract:

The invention relates to new compounds having an element of group III, associated with mono - or dianions tridentate ligand, the method of their production and their use in particular as a catalyst for (co)polymerization. Describes compounds of formulas 1 and 2

< / BR>
< / BR>
in which M represents an atom of boron, aluminum or gallium; RMrepresents a hydrogen atom, a halogen atom, especially chlorine or a methyl radical; a and b independently represent a carbon chain with 2 to 4 carbon atoms, especially carbon chain of 2 carbon atoms; L1, L2represent independently a group of formula-S5(R5)-, in which E5represents a nitrogen atom or phosphorus; R5represents a radical of the formula RR'R"E4in which E4represents a carbon atom or silicon and R, R' and R" represent independently a hydrogen atom or an alkyl radical; X1represents gecoordineerde anion relative to the element M; L3represents a group of formula-S5(R5)-, in which E5represents a nitrogen atom or phosphorus and R5represents alkyldimethyl an independently alkyl radical; and R1represents a hydrogen atom. Describes how to obtain compounds 1 and 2 and their use as polymerization catalysts. The technical result is to provide new compounds with increased activity as polymerization catalysts. 5 S. and 6 C.p. f-crystals, 6 ill., table 1.

Some mono - and gianinni tridentate ligands are known as ligands for transition metals. So, (Ph2PCH2SiMe2)2N-- a derivative used for the preparation of complexes of iridium (Fruzuk et al., Angew. Chem. Ed. Engl. (1990), 29, 73) and [(Me3SiNCH2CH2)2NSiMe3]2-- a derivative used for the preparation of complexes of zirconium dichloride (Cloke et al., J. Chem. Soc., Dalton Trans. (1995), 25). Also known derivatives of boron with [(O2CLO2)2NCH3] 2-the ligand (Contrepas et al., J. Were Obtained. Chem. (1986), 307, 1). In addition, they also described derivatives of aluminum, which is [NH(CH2CH2O)2]2-the ligand (Mehrotra et al., J. Indian Chem. Soc. (1962), 39, 677-82).

It is also known the use of Lewis acids with an element of group III of the Periodic system of elements Mendeleev, in organic synthesis (Yamamoto, N. In Organometallics in Synthesis; Schlosser, M., Ed.; John Wiley and Sons Ltd.: West Sussex, England, 1994, Chapter 7),azali, that catalysts with ligands porphyrin type, were able to form polymers having the index polymolecularity, close to one (J. Chem. Soc., Chem. Commun. (1985), 1148; Chem. Lett. (1987), 991; Makromol. Chem.

(1981), 182, 1073). In addition, these catalysts can be used to obtain alternating copolymers or block copolymers (Inoue et al., J. Am. Chem. Soc. (1983) 105, 1304; J. Am. Chem. Soc. (1985) 107, 1358; Macromolecules (1984) 17, 2217). These two properties are the result of the fact that generated a "living" polymer.

However, these catalytic systems use porphyrin ligands that are expensive and difficult, which leads to increased cost. In addition, to increase the activity, you must add the Lewis acid, which increase the complexity of catalytic systems (Inoue et al., Macromolecules (1994), 27, 2013; Macromolecules (1995) 28, 651).

Therefore, the problem was in the presence of catalytic systems, which would be more effective, which are easier to synthesize and more economical than the catalytic system, the previously recommended.

The present invention relates to new compounds having an element of group III, associated with mono - or dianions tridentate ligand, the method of their preparation and their Easom, are the products of General formula 1 and 2

< / BR>
< / BR>
in which M represents an element of group III;

RMrepresents a hydrogen atom, halogen atom or one of the following substituted (by one or more identical or different substituents) or unsubstituted radicals: alkyl, cycloalkyl, aryl, alkoxy, cycloalkane, aryloxy, alkylthio, cycloalkyl or aaltio, in which the Deputy represents halogen atom, alkyl, nitro or ceanorhaditis;

A and b represent, independently, a carbon chain with 2 to 4 carbon atoms, optionally substituted by one of the following substituted (by one or more identical or different substituents) or unsubstituted radicals: alkyl, cycloalkyl or aryl, in which the Deputy is a halogen atom, alkyl, nitro or ceanorhaditis;

