RU2340593C2 - Method of obtaining low-moilecular iodised organic substances and low-molecular iodised organic substances - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method of obtaining one or more iodised organic substances with molecular weight less than 2000 (substance S) using (A) one substance generating free radicals, which is selected from peroxides, diazocompounds, dialkyldiphenylalkanes, substances obtained from tetraphenylethane, boranes and substances - chain-transmitters, containing one thiuram disulfide group, (B) unsaturated substance with ethylene double bond, able to bind free radical to its ethylene double bond and (C) molecular iodine, which includes stages at which fraction (A), fraction (B) and fraction (C) are introduced into reactor and then reactor content is introduced into reaction, adding possibly remaining (A), possibly remaining (B) and possibly remaining (C) until reactor content represents mixture containing one or more substances S. Also claimed are iodized organic substances, which can be especially efficiently obtained by said method, and method of obtaining polymers by free-radical polymerisation of one unsaturated monomer with ethylene bond, substance, generating free radicals and one or more substances S, obtained by claimed method.

EFFECT: cheap and safe method of obtaining low-molecular iodised organic substances.

16 cl, 1 dwg, 5 ex

Description

The present invention relates to a method for producing low molecular weight iodinated organic substances, to low molecular weight iodinated organic substances and to a method for producing a polymer comprising these low molecular weight iodinated organic substances.

US-A-5 144067 describes a process for the co-production of, on the one hand, alkyl iodide and, on the other hand, mono-α-iodocarboxylic acid and / or its anhydride, according to which a mixture of an iodinated compound, for example molecular iodine, carboxylic acid anhydride, for example acetic anhydride and peroxide, for example hydrogen peroxide, are reacted at high temperature.

US-A-5 430208 describes a process for the synthesis of 1-chloro-1-iodoethane, according to which hydroiodic acid is reacted with vinyl chloride in the presence of an iodine-containing catalyst, organic (e.g. 1,2-diiodoethane) or inorganic (e.g. potassium iodide or molecular iodine).

Heasley et al., J. Org. Chem., 1988, pp. 198-201, various iodinated organic compounds were synthesized by the reaction of tert-butyl hypoiodide with various ethylenically unsaturated compounds in the presence of BF ₃ or under the influence of ultraviolet radiation. In particular, they synthesized a substance of the formula (CH ₃ ) ₃ —CO — CH ₂ —CHFI, where Φ is a phenyl group.

Cambie et al., J. Chem. Soc. Chem. Comm., 1973, vol. 11, pp. 359-360 also synthesized the substance (CH ₃ ) ₃ -CO-CH ₂ -CHPI by the reaction of styrene, molecular iodine and thallium (I) acetate.

Methods for the synthesis of iodinated organic compounds with a low molecular weight of the prior art are complex. In addition, they require the use of expensive and / or hazardous materials to handle. Therefore, the low molecular weight iodinated organic compounds thus obtained are very expensive.

It is also known that some low molecular weight iodinated organic compounds can be used as initiators of controlled free radical polymerization ("ITP" type polymerization).

However, the “best” choice in terms of the efficiency of initiating polymerization and the properties of the resulting polymers often depends on the real nature of the monomers; therefore, for the polymerization of monomers of various chemical nature and under optimal conditions, it is necessary to have a wide range of iodinated organic initiators.

An object of the present invention is a production method that has all the advantages of prior art methods and is free from all their disadvantages.

The purpose of the present invention is a method for producing one or more iodinated organic substances with a molecular weight of less than 2000 (substance (S)) using:

(A) at least one free radical generating substance selected from peroxides, diazocompounds, dialkyl diphenylalkanes, substances derived from tetraphenylethane, as well as boranes and chain transfer agents containing at least one thiuram disulfide group,

(B) at least one organic substance containing at least one ethylene double bond, capable of attaching a free radical to an ethylene double bond,

(C) molecular iodine,

which includes the stages according to which:

(1) at least part (A), at least part (B) and at least part (C) are introduced into the reactor and then

(2) the contents of the reactor are reacted by adding a possible residue (A), a possible residue (B), and a possible residue (C) until the contents of the reactor are a mixture containing one or more substances (S) [ mixture (M)].

In addition to substances (S) according to the method of the present invention, it is optionally possible to obtain one or more iodinated organic substances other than substances (S) [substances (S ')].

The mass of iodinated organic substances (S ') with respect to the mass of substances (S) should preferably be less than 1, particularly preferably less than 0.2, and most preferably less than 0.05.

Preferably, the substances (S) have a molecular weight of less than 1000, particularly preferably less than 500, and most preferably less than 250.

Substances (S) have a number average molecular weight of preferably less than 500, preferably less than 250.

The term "peroxides" means both organic and inorganic peroxides.

The first family of substances, from which it is preferable to choose substances that generate free radicals, are organic peroxides.

