FR2598711A1 - Sulphur-containing polymeric products with main polymer backbone and linear or branched pendant residues connected at one or more of their ends to the said backbone, process for their manufacture and their applications to the extraction and/or separation of heavy metals - Google Patents
Sulphur-containing polymeric products with main polymer backbone and linear or branched pendant residues connected at one or more of their ends to the said backbone, process for their manufacture and their applications to the extraction and/or separation of heavy metals Download PDFInfo
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- FR2598711A1 FR2598711A1 FR8606840A FR8606840A FR2598711A1 FR 2598711 A1 FR2598711 A1 FR 2598711A1 FR 8606840 A FR8606840 A FR 8606840A FR 8606840 A FR8606840 A FR 8606840A FR 2598711 A1 FR2598711 A1 FR 2598711A1
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- c2h4s
- backbone
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- linear
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- 229920000642 polymer Polymers 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000000926 separation method Methods 0.000 title claims abstract description 6
- 238000000605 extraction Methods 0.000 title claims abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title claims abstract 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 4
- 239000005864 Sulphur Substances 0.000 title 1
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 240000002234 Allium sativum Species 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 235000004611 garlic Nutrition 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 description 18
- 239000011324 bead Substances 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 7
- 125000002123 sulfanediylbis(methylene) group Chemical group [H]C([H])(*)SC([H])([H])* 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002609 medium Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910002666 PdCl2 Inorganic materials 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 101100219382 Caenorhabditis elegans cah-2 gene Proteins 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910010084 LiAlH4 Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000004662 dithiols Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- -1 thioether macrocycles Chemical class 0.000 description 2
- PAEMPWLDXSJQRU-UHFFFAOYSA-N 1,1'-Thiobisethanethiol Chemical compound CC(S)SC(C)S PAEMPWLDXSJQRU-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- PLKWCSILUGGUOA-UHFFFAOYSA-N 1-chloro-1-(1-chloropropylsulfanyl)propane Chemical compound CCC(Cl)SC(Cl)CC PLKWCSILUGGUOA-UHFFFAOYSA-N 0.000 description 1
- HWNBTCAMDISERN-UHFFFAOYSA-N 2-[2-(2-methylsulfanylethylsulfanyl)ethylsulfanyl]ethanethiol Chemical compound CSCCSCCSCCS HWNBTCAMDISERN-UHFFFAOYSA-N 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- KWHDXJHBFYQOTK-UHFFFAOYSA-N heptane;toluene Chemical compound CCCCCCC.CC1=CC=CC=C1 KWHDXJHBFYQOTK-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- DNAHRRFQXGRERW-UHFFFAOYSA-N propyl thiohypochlorite Chemical compound CCCSCl DNAHRRFQXGRERW-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G85/00—General processes for preparing compounds provided for in this subclass
- C08G85/004—Modification of polymers by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
Abstract
Description
L'invention concerne à titre de produits industriels nouveaux, des produits polymères comportant un squelette polymère et des résidus pendants linéaires ou ramifiés, accrochés par une ou plusieurs de leurs extrémités audit squelette, caractérisés en ce que les résidus pendants comportent chacun au moins une séquence li néaire de la forme
S-(C2H4s) n avec n > 1.The invention relates, as new industrial products, to polymeric products comprising a polymer backbone and linear or branched pendant residues attached by one or more of their ends to said backbone, characterized in that the pendant residues each comprise at least one sequence li naire of the form
S- (C2H4s) n with n> 1.
L'invention concerne également la synthèse de ces polymères et leurs utilisations en particulier dans le domaine de l'extraction et/ou de la séparation des métaux en solution. The invention also relates to the synthesis of these polymers and their uses, in particular in the field of extraction and / or separation of metals in solution.
De nombreux travaux ont été consacrés à l'épu- ration des rejets industriels contenant des métaux. Il est connu d'utiliser, pour éliminer ces métaux, des agents complexants de ces métaux, mais se pose alors le problème de la séparation du métal complexé du milieu. Many studies have been devoted to the treatment of industrial discharges containing metals. It is known to use, to remove these metals, complexing agents of these metals, but then the problem arises of the separation of the complexed metal from the medium.
