LT4497B - Polytetra-ammonium salt, method for preparation and use thereof - Google Patents

Polytetra-ammonium salt, method for preparation and use thereof Download PDF

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Publication number
LT4497B
LT4497B LT98-110A LT98110A LT4497B LT 4497 B LT4497 B LT 4497B LT 98110 A LT98110 A LT 98110A LT 4497 B LT4497 B LT 4497B
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iodine
ammonium salt
iodide
preparation
diallyl ammonium
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LT98-110A
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Lithuanian (lt)
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LT98110A (en
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Joana Barkauskaitė
Rima Julė Žemaitaitienė
Algirdas Žemaitaitis
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Kauno technologijos universitetas
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Abstract

This invention belongs to the field of chemistry and might be used in particular iodine extraction, binding or detoxification technologies. Marginally soluble poly-quaternary ammonia salt - polydimethyl diallyl ammonium iodide - is obtained by mixing hydrous polydimethyl diallyl ammonium chloride and potassium or sodium iodide solutions at a component mole ratio of 1:1 and by separating forming deposits. Polydimethyl diallyl ammonium iodide is used for water and gas phase iodine absorption.

Description

Išradimas priklauso chemijos sričiai ir gali būti panaudotas specialiose jodo gavimo , surišimo arba nukenksminimo technologijose.The present invention relates to the field of chemistry and may be used in specific technologies for the production, binding or decontamination of iodine.

Žinoma daug gamtinių ir sintetinių polimerų, kurie sorbuoja jodą [žr. kn.: MojieKy/iapHbie KOMnJieKcti nomiMepoB/E.A. ΕβκτγροΒ, P.3. XaM3aMyjiHHa H ^p.-AJiMa-ATa: HayKa, Ka3axcKoft CCP, 1988.-C.132151]. Tačiau efektyviausių jodo sorbentų - polivinilo alkoholio, polivinilpirolidono trūkumas yra tas, jie tirpūs vandenyje, o tai trukdo juos panaudoti kietų sorbentų gamybai.There are many natural and synthetic polymers known to adsorb iodine. kn .: MojieKy / iapHbie KOMnJieKcti nomiMepoB / E.A. ΕβκτγροΒ, P.3. XaM3aMyjiHHa H ^ p.-AJiMa-ATa: HayKa, Ka3axcKoft CCP, 1988-C.132151]. However, the most effective iodine sorbents - polyvinyl alcohol, polyvinylpyrrolidone - have the disadvantage of being water soluble, which prevents their use in the manufacture of solid sorbents.

Prototipu parinktas polidimetildialilamonio chloridas (PDMDAAC1) taip pat reaguoja su jodu, nes įpylus jo į vandeninį jodo tirpalą labai paryškėja tirpalo spalva (žr. tirpalų šviesos absorbcijos spektrus, pateiktus 1 priede).Prototype-selected polydimethyldiallyl ammonium chloride (PDMDAAC1) also reacts with iodine because when added to an aqueous iodine solution, the color of the solution is greatly enhanced (see light absorption spectra of the solutions in Annex 1).

Polidimetildialilamonio chlorido kaip jodo surišėjo trūkumas yra tas, kad jis yra labai tirpus vandenyje.The disadvantage of polydimethyldiallyl ammonium chloride as an iodine binder is that it is highly soluble in water.