Examples of organic peroxides include:

dialkyl peroxides such as dicumyl peroxide, tert-butyl and cumyl peroxide and di-tert-butyl peroxide;

diacyl peroxides such as diisononanoyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di (2-methylbenzoyl) peroxide, dibenzoyl peroxide and di (4-chlorobenzoyl) peroxide;

- acetylcyclohexanesulfonyl peroxide;

dialkyl peroxydicarbonates such as diethyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (sec-butyl) peroxydicarbonate, dimyristyl peroxydicarbonate, dicetyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate and di (4-tert-butyl cyclohexyl) peroxide;

dialkyl peroxycarbonates such as tert-amyl peroxy-2-ethylhexyl carbonate and tert-butyl peroxy isopropyl carbonate;

- esters of peroxyacids such as cumile ester of supodeodecanoic acid, tert-amyl ester of supodeodecanoic acid, tert-butyl ester of supropivalic acid, tert-butyl ester of 2-ethylnadhexanoic acid, tert-butyl ester of supraisobutyric acid, tert-butyl ester of nadisonanoic acid Dinadbenzoic acid -2,5-dimethylhexane; nadbenzoic acid tert-butyl ester;

- peroxyketals, such as 1,1-bis (tert-butylbutylperoxy) cyclohexane and 2,2-bis (tert-butylperoxy) butane;

ketoperoxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide and acetylaceton peroxide;

- organic hydroperoxides, such as cumyl hydroperoxide, tert-butyl hydroperoxide and pinhydroperoxide.

Organic peroxides are preferably selected from dialkyl peroxides, diacyl peroxides, dialkyl peroxydicarbonates and acid esters. It is particularly preferable to select them from dialkyl peroxides and dialkyl peroxydicarbonates, and most preferably from dialkyl peroxides in which each of the alkyl chains contains a maximum of 4 carbon atoms, and dialkyl peroxydicarbonates in which each of the alkyl chains contains a maximum of 4 carbon atoms. Excellent results are obtained with di-tert-butyl peroxide and diethyl peroxydicarbonate.

The second family of substances, from which it is preferable to choose substances that generate free radicals, are inorganic peroxides.

Examples of inorganic peroxides include:

- hydrogen peroxide;

- persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate;

- perborates.

Preferred inorganic peroxides are persulfates. Excellent results were obtained with ammonium persulfate.

The third family of substances, from which it is preferable to choose substances that generate free radicals, are diazo compounds.

Examples of diazo compounds include azobis (isobutyronitrile), azobis (2,4-dimethylvaleronitrile), azoamidines and azoamidinium salts.

It is preferred that the diazo compounds contain one or more nitrile groups. Excellent results were obtained with azobis (isobutyronitrile).

Examples of dialkyl diphenylalkanes include 3,4-dimethyl-3,4-diphenylhexane and 2,3-dimethyl-2,3-diphenylbutane.

Examples of compounds derived from tetraphenylethane include:

N≡C-CF ₂ -СF ₂ -С≡N, υO-СФ ₂ -СF ₂ -Oυ, υ ₃ Si-СF ₂ -СF ₂ -Siυ ₃ , (υO) ₃ Si-СF ₂ -СF ₂ -Si (Oυ) ₃ and FO-CF ₂ -CF ₂ -OF; in the above examples, Φ represents a phenyl group and υ means a C ₁ -C ₂₀ alkyl group.

As examples of boranes, trialkylboranes (B (OOU) ₃ ) such as trimethylborane and triphenylborane (B (OOF) ₃ ), where υ and Ф are defined above, can be cited.

As chain transmitters containing at least one thiuram disulfide group, one can bring υ ₂ N- (S =) CSSC (= S) -Nυ ₂ , where the symbols υ, identical or different, are defined above.

Organic substances containing at least one ethylene double bond capable of attaching a free radical to this ethylene double bond mainly correspond to the formula CΨ ₂ = CΨΞ, where

- the symbols Ψ represent independently of each other and from Ξ (i) a hydrogen atom, (ii) a halogen atom other than iodine, or (iii) a linear or branched C ₁ -C ₂₀ alkyl group;

- Ξ represents (i) a halogen atom other than an iodine atom, (ii) a phenyl group optionally substituted with one or more atoms other than an iodine atom, and a C ₁ -C ₈ alkyl group, (iii) an —O — C group (= O) —Ω, (iv) a nitrile group, (v) a group —C (= O) —O — Ω, or (vi) a group —C (= O) —NΩ ₂ ;

- Ω represents (i) a hydrogen atom or (ii) a saturated or unsaturated ethylene or aromatic C ₁ -C ₂₀ hydrocarbon group.

In the first family of preferred compounds corresponding to the formula CΨ ₂ = CΨΞ, Ξ represents a halogen atom other than the iodine atom ([family (F1)].

Compounds of the family (F1) preferably contain a maximum of 3 carbon atoms. It is particularly preferable to select them from vinyl chloride, vinylidene chloride, trichlorethylene, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene and hexafluoropropylene. In a most preferred embodiment, they are selected from vinyl chloride, vinylidene chloride and hexafluoropropylene.

In the second family of preferred compounds of the formula CΨ ₂ = CΨΞ, Ξ represents a phenyl group optionally substituted with one or more atoms selected from halogen atoms other than the iodine atom and C ₁ -C ₈ alkyl groups ([family (F2 )].

Compounds of the family (F2) preferably correspond to the formula CH ₂ = CHΞ, where Ξ is defined in the previous section. Among all compounds of the family (F2), styrene showed excellent results.

In the third family of preferred compounds corresponding to the formula CΨ ₂ = CΨΞ, Ξ represents the group —O — C (= O) —Ω, where Ω is defined above ([family (F3)].