L1, L2and L3represent independently a group of formula-S5(R)-, in which E5represents an element of group V and R5represents a hydrogen atom; one of the following substituted (by one or more identical or different substituents) or unsubstituted radicals: alkyl, cycloalkyl or aryl, in which the Deputy is a halogen atom, al the, 'and R" represent, independently, a hydrogen atom or one of the following substituted (by one or more identical or different substituents) or unsubstituted radicals: alkyl, cycloalkyl, aryl, alkoxy, cycloalkane, aryloxy, alkylthio, cycloalkyl or aaltio, in which the Deputy represents halogen atom, alkyl, nitro or ceanorhaditis; or a radical of the formula SO2R'15in which R'15represents a halogen atom, alkyl, allogeneically or aryl radical, optionally substituted by one or more substituents selected from alkyl, halogenoalkanes radicals and halogen;

X1-is gecoordineerde anion relative to the element M;

R1represents a hydrogen atom, a radical of the formula RR'R"E14-, in which E14, R, R' and R" have the same definitions as above, or one of the following substituted (by one or more identical or different substituents) or unsubstituted radicals: alkyl, cycloalkyl or aryl, in which the Deputy is a halogen atom, alkyl, nitro or ceanorhaditis.

In the definitions above, the expression halogen atom is fluorine, chlorine, bromine ion battery alkyl radical, having from 1 to 6 carbon atoms, and especially an alkyl radical having from 1 to 4 carbon atoms, such as radicals methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

The term halogenated preferably designates the radicals in which the alkyl radical such as defined above and substituted by one or more halogen atoms, as defined above, such as, for example, bromacil, trifluoromethyl, triptorelin or pentafluoroethyl. Alkoxylation can correspond to the radicals in which the alkyl radical such as defined above. Preferred methoxy-, ethoxy, isopropoxy - or tert-butylacetoacetate. Alkylthiomethyl preferably represent radicals in which the alkyl radical such as defined above, such as, for example, methylthio or ethylthio.

Cycloalkyl radicals selected from saturated or unsaturated monocyclic cycloalkyl. Saturated monocyclic 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 radicals of cyclobutene, qi is iculum, in which cycloalkenyl radical such as defined above. The preferred cyclopropylamine, cyclopentyloxy or cyclohexyloxycarbonyl. Cycloalkylcarbonyl can correspond to the radicals, in which cycloalkenyl radical such as defined above, such as, for example, cyclohexylthio.

Aryl radicals may be radicals mono - or polycyclic type. Monocyclic aryl radicals can be selected from phenyl radicals, optionally substituted by one or more alkyl radicals, such as tolyl, xylyl, mesityl, cumenyl. Polycyclic aryl radicals can be selected from naftalina, analnyj, phenanthroline radicals. Aryloxyalkyl can correspond to the radicals in which the aryl radical such as defined above. The preferred phenoxy, 2,4,6-tri-tert-butylphenoxy, tolyloxy or mesityloxide. Keltiradigan, preferably, are intended to identify radicals in which the aryl radical such as defined above, such as, for example, phenylthio.

The anion X1-can be selected from necoordonarea anions relative to the element M, such as the anions of tetrafluoroborate, tetraphenylborate, tlie specific object of the invention is the products of General formulas 1 and 2, as defined above, characterized in that

M represents an atom of boron, aluminum or gallium;

RMrepresents a hydrogen atom, a halogen atom, especially chlorine, or a methyl radical;

A and b represent, independently, a carbon chain containing from 2 to 4 carbon atoms, especially carbon chain of 2 carbon atoms;

L1and L2represent, independently, a radical of the formula-E15(R15)-, in which E15represents a nitrogen atom or phosphorus and R15represents a radical of the formula RR'R"E14-, in which E14represents a carbon atom or silicon and R, R' and R" represent, independently, a hydrogen atom or an alkyl radical; R15in particular, is the isopropyl radical and IU3Si;

L3represents a group of formula-E15(R15)-, in which E15represents a nitrogen atom or phosphorus and R15represents an alkyl radical, especially methyl, or a radical of the formula RR'R"E14-, in which E14represents a silicon atom and R, R' and R" represent, independently, an alkyl radical, especially methyl; and R1represents a hydrogen atom.