Žinomas PDMDAAC1 gavimo būdas iš monomero dimetildialilamonio chlorido vandeniniuose tirpaluose neaukštose (iki 85°C) temperatūrose, inicijavimui naudojant peroksisulfatus [žr. VDR pat. Nr. 141029, TPK C 08 F126/04 (1979),VDR pat. Nr. 156979, TPK C 08 F 126/02 (1982)]. Kitų polidimetildialilamonio halogenidų sintezė iš jų monomerų yra žymiai sudėtingesnė, nes trukdo šalutinė - halogenu oksidavimo reakcija. Todėl polidimetildialilamonio bromidas, kuris irgi gerai tirpsta vandenyje, gaunamas sunkiau (žr. straipsnį: Youji Negi, Susumu Harada, and Osamu Ishizuka Cyclopolymerization of diallylamine derivatives in dimethyl sulforide // J Polymer Sci: Part A-l.- 1967.-Vol.5.- P.1951-1965 ). Literatūroje nerasta duomenų, apie polidimetildialilamonio jodidą (PDMDAAJ) ar jo gavimo būdus. Susintetinti įprastiniu radikalinės polimerizacijos būdu iš atitinkamo monomero greičiausiai negalima, nes jodido jono geba oksidintis dar didesnė nei bromido ar chlorido jonų (oksidacijos potencialai E° CI2/2CI' yra +1.36V, Br?/2Br‘ - + l,09V, M’ - +0,54V).Known method for the preparation of PDMDAAC1 from monomeric dimethyldiallylammonium chloride in aqueous solutions at low temperature (up to 85 ° C) by initiation using peroxysulfates [cf. GDR pat. No. 141029, TPK C 08 F126 / 04 (1979), GDR Pat. No. 156979, TPK C 08 F 126/02 (1982)]. The synthesis of other polydimethyldiallylammonium halides from their monomers is considerably more complicated due to the interference from the halogen oxidation reaction. Therefore, polydimethyldiallylammonium bromide, which is also highly soluble in water, is more difficult to obtain (see article by Youji Negi, Susumu Harada, and Osamu Ishizuka Cyclopolymerization of Diallylamine Derivatives in Dimethyl Sulforide). - P.1951-1965). No data were found in the literature on polydimethyldiallyl ammonium iodide (PDMDAAJ) or its preparation. Synthesis by conventional radical polymerization from the corresponding monomer is unlikely because the iodide ion is capable of oxidizing even more than the bromide or chloride ions (oxidation potentials E ° Cl2 / 2Cl 'are + 1.36V, Br? / 2Br' - + l, 09V, M ' - + 0.54V).

Šio išradimo tikslas - išplėsti jodą sorbuojančių medžiagų asortimentą, sukuriant mažai vandenyje tiųpią ir efektyviai jodą sorbuojančią medžiagą.Šis tikslas pasiekiamas, pagaminant polidimetildialilamonio jodidą.Jis gaunamas sumaišius polidimetildialilamonio chlorido ir neorganinio jodido tirpalus, esant moliniam komponentų santykiui 1:1. Mainų reakcija vyksta kambario terųperatūroje pagal'lygtį:The object of the present invention is to expand the range of iodine sorbents by providing a low water soluble and efficient iodine sorbent. The exchange reaction occurs at room temperature according to the condition:

CH CH3CH CH 3

CH3 CH 3

C H.C H.

Susidaro mažai tirpaus PDMDAAJ nuosėdos. Ši reakcija įrodyta nustačius išplautose ir išdžiovintose nuosėdose Kjeldalio metodu azoto kiekį, %, (rasta 5,14 %, teoriškai PDMDAAJ azoto turėtų būti 5,51 %). Tai patvirtinta chromatografijos popieriuje būdu (eliuentas - vanduo, ryškinta techniško eterio garais, o išsiskyręs jodas užtvirtintas 0,1%-tiniu krakmolo kleisteriu). Laisvi jodido jonai iš reakcijos mišinio išnešti tik naudojant KI kiekį, didesnį už stechiometrinį. Melsva jodo dėmė popieriuje identifikuota, išmatuojant leukometru (firma Kari Ceis, Jiena) šviesos atspindžio koeficientą R. Duomenys pateikti 1 lentelėje.A low soluble precipitate of PDMDAAJ is formed. This reaction has been demonstrated by determination of the nitrogen content in the washed and dried sediment by the Kjeldahl method,% (found 5.14%, theoretically PDMDAAJ should be 5.51%). This was confirmed by paper chromatography (eluent: water eluted with technical ether vapor and liberated iodine in 0.1% starch paste). The free iodide ions were removed from the reaction mixture only using an amount of KI greater than stoichiometric. The bluish iodine stain on the paper was identified by measuring the light reflectance R on a leukometer (Kari Ceis, Jiena).

lentelė. Chromatografijos popieriuje duomenys, patvirtinantys lygties stechiometrijątable. Paper chromatographic data supporting the stoichiometry of the equation