Compounds of the family (F3) preferably correspond to the formula CH ₂ = CHΞ, where Ξ is defined in the previous section. Among all the compounds of the (F3) family, vinyl acetate showed excellent results.

In the fourth family of preferred compounds corresponding to the formula CΨ ₂ = CΨΞ, Ξ represents a group selected from the nitrile group and the groups —O — C (= O) —Ω and —C (= O) —NΩ ₂ , where Ω is defined above ([family (F4)].

Compounds of the family (F4) preferably correspond to either the formula CH ₂ = CHΞ, or the formula CH ₂ = C (CH ₃ ) Ξ, or else the formula CH ₂ = CFΞ, where Ξ is defined in the previous section. In a particularly preferred embodiment, they correspond to the formula CH ₂ = CH-C (= O) -O-Ω or the formula (CH ₂ = C (CH ₃ ) -C (= O) -O-Ω, where Ω is defined above. In more in a particularly preferred embodiment, they are selected from acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethyl hexyl acrylate, methacrylic acid, methyl methacrylate and n-butyl methacrylate Methacrylate showed excellent results among all compounds of the family (F4).

As examples of organic substances containing at least one ethylene double bond and capable of attaching a free radical to this ethylene double bond, in addition to the above compounds, ethylene, propylene and butadiene can be cited.

If several organic substances containing at least one ethylene double bond and capable of attaching a free radical to this ethylene double bond are used in the method of the present invention, then at least at least one of them is selected from compounds of the family (F1) and at least another is selected from compounds of the families (F3) and (F4). Preferably, at least one of them is selected from vinyl chloride, vinylidene chloride and vinylidene fluoride and at least another compound is selected from vinyl acetate, methyl acrylate and n-butyl acrylate. In a particularly preferred embodiment, one of them is vinylidene chloride and the other is methyl acrylate.

The temperature at which the contents of the reactor are introduced into the reaction is preferably from -50 ° C to 300 ° C, preferably from 0 to 150 ° C.

Preferably, all compounds (A), (B) and (C) are introduced into the reactor in step (1).

According to a first preferred embodiment of the method of the present invention [option (1)], the contents of the reactor are introduced into the reaction until the amount (B) used in the reaction is no longer changed.

According to option (1), the number of moles (C) relative to the number of moles (A) is preferably greater than or equal to 90%, preferably greater than or equal to 100%, and particularly preferably greater than or equal to 105%. In addition, the number of moles (C) relative to the number of moles (A) is preferably less than 200% and preferably less than 150%.

According to option (1), the number of moles (C) relative to the number of moles (B) is usually greater than 0.5%. It can be more than 5% and even more than 50% and even sometimes exceed 100%, and this will not affect the successful implementation of the method of the present invention. In addition, the number of moles (C) relative to the number of moles (B) is preferably less than 200% and preferably less than 150%.

According to a second preferred embodiment of the method of the present invention, [option (2)] the method comprises, in addition to step (2), also step (3), in which the reaction is stopped, for example, by quenching the contents of the reactor.

According to option (2), the reaction is stopped mainly at the moment when the contents of the reactor change color from dark to light.

According to option (2), the number of moles (C) relative to the number of moles (A) is usually less than 100% and preferably less than 90%. In addition, the number of moles (C) relative to the number of moles (A) is preferably greater than or equal to 20%.

According to option (2), the number of moles (C) relative to the number of moles (B) is usually less than 100%. It can be less than 50% and even less than 5% and even sometimes make up less than 1%, and this will not affect the successful implementation of the method of the present invention. In addition, the number of moles (C) relative to the number of moles (B) is preferably greater than or equal to 0.01% and preferably greater than 0.1%.

The method of the present invention mainly includes another step following step (2) and, moreover, step (3), in which at least one substance (S) is isolated from the mixture (M) and possibly other substances (S) contained in the mixture (M).

The subject of the present invention is also iodinated organic substances, for the preparation of which the method of the present invention is well suited, and they have all the advantages of iodinated organic substances of the prior art and are free from their disadvantages.

For this purpose, the invention relates to a mixture of at least two iodinated organic substances with a molecular weight of less than 2000, corresponding respectively to the general formula RG _x (-CX ₂ -CXY-) _n -I and RG _x (-CX ₂ -CXY-) _{n + 1} -I, where:

- R represents (i) a hydrogen atom, (ii) an alkali metal atom, (iii) a linear or branched C ₁ -C ₂₀ alkyl group optionally substituted with one or more groups selected from phenyl, carboxyl, hydroxyl, nitrile, amine or amidine, (iv) a C ₃ -C ₈ cycloalkyl group optionally substituted with one or more groups selected from C ₁ -C ₈ alkyl groups and a nitrile group, or (v) a phenyl group optionally substituted with one or more groups which is selected from C ₁ -C ₈ alkyl groups and halogen atoms other than Volume of iodine;

- x is an integer equal to 0 or 1;

- G is —O—, —OC (= O) —O—, —C (= O) —O—, or —OS (= O) _P —O—;

if G is a group —C (═O) —O— then its fragment C (═O) is bonded to R and the moiety O is bonded to the group CX ₂ ;

- p is an integer equal to 1 or 2;

- n is an integer from 1 to 8;

- groups X represent independently from each other and from Y (i) a hydrogen atom, (ii) a halogen atom other than an iodine atom, or (iii) a linear or branched C ₁ -C ₂₀ alkyl group;

- Y represents (i) a halogen atom other than an iodine atom, (ii) a phenyl group optionally substituted with one or more atoms selected from halogen atoms other than an iodine atom, and C ₁ -C ₈ alkyl groups, (iii ) a group —O — C (= O) —Z, (iv) a nitrile group, (v) a group —C (= O) —O — Z, or (vi) a group —C (= O) —NZ ₂ ;

- Z represents (i) a hydrogen atom or (ii) a saturated or unsaturated ethylene or aromatic C ₁ -C ₂₀ hydrocarbon group;

- R, G, x, CX ₂ —CXY and n are identical for the two substances that are the subject of the invention;

- I is an iodine atom.

