CN100586917C - Iodinated organic substances with low molecular weight and process for preparing same - Google Patents
Iodinated organic substances with low molecular weight and process for preparing same Download PDFInfo
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- CN100586917C CN100586917C CN 200480010920 CN200480010920A CN100586917C CN 100586917 C CN100586917 C CN 100586917C CN 200480010920 CN200480010920 CN 200480010920 CN 200480010920 A CN200480010920 A CN 200480010920A CN 100586917 C CN100586917 C CN 100586917C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
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Abstract
The invention relates to a method for preparing an iodized organic substance or a plurality of iodized organic substances (substance(s)) with the molecular weight less than 2000. (A) At least one substance which can form free radical is used; the substance is chosen from peroxide, diazo compounds, dialkyl diphenyl alkane, the substance derived from tetraphenyl ethane, boron hydride and initiator-transfer agent-terminator which contains at least one disulfide tetra alkyl thiuram radical; (B) ethylenic linkage type unsaturated material is used, the free radical can be added on ylen double linkage by the material; (C) iodide excess is used. The method comprises the following steps that: the at least part (A), the at least part (B) and the at least part (C) are added in a reactor and reacted,meanwhile, (A) possible remainder, (B) possible remainder and (C) possible remainder are led into the reactor till the substance in the reactor becomes a compound which contains one substance or a plurality of substances. The iodized organic substance prepared with the method is very suitable.
Description
The present invention relates to a kind of method that the organic method of lower molecular weight iodate, lower molecular weight iodate organism and preparation comprise this lower molecular weight iodate organic polymer thing for preparing.
Patent US-A-5144067 described prepare alkiodide on the one hand, preparation list-alpha-iodine is for the combined preparation method of carboxylic acid and/or acid anhydrides on the other hand, according to this method, iodinated compounds for example iodine molecule, carboxylic acid anhydride for example diacetyl oxide and superoxide for example the mixture of hydrogen peroxide at high temperature react.
Patent US-A-5430208 has described a kind of method of synthetic 1-chloro-1-iodoethane, according to this method, hydroiodic acid HI and vinylchlorid contain iodine catalyst in the presence of react, this contains iodine catalyst is organism (for example 1,2-ethylidene periodide) or inorganics (for example potassiumiodide or iodine molecule).
Heasley etc. are at J.Org.Chem., 1988, in Pp.198～201 by making tertiary butyl hypoiodite and different ethylenic unsaturated materials at BF
3Existence or ultraviolet irradiation be the synthetic various iodate organism of reaction down.Especially, they thereby to have synthesized general formula be (CH
3)
3-C-O-CH
2The material of-CH φ I, wherein φ refers to phenyl.
Cambie etc. are at J.Chem.Soc., Chem.Comm., and 1973, vol.11 is (CH by making vinylbenzene, molecular iodine and thaliium acetate (I) reaction also synthesize general formula in pp.359～360
3)
3-C-O-CH
2The material of-CH φ I.
The organic method of synthetic lower molecular weight iodate of the prior art is complicated method.They require to use extraly the raw material of costliness and/or operational hazards.So the lower molecular weight iodate organism of preparation itself is very expensive.
Same known many lower molecular weight iodate organism can be used as the initiator of control radical polymerization (polymerization of " ITP " type).
Yet, with regard to efficient and the polymer properties for preparing like this that polymerization causes, the characteristic of monomer itself is depended in the selection of " best " usually, if therefore wish the monomer of polymerization different chemical character, the iodate organic initiators of the wider range that they need be able to use, all are in optimal conditions.
Theme of the present invention is a kind of preparation method, and it promptly has the advantage of prior art and has avoided all shortcomings wherein again.
For this reason, the present invention relates to a kind ofly use following material to prepare the method for one or more molecular weight less than 2000 iodate organism (material (S)):
(A) material of at least a generation free radical is selected from superoxide, diazonium compound, dialkyl group phenylbenzene alkane, the material by the tetraphenyl ethane derivative, borine and comprises the iniferter of at least a thiuram disulfide (thiuram disulphide) group;
(B) at least a organism that contains the two keys of at least one alkene formula, this organism can be added to free radical on the two keys of its alkene formula;
(C) molecular iodine,
Described method comprises the steps:
(1) near small part (A), be added in the reactor, then to small part (B) with to small part (C)
(2) make substance reaction in the reactor, to wherein adding possible residuum of (A) possible residuum, (B) and (C) possible residuum, the material in reactor is for containing the mixture [mixture (M)] of one or more materials (S) simultaneously.
Except material (S), the method according to this invention is optional can to prepare one or more iodate organism that are different from material (S) (material (S ')).
The weight of iodate organism (S ') with respect to the weight of material (S) preferably less than 1, in particularly preferred mode less than 0.2, in most preferred mode less than 0.05.
The molecular weight of material (S) is preferably less than 1000, in particularly preferred mode less than 500, in most preferred mode less than 250.
The number-average molecular weight of material (S) is advantageously less than 500, preferably less than 250.
The statement of superoxide can be understood as and refers to that promptly organo-peroxide refers to inorganic peroxide again.
First kind material is an organo-peroxide in the material of preferred generation free radical.
