JP2006524215A - Low molecular weight iodinated organic substances and methods for their preparation - Google Patents

Abstract

One or more iodinated organic substances (substance (S)) having a molecular weight of less than 2000 (A) substances derived from peroxides, diazo compounds, dialkyldiphenylalkanes, tetraphenylethane, borane and at least one thiuram disulfide group. At least one free radical-generating substance selected from the iniferter substance containing, (B) an ethylenically unsaturated substance capable of adding a free radical to an ethylene double bond, (C) for preparing using molecular iodine A method comprising introducing at least a portion of (A), at least a portion of (B) and at least a portion of (C) into a reactor, then a possible remainder of (A), (B) The reactor content until the content of the reactor is a mixture containing one or more substances (S) while introducing the possible remainder of (C) into it. Including the step of reacting Method. Iodinated organic materials for which the preparation of the above method is particularly well suited.

Description

Detailed Description of the Invention

  The present invention relates to a method for preparing a low molecular weight iodinated organic material, a low molecular weight iodinated organic material, and a method for preparing a polymer containing these low molecular weight iodinated organic materials.

U.S. Pat.No. 5,144,067 describes a process for the simultaneous preparation of alkyl iodides, one of which is alkyl iodide and the other is mono-α-iodocarboxylic acid and / or anhydride, which is an iodinated compound such as molecular iodine. A mixture of a carboxylic acid anhydride, such as acetic anhydride, and a peroxide, such as hydrogen peroxide, is reacted at an elevated temperature.
U.S. Patent Application No. 5 430 208 describes a method for synthesizing 1-chloro-1-iodoethane, wherein hydroiodic acid and vinyl chloride are combined with organic (e.g., 1,2-diiodoethane) or inorganic (e.g., The reaction is carried out in the presence of an iodine-containing catalyst (potassium iodide or molecular iodine).
Heasley et al., J. Org. Chem. Soc., 1988, pp. 198-201 includes tert-butyl hypoiodide and various ethylenically unsaturated substances in the presence of BF ₃ or the action of UV light. Various iodinated organic substances have been synthesized by reacting with each other. In particular, this has synthesized a substance of the formula (CH ₃ ) ₃ —CO—CH ₂ —CHΦI, where Φ is a phenyl group.
Cambie et al., J. Chem. Soc., Chem. Comm., 1973, vol. 11, pp. 359-360 is also reacted with styrene, molecular iodine and thallium (I) acetate (CH ₃ ) ₃ -CO-CH ₂ -CHΦI is synthesized.

Prior art methods of synthesizing low molecular weight iodinated organic materials are complex methods. Furthermore, it requires the use of raw materials that are expensive and / or dangerous to process. The low molecular weight iodinated organic material thus produced is itself very expensive.
It is also known that some low molecular weight iodinated organic materials can be used as initiators for controlled free radical polymerization ("ITP" type polymerization).
However, the “best” choice for the efficiency of the initiation of polymerization and the properties of the polymer thus produced often depends on the actual type of monomer, so that all monomers of different chemical properties are polymerized under optimal conditions. It is necessary to be able to utilize a fairly wide range of iodinated organic initiators when required to do so.

The subject of the present invention is a preparation method which allows both the advantages of the prior art methods and avoids all of their drawbacks.
For this purpose, the present invention relates to one or more iodinated organic substances (substance (S)) having a molecular weight of less than 2000.
(A) at least one free radical-generating substance selected from peroxides, diazo compounds, dialkyldiphenylalkanes, substances derived from tetraphenylethane, borane and an iniferter substance containing at least one thiuram disulfide group,
(B) at least one organic substance having at least one ethylene double bond capable of adding a free radical to the ethylene double bond,
(C) Molecular iodine
A method for preparing using
(1) introducing at least part of (A), at least part of (B) and at least part of (C) into the reactor, then (2) possible remainder of (A), (B Until the time when it is reached that the content of the reactor is a mixture [mixture (M)] containing one or more substances (S) while introducing the possible remainder of (C) into it The method comprising reacting the contents of the reactor.

In addition to substance (S), one or more iodinated organic substances other than substance (S) can optionally be prepared by the method of the present invention [substance (S ′)].
The mass of the iodinated organic substance (S ′) expressed relative to the mass of the substance (S) is preferably less than 1, particularly preferably less than 0.2, most preferably less than 0.05.
The molecular weight of the substance (S) is preferably less than 1000, particularly preferably less than 500, most preferably less than 250.
The number average molecular weight of the substance (S) is advantageously less than 500, preferably less than 250.
The expression peroxide is understood to mean both organic and inorganic peroxides.
The first family of materials for which free radical generating materials are preferably chosen are organic peroxides.