[KI]:[PDMDAAC1] [OFF]: [PDMDAAC1] (1-Λ)2 * 2R(1-Λ) 2 * 2R Δ Δ 0 0 0,020 0.020 0 0 0,5 0.5 0,020 0.020 0 0 0,8 0.8 0,020 0.020 0 0 0,9 0.9 0,020 0.020 0 0 1,0 1.0 0,020 0.020 0 0 1,1 1.1 0,026 0.026 0,006 0.006 1,2 1.2 0,031 0.031 0,011 0.011 1,3 1.3 0,039 0.039 0,019 0.019 1,4 1.4 0,046 0.046 0,026 0.026

* - Kubelkos-Munko funkcija, rodanti spalvos intensyvumą.* - Kubelka-Munk function to display color intensity.

Polidimetildialilamonio jodidas, gautas mainų reakcijos būdu, yra baltos spalvos smulkiadispersinė amorfinė medžiaga. 240-260°C temperatūroje skyla nesilydydama. Netirpsta įprastiniuose organiniuose tirpikliuose, silpnai brinksta metanolyje, acetone, dichloretane. Vandenyje kambario temperatūroje ištirpsta iki 0,3 g/1, tirpumas priklauso nuo polimero molekulinės masės (2 lentelė) - jai didėjant tirpumas mažėja. Ištirpinus aukštesnėje temperatūroje ir po to aušinant gaunami persotinti tirpalai, kurie lėtai drumsčiasi laike dienų ar savaičių. Prototipo - polidimetildialilamonio chlorido tirpumas yra begalinis, išdžiovintas jis godžiai sorbuoja .drėgmę, o tirpalai maišosi su vandeniu bet kokiais santykiais.The polydimethyldiallylammonium iodide obtained by the exchange reaction is a white fine dispersion amorphous substance. Decomposes without melting at 240-260 ° C. Insoluble in common organic solvents, slightly swellable in methanol, acetone, dichloroethane. Dissolves in water at room temperature up to 0.3 g / l, solubility dependent on molecular weight of polymer (Table 2), decreasing with increasing solubility. Dissolving at a higher temperature and then cooling gives saturated solutions that slowly cloud over time for days or weeks. The prototype - polydimethyldiallyl ammonium chloride has infinite solubility, when dried, it greedily absorbs moisture, and the solutions are miscible with water in any ratio.

Jodo sorbcija polidimetildialilamonio jodidu taip pat priklauso nuo polimero molekulinės masės ir yra labai didelė - siekia 200% nuo jo masės. Tai patvirtina 3 lentelėje pateikti duomenys. Išlaikius PDMDAAJ miltelius uždarame inde jodu prisotintame ore (virš jodo kristalų), jų spalva kinta nuo baltos iki tamsiai rudos ir galiausiai mėlynai juodos, padidėja jų masė. Tai rodo, kad ši medžiaga gali sorbuoti jodą ir iš dujų fazės.The sorption of iodine with polydimethyldiallyl ammonium iodide is also dependent on the molecular weight of the polymer and is very high, up to 200% by weight. This is supported by the data in Table 3. The PDMDAAJ powder, when kept in a sealed container in iodine-saturated air (above the iodine crystals), changes color from white to dark brown and eventually blue to black, increasing in weight. This indicates that this material can also adsorb iodine from the gas phase.

lentelė. Skirtingų molekulinių masių PDMDAAJ tirpumas vandenyjetable. Water solubility of PDMDAAJ of different molecular weights

M M T,°C T, ° C Ištirpusips medžiagos kiekis g/1 Soluble matter in g / l 2700 2700 18-20 18-20 0,3 0.3 18-20* 18-20 * 12,7 12.7 95 95 65,0 65.0 111900 111900 18-20 18-20 0,15 0.15 95 95 55,0 55.0

* tirpalas prisotintas virimo temperatūroje ir paliktas aušti.* the solution is saturated at boiling point and allowed to cool.

lentelė. Jodo sorbcija polidimetildialilamonio jodidu iš vandeninių tirpalų ir dujųtable. Sorption of iodine with polydimethyldiallyl ammonium iodide from aqueous solutions and gases