More specifically, the subject invention are the products that are described below in the examples, h>AlCl;

-[(Me3SiNCH2CH2)2NMe]AlCl;

-[(Me3SiNCH2CH2)2NMe]AlH;

-[(Me3SiNCH2CH2)2NMe]AlCH3;

-[(Me3SiNCH2CH2)2NSiMe3]GaCl;

-{[((CH3)2NCH2CH2)((CH3)2CHNHCH2CH2)NMe]AlCl}{AlCl4};

-{[(Me3SiNCH2CH2)(Me3SiNHCH2CH2)NSiMe3]AlCl}{AlCl4}.

The subject of the invention is also a method of obtaining the products of General formula 1 and 2, as defined above, characterized in that the product of the formula I

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

in which L1AND L3, And L2have the meanings indicated above and Y represents an ORGANOMETALLIC group, a metal or a hydrogen atom, allow to react with the product of formula II

RMMZ1Z2(II)

in which RMand M have the meanings given above and Z1and Z2represent, independently, a leaving group, to obtain a product of formula 1

< / BR>
which you can give to react with the compound of the formula (III)

R1X1(III)

in which R1and X1have the meanings indicated above, to obtain sootvetstvuyshee compounds of General formula 1 can be carried out in an inert atmosphere, for example in an atmosphere of freon or argon, in an aprotic solvent at a temperature between -60 and +50oC. If the reaction which produces compound 2, on the basis of the corresponding compound 1, compound 1 is allowed to react in an inert atmosphere and at room temperature with compound III in aprotic medium.

The subject invention is also a method of obtaining the products of General formula 2, as defined above, characterized in that the product of formula (IV)

< / BR>
in which R1, L1AND L3, And L2have the meanings given above and X represents a coordinating anion relative to the element M, allow to react with the compound of the formula (V)

MX'3(V)

in which M has the meanings indicated above and X' represents a halogen atom, alkyl or alkoxyalkyl, as previously defined, to obtain the corresponding product 2.

The reaction that forms a compound of General formula 2 from the corresponding compounds of General formula IV can be carried out in an inert atmosphere such as an atmosphere of freon or argon, at elevated temperature with a compound V in aprotic medium.

Compound 2 can also be obtained from compound IV in sootvetstvie group III.

Regardless of the method used to obtain the thus obtained compounds 1 and 2 are cleaned using standard cleaning methods. Compound 2 can also be obtained in situ from compounds IV, in an environment in which its later use.

The product of formula IV can be obtained by reaction of compounds of formula VI

(R1L1-A-L3-B-L2)-, Y1+, (VI)

in which R1, L1AND L3, And L2have the meanings indicated above and Y1represents an ORGANOMETALLIC group, a metal or a hydrogen atom, the product of formula VII

RMZ3, (VII)

in which RM, M and X have the meanings given above and Z3represents a leaving group. This reaction can be carried out in an inert atmosphere such as an atmosphere of freon and argon, in an aprotic solvent at a temperature between -60 and +50oC.

The product of formula IV can be obtained by reaction of compounds of formula I, as defined above, with a compound of formula (VIII) R1X, in which R1and X have the meanings indicated above. The reaction can be carried out in an inert atmosphere such as an atmosphere of freon and argon, in an aprotic solvent at a temperature between -60 and +50o

In compounds I and VI, Y and Y1represent, independently, 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, alkoxy, cycloalkane or aryloxyalkyl, as defined previously, M1represents an atom of zinc or mercury and M2represents an atom of tin or lead; metal-organic group preferably selected from groups ZnMe, Sn3, Snu3or Pb3. The metal can be alkali metal selected from lithium, sodium or potassium, or alkaline earth metal such as magnesium.

In the compounds II and VII Z1, Z2and Z3represent, independently, a leaving group such as halogen atom, alkyl, cycloalkyl, alkoxy, aryl or alloctype, as defined above, or also methansulfonate, benzosulfimide or p-toluensulfonate.

In connection IV X represents a coordinating anion relative to the ale and bromine.

The initial product of the formula I and the product of formula VI are known products or you can get them from known products. To obtain them we can mention the following links: Cloke et al., J. Chem. Soc., Dalton Trans. (1995) 25; Wilkinson and Stone, Comprehensive Organometallic Chemistry (1982) vol. 1, 557.

The products of formula III and VIII commercial or can be obtained by methods known to the expert of this field.

The products of formula IV are new. Therefore, the subject invention are also as new industrial products, the compounds of formula IV, as defined above.