Examples of organic peroxides include the following compounds.
-Dialkyl peroxides, e.g. dicumyl peroxide, tert-butyl peroxide, cumyl peroxide, ditert-butyl peroxide);
A diacyl peroxide, for example diisononanoyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di (2-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-chlorobenzoyl) peroxide;
-Acetylcyclohexanesulfonyl peroxide;
-Dialkyl peroxydicarbonates such as diethyl peroxydicarbonate, diisopropyl peroxycarbonate, di (sec-butyl) peroxydicarbonate, dimyristyl peroxydicarbonate, dicetyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate;

-Dialkyl percarbonates, such as tert-amylperoxy-2-ethylhexyl carbonate, tert-butylperoxyisopropyl carbonate;
-Peresters such as cumyl perneodecanoate, tert-amyl perneodecanoate, tert-butyl perpivalate, tert-butyl per (2-ethylhexanoate), tert-butyl perisobutyrate, tert-butyl perisononanoate, 2,5-dimethylhexane 2,5-diperbenzoate, tert-butyl perbenzoate;
-Perketals, such as 1,1-bis (tert-butylbutylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane;
-Ketone peroxides, e.g. methyl ethyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide;
Organic hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, pinane hydroperoxide).

  The organic peroxide is preferably selected from dialkyl peroxides, diacyl peroxides, dialkyl peroxydicarbonates and peresters. Particularly preferred are dialkyl peroxides and dialkyl peroxydicarbonates, most preferably dialkyl peroxides each containing at most 4 carbon atoms and dialkyl peroxydicarbonates each containing at most 4 carbon atoms. To be elected. Di tert-butyl peroxide and diethyl peroxydicarbonate showed excellent results.

A second family of materials for which free radical generating materials are preferably chosen are inorganic peroxides.
Examples of inorganic peroxides include the following compounds.
-Hydrogen peroxide;
-Persulfates, e.g. ammonium persulfate, sodium persulfate, potassium persulfate;
-Perborate.
The inorganic peroxide is preferably a persulfate. Ammonium persulfate showed excellent results.
A third family of materials for which free radical generating materials are preferably chosen are diazo compounds.
Examples of diazo compounds include azobis (isobutyronitrile), azobis (2,4-dimethylvaleronitrile), azoamidine, and azomidinium salt.
The diazo compound preferably has one or more nitrile groups. Azobis (isobutyronitrile) showed excellent results.
Examples of dialkyldiphenylalkanes include 3,4-dimethyl-3,4-diphenylhexane and 2,3-dimethyl-2,3-diphenylbutane.
Examples of substances derived from tetraphenylethane include
_{N≡C-CΦ 2 -CΦ 2 -C≡N,} υO-CΦ 2 -CΦ 2 -Oυ, υ 3 Si-CΦ 2 -CΦ 2 -Siυ 3, (υO) 3 Si-CΦ 2 -CΦ 2 -Si (Oυ) ₃ , ΦO-CΦ ₂ -CΦ ₂ -OΦ. In the materials exemplified above, Φ is a phenyl group and υ is a C ₁ -C ₂₀ alkyl group.

Examples of borane include trialkylborane (B (OOυ) ₃ ), for example, trimethylborane, triphenylborane (B (OOΦ) ₃ ), where υ and Φ are as defined above.
Examples of iniferter substances containing at least one thiuram disulfide group can include υ ₂ N- (S =) CSSC (= S) -Nυ ₂ , where the υ symbols are the same or different and are defined above. That's right.

Organic substances having at least one ethylene double bond capable of adding free radicals to the ethylene double bond advantageously correspond to the formula CΨ ₂ = CΨΞ, where
-Ψ symbols are independently of each other and Ξ (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;
-Ξ is (i) a halogen atom other than iodine atom, (ii) a phenyl group optionally substituted with one or more atoms selected from halogen atoms other than iodine atom and C ₁ -C ₈ alkyl group, (iii ) -OC (= O) -Ω group, (iv) nitrile group, (v) -C (= O) -O-Ω group, or (vi) group C (= O) -NΩ ₂ ;
-Ω is (i) a hydrogen atom, or (ii) a saturated or ethylenically unsaturated or aromatic C ₁ -C ₂₀ hydrocarbon group.
A first family of preferred substances corresponding to the formula CΨ ₂ = CΨΞ is that in which Ξ is a halogen atom other than iodine atoms ([Family (F1)]).
The material of family (F1) preferably has at most 3 carbon atoms. Particularly preferably, it is selected from vinyl chloride, vinylidene chloride, trichloroethylene, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene and hexafluoropropylene. Most preferably, it is selected from vinyl chloride, vinylidene chloride and hexafluoropropylene.
A second family of preferred materials corresponding to the formula CΨ ₂ = CΨΞ is a phenyl group optionally substituted with one or more atoms selected from halogen atoms other than iodine atoms and C ₁ -C ₈ alkyl groups. There is something [Family (F2)].
The material of family (F2) preferably corresponds to the formula CH ₂ = CHΞ, where Ξ is as defined in the previous paragraph. Of all the materials in the family (F2), styrene showed excellent results.