Une solution pour éviter ce problème consiste à utiliser un agent complexant insoluble ou à fixer un agent complexant sur un support insoluble. Des composés soufrés de ce type sont connus. M. Tomoi, O. Abe, N. Takasu,
H. Kakiushi (Makromol. Chem. 184, 2431-2436 (1933) ont étudié la synthèse et les propriétés complexantes de macrocycles polythioéthers supportés par des polymères.One solution to avoid this problem is to use an insoluble complexing agent or to fix a complexing agent on an insoluble support. Sulfur compounds of this type are known. Mr Tomoi, O. Abe, N. Takasu,
H. Kakiushi (Makromol Chem 184, 2431-2436 (1933) studied the synthesis and complexing properties of polythioether macrocycles supported by polymers.
Mais la synthèse délicate des macrocycles thioéthers (thioéthercouronnes) rend ces produits chers ; par ailleurs, la rigidité des macrocycles est un facteur limitant pour la complexation. En outre, on connait des résines commerciales portant des groupements thiols, en particulier des résines à matrice en polystyrène macroporeux portant des groupements fonctionnels SH, mais ces résines présentent des problèmes de stabilité liés notamment à leur sensibilité à l'acidité du milieu et à l'oxydation, ce qui nécessite des régénérations périodiques.But the delicate synthesis of thioether macrocycles (thioethercouronnes) makes these products expensive; moreover, the rigidity of the macrocycles is a limiting factor for the complexation. In addition, commercial resins bearing thiol groups are known, in particular macroporous polystyrene matrix resins carrying SH functional groups, but these resins have stability problems related in particular to their sensitivity to the acidity of the medium and to the presence of oxidation, which requires periodic regeneration.
On a également proposé récemment (VF Fadeeva
Tetsu, Metally Moscou, 1985, 10, 49-50) d'utiliser pour la fixation du mercure des thioéthers polymères de la forme (CH2s) n qui présentent l'avantage d'être synthétisés de fanon relativement simple, encore que le contrôle de la réaction soit délicat, par condensation du formaldéhyde avec le sulfure de sodium, mais de tels produits dans lesquels les éléments complexants se trouvent dans le squelette n'offrent pas une accessibilité suffisante des atomes de soufre.We also proposed recently (VF Fadeeva
Tetsu, Metally Moscow, 1985, 10, 49-50) to use, for the fixation of mercury, polymeric thioethers of the form (CH2s) n which have the advantage of being synthesized with a relatively simple baffle, although the control of the reaction is delicate, by condensation of formaldehyde with sodium sulphide, but such products in which the complexing elements are in the backbone do not offer sufficient accessibility of the sulfur atoms.
Les produits selon l'invention pallient les inconvénients des différents produits soufrés immobilisés connus jusqu'à présent en permettant
- du fait de la bonne accessibilité des groupements thioéthers, des cinétiques rapides et des capacités enlevées de fixation des métaux
- du fait de la présence de groupements "pen dants" une bonne résistance chimique et mécanique, puisque la coupure d'un groupement pendant n'entraîne pas la dégradation mécanique du produit, ce qui serait le cas si les groupements complexants faisaient partie du squelette.The products according to the invention overcome the disadvantages of the various immobilized sulfur products known until now by allowing
- because of the good accessibility of the thioether groups, the fast kinetics and the removed capacities of fixation of the metals
- Due to the presence of "pendant" groups a good chemical and mechanical resistance, since the cleavage of a pendant group does not lead to the mechanical degradation of the product, which would be the case if the complexing groups were part of the skeleton .
La présente invention concerne donc des produits comportant un squelette polymère de motif A et des groupements pendants R, linéaires ou ramifiés et reliés en une ou plusieurs de leurs extrémités audit squelette et comportant chacun au moins une chaîne linéaire de la forme S-(C2H4S)n avec n > 1. The present invention therefore relates to products comprising a polymer backbone of unit A and linear or branched pendant groups R and connected at one or more of their ends to said backbone and each comprising at least one linear chain of the form S- (C2H4S) n with n> 1.
Comme exemple de squelette polymère, on citera des matrices organiques comme le polystyrène, les polymères acryliques ou méthacryliques, l'agarose, les polyamides et des matrices inorganiques comme, par exemple, des silices fonctionnalisées ou non. As an example of a polymer backbone, mention may be made of organic matrices such as polystyrene, acrylic or methacrylic polymers, agarose, polyamides and inorganic matrices such as, for example, functionalized or non-functional silicas.
