NO145976B - APPLICATION OF ETHERS OF POLYHYDROXYMYL METHOD AS IONE EXCHANGERS - Google Patents
APPLICATION OF ETHERS OF POLYHYDROXYMYL METHOD AS IONE EXCHANGERS Download PDFInfo
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- NO145976B NO145976B NO763099A NO763099A NO145976B NO 145976 B NO145976 B NO 145976B NO 763099 A NO763099 A NO 763099A NO 763099 A NO763099 A NO 763099A NO 145976 B NO145976 B NO 145976B
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- ethers
- water
- mol
- polyhydroxymethylene
- exchangers
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- 150000002170 ethers Chemical class 0.000 title claims description 8
- 238000000034 method Methods 0.000 title description 10
- -1 polyhydroxymethylene Polymers 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000006266 etherification reaction Methods 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002168 alkylating agent Substances 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 4
- 229920003086 cellulose ether Polymers 0.000 description 4
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- CSPHGSFZFWKVDL-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl)-trimethylazanium;hydrochloride Chemical compound Cl.C[N+](C)(C)CC(O)CCl CSPHGSFZFWKVDL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229960005215 dichloroacetic acid Drugs 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- CNGZUJQPNVPPCJ-UHFFFAOYSA-N 1-chloroethylphosphonic acid Chemical compound CC(Cl)P(O)(O)=O CNGZUJQPNVPPCJ-UHFFFAOYSA-N 0.000 description 1
- YMDNODNLFSHHCV-UHFFFAOYSA-N 2-chloro-n,n-diethylethanamine Chemical compound CCN(CC)CCCl YMDNODNLFSHHCV-UHFFFAOYSA-N 0.000 description 1
- FXKMTSIKHBYZSZ-UHFFFAOYSA-N 2-chloroethanesulfonic acid Chemical compound OS(=O)(=O)CCCl FXKMTSIKHBYZSZ-UHFFFAOYSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- FZLSDZZNPXXBBB-KDURUIRLSA-N 5-chloro-N-[3-cyclopropyl-5-[[(3R,5S)-3,5-dimethylpiperazin-1-yl]methyl]phenyl]-4-(6-methyl-1H-indol-3-yl)pyrimidin-2-amine Chemical compound C[C@H]1CN(Cc2cc(Nc3ncc(Cl)c(n3)-c3c[nH]c4cc(C)ccc34)cc(c2)C2CC2)C[C@@H](C)N1 FZLSDZZNPXXBBB-KDURUIRLSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000219823 Medicago Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- KJVAGIFECBAUOL-UHFFFAOYSA-N chloroethane phosphoric acid Chemical compound P(=O)(O)(O)O.ClCC.ClCC.ClCC KJVAGIFECBAUOL-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08F8/02—Alkylation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Oppfinnelsen vedrører anvendelse av etere av polyhydroksymetylen som ioneutvekslere. The invention relates to the use of ethers of polyhydroxymethylene as ion exchangers.
Som erstatning av stivelse og gelatin i klebestoffer og binde-midler eller som emulgeringsmidler har det i den kjemiske teknikk i lengere tid blitt anvendt blant annet cellulose-derivater. Dessuten krever spesielt den biokjemiske teknikk - i de senere år i stigende grad - for kromatografiske skille-fremgangsmåter ved siden av adsorpsjonsmaterialer av generell type, spesielt ioneutvekslere, for f.eks. å få aminosyre-eller proteinfraksjoner fra foreliggende blandinger. Det er kjent for å oppfylle disse krav, f.eks. å anvende celluloseetere. For generelt å foretre cellulose omsettes denne i alkalisk medium i uhomogen fase med alkyleringsmidler, f.eks. med halogenfettsyrer. Hvis celluloseetrene skal anvendes som ioneutvekslere, benytter man til deres fremstilling foretringsmidler med substituenter som har ioniske grupper. Fortrinnsvis angripes ved disse foretringer de primære hydroksylgrupper av anhydroglukoseenheten, først i annen rekke de sekundære hydroksylgrupper. As a substitute for starch and gelatin in adhesives and binders or as emulsifiers, cellulose derivatives, among other things, have been used in chemical engineering for a long time. Moreover, the biochemical technique in particular requires - in recent years increasingly - for chromatographic separation methods in addition to adsorption materials of a general type, especially ion exchangers, for e.g. to obtain amino acid or protein fractions from the present mixtures. It is known to meet these requirements, e.g. to use cellulose ethers. In order to generally etherify cellulose, this is reacted in an alkaline medium in an inhomogeneous phase with alkylating agents, e.g. with halogenated fatty acids. If the cellulose ethers are to be used as ion exchangers, etherification agents with substituents that have ionic groups are used for their production. Preferably, with these preferences, the primary hydroxyl groups of the anhydroglucose unit are attacked, first, secondarily, the secondary hydroxyl groups.