A third family of preferred materials corresponding to the formula Cψ ₂ = CψΞ is that where Ξ is a -OC (= O) -Ω group, where Ω is as defined above [Family (F3)].
The material of family (F3) preferably corresponds to the formula CH ₂ = CHΞ, where Ξ is as defined in the previous paragraph. Among all the materials in the family (F3), vinyl acetate showed excellent results.
A fourth family of preferred substances corresponding to the formula CΨ ₂ = CΨΞ is where Ξ is a nitrile group and a group selected from the groups -C (= O) -O-Ω and -C (= O) -NΩ ₂ And Ω is as defined above [Family (F4)].
Substances of family (F4) preferably correspond to the formula CH ₂ = CHΞ, or the formula CH ₂ = C (CH ₃ ) Ξ, or the formula CH ₂ = CFΞ, where Ξ is as defined in the previous paragraph. is there. Particularly preferably, corresponding to the formula CH ₂ = CH-C (= O) -O-Ω or the formula (CH ₂ = C (CH ₃ ) -C (= O) -O-Ω, Ω is defined above. More particularly preferred are selected from acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate and n-butyl methacrylate. Among all the substances of (F4), methyl acrylate showed excellent results.
Examples of the organic material having at least one ethylene double bond and capable of adding a free radical to an ethylene double bond other than the above materials include ethylene, propylene, and butadiene.

When the method of the invention uses several organic materials having at least one ethylene double bond, which can add free radicals to the ethylene double bond, advantageously at least one of the materials of family (F1) And at least the other is selected from the materials of families (F3) and (F4). Preferably, at least one is selected from vinyl chloride, vinylidene chloride and vinylidene fluoride, and at least the other is selected from vinyl acetate, methyl acrylate and n-butyl acrylate. Particularly preferably, one is vinylidene chloride and the other is methyl acrylate.
The temperature at which the reactor contents react is advantageously -50 ° C to 300 ° C, preferably 0 to 150 ° C.
Preferably, all of (A), (B), (C) are introduced into the reactor in step (1).

According to a preferred first variant of the process of the invention [variation (1)], the reactor contents are reacted until the amount of (B) consumed by the reaction no longer changes.
According to variant (1), the number of moles of (C) expressed relative to the number of moles of (A) is advantageously 90% or more, preferably 100% or more, particularly preferably 105% or more. is there. Furthermore, the number of moles of (C) expressed relative to the number of moles of (A) is advantageously less than 200%, preferably less than 150%.
According to variation (1), the number of moles of (C) expressed relative to the number of moles of (B) is typically greater than 0.5%. The good operation of the method of the present invention is unaffected and may be greater than 5%, greater than 50% and often greater than 100%. Furthermore, the number of moles of (C) expressed relative to the number of moles of (B) is advantageously less than 200%, preferably less than 150%.

According to a preferred second modification of the method of the present invention [Modification (2)], after step (2), further comprising step (3), the ongoing reaction may be performed, for example, by rapidly diluting the contents of the reactor. Stop by cooling to.
According to variant (2), when the ongoing reaction is stopped, it is advantageously when the color of the reactor contents changes from a dark color to a light color.
According to variant (2), the number of moles of (C) expressed relative to the number of moles of (A) is advantageously less than 100%, preferably less than 90%. Furthermore, the number of moles of (C) expressed relative to the number of moles of (A) is advantageously 20% or more.
According to variation (2), the number of moles of (C) expressed in relation to the number of moles of (B) is usually less than 100%. It may be less than 50% or less than 5% and often less than 1% without affecting the good operation of the process of the invention. Furthermore, the number of moles of (C) expressed relative to the number of moles of (B) is advantageously greater than or equal to 0.01%, preferably greater than 0.1%.
The method of the present invention advantageously comprises, after step (2), further after step (3), if the method comprises said step (3), further comprising one step, wherein at least one of the mixtures (M) The substance (S) and other possible substances (S) contained in the mixture (M) are separated.
The subject of the present invention is also an iodinated organic material for preparation, the process which is the subject of the present invention is particularly well suited and all do not show the disadvantages of the prior art iodinated organic materials. Have.

In this context, the present invention is a mixture comprising at least two iodinated organic substances having a molecular weight of less than 2000, each having the general formulas RG _x- (CX ₂ -CXY-) _n -I and RG _x- (CX ₂ -CXY-) _{n + 1} -I
(In the formula, -R is one or more selected from (i) a hydrogen atom, (ii) an alkali metal atom, (iii) a phenyl group, a carboxyl group, a hydroxyl group, a nitrile group, an amine group or an amidine group). linear or branched C ₁ -C ₂₀ alkyl group optionally substituted by a group, (iv) C ₁ -C ₈ alkyl and C which are optionally substituted with one or more groups selected from nitrile group _{A 3-} C ₈ cycloalkyl 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 atoms;
-x is an integer equal to 0 or 1;
-G is -O-, -OC (= O) -O-, -C (= O) -O- or -OS (= O) _p -O-;
When G is a group -C (= O) -O-, the fragment C (= O) is bound to R and the fragment O is bound to the group CX ₂ ;
-p is an integer equal to 1 or 2;
-n is an integer equal to 1-8;
The groups X are independently of each other and 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 is, (i) a halogen atom other than an iodine atom, (ii) 1 or more optionally substituted phenyl group atom selected from halogen atoms and C ₁ -C ₈ alkyl group other than an iodine atom, ( iii) group -OC (= O) -Z, (iv) nitrile group,
(v) a group -C (= O) -OZ, or (vi) a group -C (= O) -NZ ₂ ;
- Z is an (i) a hydrogen atom, or (ii) saturated or ethylenically unsaturated or aromatic C ₁ -C ₂₀ hydrocarbon group;
-R, G, x, CX2-CXY and n are identical in the two substances that are the subject of the present invention;
-I is an iodine atom
[Substance (S2)]. )
Which relates to the mixture.