As the example of organo-peroxide, mention as following:
-dialkyl peroxide, for example dicumyl peroxide base, tert-butyl peroxide and cumyl and di-t-butyl peroxide;
-diacyl peroxide is as peroxidation two different nonanoyl, dioctanoyl peroxide base, didecanoyl peroxide base, dilauroyl peroxide base, peroxidation two (2-methyl benzoyl), dibenzoyl peroxide base and peroxidation two (4-chlorobenzene formacyl);
-ethanoyl peroxidation sulfonyl hexanaphthene;
-dialkyl peroxydicarbonates class is as diethyl peroxy dicarbonate, diisopropyl peroxydicarbonate, two (second month in a season-butyl) peroxy dicarbonate, two (tetradecyl) peroxy dicarbonate, two (hexadecyl) peroxy dicarbonate, two (2-ethylhexyl) peroxy dicarbonate and two (4-tert-butyl cyclohexyl) peroxy dicarbonate;
-dialkyl group peroxocarbonate is as uncle-amyl peroxy-2-ethylhexyl carbonic ether and tert-butyl peroxy isopropyl base carbonic ether;
-peresters, crossing ester in new last of the ten Heavenly stems, uncle-amyl group as cumyl crosses ester in new last of the ten Heavenly stems, tert-butyl and crosses pivalate, tert-butyl and cross that (2-ethylhexanoate), tert-butyl are crossed isobutyrate, tert-butyl is crossed different pelargonate, 2,5-dimethylhexane 2,5-two perbenzoates, TBPB tertiary butyl perbenzoate;
-cross ketal as 1,1-two (tert-butyl peroxidation butyl) hexanaphthene and 2,2-two (peroxide tert-butyl) butane;
-ketone peroxide is as methyl ethyl ketone peroxide, cyclohexanone peroxide and acetyl peroxide benzylacetone;
-organic hydroperoxide, for example cumene hydroperoxide, t-butyl hydroperoxide and pinane hydroperoxide.
Organo-peroxide is preferably selected from dialkyl peroxide, diacyl peroxide, dialkyl peroxydicarbonates and peresters.They are selected from dialkyl peroxide and dialkyl peroxydicarbonates in particularly preferred mode, they are selected from wherein each alkyl chain and comprise at the most that dialkyl peroxide and wherein each alkyl chain of 4 carbon atoms comprise the dialkyl peroxydicarbonates of 4 carbon atoms at the most in most preferred mode.Two-tert-butyl peroxide and diethyl peroxy dicarbonate have fabulous result.
The second class material is an inorganic peroxide in the material of preferred generation free radical.
As the organic embodiment of peroxidation, mention as following:
-hydrogen peroxide;
-persulphate is as ammonium persulphate, Sodium Persulfate and Potassium Persulphate;
-perborate.
Inorganic peroxide is preferably persulphate.Ammonium persulphate has fabulous result.
The 3rd class material in the material of preferred generation free radical is a diazonium compound.
As the example of diazonium compound, mention: Diisopropyl azodicarboxylate, azo two (2, the 4-methyl pentane nitrile), azo amidine and azomidinium salt as following.
Diazonium compound preferably has one or more nitrile groups.Diisopropyl azodicarboxylate has fabulous result.
As the embodiment of dialkyl group phenylbenzene alkane, following mentioning: 3,4-dimethyl-3,4-phenylbenzene hexane and 2,3-dimethyl-2,3-diphenyl butane.
As the example of tetraphenyl ethane derivative material, following mentioning:
N≡C-CΦ
2-CΦ
2-C＝N，θO-CΦ
2-CΦ
2-Oθ，θ
3Si-CΦ
2-CΦ
2-Siθ
3，
(θ O)
3Si-C Φ
2-C Φ
2-Si (O θ)
3With Φ O-C Φ
2-C Φ
2-O Φ; In the material of above example, Φ refers to phenyl, and θ is C
1～C
20Alkyl.
As the embodiment of borine, as the following trialkylborane of mentioning (B (OO θ)
3), trimethylammonium borine and triphenylborane (B (OO θ) for example
3), wherein Φ and θ are as above definition.
As the embodiment of the iniferter material that contains at least one thiuram disulfide, that can mention has: θ
2N-(S=) C-S-S-C (=S)-N θ
2, wherein θ can be identical or different for as defined above.
Contain at least one organism that free radical can be added to the alkene double bond on its alkene double bond advantageously corresponding to general formula C Ψ
2=C Ψ Ξ, wherein
-symbol Ψ is expression independently respectively: (i) hydrogen atom, the (ii) halogen atom except the iodine atom, or (iii) straight or branched C
1～C
20Alkyl;
-Ξ represents (i) halogen atom except the iodine atom, and is (ii) optional by one or more halogen atom and C except that the iodine atom
1～C
8The phenyl that alkyl replaces, (iii) group-O-C (=O)-Ω, (iv) nitrile group, (V) group-C (=O)-O-Ω, or (Vi) group-C (=O)-N Ω
2
-Ω represents (i) hydrogen atom, or (ii) saturated or ethylenic is unsaturated or aromatic series C
1～C
20Hydrocarbyl group.
Corresponding to general formula C Ψ
2Ξ in the first kind preferred substance of=C Ψ Ξ represents the halogen atom [(F1) class] except the iodine atom.
(F1) the class material preferably has 3 carbon atoms at the most.In particularly preferred mode, they are selected from vinylchlorid, vinylidene chloride, trieline, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, trifluoro-ethylene, tetrafluoroethylene and R 1216.In most preferred embodiments, they are selected from vinylchlorid, Ethylene Dichloride and R 1216.
