CN102399310B - Composition and method used for inhibiting premature polymerization - Google Patents
Composition and method used for inhibiting premature polymerization Download PDFInfo
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- CN102399310B CN102399310B CN2010102800111A CN201010280011A CN102399310B CN 102399310 B CN102399310 B CN 102399310B CN 2010102800111 A CN2010102800111 A CN 2010102800111A CN 201010280011 A CN201010280011 A CN 201010280011A CN 102399310 B CN102399310 B CN 102399310B
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N Nc1cc(N)ccc1 Chemical compound Nc1cc(N)ccc1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N c1cnc2c(nccc3)c3ccc2c1 Chemical compound c1cnc2c(nccc3)c3ccc2c1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
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Abstract
The invention relates to a composition. The composition comprises at least one vinyl compound which can be subject to free radical polymerization, and an active dose of a polymerization inhibiting composition comprising metal ions, halogen ions and ligands. The ligands comprise donor atoms selected from oxygen atoms, nitrogen atoms, sulfur atoms, phosphor atoms or a combination thereof. The metal ions are selected from titanium ions, molybdenum ions, rhenium ions, ruthenium ions, iron ions, rhodium ions, nickel ions, palladium ions, cobalt ions, osmium ions, copper ions or any combination thereof. The composition does not contain secondary amine nitroxyl compounds without a hydrogen atom on an alpha-carbon atom. The invention also relates to a method used for preventing the premature polymerization of the vinyl compound which can be subject to free radical polymerization. The method comprises a step that: an active dose of the polymerization inhibiting composition is added to at least one vinyl compound which can be subject to free radical polymerization.
Description
Technical field
The present invention relates to a kind of composition and method that suppresses premature polymerization.Particularly, the present invention relates to suppress the composition and the method for the vinyl compound generation premature polymerization of free redical polymerization.
Background technology
Polymerization easily takes place in many unsaturated compounds under the free radical state.When the crude product that obtains is on a large scale purified in fractionation, therefore need to add suitable stablizer or stopper such as fragrant vinyl compounds such as vinylbenzene, alpha-methyl styrenes and make it stable, in order to avoid premature polymerization.Usually stablizer or stopper are that adding will fractionated crude product before the beginning of purifying or in carrying out.
Chinese patent discloses a kind of mixture No. 97197209.5, and it contains: (A) contain alkenyl compound; (B) inhibition of active dose contains the mixture of alkenyl compound premature polymerization, and it comprises: (i) at least a alpha-carbon atom not with the secondary amine N-oxycompound of hydrogen atom; (ii) at least a iron containing compounds; (C) as suitably, nitro-compound; (D) as suitably, co-stabilizer.
Chinese patent relates to a kind of mixture No. 98806312.3, and it contains: (A) one or more contain alkenyl compound; (B) stablizer, it comprises: (b1) on one or more volatile alpha-carbon atoms not with the secondary amine nitroxyl compound of hydrogen atom; (b2) on one or more difficult evaporable alpha-carbon atoms not with the secondary amine nitroxyl compound of hydrogen atom; (b3) as needs, one or more fragrant nitro-compounds; (b4) as needs, one or more iron cpds.
In the Chinese patent No. 97197209.5 and No. 98806312.3, all not mainly essential component on the alpha-carbon atom with secondary amine nitroxyl (the N-oxygen base) compound of hydrogen atom.But nitroxyl (N-oxygen base) compound is expensive usually, also should not adopt in some occasion.In addition, in large-scale industrial application, also can cause a large amount of unwanted by products after a spot of polymkeric substance accumulation.So, always exist for the demand of cheap, respond well stopper.
In view of said circumstances, need exploitation can prevent the novel composition and the novel method of premature polymerization.
Summary of the invention
The purpose of this invention is to provide a kind of composition and method that suppresses premature polymerization.
The composition that the present invention relates to comprises: the vinyl compound of at least a free redical polymerization; And the poly-composition of the resistance of active dose, it comprises metal ion, halogen ion and ligand, this ligand contains donor atom, this donor atom is selected from oxygen, nitrogen, sulphur, phosphorus atom or its combination, and this metal ion is selected from titanium, molybdenum, rhenium, ruthenium, iron, rhodium, nickel, palladium, cobalt, osmium, cupric ion or its arbitrary combination; Wherein do not contain on the alpha-carbon atom not secondary amine nitroxyl compound in the composition with hydrogen atom.
The present invention also relates to a kind of method that is used to prevent the vinyl compound premature polymerization of at least a free redical polymerization, this method comprises: the poly-composition of resistance that adds active dose in the vinyl compound of described at least a free redical polymerization, the poly-composition of this resistance comprises: metal ion, halogen ion and ligand, this ligand contains donor atom, this donor atom is selected from oxygen, nitrogen, sulphur, phosphorus atom or its combination, and this metal ion is selected from titanium, molybdenum, rhenium, ruthenium, iron, rhodium, nickel, palladium, cobalt, osmium, cupric ion or its arbitrary combination; Wherein do not contain on the alpha-carbon atom not secondary amine nitroxyl compound in the poly-composition of resistance with hydrogen atom.
The invention still further relates to a kind of composition, it comprises: the vinyl compound of at least a free redical polymerization; And the poly-composition of the resistance of active dose, it comprises metal ion, halogen ion and ligand, this ligand contains donor atom, this donor atom is selected from oxygen, nitrogen, sulphur, phosphorus atom or its combination, and this metal ion is selected from titanium, molybdenum, rhenium, ruthenium, iron, rhodium, nickel, palladium, cobalt, osmium, cupric ion or its arbitrary combination; Wherein when iron ion, do not contain on the alpha-carbon atom not secondary amine nitroxyl compound in the composition with hydrogen atom.