The number average molecular weight of the substance (S2) is advantageously less than 500, preferably less than 250.
The molecular weight of each of the substances (S2) is preferably less than 1000, particularly preferably less than 500, most particularly preferably less than 250.
Examples of alkali metal atoms that can constitute the group R include sodium and potassium.
Examples of unsubstituted alkyl groups that can constitute the group R include methyl, ethyl, isopropyl, sec-butyl, tert-butyl, tert-amyl, n-heptyl, (1-ethyl) Examples thereof include a pentyl group, (2-ethyl) hexyl group, (2-methyl)-(4,4-dimethyl) pentyl group, n-nonyl group, n-undecyl group, myristyl group and cetyl group.
Examples of substituted alkyl groups that can constitute the group R include cumyl, —C (C≡N) — (CH ₃ ) ₂ , (2-phenyl) propyl and (2-phenyl) butyl groups. it can.
Examples of substituted or unsubstituted cycloalkyl groups that can constitute the group R include cyclohexyl and pinyl.
Examples of substituted phenyl groups that can constitute the group R include (2-methyl) phenyl and (4-chloro) phenyl groups.

For the substance (S2), n is usually less than 7 and often less than 5.
For the substance (S2), G is preferably selected from the groups -OC (= O) -O-, -O-, -OS (= O) -O- and -OS (= O) ₂ -O- . Two groups G are particularly preferred: one is a group —OC (═O) —O—; the other is a group OS (═O) ₂ —O—.
The mixtures according to the invention advantageously exclude iodinated organic substances having a molecular weight of 2000 or higher; preferably iodinated organic substances having a molecular weight of 1000 or higher.
The expression “excluding (...)” is understood to mean “contains no detectable amount of (...) by any size exclusion chromatography method known to those skilled in the art”.
A first family of preferred substances (S2) is that of substance (S2) wherein Y is a halogen atom other than iodine atoms [family (F′1)].

The group — (CX ₂ —CXY) — of the substance (S2) of the family (F′1) preferably has at most 3 carbon atoms. Preferably, group _{- (CH 2 -CHCl) -,} - (CH 2 -CCl 2) -, - (CCl 2 -CHCl) -, - (CF 2 -CFCl) -, - (CH 2 -CHF) -, It is selected from-(CH ₂ -CF ₂ )-,-(CF ₂ -CHF)-,-(CF ₂ -CF ₂ )-and-(CF ₂ -CF (CF ₃ ))-. Particularly preferably the group _{- (CH 2 -CHCl) -,} - (CH 2 -CCl 2) -, - (CH 2 -CF 2) - and _{- (CF 2 -CF (CF 3} )) - is from chosen.
Preferred second family of materials (S2) is a Y phenyl group optionally substituted with one or more atoms chosen from halogen atoms and C ₁ -C ₈ alkyl group other than an iodine atom substance (S2) [Family (F'2)].
The group-(CX ₂ -CXY)-of the substance (S2) of the family (F'2) advantageously corresponds to the formula-(CH ₂ -CHY)-, where Y is as defined in the previous paragraph It is. Of all these groups, the group — (CH ₂ —CHΦ) — (wherein Φ is a phenyl group) is preferred.
A third family of preferred substances (S2) are substances (S2) in which Y is a group —OC (═O) —Z, where Z is as defined above [family (F′3)].

The group-(CX ₂ -CXY)-of the substance (S2) of the family (F'3) advantageously corresponds to the formula-(CH ₂ -CHY)-, where Y is as defined in the previous paragraph It is. Of all these groups, the acetyl group is preferred.
A fourth family of preferred substances (S2) are substances (S2) in which Y is a group selected from nitrile groups, groups -C (= O) -OZ and -C (= O) -NZ ₂ and Z is [Family (F'4)] as defined above.
The group-(CX ₂ -CXY)-of the substance (S2) of the family (F'4) is advantageously of the formula-(CH ₂ -CHY)-or the formula-(CH ₂ -C (CH ₃ ) Y )-Or the formula-(CH ₂ -CFY)-, where Y is as defined in the previous paragraph. Preferably, corresponding 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 Particularly preferably, one of the following substances: acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate and n-butyl methacrylate Selected from the groups formed by the open chain of two ethylene double bonds, among all these groups the group-(CH ₂ -CH (C (= O) O (CH ₃ )))-, ie acrylic Most particularly preferred are groups formed by the open chain of an ethylene double bond of methyl acid.