The subject of the invention is also the use of products of formula 1 and 2, as defined above, as catalysts for the (co)polymerization, i.e., polymerization or copolymerization. The compounds of formula 1 and 2 is particularly suitable for carrying out the polymerization of heterocycles. Heterocycles may contain one or more heteroatoms of groups 15 and/or 16 and have a size ranging from three to eight members. As examples of compounds corresponding to the above formulation, we can mention epoxides, diepoxides, cyclic esters or thioesters, such as lactones, lactams and anhydrides. The compounds of formula 1 and 2 of morimura cyclic esters can be mentioned a polymer of cyclic esters of lactic and/or glycolic acid. Random copolymers or block copolymers can be obtained in accordance regardless, enter whether the monomers together with the beginning of the reaction or thereafter, during a reaction.

The subject of the invention is also a method of producing polymers or copolymers, which is that contacting one or more monomers, a polymerization catalyst and a solvent polymerization and characterized by the fact that the polymerization catalyst is chosen from the products of the invention.

The reaction solvent may be a substrate (or one of) substrates used in catalytic reactions. Suitable solvents which do not inhibit the catalytic reaction. As examples of such solvents may be mentioned saturated or aromatic hydrocarbons, ethers, aliphatic or aromatic halides.

The reaction is carried out at temperatures between room temperature and approximately 150oWith; very favorable temperature range between 40 and 100oC. the duration of the reaction is from 1 to 300 hours, preferably from 4 to 72 hours.

Products are usually isolated after adding to the reaction medium proton dissolve the changes of the element M by centrifugation.

This method (co)polymerization is particularly suitable for producing (co)polymers of cyclic esters, particularly a polymer of cyclic esters of lactic and/or glycolic acid. The resulting products, such as glycolic-lactic copolymer, which biorstwami favorably used as carriers of therapeutic compositions with prolonged action. The method is also particularly suitable for the polymerization of epoxides, especially propylene oxide. The resulting polymers are compounds that can be used for the synthesis of organic liquid crystals or as a semi-permeable membranes.

The following examples are presented to illustrate the above procedures and should in no case be construed as limiting the scope of the invention.

Example 1. [(Me3SiNCH2CH2)2NSiMe3]AlCl

Connection 1, in which M=Al; RM=CL; a=b=-CH2CH2-; L1=L2=L3=NSiMe3< / BR>
3,26 g (9.6 mmol) of [(Me3SiNCH2CH2)2NSiMe3]2-, 2Li+and 100 ml of tetrahydrofuran sequentially injected into the tube Slinka, equipped with a magnetic stirrer and purged with argon. Reaction medium, the cooling gap is authorized environment allow to return to room temperature and then left under stirring at room temperature for 18 hours. The solvent is then evaporated. The remainder of the sublimate in a vacuum (0.05 mm RT. Art.) at 80oC. the Target compound is isolated in the form of white crystals. This connection is characterized by x-ray diffraction (see below Fig. 1 and table). The melting point of 10-13oC.

Example 2. [(Me3SiNCH2CH2)2NMe]AlCl

Connection 1, in which M=Al; RM=Cl; a=b=-CH2CH2-; L1=L2=NSi3; L3=NMe

This connection receive in accordance with the methodology described above. This connection is characterized by x-ray diffraction (see below Fig. 2 and table). The melting point 130oC (decomposition).

Example 3. [(Me3SiNCH2CH2)2NMe]AlH

Connection 1, in which M=Al; RM=H; A=B=-CH2CH2-; L1=L2=NSiMe3; L3=NMe

2.30 g (8,8 mmol) (Me3SiNHCH2CH2)2NMe and 50 ml of tetrahydrofuran sequentially injected into the tube Slinka, equipped with a magnetic stirrer and purged with argon. The reaction medium is cooled to -40oWith, then give 0.33 g (8,8 mmol) of LiAlH4in suspension in 70 ml of tetrahydrofuran. There is gas. The reaction medium allowed to return to room temperature is evaporated, then the remainder of the sublimate in a vacuum (0.05 mm RT. Art.) at the 90oC. the Target compound is isolated in the form of white crystals. This connection is characterized by x-ray diffraction (see below Fig. 3 and table). The melting point of the 15oC.

