RU2011149550A

RU2011149550A - COMPOUNDS OF O-IMINO-ISOMOUROUS AND THEIR POLYMERIZABLE COMPOSITIONS

Info

Publication number: RU2011149550A
Application number: RU2011149550/02A
Authority: RU
Inventors: Петер НЕСФАБДА; ФОЛЬГЕР Люсьен БУНЬОН; Антуан КАРРУА; Марк ФАЛЛЕР; Бруно СПОНИ
Original assignee: Басф Се
Priority date: 2009-05-07
Filing date: 2010-05-05
Publication date: 2013-06-20

Claims

1. The use of O-imino-isourea compounds of the general formula (I) as a source of radicals, in particular as polymerization initiators

where n represents 1, 2, 3 or 4,

R ₁₀₀ and R ₁₀₁ independently represent hydrogen (H), C _1-18 alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl, C ₁ -C ₁₄ heteroaryl, C ₇ -C ₁₅ aralkyl, C ₂ - C ₁₄ heteroaralkyl, cyano, or R ₁₀₀ and R ₁₀₁ form, together with the carbon atom to which they are attached, a mono or polycyclic C ₃ -C ₁₈ carbocyclic or C ₁ -C ₁₈ heterocyclic ring;

R ₁₀₂ and R ₁₀₃ independently represent C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ aryl, substituted one or more times with C ₁ -C ₁₈ alkyl; C ₇ -C ₁₅ aralkyl, (CH ₃ ) ₃ Si-; or R ₁₀₂ and R ₁₀₃ are C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl, C ₇ -C ₁₅ aralkyl, or R ₁₀₂ and R ₁₀₃ are C ₁ -C ₁₈ alkyl , C ₃ -C ₁₂ cycloalkyl, which are interrupted or substituted by an oxygen atom (O) or N-containing groups selected from C ₁ -C ₁₈ alkylamino, bis (C ₁ -C ₁₈ alkyl) amino or tris (C ₁ -C _1t alkyl) ammonium;

R ₁₀₄ , if n is 1, is H, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₄ aralkyl, C ₆ -C ₁₄ aryl or acyl selected from the group consisting of the following acyls :

-C (= O) -H, -C (= O) -C ₁ -C ₁₈ alkyl, -C (= O) -C ₂ -C ₁₈ alkenyl, -C (= O) -C ₆ -C ₁₄ aryl , -C (= O) -C ₂ -C ₁₈ alkenyl-C ₆ -C ₁₄ aryl, -C (= O) -O-C ₁ -C ₁₈ alkyl, -C (= O) -O-C ₆ - C ₁₄ aryl, -C (= O) -NH-C ₁ -C ₁₈ alkyl, -C (= O) -NH-C ₆ -C ₁₄ aryl and -C (= O) -N (C ₁ -C ₁₈ alkyl) ₂ ; or

R ₁₀₂ and R ₁₀₄ , if n is 1, together with the nitrogen atom to which they are attached form 5-12 membered ring, which may contain additional heteroatoms;

R ₁₀₄ , if n is greater than 1, is di-, tri-, tetra-C ₁ -C ₁₈ alkylidene, diacyl, triacyl or tetraacyl,

and their salts.

2. The use of compounds of O-imino-isourea of the general formula (I) according to claim 1, where n is 1

where R ₁₀₀ and R ₁₀₁ independently represent H, C _1-18 alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl, C ₁ -C ₁₄ heteroaryl, C ₇ -C ₁₅ aralkyl, C ₂ -C ₁₄ heteroalkyl, cyano, or R ₁₀₀ and R ₁₀₁ together with the carbon atom to which they are attached form a mono or polycyclic C ₃ -C ₁₈ carbocyclic or C ₁ -C ₁₈ heterocyclic ring;

R ₁₀₂ and R ₁₀₃ independently represent C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ aryl, substituted one or more times with C ₁ -C ₁₈ alkyl; C ₇ -C ₁₅ aralkyl, (CH ₃ ) ₃ Si-; or R ₁₀₂ and R ₁₀₃ are C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl, C ₇ -C ₁₅ aralkyl, or R ₁₀₂ and R ₁₀₃ are C ₁ -C ₁₈ alkyl , C ₃ -C ₁₈ cycloalkyl, which are interrupted or substituted by an oxygen atom or N-containing groups selected from C ₁ -C ₁₈ alkylamino, bis (C ₁ -C ₁₈ alkyl) amino or tris (C ₁ -C _1t alkyl) ammonium ;

R ₁₀₄ represents H, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₄ aralkyl, C ₆ -C ₁₄ aryl or acyl selected from the group consisting of the following acyls:

-C (= O) -H, -C (= O) -C ₁ -C ₁₈ alkyl, -C (= O) -C ₂ -C ₁₈ alkenyl, -C (= O) -C ₆ -C ₁₄ aryl , -C (= O) -C ₂ -C ₁₈ alkenyl-C ₆ -C ₁₄ aryl, -C (= O) -O-C ₁ -C ₁₈ alkyl, -C (= O) -O-C ₆ - C ₁₄ aryl, -C (= O) -NH-C ₁ -C ₁₈ alkyl, -C (= O) -NH-C ₆ -C ₁₄ alkyl, and -C (= O) -N (C ₁ -C ₁₈ alkyl) ₂ ; or

R ₁₀₂ and R ₁₀₄ together with the nitrogen atom to which they are attached form a 5-12 membered ring, which may contain additional heteroatoms,

and their salts.