The present invention also includes the following general formula:
RG- (CX ₂ -CXY) _q -I (I)
(Wherein R, G, X, Y, I are as defined above for substance (S2), q is an integer greater than 1 and less than 10).
Relates to an iodinated organic substance having a molecular weight of less than 2000.
The molecular weight of the substance corresponding to formula (I) is preferably less than 1000, particularly preferably less than 500, and most preferably less than 250.
q is usually less than 7, often less than 5.
For substances corresponding to formula (I), G is preferably a group -OC (= O) -O-, -O-, -OS (= O) -O- and -OS (= O) _2- Selected from O-. Two groups G are particularly preferred: one is a group —OC (═O) —O—; the other is a group —OS (═O) ₂ —O—.
A first family of preferred substances corresponding to formula (I) is that in which Y is a halogen atom other than iodine atoms [family (F ″ 1).
The group (-CX ₂ -CXY)-of the substance of the family (F''1) preferably has the same properties and conditions as the group (S2) of the substance (S2) of the family (F'1)-(CX ₂ -CXY)- To meet.

The second family of preferred substances corresponding to formula (I), Y is optionally substituted with one or more atoms chosen from halogen atoms and C ₁ -C ₈ alkyl group other than an iodine atom, a phenyl group [Family (F''2)].
The group (-CX ₂ -CXY)-of the substance of the family (F''2) preferably has the same properties and conditions as the group (S2) of the substance (S2) of the family (F'2)-(CX ₂ -CXY)- To meet.
A third family of preferred substances corresponding to formula (I) are those in which Y is a group -OC (= O) -Z, where Z is as defined above [Family (F''3) ].
The group (-CX ₂ -CXY)-of the substance of the family (F''3) preferably has the same properties and conditions as the group (S2) of the substance (S2) of the family (F'3)-(CX ₂ -CXY)- To meet.
A fourth family of preferred materials corresponding to formula (I) is one in which Y is a group selected from a nitrile group, groups -C (= O) -OZ and -C (= O) -NZ ₂ ; Is as defined above [Family (F''4)].
The group (-CX ₂ -CXY)-of the substance of the family (F''4) preferably has the same properties and conditions as the group (S2) of the substance (S2) of the family (F'4)-(CX ₂ -CXY)- To meet.

The present invention also includes the following general formula:
ROC (= O) -O (CX ₂ -CXY) -I (II)
(Wherein R, X, Y and I are as defined above as substance (S2).)
Relates to an iodinated organic substance having a molecular weight of less than 2000.
The molecular weight of the substance corresponding to formula (II) is preferably less than 1000, particularly preferably less than 500, most preferably less than 250.
A first family of preferred substances corresponding to formula (II) is one in which Y is a halogen atom other than iodine atoms [family (F ″ ′ 1)].
The group (-CX ₂ -CXY)-of the substance of the family (F '''1) is preferably the same properties and conditions as the group (S2) of the substance (S2) of the family (F'1)-(CX ₂ -CXY)- It satisfies.
The second family of preferred substances corresponding to formula (II), Y is optionally substituted with one or more atoms chosen from halogen atoms and C ₁ -C ₈ alkyl group other than an iodine atom, a phenyl group [Family (F '''2)].
The group (-CX ₂ -CXY)-of the substance of the family (F '''2) is preferably the same properties and conditions as the group (S2) of the substance (S2) of the family (F'2)-(CX ₂ -CXY)- It satisfies.

A third family of preferred substances corresponding to formula (II) are those in which Y is a group (-OC (= O) -Z), Z is as defined above [Family (F '''3)].
The group (-CX ₂ -CXY)-of the substance of the family (F '''3) is preferably the same properties and conditions as the group (S2) of the substance (S2) of the family (F'3)-(CX ₂ -CXY)- It satisfies.
A fourth family of preferred materials corresponding to formula (II) is one in which Y is a group selected from a nitrile group, -C (= O) -OZ and -C (= O) -NZ ₂ ; Is as defined above [Family (F '''4)].
The group (-CX ₂ -CXY)-of the substance of the family (F '''4) is preferably the same properties and conditions as the group (S2) of the substance (S2) of the family (F'4)-(CX ₂ -CXY)- It satisfies.

The present invention also includes the following general formula:
ROS (= O) _p -O- (CX ₂ -CXY) -I (III)
(Wherein R, X, Y, I, p are as defined above for substance (S2).)
Relates to an iodinated organic substance having a molecular weight of less than 2000.
The molecular weight of the substance corresponding to formula (III) is preferably less than 1000, particularly preferably less than 500, and most preferably less than 250.
For substances corresponding to formula (III), p is preferably 2.
A first family of preferred substances corresponding to formula (III) is one in which Y is a halogen atom other than iodine atoms (family [F ^IV 1)].
Family (F ^IV 1) substance group-(CX ₂ -CXY)-preferably satisfies the same properties and conditions as the family (F'1) substance (S2) group-(CX ₂ -CXY)- Is.
A second family of preferred substances corresponding to formula (III) is a phenyl group, wherein Y is preferably substituted with one or more atoms selected from halogen atoms other than iodine atoms and C ₁ -C ₈ alkyl groups [Family (F ^IV 2)].
The group (-CX ₂ -CXY)-of the substance of the family (F ^IV 2) preferably satisfies the same properties and conditions as the group (S2) of the substance (S2) of the family (F'2)-(CX ₂ -CXY)- Is.