Les groupements -R comprenant au moins un chaînon -S(C2H4S)n avec n > i peu-ent en particulier être de l'une des formes suivantes :
R1A' où R1 désigne une chaîne linéaire de la forme -S(C2H4S)n avec n > , I et A' désigne de l'hydrogène, un alkyle ou un motif polymèrique identique à A appartenant ou non à la même chaîne que A
R2XR3A' où A a la signification donnée précédemment, R2 et R3 sont des groupements itiques ou différents de la forme -S(C2H4S)n avec n > 1 e où X désigne un groupement divalent choisi parmi les groupements
où A' et A' 2 sont identiques ou différents et ont la signification donnée précédemment pour A' et R , R5 et R6 sont identiques ou différents de la forme -S(C2H4S)n avec n > 1 et Y est un groupement trivalent choisi parmi les groupements :
The groups -R comprising at least one -S (C2H4S) n group with n> i may in particular be of one of the following forms:
Where R1 denotes a linear chain of the form -S (C2H4S) n with n>, I and A 'denote hydrogen, an alkyl or a polymeric unit identical to A belonging or not to the same chain as A;
R2XR3A 'where A has the meaning given above, R2 and R3 are itic or different groups of the form -S (C2H4S) n with n> 1 e where X denotes a divalent group chosen from groups
where A 'and A' 2 are the same or different and have the meaning given above for A 'and R, R5 and R6 are the same or different from the form -S (C2H4S) n with n> 1 and Y is a trivalent group chosen among the groupings:
L'invention concerne également des procédés de fabrication des produits de l'invention : ils peuvent d'une façon générale être obtenus soit par greffage de groupes pendants sur des polymères activés susceptibles de réagir avec des réactifs comprenant des groupements S-(C2H4S) avec n a 1 (procédé I), soit par polymérisation ou copolymérisation de monomères contenant l'enchaî- nement désiré dans le groupement "pendant" du polymère final (procédé II). The invention also relates to processes for producing the products of the invention: they can generally be obtained either by grafting pendant groups onto activated polymers capable of reacting with reagents comprising S- (C2H4S) groups with No. 1 (method I), or by polymerization or copolymerization of monomers containing the desired linkage in the "pendant" group of the final polymer (method II).
Comme polymère activé dans le procédé I, on citera : le polystyrène chlorométhylé de motif
es silices activées
Comme groupernts a greffer dans le procédé I, on citera
- les chaînes linéaires susceptibles de se greffer en une de leurs extrémités sur le squelette polymère, du type
HS -#C2H4S#- CH3 avec n > 1
- les chaînes linéaires susceptibles de se greffer en deux de leurs extrémités sur la chaîne principale du type
HS -#C2H4S#n H avec n > 1
les groupements présentant plusieurs ramifications comprenant chacune un motif S-(C2H4S)n avec n > 1, du type ::
As activated polymer in process I, mention may be made of: chloromethylated polystyrene
activated silicas
As groups to be grafted into process I, mention will be made of
linear chains capable of grafting at one of their ends onto the polymer skeleton, of the type
HS - # C2H4S # - CH3 with n> 1
the linear chains capable of being grafted in two of their ends on the main chain of the type
HS - # C2H4S # n H with n> 1
groups having several branches each comprising a S- (C2H4S) n unit with n> 1, of the type ::
Le procédé II utilisera avantageusement en vue de la polymérisation ou de la copolymérisation des monomères de la forme
Process II will advantageously be used for the polymerization or copolymerization of monomers of the form
La présente invention concerne également des applications des produits de l'invention en particulier leurs applications pour le traitement par voie solide/ liquide de solutions aqueuses à pH 4 7 de métaux lourds en vue de leur extraction et/ou de leur séparation. The present invention also relates to applications of the products of the invention, in particular their applications for the solid / liquid treatment of aqueous solutions at pH 47 of heavy metals with a view to their extraction and / or their separation.
Les produits solides de l'invention pourront être utilisés sous différentes formes pour ce traitement en particulier sous forme de lit de billes. The solid products of the invention may be used in various forms for this treatment, in particular in the form of a bed of beads.
Les solutions de métaux lourds à traiter seront en particulier sous forme de milieu chlorhydrique, sulfurique ou nitrique. The solutions of heavy metals to be treated will be in particular in the form of hydrochloric, sulfuric or nitric medium.
Exemples
Les exemples suivants, donnés à titre non limitatif, ont été réalisés par greffage de groupements "pendants" sur des billes de polystyrène chlorométhylé à 6,5 z de divinylbenzbne dont le diamètre des pores est de 1000 A et le taux de chlore de 20 %.Examples
The following examples, given in a non-limiting manner, were carried out by grafting "pendant" groups onto 6.5% chloromethyl polystyrene beads of divinylbenzene having a pore diameter of 1000 A and a chlorine content of 20%. .