Eilės Nr. Queues No. M M Sorbuoto jodo kiekis, g/g polimero Content of sorbed iodine, g / g of polymer Masės prieaugis, % Weight gain, % Pagal jodo titravimo duomenis According to iodine titration data Gravimetrinis metodas Gravimetric method 1 1 2700 2700 1,78 1.78 1,3 1.3 130 130 2 2 111900 111900 1,97 1.97 1,99 1.99 199 199 3 3 2700 2700 0,65 0.65 - - - -

Pastaba: Nr. 1 ir 2 - pusiausvyroji jodo sorbcija iš vandeninių tirpalų; Nr. 3 - jodo sorbcija iš dujų fazės statinėse sąlygose 18-20°C temperatūroje per 19 parų.Note: 1 and 2 - equilibrium sorption of iodine from aqueous solutions; No. 3 - Sorption of iodine from the gas phase under static conditions at 18-20 ° C for 19 days.

Siūlomas jodą sorbuojančios medžiagos, polidimetildialilamonio jodido, gavimo būdas realizuojamas taip: į vandeninį PDMDAACI tirpalą maišant pilamas vandeninis neorganinio jodido (KI, NaI) tirpalas, esant veikliųjų medžiagų moliniam santykiui.l:l ir atskiriamos iškritusios nuosėdos. Kalio jodido atveju šis santykis atitinka ir masių santykį 1:1 (g-ekv PDMDAACI=162, g-ekv KI=166).The proposed process for the preparation of an iodine sorbent, polydimethyldiallyl ammonium iodide, is carried out as follows: an aqueous solution of inorganic iodide (KI, NaI) is added to the aqueous solution of PDMDAACI in a molar ratio of the active ingredients. In the case of potassium iodide, this ratio also corresponds to a weight ratio of 1: 1 (g-eq PDMDAACI = 162, g-eq KI = 166).

Išradimas iliustruojamas pateiktais pavyzdžiais.The invention is illustrated by the following examples.

Polidimetildialilamonio jodido gavimas pavyzdysExample preparation of polydimethyldiallyl ammonium iodide

Į lOOg 27%-io pagal veikliąją medžiagą PDMDAACI (TU 6-05-2009-86) tirpalo maišant supilama 73 ml 30%-io KI (GOST 4232-74) tirpalo. Leidžiama73 ml of 30% KI (GOST 4232-74) solution are added to 100 g of a 27% solution of the active ingredient PDMDAACI (TU 6-05-2009-86) with stirring. Allowed

0,5-1 vai nusistoti, tirpalas nupilamas, nuosėdos nufiltruojamos, ir išdžiovinamos 60 - 100°C temperatūroje. Gaunamas produktas, turintis:After 0.5 to 1 hour to settle, the solution is drained, the precipitate is filtered off and dried at 60 to 100 ° C. The product obtained is:

87,6% PDMDAAJ,87.6% PDMDAAJ,

5,6% NaCl,5.6% NaCl,

6,5% KC1,6.5% KCl,

0,07% Kl.0.07% Cl.

pavyzdysexample

Pagal 1 pavyzdį, tik gautos nuosėdos ant filtro 3 kartus praplaunamos vandeniu (po 50 ml). Gaunamas produktas, kuriame yra 98% PDMDAAJ ir apie 1,5% KClir NaCl.According to Example 1, only the resultant precipitate is washed on the filter 3 times with water (50 ml each). The product obtained is 98% PDMDAAJ and about 1.5% KCl and NaCl.

pavyzdysexample

Pagal 2 pavyzdį, tik vietoj Kl tirpalo naudojama 77 ml 30%- tinio NaKHkO (GOST 8422-76) tirpalo.According to example 2, only 77 ml of 30% NaKHkO (GOST 8422-76) solution is used instead of Kl solution.