Example 4. [(Me3SiNCH2CH2)2NMe]AlCH3< / BR>
Connection 1, in which M=Al; RM=CH3;==- CH2CH2-; L1=L2=NSiMe3; L3=NMe

of 3.53 g (8,8 mmol) (Me3SiNHCH2CH2)2NMe and 50 ml of tetrahydrofuran sequentially injected into the tube Slinka, equipped with a magnetic stirrer and purged with argon. The reaction medium is cooled to -60oWith, then enter 6,7 ml of 2 M solution l3in toluene. The reaction medium allowed to return to room temperature, then heated at 100oWith in 12 hours. The solvent is evaporated, then the residue sublimate in a vacuum (0.05 mm RT. Art.) at 70oC. the Target compound is isolated in the form of white crystals. This connection is characterized by x-ray diffraction (see below Fig. 4 and table). The melting point 67oC.

Example 5. [(Me3SiN2CH2)2NSiMe3]GaCl

Connection 1, in which M=Ga; RM=Cl; A=B=-CHNSiMe3]2-, 2Li+and 50 ml of tetrahydrofuran sequentially injected into the tube Slinka, equipped with a magnetic stirrer and purged with argon. The reaction mixture was cooled to -40oWith, then give 0.33 g (8,8 mmol) GaCl2in solution in 50 ml of tetrahydrofuran. The reaction mixture is allowed to return to room temperature, then left under stirring at room temperature for 18 hours. Observed sediment. After filtration the solvent is evaporated. The remainder of the sublimate in a vacuum (0.05 mm RT. Art. ) at the 90oC. the Target compound is isolated in the form of white crystals. This connection is characterized by x-ray diffraction. The melting point of 62oC.

< / BR>
< / BR>
NMR29Si (C6D6; 79,49 MHz): -3,70; -3,05.

Example 6. {[((CH3)2N2CH2)((CH3)2CHNHCH2CH2)NMe]AlCl}{Alll4}

Compound 2, where M= Al; RM= Cl; R1= H; A=B=-CH2CH2-; L1=L2= N(CH3)2; L3=NMe; X1-=AlCl4-< / BR>
1,03 g (3.2 mmol) of [(Me2CHNCH2CH2)2NCH3]AlCl and 30 ml of toluene sequentially injected into the tube Slinka, equipped with a magnetic stirrer and produttore in diethyl simple ether. The reaction medium allowed to return to room temperature; it is left under stirring at room temperature for 18 hours. The solvent is then evaporated to a volume of 5 ml and left at -30oC. the Thus obtained compound (IV) is recovered in the form of white crystals. This connection is characterized by x-ray diffraction (see below Fig. 5 and table; melting point 160oC (decomposition)). The addition of one equivalent of trichloride aluminum in suspension in toluene allows to obtain the target compound.

Example 7. {[(Me3SiNCH2CH2)(Me3SiN2CH2)NSi3]All}{All4}

Compound 2, where M=Al; RM=Cl; R1=H; A=B=-CH2CH2-; L1=L2=L3=NSiMe3; X1-=AlCl4-< / BR>
to 0.19 g (0.5 mmol) of [(Me3SiNCH2CH2)2NSiMe3]AlCl, 4 ml of toluene and 1 mmol of hydrochloric acid in solution in diethyl simple ether successively injected into the tube Slinka, equipped with a magnetic stirrer and purged with argon. Observed sediment. Then add at room temperature 89 mg (0.67 mmol) of trichloride aluminum in suspension in 3 ml of toluene. The reaction mixture . actuarial then evaporated to a volume of 0.5 ml and left at room temperature. The target compound is isolated in the form of white crystals. This connection is characterized by x-ray diffraction (see below Fig. 6 and table).