Pour plus de simplicité, on parlera dans les exemples de polystyrène. For simplicity, we will speak in the examples of polystyrene.
Exemple 1
Résine 1, de motif
Example 1
Resin 1, pattern
A. Synthèse
Réactifs
- éthanol "absolu" distillé sur Mg (100 ml)
- sodium : 1,15 g (0,05 mole)
- mercapto-2-éthyl sulfure tech. 90 % distillé sous pression réduite : ,o3 g (0,44 mole) répondant à l'analyse élémentaire suivante
Théorique Expérimentale
% C = 31,13 t C = 31,21
% H = 6,53 % H = 6,59
% S = 62,34 % S = 62,35
Total (C, H, S) = 100,15 %
Température d'ébullition : 57-590C/0,01 mm Hg
THF distillé sur CaH2 puis sur LiAlH4 (100 ml)
Billes de polystyrène chlorométhylé (5,9 mmoles
Cl/g) réticulé avec 6,5 % DVB, lavées avec des mélanges eau-THF puis du THF. Séchage à 600C pendant 12 heures sous vide : 5,0 g.A. Summary
Reagents
- "absolute" ethanol distilled on Mg (100 ml)
sodium: 1.15 g (0.05 mol)
mercapto-2-ethyl sulfide tech. 90% distilled under reduced pressure: o3 g (0.44 mol) corresponding to the following elemental analysis
Experimental Theoretical
% C = 31.13 t C = 31.21
% H = 6.53% H = 6.59
% S = 62.34% S = 62.35
Total (C, H, S) = 100.15%
Boiling temperature: 57-590C / 0.01 mm Hg
THF distilled on CaH2 then on LiAlH4 (100 ml)
Chloromethylated polystyrene beads (5.9 mmol
Cl / g) cross-linked with 6.5% DVB, washed with THF-water and then THF mixtures. Drying at 600C for 12 hours under vacuum: 5.0 g.
Mode opératoire
La manipulation se déroule sous atmosphère inerte dans un tricol équipé d'un réfrigérant, en introduisant successivement l'éthanol puis le sodium ; apres dissolution totale du sodium, on introduit le dithiol dissous dans 100 ml de THF anhydre puis les billes de polystyrène.Operating mode
The handling is carried out under an inert atmosphere in a tricolor equipped with a refrigerant, successively introducing ethanol then sodium; after complete dissolution of the sodium, the dissolved dithiol is introduced into 100 ml of anhydrous THF and then the polystyrene beads.
On chauffe sous reflux pendant environ 80 heures en agitant légèrement, puis on récupère les billes par filtration. Celles-ci sont lavées (eau-THF) et extraites au
Soxhlet avec du THF sec pendant 16 heures. Après séchage, on obtient 5,9 g de billes greffées.The mixture is refluxed for approximately 80 hours with gentle stirring and the beads are recovered by filtration. These are washed (water-THF) and extracted
Soxhlet with dry THF for 16 hours. After drying, 5.9 g of grafted beads are obtained.
Analyse élémentaire
C = 9,7 t ; H = 6,79 % ; S = 19,97 % ; Cl = 3,26 %
T (C, H, S, Cl) = 99,78 %
Le rendement du greffage basé sur la substitution du chlore est de 81 %. La capacité calculée d'après l'analyse élémentaire est de 2,1 mmoles de ligand/g de bille greffée.Elemental analysis
C = 9.7 t; H, 6.79%; S = 19.97%; Cl = 3.26%
T (C, H, S, Cl) = 99.78%
The graft yield based on chlorine substitution is 81%. The capacity calculated from the elemental analysis is 2.1 mmol ligand / g grafted bead.
B. Capacité de complexation des métaux
L'étude des capacités est menée en milieu aqueux en mettant les billes greffées en contact avec des concentrations croissantes de solution des différents métaux.B. Complexity of metals
The study of the capacities is carried out in an aqueous medium by putting the grafted balls in contact with increasing concentrations of solution of the different metals.