With general formula C Ψ
2Ξ represents phenyl group in the second class preferred substance of=C Ψ Ξ correspondence, and it is optional by one or more sub-iodine atom outer halogen atom and C of selecting
1～C
8Alkyl replaces [(F2) class].
(F2) the class material is preferably corresponding to general formula CH
2=CH Ξ, Ξ such as leading portion define.In all (F2) class materials, vinylbenzene has excellent results.
With general formula C Ψ
2In the 3rd class preferred substance of=C Ψ Ξ correspondence Ξ represent group-O-C (=O)-Ω, Ω such as leading portion definition [(F3) class].
(F3) the class material preferably with general formula CH
2=CH Ξ correspondence, Ξ such as leading portion define.In all (F3) class materials, vinyl acetate has excellent results.
With general formula C Ψ
2In the 4th class preferred substance of=C Ψ Ξ correspondence Ξ be selected from itrile group and be selected from group-C (=O)-O-Ω and-C (=O)-N Ω
2, Ω such as leading portion definition [(F4) class].
(F4) the class material is preferably corresponding to general formula CH
2=CH Ξ or corresponding to general formula CH
2=C (CH
3) Ξ or corresponding to general formula CH
2=CF Ξ, Ξ such as leading portion define.In particularly preferred mode, they are corresponding to general formula CH
2=CH-C (=O)-O-Ω or corresponding to general formula (CH
2=C (CH
3)-C (=O)-and O-Ω, wherein Ω such as leading portion define.In preferred mode, they are selected from vinylformic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, 2-EHA, methacrylic acid, methyl methacrylate and n-BMA.In all substances of (F4) class, methyl acrylate has excellent results.
As containing the two keys of at least one alkene formula and on this pair key, can adding the organic example of free radical, except above-mentioned, can also be ethene, propylene and divinyl.
When using the multiple organism that contains the two keys of at least one alkene formula that on two keys, can add free radical in the method according to this invention, advantageously at least a organism is selected from (F1) class material, and another kind is selected from (F3) class and (F4) material of class at least.Preferably, at least a organism is selected from vinylchlorid, vinylidene chloride and vinylidene fluoride, and another kind is selected from vinyl acetate, methyl acrylate and n-butyl acrylate at least.In preferred mode, be that vinylidene chloride and another are methyl acrylates one of in them.
Temperature when inducing reaction substance reaction in the device advantageously is-50 ℃～300 ℃, is preferably 0～150 ℃.
Preferably, in step (1), all be added in the reactor with (A), (B) with (C).
According to first advantageous variant of the inventive method [changing (1)], the substance reaction in the reactor is till the consumption of material (B) no longer changes in the reaction.
According to changing (1), mole number (C), is preferably greater than or equals 100% advantageously more than or equal to 90% with respect to the mole number of (A), in particularly preferred mode more than or equal to 105%.In addition, mole number (C) with respect to the mole number of (A) advantageously less than 200%, preferably less than 150%.
According to changing (1), mole number (C) with respect to the mole number of (B) usually greater than 0.5%.It can be greater than 5%, or even greater than 50%, even can surpass 100% sometimes, to the not influence of excellent operation of the inventive method.In addition, mole number (C) with respect to the mole number of (B) advantageously less than 200%, preferably less than 150%.
According to second kind of advantageous variant [changing (2)] of the inventive method, in step (2) afterwards, method also additionally comprises step (3), and ongoing reaction stops according to this step, for example by the material in the unexpected cooling reactor.
According to changing (2), the favourable moment that ongoing reaction stops is that the color of material in reactor is when dark color becomes light color.
According to changing (2), mole number (C) with respect to the mole number of (A) advantageously less than 100%, preferably less than 90%.In addition, mole number (C) with respect to the mole number of (A) more than or equal to 20%.
According to changing (2), mole number (C) with respect to the mole number of (B) usually less than 100%.It can be less than 50% or even less than 5%, and sometimes even can be less than 1%., this is to the not influence of excellent operation of the inventive method.In addition, mole number (C) advantageously more than or equal to 0.01%, is preferably greater than 0.1% with respect to the mole number of (B).
The inventive method advantageously comprises the another one step, in step (2) afterwards, and when described method comprises described step (3) in step (3) afterwards, according at least a material (S) in this step separating mixture (M) with may be contained in other material (S) in the mixture (M).
Purpose of the present invention also is the iodate organism, because the method for preparing this material is particularly suitable as the objective of the invention is, these materials have organic all advantages of iodate in the prior art and do not have wherein shortcoming.