Embodiment
The composition that the present invention relates to comprises: the vinyl compound of at least a free redical polymerization; And the poly-composition of the resistance of active dose, it comprises metal ion, halogen ion and ligand, this ligand contains donor atom, this donor atom is selected from oxygen, nitrogen, sulphur, phosphorus atom or its combination, and this metal ion is selected from titanium, molybdenum, rhenium, ruthenium, iron, rhodium, nickel, palladium, cobalt, osmium, cupric ion or its arbitrary combination; Wherein do not contain on the alpha-carbon atom not secondary amine nitroxyl compound in the composition with hydrogen atom.
The present invention also relates to a kind of method that is used to prevent the vinyl compound premature polymerization of at least a free redical polymerization, this method comprises: the poly-composition of resistance that adds active dose in the vinyl compound of described at least a free redical polymerization, the poly-composition of this resistance comprises: metal ion, halogen ion and ligand, this ligand contains donor atom, this donor atom is selected from oxygen, nitrogen, sulphur, phosphorus atom or its combination, and this metal ion is selected from titanium, molybdenum, rhenium, ruthenium, iron, rhodium, nickel, palladium, cobalt, osmium, cupric ion or its arbitrary combination; Wherein do not contain on the alpha-carbon atom not secondary amine nitroxyl compound in the poly-composition of resistance with hydrogen atom.
The invention still further relates to a kind of composition, it comprises: the vinyl compound of at least a free redical polymerization; And the poly-composition of the resistance of active dose, it comprises metal ion, halogen ion and ligand, this ligand contains donor atom, this donor atom is selected from oxygen, nitrogen, sulphur, phosphorus atom or its combination, and this metal ion is selected from titanium, molybdenum, rhenium, ruthenium, iron, rhodium, nickel, palladium, cobalt, osmium, cupric ion or its arbitrary combination; Wherein when iron ion, do not contain on the alpha-carbon atom not secondary amine nitroxyl compound in the composition with hydrogen atom.
The vinyl compound of free redical polymerization can be the have structural formula compound of (I) among the present invention:
Wherein, R
1, R
2, R
3And R
4Independently be hydrogen, C respectively
1-C
6-alkyl, C
2-C
6-thiazolinyl, replacement or unsubstituted aryl or heteroaryl or halogen do not replace or unsubstituted aryl or heterocyclic aryl group, perhaps R but do not exist simultaneously more than 2
1With R
3Common or R
2With R
4Saturated or the undersaturated C of common formation
3-, C
4-, C
5-or C
6-alkylidene bridge, 2 non-conterminous carbon atoms of as many as can be by N, NH, N (C in the alkylidene bridge
1-C
4-alkyl), N (C
6-C
10-aryl) or oxygen displacement.
C
1-C
6-alkyl comprises methyl, the ethyl straight chained alkyl until hexyl, also comprises corresponding branched alkyl group.Similarly, C
2-C
6-thiazolinyl comprises that vinyl, propenyl until vinyl, also comprise the group of saturated part branching.Replace or unsubstituted aryl or heterocyclic aryl comprise such as phenyl, pyridyl, alkyl phenyl or-pyridyl; as aminomethyl phenyl or-pyridyl; or ethylphenyl or-pyridyl; the thiazolinyl phenyl or-pyridyl; as ethenylphenyl or vinyl pyridine base; carboxyl phenyl or-pyridyl; the formyl radical phenyl or-pyridyl; the sulfo group phenyl or-pyridyl; hydroxy phenyl or-pyridyl; aminophenyl or-pyridyl, nitrophenyl or-pyridyl, also comprise naphthyl or the naphthyl that is replaced by alkyl, thiazolinyl, carboxyl, formyl radical, sulfo group, hydroxyl, amino or nitro etc.The general halogen that adopts is a fluorine or chlorine, also uses bromine sometimes.
For instance, if consider to contain aryl or heterocyclic aryl and C
1-C
6If the compound of-alkyl is and R
1, R
2, R
3And R
4Two of middle remainder is hydrogen, then the vinyl compound of free redical polymerization can be: 2 kinds of isomer (suitable-1-phenyl-1-butylene, anti--1-phenyl-1-butylene) of alpha-methyl styrene (2-phenyl-1-propylene), the cinnamic 2 kinds of isomer of Beta-methyl (suitable-1-phenyl-1-propylene, anti--1-phenyl-1-propylene), α-ethyl styrene (2-phenyl-1-butylene), β-ethyl styrene, and until α-hexyl benzene ethene (2-phenyl-1-octene) or the cinnamic 2 kinds of isomer of β-hexyl (suitable-1-phenyl-1-octene, anti--1-phenyl-1-octene).
Similarly, when replacing phenyl with pyridyl, can obtain compound: 2-pyridyl-1-propylene, suitable-1-pyridyl-1-propylene, anti--1-pyridyl-1-propylene, 2-pyridyl-1-butylene, suitable-1-pyridyl-1-butylene, anti--1-pyridyl-1-butylene, until 2-phenyl-1-octene and suitable-1-pyridyl-1-octene, anti--1-pyridyl-2 kinds of isomer of 1-octene.Be also included within the row of the vinyl compound of free redical polymerization of the present invention with respect to the different isomer that produce in position of the company's key that connects vinyl and pyridyl owing to the pyridyl nitrogen-atoms.Replaced by above-mentioned group as phenyl or pyridyl, available compound is as alpha-methyl styrene sulfonic acid (2-sulfo group phenyl-1-propylene), Alpha-Methyl nitrostyrolene (2-nitrophenyl-1-propylene), α-ethyl styrene sulfonic acid (2-sulfo group phenyl-1-butylene), α-ethyl-nitrobenzene ethene (2-nitrophenyl-1-butylene), and pyridine compounds and their similarly, and the cis of corresponding β substitution compound, trans-isomer(ide).Because substituting group is with respect to the position difference of phenyl-vinyl bonds on the phenyl ring, or because the different isomer that produce of relative position of pyridyl nitrogen-atoms, substituting group and the pyridyl-vinyl bonds of replacement are also included within the row of the vinyl compound of free redical polymerization of the present invention.