Polidimetildialilamonio jodido panaudojimas jodo sorbcijai pavyzdysExample of use of polydimethyldiallyl ammonium iodide for sorption of iodine

Įbėrus Ig pagal 1 pavyzdį gauto produkto į 200 ml 0,ln jodo tirpalo, po 30 min šio halogeno koncentracija tirpale sumažėjo 3,9 kartų, o nuosėdos, jas atskyrus ir išdžiovinus, pasunkėjo 190%.After the addition of Ig from Example 1 into 200 ml of 0.1 micron of iodine solution, the concentration of this halogen in solution was reduced 3.9-fold after 30 min, and the precipitate, after separation and drying, increased by 190%.

pavyzdysexample

Išlaikius lg pagal 1 pavyzdį gauto produkto miltelių Petri lėkštelėje virš jodokristalų sočioje jodo garų atmosferoje 18-20°C temperatūroje 19 parų, jie sorbavo apie 65% jodo nuo savo pradinės masės.After retaining Ig powder of the product of Example 1 in a petri dish over iodocrystals in a saturated iodine vapor atmosphere at 18-20 ° C for 19 days, they sorbed about 65% of iodine from its initial weight.

Pagal 2 ir 3 pavyzdžius gauto PDMDAAJ jodo sorbcinė geba yra labai panaši.The PDMDAAJ obtained according to Examples 2 and 3 has a very similar sorption capacity.

Pateikti pavyzdžiai patvirtina, kad sumaišius vandeninius PDMDAAC1 ir neorganinio jodido tirpalus, esant reagentų moliniam santykiui 1:1 gaunama mažai tirpi didele jodo sorbcine geba (iki 200% nuo polimero masės) pasižyminti medžiaga.The following examples confirm that when the aqueous solutions of PDMDAAC1 and inorganic iodide are mixed, a 1: 1 molar ratio of reactants yields a low soluble high iodine sorbent (up to 200% by weight of polymer).

Claims (4)

Išradimo apibrėžtisDefinition of the Invention 1. Poliketvirtinė amonio druska, kurios formulė F CH— CH— CH—CH^A polyketide ammonium salt of the formula F CH-CH-CH-CH ^ CH2i CH? CH 2i CH ? CH.CH. CH3 CH 3 2. Poliketvirtinės amonio druskos pagal 1 punktą gavimo būdas, besiskirian t i s tuo, kad į polidimetildialilamonio chlorido tirpalą pila neorganinio jodido tirpalus, esant komponentų molių santykiui 1:1, ir atskiria susidariusias nuosėdas.2. A process for the preparation of a polyketide ammonium salt according to claim 1, characterized in that the solution of inorganic iodide is added to the polydimethyldialylammonium chloride solution in a molar ratio of components of 1: 1 and the precipitate formed is separated off. 3. Poliketvirtinės amonio druskos gavimo būdas pagal 2 punktą, besiskirian t i s tuo, kad kaip neorganinį j odidą naudoj a KI arba NaI.3. A process for the preparation of a polyketide ammonium salt according to claim 2, characterized in that CI or NaI are used as the inorganic iodide. 4. Poliketvirtinės amonio druskos pagal 1 punktą panaudojimas jodo sugėrimui iš vandens ir dujų fazės.Use of a polyketide ammonium salt according to claim 1 for the absorption of iodine from the water and gas phase.
LT98-110A 1998-08-06 1998-08-06 Polytetra-ammonium salt, method for preparation and use thereof LT4497B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LT4725B (en) 2000-02-23 2000-11-27 Kauno technologijos universitetas Sorbent for iodine and method for the preparation thereof
LT5802B (en) 2011-05-20 2012-01-25 Kauno technologijos universitetas, , Cationic starch-triiodide bactericide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE156979C (en)
DE141029C (en) 1902-08-14 1903-05-04

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE156979C (en)
DE141029C (en) 1902-08-14 1903-05-04

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
E. A. BEKTUROB ET AL.: "Molekuljarnije komplekcij polimerov", pages: 132 - 151
YOUJI NEGI, SUSUMU HARADA, OSAMU ISHIZUKA: "Cyclopolymerization of diallylamine derivatives in dimethyl sulfoxide", JOURNAL OF POLYMER SCIENCE PART A-1: POLYMER CHEMISTRY, 1967, pages 1951 - 1965

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LT4725B (en) 2000-02-23 2000-11-27 Kauno technologijos universitetas Sorbent for iodine and method for the preparation thereof
LT5802B (en) 2011-05-20 2012-01-25 Kauno technologijos universitetas, , Cationic starch-triiodide bactericide

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