Les capacités maximales sont données ci-après
Capacités maximales
Milieu (m eq.jg de bille)
HgCl2 ; H2O pH 3-3,5 6,1
Hg(N03)2 ; 0,1 N HNO3 1,6
HgSO4 ; 1 N H2S04 * 1,4
PdCl2 ; 0,1 N HCl 0,29
PdCl2 ; 1 N HCl 0,25
CuCl2 ; H20 0,1 CdCl2 ; H20 < 0,1
FeCl3 ; 0,1 N HCl < 0,1
AgNO3 ; H2O 4,4
C. Cinétique de complexation
L'étude est réalisée sur une solution de chlorure mercurique en milieu aqueux (pH - 3,) en utilisant un rapport métal/ligand de 40. Le temps de demi-équilibre (50 % de capacité) est de 20 minutes, le temps d'équilibre (90 % de la capacité) est de 4-6 heures.Maximum capacities are given below
Maximum capacities
Middle (m eq.jg of ball)
HgCl2; H2O pH 3-3.5 6.1
Hg (NO 3) 2; 0.1 N HNO3 1.6
HgSO4; 1 N H2S04 * 1.4
PdCl2; 0.1 N HCl 0.29
PdCl2; 1 N HCl 0.25
CuCl2; H20 0.1 CdCl2; H20 <0.1
FeCl3; 0.1 N HCl <0.1
AgNO3; H2O 4.4
C. Kinetics of complexation
The study is carried out on a solution of mercuric chloride in aqueous medium (pH - 3,) using a metal / ligand ratio of 40. The half-equilibrium time (50% of capacity) is 20 minutes, the time of balance (90% of capacity) is 4-6 hours.
Exemple 2 - Résine 2, de motif
Example 2 - Resin 2, pattern
A. Synthèse
a) Préparation du greffon (tétrathia-1,4,7,10undécane)
On a réalisé la synthèse de ce composé qui n'est pas commercialisé.A. Summary
a) Preparation of the graft (tetrathia-1,4,7,10undecane)
The synthesis of this compound which is not commercialized was carried out.
Réactifs
Ethanol "absolu" distillé sur Mg (100 ml)
Sodium : 1,20 g (0,052 mole)
Mercapto-2-éthyl sulfure distillé : 8,52 g (0,052 mole)
Chloro-2-éthylméthylsulfure, 97 % 5,53 g
(0,050 mole). Reagents
Ethanol "absolute" distilled on Mg (100 ml)
Sodium: 1.20 g (0.052 mole)
Mercapto-2-ethyl distilled sulfide: 8.52 g (0.052 mol)
Chloro-2-ethylmethylsulfide, 97% 5.53 g
(0.050 moles)
Mode opératoire
Dans un tricol équité d'un réfrigérant, on dissout le sodium dans l'éthanol sous atmosphère inerte après dissolution totale du sodium, on introduit le dithiol suivi de l'addition goutte à goutte de chloro-2éthylméthylsulfure en portant le milieu réactionnel sous reflux. On maintient l'agitation et le chauffage pendant 24 heures, temps au bout duquel on filtre le mélange réactionnel. Le filtrat est distillé et le résidu est repris dans 250 ml de chloroforme. La phase organique est lavée à l'eau, séchée puis distillée sous pression réduite. On obtient 2,8 g (rendement 25 %) de produit pur après recristallisation dans le mélange toluèneheptane.Operating mode
In a tricolor fairness of a condenser, the sodium is dissolved in ethanol under an inert atmosphere after total dissolution of sodium, the dithiol is introduced followed by the dropwise addition of chloro-2-methylmethylsulfide while bringing the reaction medium under reflux. Stirring and heating are maintained for 24 hours, after which time the reaction mixture is filtered. The filtrate is distilled and the residue is taken up in 250 ml of chloroform. The organic phase is washed with water, dried and then distilled under reduced pressure. 2.8 g (25% yield) of pure product are obtained after recrystallization from tolueneheptane.
Analyse élémentaire
Théorique Expérimentale
% C = 36,80 % C = 36,66
% H = 7,06 % H = 6,59
% S = 56,14 % S = 56,07
Total (C, H, S) = 99,32 %
Point de fusion = 88-920C
b) Greffage sur bille de polystyrène
Réactifs
Ethanol "absolu" distillé sur Mg (75 ml)
Sodium : 0,18 g (7,8 mmoles)
Tétrathia-1,4,7,10-undécane : 1,76 g (7,8 mmoles)
THF distillé sur CaH2 puis sur LiAlH4 (100 ml)
Billes lavées puis séchées à 600C pendant 12 heures sous vide : 1,0 g.Elemental analysis
Experimental Theoretical
% C = 36.80% C = 36.66
% H = 7.06% H = 6.59
% S = 56.14% S = 56.07
Total (C, H, S) = 99.32%
Melting point = 88-920C
b) Grafting on polystyrene ball
Reagents
Ethanol "absolute" distilled on Mg (75 ml)
Sodium: 0.18 g (7.8 mmol)
1,4,7,10-tetrathia-undecane: 1.76 g (7.8 mmol)
THF distilled on CaH2 then on LiAlH4 (100 ml)
Beads washed and then dried at 600C for 12 hours under vacuum: 1.0 g.