Selecting a substituting group is aryl or heterocyclic aryl, and another substituting group is C
2-C
6-thiazolinyl, and all the other two substituting groups can derive the vinyl compound of the free redical polymerization that replaces butadiene type when all being hydrogen.For example, 1-phenyl butadiene, 2-phenyl butadiene, 1-pyridyl divinyl, 2-pyridyl divinyl, and corresponding cis, trans-isomer(ide).Under the situation of pyridyl, because the isomer that nitrogen-atoms produces with respect to the difference of the position of pyridyl-vinyl key is also within the scope of application of the present invention.Above-mentioned various substituting group also may appear on aryl equally, here or the heterocyclic aryl.
In addition, the vinyl compound that the alleged free redical of the present invention replaces also can be the ethene of aryl or heterocyclic aryl replacement, as vinylbenzene, vinyl pyridine, Vinylstyrene, nitrostyrolene, styrene sulfonic acid, Vinyl toluene, if and suitable, the isomer of aforesaid compound.
The compound of structural formula (I) also can be single substituted vinyl compound, i.e. radicals R
1, R
2, R
3And R
4In have 3 to be hydrogen, only 1 is aryl or the heterocyclic aryl that does not replace or replace, as phenyl, pyridyl, ethenylphenyl, nitrophenyl, sulfo group phenyl and aminomethyl phenyl.If needed, compound also can be two substituted vinyl compound, i.e. radicals R
1, R
2, R
3And R
4In to have 2 or 4 be hydrogen, all the other then are aryl or heterocyclic aryl.Usually this compounds is the stilbene compound that symmetry replaces, as 4, and 4 '-diaminostilbene, 4,4 '-dinitrobenzene stilbene, 4,4 '-dinitrobenzene stilbene-2,2 '-disulfonic acid, 4,4 '-diaminostilbene-2,2 '-disulfonic acid or their cis, trans-isomer(ide).Certainly compound also can be owing to the different various isomer that produce in the relative vinyl of the substituting group position on fragrance or the heteroaromatic system.According to structural formula (I), radicals R in the above-mentioned stilbene compound
1, R
2, R
3And R
4In 2 be hydrogen, all the other groups are non-conterminous but identical, are followed successively by aminophenyl, nitrophenyl, nitro sulfo group phenyl and amino sulfo group phenyl.
In the composition involved in the present invention, also can adopt halide-containing, as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl bromide, chloroprene (chlorbutadiene) etc.
As R
1And R
3Or R
2And R
4Saturated or the undersaturated C of common composition
3-, C
4-, C
5-or C
6-alkylidene bridge then can be with R
2, R
4Replace and (or be equal to R naturally fully
1, R
3Replace) and obtain listed as described later compound
R wherein
2, R
4Can independently be respectively hydrogen or C
1-C
6-alkyl, wherein methyl or ethyl are particularly preferred alkyl.Alkylidene bridge on this compounds can also be further unsaturated, produces such as compound
This compounds comprises certainly owing to the different isomeric compounds that produce of relative position between each pair key.
In addition, also 2 non-conterminous carbon atoms of as many as in the compound can be replaced with N, NH, N (C
1-C
4-alkyl), N (C
6-C
10-aryl) or oxygen.The compound that obtains is following listed, and the present invention also comprises following compounds certainly because the different isomeric compounds that produce of the one or more relatively position of double bond of one or more heteroatomss:
N (C
1-C
4-alkyl) in, preferred alkyl is methyl and ethyl; N (C
6-C
10-aryl) in, preferred aryl groups is phenyl, right-tolyl and 2,4, the 6-trimethylphenyl.
Certainly, composition involved in the present invention not only comprises the vinyl compound of all kinds of free redical polymerizations and their mixture of isomers, the mixture that also comprises the vinyl compound of various free redical polymerizations itself is as the crude product that obtains in their preparation process.
In addition, the vinyl compound of the free redical polymerization that comparatively suits also can be the compound of tool structural formula (II): H
2C=CZ
4-Q-Z
1(II), wherein Q be chemical single bond, oxygen or-NZ
2-; Z
1Be
Or-Z
3Z
2Be hydrogen, C
1-C
4-alkyl is perhaps with Z
3Saturated or the undersaturated C of common formation
3-, C
4-or C
5-alkylidene bridge, 2 non-conterminous carbon atoms of as many as can be N, NH, N (C in the alkylidene bridge
1-C
4-alkyl), N (C
6-C
10-aryl) or oxygen replace; Z
3Be hydrogen, hydroxyl, cyano group, C
1-C
8Alkoxyl group, C
1-C
8Alkyl or and Z
2Saturated or the undersaturated C of common formation
3-, C
4-, or C
5The group of-alkylidene bridge, 2 non-conterminous carbon atoms of as many as can be N, NH, N (C in the alkylidene bridge
1-C
4-alkyl), N (C
6-C
10-aryl) or oxygen is replaced and two CH groups of as many as can be replaced by N.Z
4Be hydrogen or C
1-C
4Alkyl.