Example 8. Polymerization of propylene oxide

0.15 g (0.4 mmol) of [(Me3SiNCH2CH2)2NSiMe3]AlCl and 4.5 ml (63 mmol) of propylene oxide are sequentially injected into the tube Slinka, equipped with a magnetic stirrer and purged with argon. The reaction mixture is left under stirring at 30oC for 144 hours, the excess propylene oxide is evaporated, then add 20 ml of methanol. After centrifugation the liquid phase is removed and the solvent is evaporated. Obtain 0.55 g of a mixture of oligomers and polymers. This mixture is characterized by NMR nuclei of carbon and proton. According to GPC analysis (gel permeation chromatography) using a calibration carried out on the basis of polyethylene glycol (PEG) as standards with masses from 194 to 22000 and extrapolation for higher masses, the sample consists of oligomers with average masses 798 Dalton and polymers having similar mass (Mw(average-weight molecular weight)/MP(srednekislye molecular mass, as in example 8 except that as the catalyst used chiral cation { [(Me3SiN2CH2)((Me3SiNHCH2CH2)NSiMe3] AlCl}{AlCl4}. After centrifugation the liquid phase was removed and the solvent evaporated. Received 2.17 g of a mixture of polymers. This polymer was characterized by NMR nuclei of carbon and proton. According to GPC analysis (gel permeation chromatography) using a calibration carried out on the basis of polyethylene glycol (PEG) as standards with masses from 194 to 22,000, the sample is a mixture of polymers is very close masses (Mw/Mn=1,17) and Mw=1446 Dalton.

Example 10. Polymerization of D,L-lactide

0.05 g (0,17 mmol) of [(Me3SiNCH2CH2)2NMe]AlH and 1.15 g of D,L-lactide and 30 ml of toluene sequentially injected into the tube Slinka, equipped with a magnetic stirrer and purged with argon. The reaction mixture is left under stirring at 120oC for 120 hours. The solvent is evaporated, then add 20 ml of THF. After centrifugation the liquid phase is isolated and the solvent is evaporated. Obtain 1.04 g of the mixture of D,L-lactide (32%) and polymers (68%). This mixture is characterized by NMR nuclei of carbon and proton. According to GPC analysis, using what Asia for higher masses, polymers are a mixture of macromolecules with similar masses (Mw(average-weight molecular weight)/MP(srednekislye molecular mass)=1,61) and Mw=21659.

Example 11. Polymerization of a mixture of D,L-lactide and glycolide

0.08 g (0,17 mmol) of {[(Me3SiN2CH2)((Me3SiNHCH2CH2)-NSiMe3]AlCl}{AlCl4} , 0.17 g (3 mmol) of propylene oxide are sequentially injected into the tube Slinka, equipped with a magnetic stirrer and purged with argon. The reaction mixture is left under stirring at 30oC for 1.5 hours, then the propylene oxide is evaporated. Successively added to 1.15 g of D,L-lactide, 0,93 g glycolide and 30 ml of benzene. The reaction mixture is left under stirring at 80oC for 240 hours. The solvent is evaporated, then add 20 ml of THF. After centrifugation the liquid phase is isolated and the solvent is evaporated. Obtain 1.47 g of a mixture of copolymers. This mixture is characterized by NMR nuclei of carbon and proton. According to GPC analysis using a calibration carried out on the basis of glycols as standards with masses from 194 to 22000 and extrapolation for higher masses, the sample is a mixture of copolymers (Mw(average-weight molecular weight)/MP(sereneceline is no a boron atom, aluminum or gallium;

RMrepresents a hydrogen atom, a halogen atom, especially chlorine or a methyl radical;

A and b independently represent a carbon chain with 2 to 4 carbon atoms, especially carbon chain of 2 carbon atoms;

L1, L2represent independently a group of formula-S5(R5)-, in which E5represents a nitrogen atom or phosphorus, R5represents a radical of the formula RR'R"E4in which E4represents a carbon atom or silicon and R, R' and R" represent independently a hydrogen atom or an alkyl radical;

X1represents gecoordineerde anion relative to the element M;

L3represents a group of formula-S5(R5)-, in which E5represents a nitrogen atom or phosphorus and R5represents an alkyl radical or a radical of the formula RR'R"E4-, in which E4represents a silicon atom and R, R' and R" are independently alkyl radical;

R1represents a hydrogen atom.

2. The compounds of formula 1 and 2 on p. 1, characterized in that theMrepresents a hydrogen atom, a chlorine atom or a methyl radical, Oh, regardless, isopropylamino radical or IU3SiN, L3is methylamino radical or IU3SiN.

3. The compounds of formula 1 according to any one of paragraphs. 1-2, corresponding to the following formula:

-[(Me3SiNCH2CH2)2NSiMe3] AlCl;

-[(Me3SiNCH2CH2)2NMe] AlCl;

-[(Me3SiNCH2CH2)2NMe] AlH;

-[(Me3SiNCH2CH2)2NMe] AlCH3;

-[(Me3SiNCH2CH2)2NSiMe3] GaCl;

-{ [((CH3)2NCH2CH2)((CH3)2CHNHCH2CH2)NMe] AlCl} { AlCl4} ;

-{ [(Me3SiNCH2CH2)(Me3SiNHCH2CH2)NSiMe3] AlCl} { AlCl4} .