Mode opératoire
Sous atmosphère inerte, on dissout à froid le sodium dans 75 ml d'éthanol anhydre, puis le composé soufré synthétisé est introduit dans le tricol. Le mélange est porté sous reflux après l'addition du THF et des billes. On maintient une agitation légère et le chauffage pendant 80 heures. Les billes sont récupérées par filtration, lavées, extraites au Soxhlet et séchées sous vide. On obtient 1,87 g de billes greffées (rendement basé sur le chlore : 80 %) contenant 31,8 % de soufre. La capacité calculée est de 2,4-2,5 mmoles de ligand par gramme de billes greffées.Operating mode
Under an inert atmosphere, the sodium is dissolved cold in 75 ml of anhydrous ethanol, and the sulfur compound synthesized is introduced into the tricol. The mixture is refluxed after addition of THF and beads. Mild agitation is maintained and heating for 80 hours. The beads are recovered by filtration, washed, extracted with Soxhlet and dried under vacuum. 1.87 g of grafted beads (yield based on chlorine: 80%) containing 31.8% of sulfur are obtained. The calculated capacity is 2.4-2.5 mmol of ligand per gram of grafted beads.
La composition des produits a été déterminée par analyse élémentaire : % C = 59,93 ; % H = 6,85 8 S = 31,83 ; % Cl = 0,92. The composition of the products was determined by elemental analysis:% C = 59.93; % H = 6.85 δ S = 31.83; % Cl = 0.92.
T (C, H, S, Cl) = 99,53 %
B. Capacité de complexation des métaux
On procède comme dans l'exemple 1 en remplaçant la résine 1 par la résine 2. Les capacités maximales obtenues en fonction du milieu sont les suivantes
Capacités maximales
Milieu (m eq./g. de billes)
HgCl2 ; H2O pH 3-3,5 5,2
Hg(NO3)2 ; HNO3 0,1 N 1,1
PdCl2 ; HCl 0,1 N 1,1
PdCl2 ; HCl 1 N 1,0
AgNO3 ; H2O 5,4
CdCl2 ; H2O < 0,1
CuCl2 ; H2O < 0,5
CuCl2 ; HCl 1N 0,1
FeCl3 ; HCl 0,1 N < 0,1
C. Cinétique de complexation
L'étude réalisée dans les mêmes conditions que pour la résine 1 conduit à un temps de demi-équilibre de 5-7 minutes et à un temps d'équilibre de 12 heures.T (C, H, S, Cl) = 99.53%
B. Complexity of metals
The procedure is as in Example 1, replacing the resin 1 with the resin 2. The maximum capacities obtained according to the medium are as follows:
Maximum capacities
Medium (meq / g of beads)
HgCl2; H2O pH 3-3.5 5.2
Hg (NO3) 2; HNO3 0.1 N 1.1
PdCl2; 0.1 N HCl 1.1
PdCl2; HCl 1 N 1.0
AgNO3; H2O 5.4
CdCl2; H2O <0.1
CuCl2; H2O <0.5
CuCl2; HCl 1N 0.1
FeCl3; 0.1 N HCl <0.1
C. Kinetics of complexation
The study carried out under the same conditions as for resin 1 leads to a half-equilibrium time of 5-7 minutes and an equilibrium time of 12 hours.
Exemple 3 - Résine 3, de motif
Example 3 - Resin 3, pattern
A. Synthèse
a) Synthèse du greffon. HS(C2H4S)2CH3
On procède comme à l'exemple 2 suivant le schéma réactionnel suivant
A. Summary
a) Synthesis of the graft. HS (C2H4S) 2CH3
The procedure is as in Example 2 according to the following reaction scheme
<tb> <SEP> HS/CH <SEP> ru <SEP> + <SEP> 2 <SEP> a
<tb> <SEP> HS <SEP> H <SEP> + <SEP> Cl <SEP> S-CH3
<tb> EtO <SEP> Na <SEP> /EtOH <SEP> / <SEP> a <SEP> r <SEP> + <SEP> CH2
<tb> <SEP> reflux <SEP> HS <SEP> S <SEP> / <SEP> S-CH3
<tb>
+ produits secondaires
Le rendement obtenu est de 60 %, en utilisant
un excès (3 fois) d'éthanedithiol-1,2 par rapport au
chloro 2-éthylméthylsulfure.<tb><SEP> HS / CH <SEP> ru <SEP> + <SEP> 2 <SEP> a
<tb><SEP> HS <SEP> H <SEP> + <SEP> Cl <SEP> S-CH3
<tb> EtO <SEP> Na <SEP> / EtOH <SEP> / <SEP> a <SEP> r <SEP> + <SEP> CH2
<tb><SEP> reflux <SEP> HS <SEP> S <SEP> / <SEP> S-CH3
<Tb>
+ secondary products
The yield obtained is 60%, using
an excess (3 times) of 1,2-ethanedithiol compared to
chloro 2-ethylmethylsulfide.