For this reason, the present invention relates to contain the mixture of at least two kinds of molecular weight less than 2000 iodate organism [material (S2)], it corresponds respectively to general formula
With
Wherein:
-R represents (i) hydrogen atom, (ii) alkali metal atom, (iii) straight or branched C
1～C
20Alkyl, it is optional by one or more groups replacements that are selected from phenyl, carboxyl, hydroxyl, nitrile, amine or amidine, (iv) C
3-C
8Cycloalkyl, it is optional by one or more C that are selected from
1-C
8The group of alkyl and itrile group replaces, or (v) phenyl, it is optional by one or more C that are selected from
1-C
8The group of alkyl and the halogen atom except the iodine atom replace;
-x represents 0 or 1 integer;
-G represents-O-,-O-C (=O)-O-,-C (=O)-O-or-O-S (=O)
p-O-;
If G be group-C (=O)-O-, so its fragment C (=O) be connected its fragment O and group CX with R
2Connect;
-p represents to equal 1 or 2 integer;
-n represents the integer from 1～8;
-radicals X is represented (i) hydrogen atom, the (ii) halogen atom except the iodine atom, or (iii) straight or branched C
1～C
20Alkyl, and independent separately, irrelevant with Y;
-Y represents (i) halogen atom except the iodine atom, (ii) phenyl, and it is optional by one or more halogen atom and C that are selected from except the iodine atom
1-C
8Alkyl replaces, (iii) group-O-C (=O)-Z, (iv) itrile group, (v) group-C (=O)-O-Z, or (vi) group-C (=O)-NZ
2
-Z represents (i) hydrogen atom, or (ii) saturated or the alkene key is undersaturated or aromatic series C
1～C
20Hydrocarbyl group;
-R, G, x, CX
2-CXY and n are identical for two kinds of materials of the object of the invention;
-I is the iodine atom.
The number-average molecular weight of material (S2) is advantageously less than 500, preferably less than 250.
The molecular weight of various materials (S2) is preferably less than 1000, in particularly preferred mode less than 500, in most preferred mode less than 250.
As the example of the alkali metal atom that can constitute radicals R, can comprise sodium and potassium.
Example as the unsubstituted alkyl that can constitute radicals R, can comprise methyl, ethyl, sec.-propyl, sec-butyl, the tertiary butyl, tert-pentyl, n-heptyl, (1-ethyl) amyl group, (2-ethyl) hexyl, (2-methyl)-(4, the 4-dimethyl) amyl group, n-nonyl, n-undecane base, tetradecyl and hexadecyl.
As the example of the substituted alkyl that can constitute radicals R, can be cumyl ,-C (C N)-(CH
3)
2, (2-phenyl) propyl group and (2-phenyl) butyl.
As the example of replacement that can constitute radicals R or unsubstituted ring alkyl, can be cyclohexyl and pinyl base.
As the example of the substituted-phenyl that can constitute radicals R, can be (2-methyl) phenyl and (4-chlorine) phenyl.
About material (S2), n is generally less than 7, usually less than 5.
About material (S2), G be preferably selected from group-O-C (=O)-O-,-O-,-O-S (=O)-O-and-O-S (=O)
2-O-.Two group G are especially preferred: one be group-O-C (=O)-O-; Another is-O-S (=O)
2-O-.
Mixture of the present invention does not advantageously contain molecular weight more than or equal to 2000 iodate organism; The preferred molecular weight that do not contain is more than or equal to 1000 iodate organism.
The statement that " does not contain (...) " can be understood as " not containing by (...) that well known to a person skilled in the art size exclusion chromatography, energy detection limit ".
The first kind of preferred substance (S2) is that wherein Y represents the material (S2) [(F ' 1) class] of the halogen atom except that the iodine atom.
The group of (F ' 1) class material (S2)
Advantageously have 3 carbon atoms at the most.They are preferably selected from group
With
In particularly preferred mode, they are selected from group
With
Second class of preferred substance (S2) is that wherein Y represents the material (S2) [(F ' 2) class] of phenyl, and wherein phenyl is optional by one and a plurality of halogen atom and C that are selected from except that the iodine atom
1～C
8Alkyl replaces.
The group of (F ' 2) class materials (S2)
Advantageously corresponding to general formula
Wherein Y such as leading portion define.In all these groups, group
Preferably, wherein Φ represents phenyl.
The 3rd class of preferred substance (S2) be wherein Y represent group-O-C (=O)-material (S2) [(F ' 3) class] of Z, wherein Z such as leading portion define.
The group of (F ' 3) class materials (S2)
Advantageously corresponding to general formula
Wherein Y such as epimere define.In all these groups, ethanoyl is preferred.
The 4th class of preferred substance (S2) be wherein Y representative be selected from itrile group ,-O-C (=O)-Z and-C (=O)-NZ
2Material (S2) [(F ' 4) class], wherein Z such as leading portion define.
The group of (F ' 4) class materials (S2)
Advantageously corresponding to general formula
Or general formula
Or general formula
Wherein Y such as leading portion define.They are preferably corresponding to general formula
Or general formula
Wherein Z such as leading portion define.In preferred mode, they are selected from by the two keys of a kind of alkene formula in the following material and open the group that forms: vinylformic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, 2-EHA, methacrylic acid, methyl methacrylate and n-BMA.In all these groups, group
The group of promptly being opened by the two keys of the alkene formula of methyl acrylate and forming is most preferred.
The present invention also relates to a kind of molecular weight less than 2000 iodate organism, corresponding to general formula:
R wherein, G, X, Y is identical with above definition to material (S2) with I, and wherein the q representative is greater than 1 and less than 10 integer.
The molecular weight of material corresponding with general formula (I) be preferably less than 1000, in particularly preferred mode less than 500, in most preferred mode less than 250.
Q is generally less than 7, usually less than 5.
About the material of corresponding general formula (I), G be preferably selected from group-O-C (=O)-O-,-O-,-O-S (=O)-O-and-O-S (=O)
2-O-.In preferred two group G, group is-O-C (=O)-O-; Another group is-O-S (=O)
2-O-.
Corresponding to the halogen atom of Y representative in the first kind preferred substance of general formula (I) except that the iodine atom [(F " 1) class].