[substances (S2)].

Substances (S2) have a number average molecular weight of preferably less than 500, preferably less than 250.

Each of the substances (S2) has a molecular weight of preferably less than 1000, particularly preferably less than 50, and most preferably less than 250.

Examples of alkali metal atoms capable of representing the R group include sodium and potassium.

Examples of unsubstituted alkyl groups capable of representing the R group include methyl, ethyl, isopropyl, sec-butyl, tert-butyl, tert-amyl, n-heptyl, (l-ethyl) pentyl, (2-ethyl) hexyl, (2-methyl) - (4,4-dimethyl) pentyl, n-nonyl, n-undecyl, myristyl and cetyl.

Cumyl, —C (C≡N) - (CH ₃ ) ₂ , (2-phenyl) propyl and (2-phenyl) butyl can be exemplified as substituted alkyl groups capable of representing the R group.

As examples of substituted or unsubstituted cycloalkyl groups capable of representing the R group, cyclohexyl and pinyl can be mentioned.

Examples of substituted phenyl groups capable of representing the R group are (2-methyl) phenyl and (4-chloro) phenyl.

In the case of substances (S2), n is usually less than 7 and often less than 5.

In the case of substances (S2), G is preferably selected from the groups —OC (═O) —O—, —O—, —O — S (= O) —O— and —OS (= O) ₂ —O—. Two G groups are particularly preferred: one is the group —OC (═O) —O—; the other is the group —O — S (= O) ₂ —O—.

The mixture according to the invention mainly does not contain iodinated organic substances with a molecular weight greater than or equal to 2000; preferably, it does not contain iodinated organic substances with a molecular weight greater than or equal to 1000.

The expression "without (...)" means "not containing the quantities (...) determined by the method of size exclusion chromatography known to specialists."

In the first family of preferred substances (S2), Y represents a halogen atom other than the iodine atom [family (F'1)].

The groups (CX ₂ -CXY-) of substances (S2) of the family (F'1) mainly contain a maximum of 3 carbon atoms. They are selected from the groups (-CH ₂ -CHCl), (-CH ₂ -CCl ₂ -), (-CCl ₂ -CHCI), (-CF ₂ -CFCl-), (-CH ₂ -CHF), (-CH ₂ -CF ₂ -), (-CF ₂ -CHF-), (-CF ₂ -CF ₂ -) and (-CF ₂ -CF (CF ₃ ) -). It is particularly preferred to select them from the groups (—CH ₂ —CHCl—), (—CH ₂ —CCl ₂ -), (—CH ₂ —CF ₂ ), and (—CF ₂ —CF (CF ₃ ) -).

In the second family of preferred substances (S2), Y represents a phenyl group optionally substituted with one or more atoms selected from halogen atoms other than iodine and C ₁ -C ₈ alkyl groups [family (F'2)].

The groups (-CX ₂ -CXY-) of substances (S2) of the family (F'2) predominantly correspond to the formula (-CH ₂ -CHY-), where Y is defined in the previous section. Among these groups, the group (—CH ₂ —CHF) is preferred, where Φ is a phenyl group.

In the third family of preferred substances (S2), Y represents a group —O — C (= O) —Z, where Z is as defined above [family (F'3)].

The groups (-CX ₂ -CXY-) of substances (S2) of the family (F'3) mainly correspond to the formula (-CH2-CHY-), where Y is defined in the previous section. Among these groups, an acetyl group is preferred.

In the fourth family of preferred substances (S2), Y represents a group selected from the nitrile group, groups —C (═O) —O — Z and —C (O) —NZ ₂ , where Z is defined above [family (F'4) ].

The groups (—CX ₂ —CXY—) of substances (S2) of the family (F′4) predominantly correspond to either the formula (—CH ₂ —CHY—) or the formula (—CH ₂ —C (CH ₃ ) Y—), or formula (-CH ₂ -CFY-), where Y is defined in the previous section. They preferably correspond to the formula (-CH ₂ -CH (C (= O) OZ-) or the formula (-CH ₂ -C (CH ₃ ) (C (= O) OZ) -), where Z is defined above. In a particularly preferred they are selected from the groups formed by the opening of an ethylene double bond in one of the following substances: acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethyl hexyl acrylate, methacrylic acid, methyl methacrylate and n-butyl methacrylate. ₂ -CH (C (= O) O (CH ₃ )) -), i.e., the group formed upon the opening of the ethylene double bond in methyl acrylate is the most respectful.