4. The method of obtaining the compounds of formulas 1 and 2 on p. 1, where the compound of the formula I

(L1-A-L3-D-L2)2-, 2Y+(I)

in which L1, A, L3B and L2have the values listed in paragraph 1;

Y is an ORGANOMETALLIC group, a metal or a hydrogen atom, to react with the compound of the formula II

RMMZ1Z2(II)

in which RMand M have the meanings specified in paragraph 1;

Z1and Z2represent independently a leaving group, to obtain the
in which R1and X1have the values listed in paragraph 1,

to obtain the compounds of formula 2.

5. The method of obtaining compounds of General formula 2, as stated in paragraph 1, where the compound of formula IV

< / BR>
in which R1, L1, A, L3B and L2have the values listed in paragraph 1;

X represents a coordinating anion relative to the element M,

reacts with the compound of the formula V

MX'3(V)

in which M has the values specified in paragraph 1;

X' represents a halogen atom, alkyl or alkoxyalkyl.

6. Compounds of General formula 1 and 2 according to any one of paragraphs. 1-3 as a catalyst for (co)polymerization.

7. Connection on p. 6 for the (co)polymerization of heterocycles, especially epoxides such as propylene oxide.

8. Connection on p. 6 for the (co)polymerization of cyclic ethers, especially cyclic polymer of esters of lactic and/or glycolic acid.

9. A method of obtaining a heterocyclic polymers and copolymers, which consists in the introduction of one or more monomers, polymerization catalysts and solvent polymerization at a temperature between room temperature and 150oC for 1 d is 0. The method according to p. 9, characterized in that the monomer is chosen from epoxides and preferably of propylene oxide, or cyclic esters, preferably polymeric cyclic esters of lactic and/or glycolic acid.

11. The compounds of formula IV under item 5 for use as industrial products.

 

Same patents:

The invention relates to chemistry and can be used in medicine for diagnosis and evaluation of severity of diabetes

The invention relates to the chemistry of polymers, namely a process for the production of flame retardants, intended for the modification of polyolefins, and can be used in the chemical industry

The invention relates to catalysts for (co)polymerization of ethylene containing chromium trioxide deposited on a solid inorganic oxide carrier of nature, i.e

The invention relates to a polyethylene having a narrow molecular weight distribution and narrow composition distribution

The invention relates to storage-based catalysts on the media that are used in the polymerization of olefins

The invention relates to methods of producing ultra-high molecular weight polyethylene (UHMWPE), synthesized in powder form in the conditions of suspension polymerization of ethylene in the environment of a hydrocarbon diluent at temperatures of 40-70oWith the use of supported catalysts ziperovich type

The invention relates to the field of multi-stage polymerization of olefins of General formula CH2=CHR, where R is hydrogen, or alkyl, or cycloalkyl, or aryl radical with 1-10 carbon atoms, carried out in one or more reactors, in the presence of catalyst

Multistage polymerization processes of olefins carried out in two or more reactors are widely known from the patent literature and are of practical interest

The invention relates to an activated catalyst system for the (co)polymerization of alpha-olefins

The invention relates to compositions of (co)polymer of olefins and method of reception and catalyst for (co)polymerization of olefins and method thereof

The invention relates to hydro - and oleophobic means to protect building materials from the harmful effects of the environment and relates, in particular, new forbrenningsprosessen compounds containing organofluorine and silicone fragments, United amide bond

The invention relates to the field of hydro - and oleophobic means to protect building materials from the harmful effects of the environment and relates, in particular, the use of silicon amide perfluoroine carbonic acid as hydro and alfamega tools, designed to protect the stone buildings and structures from atmospheric precipitation

The invention relates to new diorganodichlorosilanes short-chain, linear or cyclic, or triorganotin having filter sections sulfonamidnuyu function, selected from among the derivatives of 3-benzylideneacetone, benzotriazole, benzophenone and benzimidazoles more specifically, these compounds applicable as organic solar filters in cosmetic compositions intended for protecting the skin and hair against ultraviolet radiation
Up!