The group of (F " 1) class material
Has group preferred and (F ' 1) class material (S2)
Identical feature and state.
Represent phenyl corresponding to Y in the second class preferred substance of general formula (I), it is optional by one and a plurality of halogen atom and C that are selected from except that the iodine atom
1-C
8The alkyl replacement [(F " 2) class].The group of (F " 2) class material
Have groups preferred and (F ' 2) class materials (S2)
Identical character and state.
Corresponding to Y in the 3rd class preferred substance of general formula (I) represent group-O-C (=O)-Z, Z [(F " 3) class] as defined above wherein.
The group of (F " 3) class material
Have groups preferred and (F ' 3) class materials (S2)
Identical character and state.
Corresponding to Y representative in the 4th class preferred substance of general formula (I) be selected from itrile group, group-C (=O)-O-Z and-C (=O)-NZ
2Group, wherein Z as above defines [(F " 4) class].
The group of (F " 4) class material
Have groups preferred and (F ' 4) class materials (S2)
Identical character and state.
The invention still further relates to a kind of molecular weight less than 2000 iodate organism, it is corresponding to following general formula:
R wherein, X, Y and I such as above definition to material (S2).
Corresponding to the molecular weight of the material of general formula (II) preferably less than 1000, in particularly preferred mode less than 500, in most preferred mode less than 250.
Corresponding to the halogen atom of Y representative in the first kind preferred substance of general formula (II) except that the iodine atom [(F " ' 1) class].
The group of (F " ' 1) class material
Has group preferred and (F ' 1) class material (S2)
Identical character and state.
Represent phenyl corresponding to Y in the second class preferred substance of general formula (II), it is optional by one and a plurality of halogen atom and C that are selected from except that the iodine atom
1～C
8The alkyl replacement [(F " ' 2) class].
The group of (F " ' 2) class material
Have groups preferred and (F ' 2) class materials (S2)
Identical character and state.
Corresponding to Y in the 3rd class preferred substance of general formula (II) be-O-C (=O)-the Z group, Z [(F " ' 3) class] as defined above wherein.
The group of (F " ' 3) class material
Have groups preferred and (F ' 3) class materials (S2)
Identical character and state.
Corresponding to Y representative in the 4th class preferred substance of general formula (II) be selected from itrile group ,-O-C (=O)-Z and-C (=O)-NZ
2Group, Z [(F " ' 4) class] as defined above wherein.
The group of (F " ' 4) class material
Have groups preferred and (F ' 4) class materials (S2)
Identical character and state.
The invention still further relates to molecular weight less than 2000 iodate organism, it is corresponding to following general formula:
R wherein, X, Y, I and p in the above material (S2) definition.
Corresponding to the molecular weight of the material of general formula (III) preferably less than 1000, in particularly preferred mode less than 500, in most preferred mode less than 250.
About the material corresponding to general formula (III), p preferably equals 2.
Corresponding to the halogen atom [(F of Y representative except that the iodine atom in the first kind preferred substance of general formula (III)
IV1) class].
(F
IV1) group of class material
Has group preferred and (F ' 1) class material (S2)
Identical character and state.
Represent phenyl corresponding to Y in the second class preferred substance of general formula (III), it is preferably by one and a plurality of halogen atom and C that are selected from except that the iodine atom
1-C
8Alkyl replaces [(F
IV2) class].
(F
IV2) group of class material
Have groups preferred and (F ' 2) class materials (S2)
Identical character and state.
Corresponding to Y in the 3rd class preferred substance of general formula (III) be-O-C (=O)-material of Z, Z [(F as defined above wherein
IV3) class].
(F
IV3) group of class material
Have groups preferred and (F ' 3) class materials (S2)
Same nature and state.
Corresponding to Y representative in the 4th class preferred substance of general formula (III) be selected from itrile group, group-C (=O)-O-Z and-C (=O)-NZ
2Group, Z [(F as defined above wherein
IV4) class].
(FIV4) group of class material
Have groups preferred and (F ' 4) class materials (S2)
Same nature and state.
Last purpose of the present invention is a kind of method of controlling Raolical polymerizable, described polyreaction is used according to the present invention or is passed through the iodate organism of the synthetic method preparation of invention, described method has all advantages of control Raolical polymerizable in the prior art, and does not have shortcoming wherein.
For this reason, the present invention relates to a kind ofly, use following material in the polyreaction by the incompatible method for preparing polymkeric substance of at least a ethylenically unsaturated monomers radical polymerization:
(A ') ethylenically unsaturated monomers;
(B ') at least a free-radical generating agent, it is selected from superoxide, diazonium compound, dialkyl group phenylbenzene alkane, the material by the tetraphenyl ethane derivative, borine, the iniferter that contains at least a thiuram disulfide, vinylbenzene and styrenic material and uviolizing;
One or more are selected from (C ') above-mentioned material (S) by the preparation of the organic method of preparation iodate, the iodate organism (S2) in the said mixture and above-mentioned iodate organism and choose wantonly and have in addition,
(D ') at least a metal complex that is selected from transition metal, group of the lanthanides, actinium series and IIIa family metal, and the complex compound of this metal ligand.
As the example of ethylenically unsaturated monomers, can be vinyl ester such as vinyl acetate, vinylformic acid, esters of acrylic acid such as methyl acrylate, methacrylic acid, methyl acrylic ester such as methyl methacrylate, nitrile and acrylic acid amides or methacrylic acid acid amides, styrene monomer such as vinylbenzene, olefinic monomer such as divinyl and halogenated vinyl monomer.