As Q in the structural formula (II) is chemical single bond, then Z
1Group is-CO-Z
3Group or Z
3Group itself.Z in the case
3Group may be hydroxyl or C
1-C
8Alkoxyl group as methoxyl group, oxyethyl group, propoxy-, tert.-butoxy, n-butoxy and 2-ethyl hexyl oxy, is a cyano group under the latter event.
Z
4Be hydrogen or C
1-C
4Alkyl, wherein preferred hydrogen and methyl.Thereby the vinylformic acid, methacrylic acid, its corresponding methyl, ethyl, propyl group, the tertiary butyl, normal-butyl and the 2-(ethyl hexyl) ester that produce, and vinyl cyanide and methacrylonitrile are the vinyl compound that preferably has the free redical polymerization of structural formula (II) in the present composition.
The vinyl compound that has the free redical polymerization of structural formula (II) in the present composition also can contain aerobic as variable Q.Preferred vinyl ester in this compounds, i.e. Z wherein
1Group correspondence-CO-Z
3Group can also be a vinyl ether, i.e. its Z
1Group and Z
3Group is identical, and its Z
3Be preferably C
1-C
8-alkyl group, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl or 2-ethylhexyl.
As variable Q be-NZ
2-group, then comparatively suitable Z
1Be-CO-Z
3Group.
Remove above-mentioned every, suitable Z
3Group also can be and-NZ
2-constitute the first ring of saturated or undersaturated 5-to 7-jointly, for example:
At above-mentioned Z
2, Z
3N (the C that mentions in the group
6-C
10-aryl) C in
6-C
10-aryl preferably includes can be by one or more C
1-C
4The phenyl that-alkyl replaces.Exist under two or more substituent situations, the total number of carbon atoms is no more than 4.On the phenyl ring this type of replaces situation to be had, for example 3 methyl, 1 methyl and 1 propyl group or 1 tertiary butyl.Can be at Z
2, Z
3Group N (C
6-C
10-aryl) C that exists in
1-C
4Other examples of-alkyl are above being mentioned.Possible C
10-aryl also comprises naphthyl.
Vinyl compound that is suitable, free redical polymerization can be N-vinyl formamide, N-vinyl-2-Pyrrolidone, N-vinyl-ε-Ji Neixianan, vinylformic acid, vinyl-acetic ester, vinyl cyanide, methyl acrylate, n-butylacrylate and above-mentioned C in the present composition
1-C
8-alkyl vinyl ether.
The poly-composition of resistance of the present invention comprises metal ion, halogen ion and ligand, this ligand contains donor atom, this donor atom is selected from oxygen, nitrogen, sulphur, phosphorus atom or its combination, and this metal ion is selected from titanium, molybdenum, rhenium, ruthenium, iron, rhodium, nickel, palladium, cobalt, osmium, cupric ion or its arbitrary combination.Metal ion should be in oxidation state, is preferably to have the oxidation state that maximum is closed valency, as Fe
3+, Cu
2+Deng.
Containing the oxygen ligand comprises such as vitriol, acetate, oxalate, Citrate trianion, tartrate, lactic acid salt, gluconate or acetylacetonate.Other ligands that contain oxygen or main oxygen containing metal ion (as ferric iron) are many cyclic ethers class also, such as the representative group of the open chain of spherical, cave-shaped, cave-shaped sphere, hemispherical, crown ligand or these ethers, and pod shape ligand.Except that Sauerstoffatom, also can contain nitrogen and/or sulphur and/or phosphorus and/or arsenic atom in the many representative group of this compounds.
In addition, also can adopt 10-phenanthroline, 1,8-naphtho-pyridine, 2 such as quadrol, 1,2 '-dipyridyl, 5,5 '-alkane generation-2,2-dipyridyl, dibenzo (b, i)-1,4,8,11-four azepines-(14)-nitrogenous sequestrant ligands such as annulene, and porphyrin ligand.Other nitrogenous ligands comprise phthalocyanine and derivative thereof.
In addition, also can adopt nitrogenous and ligand oxygen, for example ethylenediamine tetraacetic acid (EDTA) or complexon I, hydroxyquinoline and Whitfield's ointment.The preparation method of the ligand of this type of nitrogenous and oxygen is known, normally aromatics or heteroaromatic Alpha-hydroxy aldehyde and aliphatics or aromatic diamine or polyamines condensation is got.
Also can adopt such as benzenethiol, connect sulfur-bearing ligands such as sulphur carbon alcohols such as hexichol sulfuric acid and two sulphur carbonic acid classes.
Metal ion and halogen ion can coexist in metal halide.For example, as the desire iron halide, then the trivalent iron salt of chlorine and bromine can be used.
Metal ion also can be from metal species halogenide.The class iron halide compound that the present invention relates to comprises such as [Fe (CN)
6]
3-And [Fe (SCN)
3-X(H
2O)
3+X]
X+The thiocyanic acid complex compound series of (x=0,1,2).What should be used for the above-mentioned electronegative complex ion of trim is hydrogen ion, sodium ion, potassium ion, ammonium radical ion and N (CH to ion
3)
4 +What should be used for the above-mentioned positively charged complex ion of trim is chlorion, bromide anion, iodide ion, sulfate ion, H to ion
3CCO
2 -, chromate, BF
4 -And B (C
6H
5)
4 -
Among some embodiment, ligand is selected from
The 4-tert-butyl catechol,
O-Phenylene Diamine,
Mphenylenediamine,
N, N '-di-sec-butyl-p-phenyl enediamine,
Oxine,
Citric acid,
Salicylaldoxime,
1, the 10-phenanthroline,
2,2 '-dipyridyl,
4,4 '-dinonyl-2,2 '-dipyridyl,
1,4,8,11-tetramethyl--1,4,8, the 11-four azo-cycle tetradecanes,
1,1,4,7,10,10-hexamethyl Triethylenetetramine (TETA) and
Ethylenediamine tetraacetic acid (EDTA).