The invention also relates to iodinated organic substances with a molecular weight of less than 2000, corresponding to the general formula

RG (-CX ₂ -CXY-) _q -I, (I)

where R, G, X, Y and I are defined above for substances (S2) and where q represents an integer greater than 1 and less than 10.

The substance according to formula (I) has a molecular weight of preferably less than 1000, particularly preferably less than 500, and most preferably less than 250.

q is usually less than 7 and often less than 5.

As for the substances corresponding to the formula (I), G is preferably selected from the groups —OC (= O) —O—, —O—, —O — S (= O) —O— and —O-S (= O) ₂ -ABOUT-. Two G groups are particularly preferred: one is the group —OC (═O) —O—; the other is the group —OS (= O) ₂ —O—.

In the first family of preferred substances corresponding to the formula (I), Y represents a halogen atom other than an iodine atom [family (F''l)].

The groups (-CX ₂ -CXY-) of substances of the family (F''1) should preferably have the same characteristics and conditions as the groups (-CX ₂ -CXY-) in substances (S2) of the family (F'l).

In a second family of preferred compounds of formula (I), Y represents a phenyl group optionally substituted with one or more atoms selected from halogen atoms other than an iodine atom and C ₁ -C ₈ alkyl groups [family (F''2 )].

The groups (-CX ₂ -CXY-) of substances of the family (F''2) should preferably have the same characteristics and conditions as the groups (-CX ₂ -CXY-) in substances (S2) of the family (F'2).

In the third family of preferred substances corresponding to formula (I), Y represents a group —O — C (═O) —Z, where Z is as defined above [family (F''3)].

The groups (-CX ₂ -CXY-) of substances of the family (F''3) should preferably have the same characteristics and conditions as the groups (-CX ₂ -CXY-) in substances (S2) of the family (F'3).

In the fourth family of preferred substances corresponding to formula (I), Y represents a group selected from the nitrile group, groups —C (= O) —O — Z and —C (= O) —NZ ₂ , where Z is defined above [family (F''4)].

The groups (-CX ₂ -CXY-) of substances of the family (F''4) should preferably have the same characteristics and conditions as the groups (-CX ₂ -CXY-) in substances (S2) of the family (F'4).

The invention also relates to iodinated organic substances with a molecular weight of less than 2000, corresponding to the general formula

R-O-C (= O) -O- (CX ₂ -CXY-) I, (II)

where R, X, Y and I are defined above for substances (S2).

The substance according to formula (II) has a molecular weight of preferably less than 1000, particularly preferably less than 500, and most preferably less than 250.

In the first family of preferred substances corresponding to formula (II), Y represents a halogen atom other than an iodine atom [family (F "l l)].

The groups (-CX ₂ -CXY-) of substances of the family (F '''1) should preferably have the same characteristics and conditions as the groups (-CX ₂ -CXY-) in substances (S2) of the family (F'l).

In a second family of preferred compounds of formula (II), Y represents a phenyl group optionally substituted with one or more atoms selected from halogen atoms other than an iodine atom and C ₁ -C ₈ alkyl groups [family (F " 2)].

The groups (-CX ₂ -CXY-) of substances of the family (F '''2) should preferably have the same characteristics and conditions as the groups (-CX ₂ -CXY-) in substances (S2) of the family (F'2).

In the third family of preferred substances corresponding to formula (II), Y represents a group —O — C (═O) —Z, wherein Z is as defined above [family (F ″ 3)].

The groups (—CX ₂ —CXY—) of substances of the family (F ″ 3) should preferably have the same characteristics and conditions as the groups (—CX ₂ —CXY—) in the substances (S2) of the family (F′3).

In the fourth family of preferred substances corresponding to formula (II), Y represents a group selected from the nitrile group, groups —C (= O) —O — Z and —C (= O) —NZ ₂ , where Z is defined above [family (F '''4)].

The groups (—CX ₂ —CXY—) of substances of the family (F ″ 4) should preferably have the same characteristics and conditions as the groups (—CX ₂ —CXY-) in the substances (S2) of the family (F′4).

The invention also relates to iodinated organic substances with a molecular weight of less than 2000, corresponding to the general formula

R-O-S (= O) _P -O (-CX ₂ -CXY-) I, (III)

where R, X, Y, I and p are defined above for substances (S2).

The substance according to formula (III) has a molecular weight of preferably less than 1000, particularly preferably less than 500, and most preferably less than 250.

In the case of a substance corresponding to formula (III), p is preferably equal to 2.

In the first family of preferred substances corresponding to formula (III), Y represents a halogen atom other than an iodine atom [family F ^IV 1)].

The groups (-CX ₂ -CXY-) of substances of the family (F ^IV 1) should preferably have the same characteristics and conditions as the groups (-CX ₂ -CXY-) in substances (S2) of the family (F'l).

In a second family of preferred compounds of formula (III), Y represents a phenyl group optionally substituted with one or more atoms selected from halogen atoms other than an iodine atom and C ₁ -C ₈ alkyl groups [family (F ^IV 2) ].

The groups (-CX ₂ -CXY-) of substances of the family (F ^IV 2) should preferably have the same characteristics and conditions as the groups (-CX ₂ -CXY-) in substances (S2) of the family (F'2).

In the third family of preferred substances corresponding to formula (III), Y represents a group —O — C (═O) —Z, where Z is as defined above [family (F ^IV 3)].