The statement of " halogenated vinyl monomer " can be understood as and refers to such ethylenically unsaturated monomers, and it comprises one or more halogen atoms, and does not comprise except the heteroatoms this or these halogen atom.
As the example of halogenated vinyl monomer, can be vinylchlorid, vinylidene chloride, trieline, chloroprene, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, trifluoro-ethylene, tetrafluoroethylene, R 1216 and chlorotrifluoroethylene.
(A ') preferably comprises at least a halogenated vinyl monomer.In particularly preferred mode, (A ') is made up of halogenated vinyl monomer and optional other acrylate.
Polymerization process of the present invention advantageously comprises following steps:
(1 ') near small part (A '), to small part (B '), to small part (C ') be added in the reactor to small part (D ') in due course,
(2 ') make the substance reaction in the reactor, simultaneously to the possible residuum of the possible residuum of residuum, (B ') that wherein to add (A ') possible and (C ') and (D ') possible residuum in due course,
Material in reactor contains polymkeric substance.
Preferably, polymerization process according to the present invention comprises the steps:
(the near small part of 1 ") (A '), to small part (B ') with suitably be added in the reactor up to small part (D '), described reactor contains one or more materials (C ') for preparing by the organic method of above-mentioned preparation iodate in advance.
(2 ") make the substance reaction in the reactor, (D ') possible residuum to the possible residuum of the possible residuum of residuum, (B ') that wherein to add (A ') possible and (C ') and suitably time the simultaneously,
Contain polymkeric substance up to the material in reactor.
According to first kind of advantageous variant of invention polymerization process, the latter does not have to use the metal complex that is selected from transition metal, group of the lanthanides, actinium series and IIIa family metal in polymerization, and the complex compound of this metal ligand.
According to second kind of advantageous variant of invention polymerization process, the latter has used at least a metal complex that is selected from transition metal, group of the lanthanides, actinium series and IIIa family metal in polymerization, and the complex compound of this metal ligand.
The organic method of iodate produced according to the present invention has many advantages.This method is easy to realize.The raw material of its use is cheap and can danger close when handling.Iodate organism itself with this method preparation is just very cheap.
Before ITP class (not having the metal ligand complex compound) or ATRP class (in the presence of the metal ligand complex compound, atomic migration radical polymerization) control Raolical polymerizable carries out, its can be in polymerization reactor the synthetic described polymeric initiator of original position.Thereby under the condition of the holder that does not use suitable synthesis reactor and these synthetic desired raw materials, also can synthesize this class initiator.The more important thing is that these initiators can make routinely, thereby be particularly suitable for wherein using the control radical polymerization of these initiators.
Embodiment 1
With 1.627g (1.56 * 10
-2Mole) vinylbenzene, 0.0292g (1.15 * 10
-4Mole) molecular iodine, 0.0286g (1.95 * 10
-4Mole) ditertiary butyl peroxide and the benzene of 1.684g are added in the Carius pipe of 10ml.Feed the argon gas bubbling to remove oxygen wherein, then pipe is freezed in liquid nitrogen and at the vacuum lower seal.
Then, pipe put into be heated to 120 ℃ in the baking oven, initial color is that material reacts therein in the auburn pipe, sloughs fully up to color, wherein pipe is placed in the baking oven and decolours after 15 hours.
At this moment, pipe is taken out from baking oven, and general's material cool to room temperature wherein.
Reaction product is separated, measure their chemical property by the crude product in the reactor is carried out the size exclusion chromatography.
For this reason, use the equipment of being made up of Waters Associates pump, wherein said pump is equipped with the refraction of buying from Polymer Laboratories company to detect meter Shodex RIse-61 and two mixed-C PL-gel 5 μ m posts.Described equipment carries out stdn by polystyrene standard liquid.As eluant, flow velocity is 1.0ml/min with tetrahydrofuran (THF).
Can obtain following result, color atlas as shown in fig. 1:
The organic number-average molecular weight of the iodate of-prepared in reaction is 299, and is very approaching corresponding to general formula (CH
3)
3C-O (CH
2-CH Φ) molecular weight of the compound of I;
5 kinds can be separated and differentiate to-size exclusion chromatography corresponding to general formula
The iodate organism of I, wherein Φ represents phenyl, and n equals 0～4, and A represents tert.-butoxy (CH
3)
3C-O-and/or methyl, described methyl itself are considered to that β-cracking by tert.-butoxy obtains;
-can obtain following correspondence: peak 1 (molecular weight 239 zone) is relevant with n=0; Peak 2 (molecular weight 277 zone) is relevant with n=1; Peak 3 (molecular weight 367 zone) is relevant with n=2; Peak 4 (molecular weight 460 zone) is relevant with n=3; Peak 5 (molecular weight 558 zone) is relevant with n=4.
Embodiment 2
With 1 of 25ml, the diethyl peroxy dicarbonate of the vinyl acetate of 2-ethylene dichloride, 10g (0.1163 mole), the molecular iodine of 0.8g (0.0031 mole) and 1g (0.0056 mole) is added to and condenser is housed on it and places the interior 250ml two neck round-bottomed flasks of oil bath.Material in the round-bottomed flask is dark.By feeding 30 minutes nitrogen bubble so that the material in the round-bottomed flask is outgased.Material with round-bottomed flask is heated to 65 ℃ then, and makes them be reacted to decolouring fully, and wherein decolouring obtained after 73 minutes.Material in the two neck round-bottomed flasks is cooled off fast.It contains with good grounds iodate organism of the present invention.