Among some embodiment, the vinyl compound of free redical polymerization is a vinylbenzene, and the poly-composition of resistance comprises in iron(ic) chloride, the cupric chloride at least a, and 4-tert-butyl catechol, 2,2 '-dipyridyl, N, N '-di-sec-butyl-p-phenyl enediamine, 4,4 '-dinonyl-2,2 '-dipyridyl, 1,1,4,7,10,10-hexamethyl Triethylenetetramine (TETA), O-Phenylene Diamine, mphenylenediamine, oxine, salicylaldoxime, ethylenediamine tetraacetic acid (EDTA), citric acid, 1,10-phenanthroline and 1,4,8,11-tetramethyl--1,4,8, at least a in the 11-four azo-cycle tetradecanes.
Among some embodiment, the vinyl compound of free redical polymerization is a vinylbenzene, and the poly-composition of resistance contains cupric chloride, and 2,2 '-dipyridyl, O-Phenylene Diamine, N, N '-di-sec-butyl-p-phenyl enediamine, oxine, 1,10-phenanthroline, 4,4 '-dinonyl-2,2 '-dipyridyl and 1,1,4,7,10, at least a in the 10-hexamethyl Triethylenetetramine (TETA).
Among some embodiment, the vinyl compound of free redical polymerization is a vinylbenzene, and the poly-composition of resistance comprises iron(ic) chloride, and 2,2 '-dipyridyl, 4-tert-butyl catechol, O-Phenylene Diamine, mphenylenediamine, N, N '-di-sec-butyl-p-phenyl enediamine, oxine, ethylenediamine tetraacetic acid (EDTA), citric acid, salicylaldoxime, salicylaldoxime, 1,10-phenanthroline, 4,4 '-dinonyl-2,2 '-dipyridyl, 1,4,8,11-tetramethyl--1,4,8, the 11-four azo-cycle tetradecanes and 1,1,4,7,10, at least a in the 10-hexamethyl Triethylenetetramine (TETA).
Among some embodiment, the vinyl compound of free redical polymerization is a vinylbenzene, and the poly-composition of resistance comprises iron(ic) chloride, N, N '-di-sec-butyl-p-phenyl enediamine and iron protochloride.
As suitably, also can comprise nitro-compound and one or more co-stabilizers in the composition, as comprise fragrant nitroso compound, thiodiphenylamine, quinone, Resorcinol and ethers thereof, phenol and ethers thereof, azanol, and phenylenediamine etc.
Suitable fragrant nitroso compound such as right-nitrosophenol, right-nitroso-group-neighbour-cresylol or right-nitroso-group-N, N-Diethyl Aniline or the like of comprising.
Co-stabilizer is also such as following fortified phenol or hydroquinone compound: the 4-tert-butyl catechol, the methoxyl group quinhydrones, 2, the 6-di-tert-butyl-4-methy phenol, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid Octadecane base ester, 1,1,2-three-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-three (3,5-two-tertiary butyl-4-hydroxy benzyl) isocyanuric acid ester, 1,3,5-three-[β-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) propionyloxy ethyl] isocyanuric acid ester or tetramethylolmethane four [β-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) propionic ester].
Among some embodiment, the poly-composition of resistance contains iron(ic) chloride, N, N '-di-sec-butyl-p-phenyl enediamine, and
Benzoquinones,
Tetrachlorobenzoquinone and
At least a in the 2,6 ditertiary butyl p cresol.
Metal ion and halogen ion also can be present in respectively in metallic compound and the halogenide before the vinyl compound that adds free redical polymerization.Among some embodiment, the vinyl compound of free redical polymerization is a vinylbenzene, and the poly-composition of resistance comprises ferric sulfate, N, N '-di-sec-butyl-p-phenyl enediamine and sodium-chlor.
Be not meant as not having the nitryl compound of the secondary amine of hydrogen atom on the secondary amine N-oxide compound that is not loaded with hydrogen atom on the α-C atom that is disclosed in the Chinese patent No. 97197209.5 and No. 98806312.3 and the alpha-carbon atom on the alpha-carbon atom that the present invention mentions with the secondary amine nitroxyl compound of hydrogen atom.Related composition of the present invention and method effectively suppress, delay the premature polymerization of the vinyl compound of free redical polymerization with low-cost material.
Consider the particular case of application, those skilled in the technology concerned can be by activity (effectively) dosage and the best relative proportion of other components in preliminary test decision nitro-compound, co-stabilizer and the poly-composition of resistance.
The poly-composition of the resistance of effective dose can be solid-state, suspension liquid or with states such as appropriate solvent dissolved solution, in purifying or fractionation is carried out preceding or carried out middle adding, with the inhibition premature polymerization.In some cases, each component of the poly-composition of resistance also should add respectively on different locus.
The suspension of the poly-composition of resistance or solution should be done the solvent preparation for water.In addition, alcoholic solvent such as methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol are also available, and be suitable, the mixture of also available they and water.With regard to the ester of corresponding vinylformic acid and alkyl acrylic, the preferred mixture of these alcohol or they and water.