A third family of preferred substances corresponding to formula (III) are those in which Y is a group —OC (═O) —Z, where Z is as defined above [Family (F ^IV 3)] .
Family (F ^IV 3) substance group-(CX ₂ -CXY)-preferably meets the same properties and conditions as the family (F'3) substance (S2) group-(CX ₂ -CXY)- Is.
A fourth family of preferred materials corresponding to formula (III) is one in which Y is a group selected from a nitrile group, groups -C (= O) -OZ and -C (= O) -NZ ₂ ; Z is as defined above [Family (F ^IV 4)].
Family (F ^IV 4) substance group-(CX ₂ -CXY)-preferably satisfies the same properties and conditions as the family (F'4) substance (S2) group-(CX ₂ -CXY)- Is.

The subject matter of the present invention finally uses the iodinated organic material prepared according to the present invention or by the method of synthesis of the present invention, all of the advantages of the prior art controlled free radical polymerization method without showing its disadvantages. A controlled free radical polymerization process.
To this effect, the present invention is a method for preparing a polymer by free radical polymerization of at least one ethylenically unsaturated monomer,
(A ') an ethylenically unsaturated monomer,
(B ') at least one selected from peroxides, diazo compounds, dialkyldiphenylalkanes, substances derived from tetraphenylethane, borane, iniferter substances containing at least one thiuram disulfide group, styrene and styrene substances, and ultraviolet light Free radical generator,
(C ′) the material (S) prepared by the method for preparing an iodinated organic material described above, the iodinated organic material (S2) of the mixture described above and the iodination described above One or more substances selected from organic substances, and optionally further
(D ′) relates to the process, wherein a metal selected from a transition metal, a lanthanide, an actinide and a group IIIa metal and at least one complex of a ligand of this metal is used.
Examples of ethylenically unsaturated monomers include vinyl esters as vinyl acetate, acrylic acid, acrylic acid esters such as methyl acrylate, methacrylic acid, methacrylic acid esters such as methyl methacrylate, nitriles and acrylamide or methacrylamide, styrene Styrene monomer such as olefin, olefin monomer such as butadiene, and vinyl halide monomer.

The expression “halogenated vinyl monomer” is understood to mean an ethylenically unsaturated monomer containing one or more halogen atoms and no heteroatoms other than this or these halogen atoms.
Examples of vinyl halide monomers include vinyl chloride, vinylidene chloride, trichloroethylene, chloroprene and chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene. it can.
(A ′) preferably contains at least one vinyl halide monomer. Particularly preferably, (A ′) is composed of a vinyl halide monomer and optionally further an acrylic ester.

The method of polymerization of the present invention advantageously comprises:
(1 ′) at least part of (A ′), at least part of (B ′), at least part of (C ′) and, where appropriate, at least part of (D ′) in the reactor Introducing process,
(2 ') possible remainder of (A'), possible remainder of (B '), possible remainder of (C') and, where appropriate, possible remainder of (D ') in it Introducing, reacting the contents of the reactor until the time when the contents of the reactor contain polymer is reached.
Preferably, the polymerization method of the present invention comprises:
(1 ") introducing at least a portion of (A '), at least a portion of (B') and, where appropriate, at least a portion of (D ') into the reactor;
The reactor contains one or more substances (C ′) previously prepared by a method for preparing an iodinated organic substance as described above,
(2 ") possible remainder of (A '), possible remainder of (B'), possible remainder of (C ') and, where appropriate, possible remainder of (D') Introducing, reacting the reactor contents until a time is reached when the reactor contents contain polymer.

According to a preferred first variant of the polymerization method of the invention, the latter does not use in the polymerization a complex of a metal selected from transition metals, lanthanides, actinides and group IIIa metals and a ligand of this metal.
According to a preferred second variant of the polymerization method of the invention, the latter uses in the polymerization at least one complex of a metal selected from transition metals, lanthanides, actinides and group IIIa metals and a ligand of this metal.
The method for preparing iodinated organic materials of the present invention has several advantages. It is very easy to implement. Use raw materials that are inexpensive and not very dangerous to process. The iodinated organic material thus produced is itself inexpensive.
Before carrying out controlled radical polymerization of ITP type (without metal-ligand complex) or ATRP type (atom transfer radical polymerization, in the presence of metal-ligand complex) of the polymerization initiator in the polymerization reactor In that case, it is possible. Therefore, such initiators can be synthesized without the use of a suitable synthesis reactor or a storage reservoir for the raw materials required for their synthesis. Moreover, these initiators can be specially ordered so that they are particularly well suited for the controlled radical polymerization in which they are used.