The groups (-CX ₂ -CXY-) of substances of the family (F ^IV 3) should preferably have the same characteristics and conditions as the groups (-CX ₂ -CXY-) in substances (S2) of the family (F'3).

In the fourth family of preferred substances corresponding to formula (III), Y represents a group selected from the nitrile group, groups —C (= O) —O — Z and —C (= O) —NZ ₂ , where Z is defined above [family (F ^IV 4)].

The groups (-CX ₂ -CXY-) of substances of the family (F ^IV 4) should preferably have the same characteristics and conditions as the groups (-CX ₂ -CXY-) in substances (S2) of the family (F'4).

And finally, the subject of the present invention is a method for controlled free radical polymerization using iodinated organic substances of the present invention or obtained by a synthesis method of the present invention, which have all the advantages of prior art controlled free radical polymerization and are free from their disadvantages.

To this end, the invention relates to a method for producing a polymer by free radical polymerization of at least one ethylenically unsaturated monomer using in polymerization:

(A ′) an ethylenically unsaturated monomer,

(B ') at least one free radical generating reagent selected from peroxides, diazocompounds, dialkyl diphenylalkanes, substances derived from tetraphenylethane, boranes, chain transmitters containing at least one thiuram disulfide group, styrene or derivatives of styrene and ultraviolet radiation,

(C ') one or more substances that are selected from substances (S) obtained by the method for producing iodinated organic substances described above, iodinated organic substances (S2) in mixtures as described above, and iodinated organic substances described above, and also optional

(D ') at least one metal complex that is selected from transition metals, lanthanides, actinides and metals of group IIIa, and a ligand for this metal.

Examples of ethylenically unsaturated monomers include vinyl esters such as vinyl acetate, acrylic acid, acrylic esters such as methyl acrylate, methacrylic acid, methacrylic esters such as methyl methacrylate, nitriles and amides of acrylic or methacrylic acid, styrene monomers such as styrene, butadiene butyl olefin monomers vinyl monomers.

The term “halogenated vinyl monomers” means an ethylenically unsaturated monomer containing one or more halogen atoms and not containing a heteroatom other than this or these halogen atoms.

Examples of halogenated vinyl monomers include vinyl chloride, vinylidene chloride, trichlorethylene, chloroprene and chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene.

(A ') preferably includes at least one halogenated vinyl monomer. It is particularly preferred that (A ′) contains a halogenated vinyl monomer and optionally also an acrylic ester.

The polymerization method according to this invention mainly includes the stages in which:

(1 ') at least part (A'), at least part (B '), at least part (C') and, if possible, at least part (D ') are introduced into the reactor,

(2 ') the contents of the reactor are introduced into the reaction, adding a possible residue (A'), a possible residue (B '), a possible residue (C') and, if necessary, a possible residue (D '),

until the contents of the reactor will be a polymer.

Preferably, the polymerization process of the present invention includes the steps in which:

(1 ″) at least part (A ^′ ), at least part (B ′), and optionally at least part (D ′), are introduced into the reactor, said reactor containing one or more substances (C ′), obtained in advance by the method for producing iodinated organic substances, as described above,

(2 '') the contents of the reactor are introduced into the reaction by adding a possible residue (A '), a possible residue (B'), a possible residue (C ') and, if necessary, a possible residue (D'),

until the contents of the reactor will be a polymer.

According to a first preferred embodiment of the polymerization process of the present invention, the latter does not use a metal complex selected from transition metals, lanthanides, actinides and Group IIIa metals and a ligand for this metal in the polymerization.

According to a second preferred embodiment of the polymerization process of the present invention, the latter uses in polymerization at least one metal complex selected from transition metals, lanthanides, actinides and Group IIIa metals, and a ligand for this metal.

The method for producing iodinated organic substances of the present invention has many advantages. It is easy to implement. It uses inexpensive raw materials that are not hazardous to handle. Obtained in this way iodized organic matter is also not expensive.

The method allows to synthesize in situ initiators of the indicated polymerization in a polymerization reactor prior to conducting controlled free radical polymerization of the ITP type (without metal-ligand complex) or ATRP (atomic transfer radical polymerisation in the presence of metal-ligand complexes). Such initiators can be synthesized without the use of special synthesis reactors or storage tanks for the raw materials needed for synthesis. Moreover, these initiators can be custom made to be particularly well suited for the controlled free radical polymerization in which they will be used.

Example 1

Styrene (1.627 g, 1.56 × 10 ^-2 mol), molecular iodine (0.0292 g, 1.15 × 10 ^-4 mol), di-tert-butyl peroxide (0.0286 g, 1.95 × 10 ^{- 4} mol) and 1.684 g of benzene were introduced into a 10 ml Carius tube. It was purged with argon to remove oxygen and then the tube was frozen in liquid nitrogen and sealed in vacuo.

Then, the tube was placed in an air thermostat heated to 120 ° C, and the reaction mass, initially dark brown, reacted to complete discoloration, which was achieved 15 hours after the tube was placed in the thermostat.

At this point, the tube was removed from the thermostat, and its contents were cooled to room temperature.

The reaction products were separated and the chemical composition of the crude product was analyzed by size exclusion chromatography.