In addition, also can be used as the ketone that is of suspension agent or solvent (if mixture of suitable alcohol and water), such as acetone, methyl ethyl ketone, methyl propyl ketone or methyl butyl ketone etc.; Dibasic alcohol, as ethylene glycol or propylene glycol or their alkyl monoether or diether, oligomeric or polymeric ethylene glycol (polyoxyethylene glycol) or propylene glycol (polypropylene glycol) and corresponding alkyl oxide thereof; And diamines, as quadrol or propylene diamine and corresponding alkyl monoether or diether, oligomeric or polymeric quadrol (polymine) and alkyl imino ether thereof.Certainly, the vinyl compound of free redical polymerization or its mixture also can be used as suspension agent or solvent.
And crude mixture also can be used as suspension agent and solvent.For example, if distillation purifying furnace oil (the resulting mixture of dehydrogenation ethylbenzene, its main component are vinylbenzene, ethylbenzene, toluene and other aromatic hydrocarbon that is further replaced) can use this mixture as suspension agent and/or solvent.
The poly-composition of resistance involved in the present invention also can be used for stability of organic materials, prevents effect of free radicals damage.It is for example polyacrylic ester, polyolefine that the alleged organic materials of the present invention can be understood as, plastics such as polyvinyl chloride.In addition, can also be the material that in automobile finish, exterior paint (wood preservative, masonry paint etc.), is used as binding agent, or mineral oil and lubricating oil; The composition that the present invention mentions also can add the product that is used to protect biomaterial, organic materials according to suitable proportion, as adding in the sunscreen product, plays skin care effect, certainly, can not add such as the deleterious additive of possibilities such as nitro-compound in the case.The resistance that those skilled in the relevant art can mention according to the present invention gathers composition, is made into the prescription that is fit to makeup.
Example
Following experimental example can be implemented this invention for the people who has general technical ability in this area reference is provided.But these examples are not limited to the scope of claim.
All chemical material available from Sigma's aldrich (Shanghai) trade Co., Ltd of Chinese Shanghai (Sigma-Aldrich (Shanghai) Trading Co., Ltd.).
Example 1
With the vinylbenzene buied by strainer with filtering stopper 4-tert-butyl catechol, the vinylbenzene that will not contain stopper then places test tube (every part sample 5 milliliters), adds the poly-composition of an amount of resistance more respectively.The poly-composition of resistance is solvent with methyl alcohol, and every kind of composition institute's metal halides and ligand see the following form shown in 1.Subsequently test tube is added a cover with film.Add a cover the back test tube and fed argon gas 3 minutes.Sample shifts out sample subsequently in 110 ℃ of oil bath heating 1 hour (part sample heating 2,3 or 4 hours) from test tube.Sample after the heating is added 45 ml methanol make precipitate of polystyrene.Sample by the micro-filtration paper of weighing, is collected solid-state polystyrene, place 105 ℃ of baking ovens oven dry and weigh.The polystyrene that reaction generates accounts for and does not contain the cinnamic mass percent of stopper and see Table 1.Also from the part sample, get trace and carry out the 1HNMR qualitative analysis.5.5ppm it is as shown in table 1 not contain the shared per-cent of characteristic peak of 1.8ppm polystyrene in the characteristic peak summation of cinnamic characteristic peak of stopper and 1.8ppm polystyrene.
Table 1
Example 2
With the vinylbenzene buied by strainer with filtering stopper 4-tert-butyl catechol, the vinylbenzene sample (100 milliliters every part) that will not contain stopper then places three neck round-bottomed flasks, flask connects prolong and tunger tube, adds respectively to cover with film after resistance gathers composition again.The poly-composition of resistance is solvent with methyl alcohol, and every kind of poly-composition institute of resistance metal-containing material, ligand and (contained in the part sample) the 3rd component are as shown in table 2 below.In flask, put into magnetic stirrer, at room temperature fed argon gas 15 minutes, put again, stir sample and continue to feed argon gas to 110 ℃ of oil bath heating to sample.From sample, extracted 5 ml samples every 1 hour with graduated syringe, add in 45 ml methanol and make precipitate of polystyrene.Sample by the micro-filtration paper of weighing, is collected solid-state polystyrene, place 105 ℃ of baking ovens oven dry and weigh.The polystyrene that generates with reaction difference heat-up time (be oil bath 1 hour～7 hours) accounts for and does not contain the cinnamic mass percent of stopper and see Table 2.
Table 2
Though describe the present invention in conjunction with the specific embodiments, those skilled in the art will appreciate that and to make many modifications and modification the present invention.Therefore, recognize that the intention of claims is to cover all such modifications and the modification in true spirit of the present invention and the scope.
Claims (15)
1. composition, it comprises:
The vinyl compound of at least a free redical polymerization, the vinyl compound of this at least a free redical polymerization is for having the compound of structural formula (I):
(I), wherein, R
1, R
2, R
3And R
4Independently be hydrogen, C respectively
1-C
6-alkyl, C
2-C
6-thiazolinyl, replacement or unsubstituted aryl or heteroaryl or halogen do not replace or unsubstituted aryl or heterocyclic aryl group, perhaps R but do not exist simultaneously more than 2
1With R
3Common or R
2With R
4Saturated or the undersaturated C of common formation
3-, C
4-, C
5-or C
6-alkylidene bridge, 2 non-conterminous carbon atoms of as many as can be by N, NH, N (C in the alkylidene bridge
1-C
4-alkyl), N (C
6-C
10-aryl) or oxygen displacement; And
The resistance of active dose gathers composition, it comprises metal ion, halogen ion and ligand, this ligand contains donor atom, this donor atom is selected from oxygen, nitrogen, sulphur, phosphorus atom or its combination, and this metal ion is selected from titanium, molybdenum, rhenium, ruthenium, iron, rhodium, nickel, palladium, cobalt, osmium, cupric ion or its arbitrary combination;
Wherein do not contain on the alpha-carbon atom not secondary amine nitroxyl compound in the composition with hydrogen atom.