Embodiment 3
With 1 of 25ml, the diethyl peroxy dicarbonate of the molecular iodine of the vinyl acetate of 2-ethylene dichloride, 10g (0.1163 mole), 1.5g (0.0059 mole) and 1.0g (0.0056 mole) is added in the two neck round-bottomed flasks of 250ml, wherein condenser is equipped with at this flask top, and is dipped in the oil bath.Material in the round-bottomed flask is dark.By feeding 30 minutes nitrogen bubbles the material in the round-bottomed flask is carried out degasification.Then the material in the round-bottomed flask is heated to 65 ℃ and make substance reaction.With the sufficiently long time of 65 ℃ temperature maintenance, promptly 5 hours, so that the amount of the vinyl acetate that consumes in the reaction no longer changes.After the reaction, the material that can observe in the round-bottomed flask keeps dark.The gained material contains according to iodate organism of the present invention.
Embodiment 4
With 1 of 25ml, the diethyl peroxy dicarbonate of the iodine molecule of the n-butyl acrylate of 2-ethylene dichloride, 14.85g (0.116 mole), 0.8g (0.0031 mole) and 1g (0.0056 mole) is added in the two neck round-bottomed flasks of 250ml, wherein condenser is equipped with at this flask top, and is dipped in the oil bath.Material in the round-bottomed flask is dark.By feeding 30 minutes bubblings of nitrogen the material in the round-bottomed flask is outgased.Then the material in the round-bottomed flask is heated to 65 ℃, and makes substance reaction up to decolouring fully, wherein decolouring obtained after 98 minutes.Material in the two neck round-bottomed flasks is cooled off fast.It contains with good grounds iodate organism of the present invention.
Embodiment 5
With 1 of 25ml, the Diisopropyl azodicarboxylate of the iodine molecule of the n-butyl acrylate of 2-ethylene dichloride, 14.85g (0.116 mole), 1.4g (0.0055 mole) and 0.85g (0.0052 mole) is added in the two neck round-bottomed flasks of 250ml, condenser is equipped with at wherein said flask top, and is dipped in the oil bath.Material in the round-bottomed flask is dark.Then the material in the round-bottomed flask is heated to 65 ℃ and make substance reaction.With the sufficiently long time of 65 ℃ temperature maintenance, promptly 5 hours, so that till the amount of the n-butyl acrylate of consumption no longer changes in the reaction.After the reaction, the material that can observe in the round-bottomed flask keeps dark.It contains with good grounds iodate organism of the present invention.
Claims (14)
1. prepare one or more molecular weight less than the organic method of 2000 iodate, wherein said molecular weight abbreviates material S as in the following description less than 2000 iodate organism, and described method is used following material:
(A) material of at least a generation free radical is selected from material, the borine of superoxide, diazonium compound, dialkyl group hexichol alkane, tetraphenyl ethane derivative and contains the iniferter of at least a thiuram disulfide group;
(B) at least a organism that contains the two keys of at least one alkene formula, it can be added to free radical on the two keys of its alkene formula, and it is corresponding to general formula C Ψ
2=C Ψ Ξ, wherein
-symbol Ψ represents: (i) hydrogen atom, the (ii) halogen atom except the iodine atom, or (iii) straight or branched C
1～C
20Alkyl, and independent separately, irrelevant with Ξ;
-Ξ represents (i) halogen atom [(F1) class] except the iodine atom, the (ii) optional phenyl [(F2) class] that replaces by one or more halogen atoms except that the iodine atom, (iii) group-O-C (=O)-Ω [(F3) class], or (iv) group-C (=O)-O-Ω [(F4) class];
-Ω represents (i) hydrogen atom, or (ii) saturated or ethylenic is unsaturated or aromatic series C
1～C
20Hydrocarbyl group;
(C) molecular iodine;
Described method comprises the steps:
(1) near small part (A), be added in the reactor, then to small part (B) with to small part (C)
(2) the interior material of reactor is reacted under-50 ℃ to 300 ℃ temperature, add possible residuum of (A) possible residuum, (B) and (C) possible residuum simultaneously, material in reactor is the mixture that contains one or more materials S, the wherein said mixture that contains one or more materials S abbreviates mixture M in the following description as
Then
Perhaps
Till making substance reaction in the reactor consumption of material (B) no longer changing in the reaction, this scheme abbreviates as in the following description and changes 1, this variation 1 is characterised in that, (C) mole number with respect to the mole number of (A) more than or equal to 90%, and less than 200%, simultaneously the mole number of (C) with respect to the mole number of (B) greater than 0.5%, and less than 200%;
Perhaps
Described method also comprises step (3) afterwards in step (2), according to this step, ongoing reaction stops, this scheme abbreviates as in the following description and changes 2, this variation 2 is characterised in that, mole number (C) with respect to the mole number of (A) more than or equal to 20%, and less than 100%, simultaneously the mole number of (C) with respect to the mole number of (B) more than or equal to 0.01%, and less than 5%.
2. according to the method for claim 1, the molecular weight that it is characterized in that material S is less than 1000.