For this purpose, we used a setup consisting of a Waters Associates pump, a Shodex RIse-61 refractometer detector, and two 5 mm columns (mixed-C PL-gel, Polymer Laboratories). The installation was calibrated according to the polystyrene standard, tetrahydrofuran with a flow rate of 1.0 ml / min was used as an eluent.

The following results were obtained, illustrated by the chromatogram in the drawing:

- as a result of the reaction, iodinated organic substances with a number average molecular weight of 299 were formed, which is very close to the molecular weight of the compound corresponding to the formula (CH ₃ ) ₃ —CO (CH ₂ —CHF) I;

- size exclusion chromatography made it possible to isolate and identify five (pairs) iodinated organic compounds corresponding to the formula A- (CH ₂ -CHF-) _n -I, where Ф is a phenyl group, n is from 0 to 4 and A is tert-butoxy- ( CH ₃ ) ₃ C — O— and / or methyl group, said methyl group being formed upon β-cleavage of the tert-butoxy group;

- it was found that: peak 1 (molecular weight in the region of 239) corresponds to n = 0; peak 2 (molecular weight in region 277) corresponds to n = 1; peak 3 (molecular weight in the region of 367) corresponds to n = 2; peak 4 (molecular weight in the region of 460) corresponds to n = 3; peak 5 (molecular weight in the region of 558) corresponds to n = 4.

Example 2

1,2-dichloroethane (25 ml), vinyl acetate (10 g, 0.1163 mol), molecular iodine (0.8 g, 0.0031 mol) and diethyl peroxydicarbonate (1.0 g 0.0056 mol) were placed in 250 ml a two-necked round-bottom flask equipped with a refrigerator and immersed in an oil bath. The contents of the round bottom flask were dark in color. The reaction mixture in a round bottom flask was purged with nitrogen for 30 minutes. Then the contents of the round bottom flask were heated to 65 ° C, and the reaction proceeded until complete discoloration was observed after 73 minutes. The contents of the two-necked round-bottom flasks were quickly cooled. It contained iodinated organic substances of the present invention.

Example 3

1,2-dichloroethane (25 ml), vinyl acetate (10 g, 0.1163 mol), molecular iodine (1.5 g, 0.0059 mol) and diethyl peroxydicarbonate (1.0 g, 0.0056 mol) were placed in 250 ml two-necked round bottom flask equipped with a refrigerator and immersed in an oil bath. The contents of the round bottom flask were dark in color. The reaction mixture in a round bottom flask was purged with nitrogen for 30 minutes. Then the contents of the round bottom flask were heated to 65 ° C, and the reaction began. The temperature of 65 ° C was maintained for a long time (5 hours) until the amount of vinyl acetate that had reacted ceased to change. At the end of the reaction, it became clear that the contents of the round-bottom flask retained a dark color. It contained iodinated organic substances of the present invention.

Example 4

1,2-dichloroethane (25 ml), n-butyl acrylate (14.85 g, 0.116 mol), molecular iodine (0.8 g, 0.0031 mol) and diethyl peroxydicarbonate (1.0 g, 0.0056 mol) were placed in a 250 ml two-necked round-bottom flask equipped with a refrigerator, and immersed in an oil bath. The contents of the round bottom flask were dark in color. The reaction mixture in a round bottom flask was purged with nitrogen for 30 minutes. Then the contents of the round bottom flask were heated to 65 ° C, and the reaction proceeded until complete discoloration, which was observed after 98 minutes. The contents of the two-necked round-bottom flasks were quickly cooled. It contained iodinated organic substances of the present invention.

Example 5

1,2-dichloroethane (25 ml), n-butyl acrylate (14.85 g, 0.116 mol), molecular iodine (1.4 g, 0.0055 mol) and azobis (isobutyronitrile) (0.85 g, 0.0052 mol) was placed in a 250 ml two-necked round-bottom flask equipped with a refrigerator, and immersed in an oil bath. The contents of the round bottom flask were dark in color. The reaction mixture in a round bottom flask was purged with nitrogen for 30 minutes. Then the contents of the round bottom flask were heated to 65 ° C, and the reaction began. The temperature of 65 ° C was maintained for a long time (5 hours) until the amount of n-butyl acrylate that had reacted ceased to change. After the reaction, it became clear that the contents of the round-bottom flask retained a dark color. It contained iodinated organic substances of the present invention.

Claims (16)