2. composition as claimed in claim 1 is characterized in that the poly-composition of described resistance comprises metal halide and ligand.
3. composition as claimed in claim 1 is characterized in that the poly-composition of described resistance comprises metallic compound, halogenide and ligand.
4. as the described composition of the arbitrary claim of claim 1 to 3, it is characterized in that the poly-composition of described resistance further comprises in nitro-compound and the co-stabilizer at least a.
5. composition as claimed in claim 1, the vinyl compound that it is characterized in that described at least a free redical polymerization is a vinylbenzene, the poly-composition of described resistance comprises iron(ic) chloride, six Ferric Chloride Hydrateds, at least a in ferric sulfate and the cupric chloride, and 4-tert-butyl catechol, O-Phenylene Diamine, 2,2 '-dipyridyl, mphenylenediamine, oxine, 1,1,4,7,10,10-hexamethyl Triethylenetetramine (TETA), 4,4 '-dinonyl-2,2 '-dipyridyl, salicylaldoxime, N, N '-di-sec-butyl-p-phenyl enediamine, 1, the 10-phenanthroline, 1,4,8,11-tetramethyl--1,4,8, the 11-four azo-cycle tetradecanes, ethylenediamine tetraacetic acid (EDTA), sodium-chlor, at least a in iron protochloride and the citric acid.
6. composition as claimed in claim 5, it is at least a to it is characterized in that it further comprises in benzoquinones, tetrachlorobenzoquinone and the 2,6 ditertiary butyl p cresol.
7. as claim 1 or 5 described compositions, the vinyl compound that it is characterized in that described at least a free redical polymerization is a vinylbenzene, and the poly-composition of described resistance comprises cupric chloride, and 2,2 '-dipyridyl, O-Phenylene Diamine, N, N '-di-sec-butyl-p-phenyl enediamine, oxine, 1,10-phenanthroline, 4,4 '-dinonyl-2,2 '-dipyridyl and 1,1,4,7,10, at least a in the 10-hexamethyl Triethylenetetramine (TETA).
8. as claim 1 or 5 described compositions, the vinyl compound that it is characterized in that described at least a free redical polymerization is a vinylbenzene, and the poly-composition of described resistance comprises iron(ic) chloride, and 2,2 '-dipyridyl, the 4-tert-butyl catechol, O-Phenylene Diamine, mphenylenediamine, N, N '-di-sec-butyl-p-phenyl enediamine, oxine, ethylenediamine tetraacetic acid (EDTA), citric acid, salicylaldoxime, 1, the 10-phenanthroline, 4,4 '-dinonyl-2,2 '-dipyridyl, 1,4,8,11-tetramethyl--1,4,8, the 11-four azo-cycle tetradecanes and 1,1,4,7,10, at least a in the 10-hexamethyl Triethylenetetramine (TETA).
9. as claim 1 or 5 described compositions, the vinyl compound that it is characterized in that described at least a free redical polymerization is a vinylbenzene, the poly-composition of described resistance comprises iron(ic) chloride, N, N '-di-sec-butyl-p-phenyl enediamine, and it is at least a in benzoquinones, tetrachlorobenzoquinone and the 2,6 ditertiary butyl p cresol.
10. as claim 1 or 5 described compositions, the vinyl compound that it is characterized in that described at least a free redical polymerization is a vinylbenzene, and the poly-composition of described resistance comprises ferric sulfate, N, N '-di-sec-butyl-p-phenyl enediamine and sodium-chlor.
11. claim 1 or 5 described compositions, the vinyl compound that it is characterized in that described at least a free redical polymerization is a vinylbenzene, and the poly-composition of described resistance comprises iron(ic) chloride, N, N '-di-sec-butyl-p-phenyl enediamine and iron protochloride.
12. a method that is used to prevent the vinyl compound premature polymerization of at least a free redical polymerization, the vinyl compound of this at least a free redical polymerization is for having the compound of structural formula (I):
(I), wherein, R
1, R
2, R
3And R
4Independently be hydrogen, C respectively
1-C
6-alkyl, C
2-C
6-thiazolinyl, replacement or unsubstituted aryl or heteroaryl or halogen do not replace or unsubstituted aryl or heterocyclic aryl group, perhaps R but do not exist simultaneously more than 2
1With R
3Common or R
2With R
4Saturated or the undersaturated C of common formation
3-, C
4-, C
5-orC
6-alkylidene bridge, 2 non-conterminous carbon atoms of as many as can be by N, NH, N (C in the alkylidene bridge
1-C
4-alkyl), N (C
6-C
10-aryl) or oxygen displacement, this method comprises: the poly-composition of resistance that adds active dose in the vinyl compound of described at least a free redical polymerization, the poly-composition of this resistance comprises: metal ion, halogen ion and ligand, this ligand contains donor atom, this donor atom is selected from oxygen, nitrogen, sulphur, phosphorus atom or its combination, and this metal ion is selected from titanium, molybdenum, rhenium, ruthenium, iron, rhodium, nickel, palladium, cobalt, osmium, cupric ion or its arbitrary combination; Wherein do not contain on the alpha-carbon atom not secondary amine nitroxyl compound in the poly-composition of resistance with hydrogen atom.