3. according to the method for claim 1 or 2, the number-average molecular weight that it is characterized in that material S is less than 500.
4. according to the method for claim 1, it is characterized in that making the substance reaction in the reactor, the consumption of (B) no longer changes in reaction.
5. according to the method for claim 4, the mole number that it is characterized in that (C) with respect to the mole number of (A) more than or equal to 100%.
6. according to the method for claim 1, it is characterized in that comprising step (3) afterwards in step (2) in addition, according to this step stopped reaction.
7. according to the method for claim 6, it is characterized in that mole number with respect to the mole number (C) of (A) is less than 100%.
8. according to the method for aforementioned each claim, it is characterized in that afterwards in step (2), further afterwards in step (3), described method comprises a step in addition, when described method comprises step (3), according to may separating by other material S of containing at least a material S in this step mixture M and the mixture M.
9. mixture, it comprises that at least two kinds of molecular weight are less than 2000 and correspond respectively to general formula
With
The iodate organism, wherein said two kinds of molecular weight are less than 2000 and correspond respectively to general formula
With
The iodate organism abbreviate material S2 in the following description as, wherein:
-R represents (i) hydrogen atom, (ii) alkali metal atom, (iii) straight or branched C
1～C
20Alkyl, it is optional by one or more groups replacements that are selected from phenyl, carboxyl, hydroxyl, nitrile, amine or amidine, (iv) C
3～C
8Cycloalkyl, it is optional by one or more C that are selected from
1～C
8The group of alkyl and itrile group replaces, or (v) phenyl, it is optional by one or more C that are selected from
1～C
8Alkyl and the halogen atom except the iodine atom replace;
-x represents to equal 0 or 1 integer;
-G represents-O-,-O-C (=O)-O-,-C (=O)-O-or-O-S (=O)
p-O-;
If G be group-C (=O)-O-, so its fragment C (=O) be connected and its fragment O and group CX with R
2Connect;
-p represents to equal 1 or 2 integer;
-n represents to equal 1～8 integer;
-radicals X representative (i) hydrogen atom, the (ii) halogen atom except the iodine atom, or (iii) straight or branched C
1～C
20Alkyl, and independent separately, irrelevant with Y;
The halogen atom of-Y representative (i) except the iodine atom [(F1 ') class], (ii) phenyl, it is optional to be selected from halogen atoms replacement except that the iodine atom [(F2 ') class] by one or more, (iii)-O-C (=O)-the Z group [(F3 ') class], or (iv)-C (=O)-the O-Z group [(F4 ') class];
-Z represents (i) hydrogen atom, or (ii) one saturated or ethylenic is undersaturated or aromatic series C
1～C
20Hydrocarbyl group;
-R, G, x, CX
2-CXY is identical with n to two kinds of materials, and these two kinds of materials are purpose of the present invention;
-I is the iodine atom.
10. according to the mixture of claim 9, the number-average molecular weight that it is characterized in that material S2 is less than 500.
11. molecular weight is less than 2000 iodate organism, it is corresponding to general formula
R wherein, G, X, Y and I as defined in claim 9, and q represents greater than 1 and less than 10 integer.
12. molecular weight is less than 2000 iodate organism, it is corresponding to general formula
R wherein, X, Y and I are as defined in claim 9.
13. molecular weight is less than 2000 iodate organism, it is corresponding to general formula
R wherein, X, Y, I and p are as defined in claim 9.
14., it is characterized in that molecular weight is less than 1000 according to each iodate organism in the claim 11～13.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE2003/0255A BE1015478A6 (en) | 2003-04-22 | 2003-04-22 | Preparation of iodinated organic substance having low molecular mass useful for preparation of polymer by free-radical polymerization by reacting free radical-generating substance, organic substance and molecular iodine |
| BE2003/0255 | 2003-04-22 | ||
| US60/487,258 | 2003-07-16 | ||
| FR03.09561 | 2003-08-01 | ||
| FR03/09561 | 2003-08-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1777571A CN1777571A (en) | 2006-05-24 |
| CN100586917C true CN100586917C (en) | 2010-02-03 |
Family
ID=34383035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480010920 Expired - Fee Related CN100586917C (en) | 2003-04-22 | 2004-04-22 | Iodinated organic substances with low molecular weight and process for preparing same |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100586917C (en) |
| BE (1) | BE1015478A6 (en) |
-
2003
- 2003-04-22 BE BE2003/0255A patent/BE1015478A6/en not_active IP Right Cessation
-
2004
- 2004-04-22 CN CN 200480010920 patent/CN100586917C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| CONTRIBUTION A L'ETUDE DE L'ACTION OXYDANTE DUPEROXYDE DE BENZOYL, EN PRESENCE D'IODE, SURQUELQUES CARBURES D'HYDROGENE NONSATURES. A. PERRET AND R. PERROT.HELV. CHIM. ACTA,Vol.28 . 1945 |
| CONTRIBUTION A L'ETUDE DE L'ACTION OXYDANTE DUPEROXYDE DE BENZOYL,EN PRESENCE D'IODE,SURQUELQUES CARBURES D'HYDROGENE NONSATURES.A.PERRET AND R.PERROT.HELV.CHIM.ACTA,Vol.28. 1945 * |
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| Publication number | Publication date |
|---|---|
| BE1015478A6 (en) | 2005-04-05 |
| CN1777571A (en) | 2006-05-24 |
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