L'analyse élémentaire donne les résultats sui
vants
Théorique Après une distillation Après deux distillations % C = 35,67 % C = 34,69 % C = 34,97 % H = 7,19 % H = 7,09 % H = 7,22 % S = 57,14 % S = 58,18 % S = 57,69
Total (C, H, S) = 99,96 % 99,88 %
b) Synthèse de la résine linéaire 3
Les billes de polystyrène chlorométhylé brutes sont lavées et séchées.Elemental analysis gives the results
lowing
Theoretical After distillation After two distillations% C = 35.67% C = 34.69% C = 34.97% H = 7.19% H = 7.09% H = 7.22% S = 57.14% S = 58.18% S = 57.69
Total (C, H, S) = 99.96% 99.88%
b) Synthesis of the linear resin 3
The raw chloromethylated polystyrene beads are washed and dried.
Analyse élémentaire
Billes brutes Billes lavées et séchées
% C = 44,25 % C = 72,50
% H = 3,66 % H = 6,38
% Cl 12,50 % Cl= 20,19
Total (C, H, Cl) = 60,41 % Total (C, H, Cl)= 99,07 %
On possède alors des billes contenant 5,7 mmoles
Cl/g bille. Le greffage du motif sur le polystyrène chlorométhylé est réalisé suivant le mode opératoire usuel. Elemental analysis
Raw balls Washed and dried balls
% C = 44.25% C = 72.50
% H = 3.66% H = 6.38
% Cl 12.50% Cl = 20.19
Total (C, H, Cl) = 60.41% Total (C, H, Cl) = 99.07%
There are then beads containing 5.7 mmol
Cl / g ball. The grafting of the pattern on the chloromethylated polystyrene is carried out according to the usual procedure.
Schéma réactionnel
Reaction scheme
<tb> CCH-CH2t
<tb> <SEP> + <SEP> er <SEP> /CIiZ <SEP> -Hc <SEP> /CH2CH2
<tb> HS <SEP> + <SEP> 5/CE2= <SEP> S <SEP> zCH2C < <SEP> s-CH,
<tb> <SEP> H2C1
<tb> <SEP> rH-CH23
<tb> <SEP> EtO <SEP> Na <SEP> /EtOH > <SEP> <
<tb> <SEP> THF, <SEP> reflux
<tb> <SEP> s/=II2 <SEP> / <SEP> çH2--C <SEP> k <SEP> C <SEP> S-CH
<tb>
L'augmentation de masse est de 0,55 g/g de bille. L'analyse élémentaire :
% C = 63,90 ; % H = 7,05 % ; Cl = 0,85 ; % S = 27,66
T (C, H, Cl, S) = 99,46 % permet de calculer un greffage de l'ordre de 2,85 mmoles de motif par gramme de bille, ce qui correspond à un rendement de greffage de 89 %. <tb> CCH-CH2t
<tb><SEP> + <SEP><SEP> / CIiZ <SEP> -Hc <SEP> / CH2CH2
<tb> HS <SEP> + <SEP> 5 / CE2 = <SEP> S <SEP> zCH2C <<SEP> s-CH,
<tb><SEP> H2C1
<tb><SEP> rH-CH23
<tb><SEP> EtO <SEP> Na <SEP> / EtOH><SEP><
<tb><SEP> THF, <SEP> reflux
<tb><SEP> s / = II2 <SEP> / <SEP> çH2 - C <SEP> k <SEP> C <SEP> S-CH
<Tb>
The increase in mass is 0.55 g / g of ball. Elementary analysis:
% C = 63.90; % H = 7.05%; Cl = 0.85; % S = 27.66
T (C, H, Cl, S) = 99.46% makes it possible to calculate a grafting on the order of 2.85 mmol of unit per gram of bead, which corresponds to a grafting yield of 89%.