13. method as claimed in claim 12, the vinyl compound that it is characterized in that described at least a free redical polymerization is a vinylbenzene, the poly-composition of described resistance comprises iron(ic) chloride, six Ferric Chloride Hydrateds, at least a in ferric sulfate and the cupric chloride, and 4-tert-butyl catechol, O-Phenylene Diamine, 2,2 '-dipyridyl, mphenylenediamine, oxine, 1,1,4,7,10,10-hexamethyl Triethylenetetramine (TETA), 4,4 '-dinonyl-2,2 '-dipyridyl, salicylaldoxime, N, N '-di-sec-butyl-p-phenyl enediamine, 1, the 10-phenanthroline, 1,4,8,11-tetramethyl--1,4,8, the 11-four azo-cycle tetradecanes, ethylenediamine tetraacetic acid (EDTA), sodium-chlor, at least a in iron protochloride and the citric acid.
14. method as claimed in claim 13 is characterized in that the poly-composition of described resistance further comprises in benzoquinones, tetrachlorobenzoquinone and the 2,6 ditertiary butyl p cresol at least a.
15. a composition, it comprises:
The vinyl compound of at least a free redical polymerization, the vinyl compound of this at least a free redical polymerization is for having the compound of structural formula (I):
(I), wherein, R
1, R
2, R
3And R
4Independently be hydrogen, C respectively
1-C
6-alkyl, C
2-C
6-thiazolinyl, replacement or unsubstituted aryl or heteroaryl or halogen do not replace or unsubstituted aryl or heterocyclic aryl group, perhaps R but do not exist simultaneously more than 2
1With R
3Common or R
2With R
4Saturated or the undersaturated C of common formation
3-, C
4-, C
5-or C
6-alkylidene bridge, 2 non-conterminous carbon atoms of as many as can be by N, NH, N (C in the alkylidene bridge
1-C
4-alkyl), N (C
6-C
10-aryl) or oxygen displacement; And
The resistance of active dose gathers composition, it comprises metal ion, halogen ion and ligand, this ligand contains donor atom, this donor atom is selected from oxygen, nitrogen, sulphur, phosphorus atom or its combination, and this metal ion is selected from titanium, molybdenum, rhenium, ruthenium, iron, rhodium, nickel, palladium, cobalt, osmium, cupric ion or its arbitrary combination;
Wherein when iron ion, do not contain on the alpha-carbon atom not secondary amine nitroxyl compound in the composition with hydrogen atom.
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| PCT/US2011/050632 WO2012033800A1 (en) | 2010-09-09 | 2011-09-07 | Composition and method for inhibiting premature polymerization |
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| US9944577B2 (en) | 2012-10-25 | 2018-04-17 | Baker Hughes, A Ge Company, Llc | Hydroquinone compounds for inhibiting monomer polymerization |
| US9611336B2 (en) | 2012-10-25 | 2017-04-04 | Baker Hughes Incorporated | Quinone compounds for inhibiting monomer polymerization |
| DE102012223695A1 (en) * | 2012-12-19 | 2014-06-26 | Basf Se | Process for the stabilization of polymerizable compounds |
| CN106187768A (en) * | 2016-07-12 | 2016-12-07 | 中国石油化工股份有限公司 | For the collaborative suppressing method that vinyl acetate polymerization is out of control |
| CN111072831B (en) * | 2019-12-27 | 2021-07-09 | 中国科学技术大学 | Multifunctional polar polyolefin material and metal complex material thereof, preparation method and application |
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| CN101450983A (en) * | 2007-12-05 | 2009-06-10 | 华东理工大学华昌聚合物有限公司 | Synthetic process of high temperature resistant epoxy vinyl ester resin |
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| DE19651307A1 (en) | 1996-12-10 | 1998-06-18 | Basf Ag | Mixtures of compounds containing vinyl group-containing compounds and stabilizers |
| DE19725519A1 (en) | 1997-06-17 | 1998-12-24 | Basf Ag | Mixture of substances containing compounds containing vinyl groups and stabilizers |
| US5854386A (en) * | 1997-08-25 | 1998-12-29 | Arco Chemical Technology, L.P. | Stabilizers for polymer polyols |
| DE19922103A1 (en) * | 1999-05-17 | 2000-11-23 | Basf Ag | Inhibiting polymerisation of vinyl monomers using composition containing nitroxyl compound, a preferably aromatic nitro compound as retarder, oxygen and optionally transition metal compound and co-stabilizer |
| US6018078A (en) * | 1999-06-23 | 2000-01-25 | First Chemical Corporation | Stabilized N-nitrosohydroxylamines |
| US7696290B2 (en) * | 2004-12-03 | 2010-04-13 | Crompton Corporation | Aromatic sulfonic acids, amines, and nitrophenols in combination with nitroxyl radical-containing compounds or C-nitrosanilines as polymerization inhibitors |
| DE102005057894A1 (en) * | 2005-12-02 | 2007-06-06 | Basf Ag | Stabilized polymerizable mixtures |
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| Title |
|---|
| Copper(I)-Mediated Radical Polymerization of Methacrylates in Aqueous Solution;Sébastien Perrier et al.;《Journal of Polymer Science: Part A: Polymer Chemistry》;20010515;第39卷;第1696-1707页 * |
| Sébastien Perrier et al..Copper(I)-Mediated Radical Polymerization of Methacrylates in Aqueous Solution.《Journal of Polymer Science: Part A: Polymer Chemistry》.2001,第39卷第1696-1707页. |
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