Example 1
1.627 g (1.56 × 10 ⁻² mol) styrene, 0.0292 g (1.15 × 10 ⁻⁴ mol) molecular iodine, 0.0286 g (1.95 × 10 ⁻⁴ mol) di-tert-butyl peroxide and 1.684 g benzene. And introduced into a 10 ml Carius tube. Argon was bubbled through to remove oxygen, then the tube was frozen in liquid nitrogen and sealed under reduced pressure.
The tube was then placed in an oven heated to 120 ° C. and its contents, which were first dark brown in color, were allowed to react therein until their complete decolorization was obtained, and the tube was placed in the oven 15 Decolorization occurred after time.
At this time, the tube was removed from the oven and its contents cooled to room temperature.
The products of the reaction were separated and their chemistry was determined by size exclusion chromatography applied to the crude contents of the reactor.
To this end, a plant consisting of a refractive index detector Shodex RIse-61 from Polymer Laboratories and a Waters Associates pump with two mixed-C PL-gel 5 μm columns was used. The plant was standardized with polystyrene standards. Tetrahydrofuran was used as the eluent at a flow rate of 1.0 ml / min.

The following results, shown in the chromatogram in FIG. 1, were obtained.
-The reaction yielded an iodinated organic material with a number average molecular weight of 299, very close to the compound corresponding to formula (CH3) 3C-O (CH2-CHΦ) I;
-Size exclusion chromatography has the formula A- (CH ₂ -CHΦ-) _n -I _where Φ is a phenyl group, n is 0-4 and A is tert-butoxy (CH ₃ ) ₃ CO- And / or a methyl group)), which is considered to result from the β-cleavage of the tert-butoxy group. ;
-Corresponding to the following correlation: Peak 1 (molecular weight about 239) was associated with n = 0; Peak 2 (molecular weight about 277) was associated with n = 1; Peak 3 (molecular weight about 367) was Associated with n = 2; Peak 4 (molecular weight about 460) was associated with n = 3; Peak 5 (molecular weight about 558) was associated with n = 4.

Example 2
250 ml of 25 ml 1,2-dichloroethane, 10 g (0.1163 mol) vinyl acetate, 0.8 g (0.0031 mol) molecular iodine and 1.0 g (0.0056 mol) diethyl peroxydicarbonate placed in a capacitor and immersed in an oil bath Into a two-necked round bottom flask. The color of the contents of the round bottom flask was dark. The contents of the round bottom flask were degassed by bubbling nitrogen for 30 minutes. The contents of the round bottom flask were then heated to 65 ° C. and reacted until complete decolorization was obtained, and decolorization was obtained after 73 minutes. The contents of the two-necked round bottom flask were rapidly cooled. It contains the iodinated organic material of the present invention.

Example 3
250 ml of 25 ml 1,2-dichloroethane, 10 g (0.1163 mol) vinyl acetate, 1.5 g (0.0059 mol) molecular iodine and 1.0 g (0.0056 mol) diethyl peroxydicarbonate placed in a capacitor bath and immersed in an oil bath Into a two-necked round bottom flask. The color of the contents of the round bottom flask was dark. The contents of the round bottom flask were degassed by bubbling nitrogen for 30 minutes. Next, the contents of the round bottom flask were heated to 65 ° C. and reacted. The temperature of 65 ° C. was maintained for a sufficiently long time, ie 5 hours, and the amount of vinyl acetate consumed by the reaction no longer changed. After the reaction, it was observed that the contents of the round bottom flask retained a dark color. It contains the iodinated organic material of the present invention.

Example 4
25 ml of 1,2-dichloroethane, 14.85 g (0.116 mol) n-butyl acrylate, 0.8 g (0.0031 mol) molecular iodine and 1.0 g (0.0056 mol) diethyl peroxydicarbonate were placed in an oil bath with a condenser. It was introduced into an immersed 250 ml 2-neck round bottom flask. The color of the contents of the round bottom flask was dark. The contents of the round bottom flask were degassed by bubbling nitrogen for 30 minutes. The contents of the round bottom flask were then heated to 65 ° C. and allowed to react until complete decoloration was obtained, and decolorization was obtained after 98 minutes. The contents of the two-necked round bottom flask were rapidly cooled. It contains the iodinated organic material of the present invention.

Example 5
Capacitors were loaded with 25 ml of 1,2-dichloroethane, 14.85 g (0.116 mol) n-butyl acrylate, 1.45 g (0.055 mol) molecular iodine and 0.85 g (0.0052 mol) azobis (isobutyronitrile). It was introduced into a 250 ml 2-neck round bottom flask immersed in an oil bath. The color of the contents of the round bottom flask was dark. The latter was heated to 65 ° C. to react them. The temperature of 65 ° C. was maintained for a sufficiently long time, ie 5 hours, and the amount of n-butyl acrylate consumed by the reaction no longer changed. After the reaction, it was observed that the contents of the round bottom flask retained a dark color. It contains the iodinated organic material of the present invention.

2 shows the chromatographic results of the product obtained in Example 1.