Il va de soi que la présente invention n'a été décrite qu'à titre purement illustratif et nullement limitatif et que toute modification, notamment au niveau des équivalences pourra y être apportée sans sortir de son cadre. It goes without saying that the present invention has been described for purely illustrative and not limiting and any modification, including the equivalence can be made without departing from its scope.
Claims (12)
Priority Applications (1)
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FR8606840A FR2598711B1 (en) | 1986-05-13 | 1986-05-13 | SULFUR POLYMERIC PRODUCTS WITH MAIN POLYMER SKELETON AND RESIDUES PENDING LINEAR OR BRANCHED CONNECTED TO ONE OR MORE OF THEIR SKELETED AUDIT ENDS, THEIR MANUFACTURING PROCESS AND THEIR APPLICATIONS FOR EXTRACTION AND / OR SEPARATION OF HEAVY METALS |
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FR8606840A FR2598711B1 (en) | 1986-05-13 | 1986-05-13 | SULFUR POLYMERIC PRODUCTS WITH MAIN POLYMER SKELETON AND RESIDUES PENDING LINEAR OR BRANCHED CONNECTED TO ONE OR MORE OF THEIR SKELETED AUDIT ENDS, THEIR MANUFACTURING PROCESS AND THEIR APPLICATIONS FOR EXTRACTION AND / OR SEPARATION OF HEAVY METALS |
Publications (2)
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Family
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999015707A1 (en) * | 1997-09-19 | 1999-04-01 | British Nuclear Fuels Plc | Detection and extraction of an ion in a solution, particularly uranium ion |
EP0978538A1 (en) * | 1997-04-01 | 2000-02-09 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Highly stable aqueous solution of partially saponified vinyl ester resin |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1148680B (en) * | 1958-05-19 | 1963-05-16 | Bataafsche Petroleum | Lubricating oil mixture |
GB1037044A (en) * | 1962-08-17 | 1966-07-27 | Rohm & Haas | Redox polymers |
DE2523793A1 (en) * | 1974-05-30 | 1975-12-11 | Exploaterings Ab Tbf | THIOPOLYMERS AND DERIVATIVES AS WELL AS METHOD FOR MANUFACTURING AND APPLYING THE SAME |
GB2030573A (en) * | 1978-09-14 | 1980-04-10 | Dainichiseika Colore Chemicals | Hydrophilic polymer and process for producing the same |
WO1985004177A1 (en) * | 1982-01-18 | 1985-09-26 | The Dow Chemical Company | (vinylaryl)alkyl polysulfide polymers |
-
1986
- 1986-05-13 FR FR8606840A patent/FR2598711B1/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1148680B (en) * | 1958-05-19 | 1963-05-16 | Bataafsche Petroleum | Lubricating oil mixture |
GB1037044A (en) * | 1962-08-17 | 1966-07-27 | Rohm & Haas | Redox polymers |
DE2523793A1 (en) * | 1974-05-30 | 1975-12-11 | Exploaterings Ab Tbf | THIOPOLYMERS AND DERIVATIVES AS WELL AS METHOD FOR MANUFACTURING AND APPLYING THE SAME |
GB2030573A (en) * | 1978-09-14 | 1980-04-10 | Dainichiseika Colore Chemicals | Hydrophilic polymer and process for producing the same |
WO1985004177A1 (en) * | 1982-01-18 | 1985-09-26 | The Dow Chemical Company | (vinylaryl)alkyl polysulfide polymers |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0978538A1 (en) * | 1997-04-01 | 2000-02-09 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Highly stable aqueous solution of partially saponified vinyl ester resin |
EP0978538A4 (en) * | 1997-04-01 | 2001-05-30 | Nippon Synthetic Chem Ind | Highly stable aqueous solution of partially saponified vinyl ester resin |
US6573327B1 (en) | 1997-04-01 | 2003-06-03 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Highly stable aqueous solution of partially saponified vinyl ester resin |
WO1999015707A1 (en) * | 1997-09-19 | 1999-04-01 | British Nuclear Fuels Plc | Detection and extraction of an ion in a solution, particularly uranium ion |
US6372872B1 (en) | 1997-09-19 | 2002-04-16 | British Nuclear Fuels Plc | Detection and extraction of uranium and other ions in a solution |
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FR2598711B1 (en) | 1988-09-16 |
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