1. A method of obtaining one or more iodinated organic substances with a molecular weight of less than 2000 (substance (S)) using: (A) at least one free radical generating substance selected from peroxides, diazocompounds, dialkyl diphenylalkanes, substances derived from tetraphenylethane, boranes and chain transmitters containing at least one thiuramsulfide group, (B) at least one organic substance containing at least one ethylene double bond, capable of attaching a free radical to its ethylene double bond, corresponding to the formula CΨ ₂ = CΨΞ, where the symbols Ψ represent independently of each other and from Ξ (i) a hydrogen atom, (ii) a halogen atom other than iodine, or (iii) a linear or branched C ₁ -C ₂₀ alkyl group; Ξ represents (i) a halogen atom other than an iodine atom, (ii) a phenyl group optionally substituted with one or more atoms other than an iodine atom, and a C ₁ -C ₈ alkyl group, (iii) an —O — C group ( = O) - Ω, (iv) a nitrile group, (v) a group -C (= O) -O- Ω or (vi) a group -C (= O) -N Ω ₂ ; Ω represents (i) a hydrogen atom or (ii) a saturated or unsaturated ethylene or aromatic C ₁ -C ₂₀ hydrocarbon group; (C) molecular iodine, which includes the stages in which: (1) at least part (A), at least part (B) and at least part (C) are introduced into the reactor and then (2) the contents of the reactor are reacted by adding a possible residue (A), a possible residue (B) and a possible residue (C) until the contents of the reactor are a mixture containing one or more substances (S) [mixture (M)]. 2. The method according to claim 1, characterized in that the substances (S) have a molecular weight of less than 1000. 3. The method according to claim 1 or 2, characterized in that the substances (S) have a number average molecular weight of less than 500. 4. The method according to claim 1 or 2, characterized in that the contents of the reactor are introduced into the reaction until the moment when the amount (B) absorbed in the reaction no longer changes. 5. The method according to claim 4, characterized in that the number of moles (C) relative to the number of moles (A) is greater than or equal to 100%. 6. The method according to claim 1, characterized in that after stage (2) includes an additional stage (3), at which the reaction is stopped. 7. The method according to claim 6, characterized in that the reaction is stopped at the moment when the color of the contents of the reactor changes from dark to light. 8. The method according to claim 6, characterized in that the number of moles (C) relative to the number of moles (A) is less than 100%. 9. The method according to claims 1 and 6, characterized in that it includes a stage following stage (2) and then following stage (3), the method comprising said stage (3), in which at least one substance is isolated (S) in the mixture (M) and possible other substances (S) contained in the mixture (M). 10. A mixture containing at least two iodinated organic substances with a molecular weight of less than 2000, corresponding to the general formula RG _x (-CX ₂ -CXY-) _n -I and RG _x (-CX ₂ -CXY-) _{n + 1} -I obtained by method 1, where R represents (i) a hydrogen atom, (ii) an alkali metal atom, (iii) a linear or branched C ₁ -C ₂₀ alkyl group optionally substituted with one or more groups selected from phenyl, carboxyl, hydroxyl, nitrile, amine or amidine, (iv) a C ₃ -C ₈ cycloalkyl group optionally substituted with one or more groups selected from C ₁ -C ₈ alkyl groups and a nitrile group, or (v) a phenyl group optionally substituted with one or more groups selected from C ₁ -C ₈ alkyl groups and halogen atoms other than iodine atom; x represents an integer of 0 or 1; G represents —O—, —O — C (= O) —O—, —C (= O) —O— or —O — S (= O) p — O—; if G represents a group —C (═O) —O— then its fragment C (═O) is linked to R and the fragment O is linked to a group CX ₂ ; p represents an integer of 1 or 2; n represents an integer from 1 to 8; groups X represent independently from each other and from Y (i) a hydrogen atom, (ii) a halogen atom other than an iodine atom, or (iii) a linear or branched C ₁ -C ₂₀ alkyl group; Y represents (i) a halogen atom other than an iodine atom, (ii) a phenyl group optionally substituted with one or more atoms selected from halogen atoms other than an iodine atom, and C ₁ -C ₈ alkyl groups, (iii) a group -OC (= O) -Z, (iv) a nitrile group, (v) a group -C (= O) -OZ, or (vi) a group -C (= O) -NZ ₂ ; Z represents (i) a hydrogen atom or (ii) a saturated or unsaturated ethylene or aromatic C ₁ -C ₂₀ hydrocarbon group; R, G, x, CX ₂ —CXY and n are identical for the two substances that are the subject of the invention; I is an iodine atom [of substance (S2)]. 11. The mixture according to claim 10, characterized in that the substances (S2) have a number average molecular weight of less than 500. 12. Iodinated organic matter with a molecular weight of less than 2000, corresponding to the general formula RG (-CX ₂ -CXY-) _q -I, obtained according to method 1, where R, G, X, Y, and I are defined in claim 10 and where q represents an integer greater than 1 but less than 10. 13. Iodinated organic matter with a molecular weight of less than 2000, corresponding to the General formula obtained by method 1 ROC (= O) -O- (CX ₂ -CXY) -I, where R, X, Y, and I are defined in clause 10. 14. Iodinated organic matter with a molecular weight of less than 2000, corresponding to the General formula obtained by method 1 ROS (= O) _p -O- (CX ₂ -CXY) -I, where R, X, Y, I, and p are defined in clause 10. 15. Iodized organic substance according to any one of paragraphs.12-14, characterized in that it has a molecular weight of less than 2000. 16. A method of producing a polymer by free radical polymerization of at least one ethylenically unsaturated monomer using in polymerization: (A ′) ethylenically unsaturated monomer, (B ') at least one free radical generating substance selected from peroxides, diazocompounds, dialkyl diphenylalkanes, substances derived from tetraphenylethane, boranes and chain transfer agents containing at least one thiuram disulfide group, styrene or derivatives of styrene and ultraviolet radiation (C ') one or more substances that are selected from substances (S) obtained by the method according to any one of claims 1 to 9, substances (S2) from mixtures according to claim 10 or 11 and substances according to any one of claims 12-14 and also optional (D ') at least one metal complex that is selected from transition metals, lanthanides, actinides and metals of group IIIa, and a ligand for this metal.

Images