3. The use of compounds of O-imino-isourea of the General formula (I) according to claim 1 or 2, where

n is 1;

R ₁₀₀ and R ₁₀₁ independently represent H, C _1-18 alkyl, C ₅ -C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl, C ₁ -C ₁₄ heteroaryl, C ₇ -C ₁₅ aralkyl, or R ₁₀₀ and R ₁₀₁ together with the carbon atom to which they are attached form a C ₅ -C ₁₂ carbocyclic ring;

R ₁₀₂ and R ₁₀₃ independently represent C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ aryl, substituted one or more times with C ₁ -C ₁₈ alkyl; C ₇ -C ₁₅ aralkyl;

R ₁₀₄ represents H, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₇ -C ₁₄ aralkyl, C ₆ -C ₁₄ aryl or acyl selected from the group consisting of the following acyls: -C (= O ) -H, -C (= O) -C ₁ -C ₁₈ alkyl, -C (= O) -C ₂ -C ₁₈ alkenyl, -C (= O) -C ₆ -C ₁₄ aryl; or

R ₁₀₂ and R ₁₀₄ together with the nitrogen atom to which they are attached, form a 5-6 membered ring,

and their salts.

4. The use of compounds of O-imino-isourea of the General formula (I) according to claim 3, where

R ₁₀₀ and R ₁₀₁ independently are C _1-18 alkyl, C ₅ -C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl, C ₁ -C ₁₄ heteroaryl, C ₇ -C ₁₅ aralkyl, or R ₁₀₀ and R ₁₀₁ form together with the carbon atom to which they are attached, a C ₅ -C ₁₂ carbocyclic ring;

R ₁₀₂ and R ₁₀₃ independently represent C ₁ -C ₄ alkyl, cyclohexyl, C ₆ -C ₁₄ aryl; C ₆ -C ₁₄ aryl substituted one or more times with C ₁ -C ₁₈ alkyl;

R ₁₀₄ represents H, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, -C (= O) -C ₁ -C ₁₈ alkyl; or R ₁₀₂ and R ₁₀₄ form, together with the nitrogen atom to which they are attached, a 5-6 membered ring,

and their salts.

5. The use of compounds of O-imino-isourea of the general formula (I) according to claim 4, where

R ₁₀₀ and R ₁₀₁ independently represent C _1-18 alkyl, phenyl, or R ₁₀₀ and R ₁₀₁ form, together with the carbon atom to which they are attached, a C ₅ -C ₁₂ cycloalkyl ring;

R ₁₀₂ and R ₁₀₃ independently represent C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl; C ₆ -C ₁₄ aryl substituted one or more times with C ₁ -C ₆ alkyl;

R ₁₀₄ represents hydrogen or —C (═O) —C ₁ -C ₁₈ alkyl,

and their salts.

6. The use of compounds of O-imino-isourea of the General formula (I) according to claim 1, where

n is 2, 3 or 4;

R ₁₀₄ represents di-, tri-, tetra-C ₁ -C ₁₈ alkylidene, diacyl, triacyl or tetraacyl,

and their salts.

7. Compounds of O-imino-isourea of the formula I '

where n is 1, 2, 3 or 4,

R ₁₀₀ , R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ are as defined in claims 1-6, and their salts;

provided that the following compounds are excluded

and

, and

,

and

, and

and the following O-imino-isoureas derived from ketoximes

and picrate salt

and HBF ₄ salt

and HBF ₄ salt

8. The compounds of O-imino-isourea of the formula I 'according to claim 7, where n is 1

where R ₁₀₀ , R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ have the meanings defined in claim 2, and their salts.

9. A composition comprising

A) at least one ethylenically unsaturated polymerizable monomer or oligomer; and

B) at least one compound of formula I or I ', as defined in claim 1 or 7;

C) if necessary, a photoinitiator.

10. A method of producing an oligomer, co-oligomer, polymer or copolymer, characterized in that the composition according to claim 9 is subjected to the conditions of a free radical polymerization reaction.

11. A method of reducing the molecular weight of polypropylene, propylene copolymers or mixtures of polypropylene, characterized in that at least one of the compounds of formula I or I ', as defined in claim 1 or 7, is added to polypropylene, copolymers of propylene or a mixture of polypropylene, and the resulting mixture is heated.

12. The use of compounds according to claim 1 or 7 to obtain a coating.

13. The use of compounds according to claim 1 or 7 for crosslinking processes.