Claims (16)

One or more iodinated organic substances (substance (S)) with a molecular weight of less than 2000
(A) at least one free radical-generating substance selected from peroxides, diazo compounds, dialkyldiphenylalkanes, substances derived from tetraphenylethane, borane and an iniferter substance containing at least one thiuram disulfide group,
(B) at least one organic substance having at least one ethylene double bond capable of adding a free radical to the ethylene double bond;
(C) a method for preparing using molecular iodine,
(1) introducing at least a part of (A), at least a part of (B) and at least a part of (C) into a reactor;
(2) A mixture in which the content of the reactor contains one or more substances (S) while introducing the possible remainder of (A), the possible remainder of (B) and the possible remainder of (C) therein Reacting the contents of the reactor until a time is reached [Mixture (M)].   2. The method according to claim 1, wherein the molecular weight of the substance (S) is less than 1000.   3. The method according to claim 1, wherein the number average molecular weight of the substance (S) is less than 500.   4. A process according to claim 1, 2 or 3, characterized in that the contents of the reactor are reacted until the amount of (B) consumed by the reaction no longer changes.   5. The method according to claim 4, wherein the number of moles of (C) expressed relative to the number of moles of (A) is 100% or more.   The method according to claim 1, 2 or 3, further comprising step (3) after step (2), wherein the ongoing reaction is stopped.   7. A method according to claim 6, characterized in that the ongoing reaction is stopped when the color of the reactor contents changes from dark to light.   The method according to claim 6 or 7, wherein the number of moles of (C) expressed relative to the number of moles of (A) is less than 100%.   After step (2), and further after step (3), when the method includes the step (3), the method further includes a step, wherein at least one substance (S) of the mixture (M) and the mixture (M) 9. Process according to any one of claims 1 to 8, characterized in that possible other substances (S) contained are separated. A mixture comprising at least two iodinated organic substances having a molecular weight of less than 2000, each having a general formula
RG _x- (CX ₂ -CXY-) _n -I and RG _x- (CX ₂ -CXY-) _{n + 1} -I
(In the formula, -R is one or more selected from (i) a hydrogen atom, (ii) an alkali metal atom, (iii) a phenyl group, a carboxyl group, a hydroxyl group, a nitrile group, an amine group or an amidine group). linear or branched C ₁ -C ₂₀ alkyl group optionally substituted by a group, (iv) C ₁ -C ₈ alkyl and C which are optionally substituted with one or more groups selected from nitrile group _{A 3-} C ₈ cycloalkyl 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 atoms;
-x is an integer equal to 0 or 1;
-G is -O-, -OC (= O) -O-, -C (= O) -O- or -OS (= O) _p -O-;
When G is a group -C (= O) -O-, the fragment C (= O) is bound to R and the fragment O is bound to the group CX ₂ ;
-p is an integer equal to 1 or 2;
-n is an integer equal to 1-8;
The group X is independently of 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 is, (i) a halogen atom other than an iodine atom, (ii) 1 or more optionally substituted phenyl group atom selected from halogen atoms and C ₁ -C ₈ alkyl group other than an iodine atom, ( 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 is an (i) a hydrogen atom, or (ii) saturated or ethylenically unsaturated or aromatic C ₁ -C ₂₀ hydrocarbon group;
-R, G, x, CX ₂ -CXY, n are identical in the two substances that are the subject of the present invention;
-I is an iodine atom
[Substance (S2)]. )
Corresponding to said mixture.   11. Mixture according to claim 10, characterized in that the number average molecular weight of the substance (S2) is less than 500. An iodinated organic substance having a molecular weight of less than 2000, having a general formula
RG- (CX ₂ -CXY-) _q -I
(Wherein R, G, X, Y, and I are as defined in claim 10, and q is an integer greater than 1 and less than 10).
The iodinated organic substance corresponding to An iodinated organic substance having a molecular weight of less than 2000, having a general formula
ROC (= O) -O- (CX ₂ -CXY) -I
(Wherein R, X, Y and I are as defined in claim 10).
The iodinated organic substance corresponding to An iodinated organic substance having a molecular weight of less than 2000, having a general formula
ROS (= O) _p -O- (CX ₂ -CXY) -I
(Wherein R, X, Y, I and p are as defined in claim 10).
The iodinated organic substance corresponding to   The iodinated organic substance according to any one of claims 12 to 14, characterized in that the molecular weight is less than 1000. A method for preparing a polymer by free radical polymerization of at least one ethylenically unsaturated monomer comprising:
(A ') an ethylenically unsaturated monomer,
(B ′) at least one selected from peroxides, diazo compounds, dialkyldiphenylalkanes, substances derived from tetraphenylethane, borane, iniferter substances containing at least one thiuram disulfide group, styrene and styrene substances, and ultraviolet rays Two free radical generators,
(C ′) the substance (S) prepared by the method according to any one of claims 1 to 9, the iodinated organic substance (S2) of the mixture according to claim 10 or 11, and the claims 12 to 15 One or more substances selected from the substances according to any one of the above, and optionally further,
(D ′) The above method, wherein a metal selected from a transition metal, a lanthanide, an actinide and a group IIIa metal and at least one complex of a ligand of the metal are used.

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