Ulempen ved celluloseetere og således også de herav frem-stilte ioneutvekslere ligger deri at de er labile overfor kjemiske og enzymiske angrep, en egenskap som står imot deres brede anvendelse i teknikker for biokjemikere, fysiologer og medisinere. The disadvantage of cellulose ethers and thus also the ion exchangers produced from them lies in the fact that they are labile to chemical and enzymatic attacks, a property that stands against their wide application in techniques for biochemists, physiologists and medics.
Oppfinnelsens oppgave er å unngå denne ulempe. The task of the invention is to avoid this disadvantage.
Dette lykkes, idet man anvender etere av polyhydroksymetylen som ioneutvekslere. Oppfinnelsens gjenstand er følgelig anvendelsen av etere av polyhydroksymetylen med ioniske eller ioniserbare substituenter fra gruppen karboksyl-, sulfo-, fosfo-, kvarternære ammonium- eller substituerte aminorester som ioneutvekslere. Det som utgangsmaterial ved fremgangsmåten ifølge oppfinnelsen tjenende polyhydroksymetylen er en kjent polymer, hvis fremstilling f.eks. er omtalt av H.C. Haas og N.W. Schuler This is successful, as ethers of polyhydroxymethylene are used as ion exchangers. The object of the invention is consequently the use of ethers of polyhydroxymethylene with ionic or ionizable substituents from the group of carboxyl, sulfo, phospho, quaternary ammonium or substituted amino residues as ion exchangers. The polyhydroxymethylene used as starting material in the method according to the invention is a known polymer, the production of which e.g. is discussed by H.C. Haas and N.W. Schools
i J. Polym. Science, 31, 238 (1958). in J. Polym. Science, 31, 238 (1958).
Det ble overraskende funnet at polyhydroksymetylen, enskjønt det utelukkende har sekundære hydroksylgrupper er tilgjenge-lig for en substitusjon til etere. Ved fremgangsmåten til fremstilling av eterene omsettes fortrinnsvis etter de to følgende metoder: 1. Sammenblanding av komponentene polyhydroksymetylen, isopropanol og NaOH-oppløsning i knaeren og tilsetning av alkyleringsmidlet ved ca. 50-90°C, fortrinnsvis ved ca. 7 0°C. 2. Oppløsning av polyhydroksymetylenet i en ca. 20-50 vekt-%-ig NaOH-oppløsning ved værelsestemperatur og tilsetning av alkyleringsmidlet ved ca. 20-90°C, fortrinnsvis ca. 70-90°c. It was surprisingly found that polyhydroxymethylene, although it has exclusively secondary hydroxyl groups, is available for a substitution to ethers. In the method for producing the ethers, the reaction is preferably carried out according to the following two methods: 1. Mixing the components polyhydroxymethylene, isopropanol and NaOH solution in the mixer and adding the alkylating agent at approx. 50-90°C, preferably at approx. 70°C. 2. Dissolving the polyhydroxymethylene in an approx. 20-50% by weight NaOH solution at room temperature and addition of the alkylating agent at approx. 20-90°C, preferably approx. 70-90°c.
Disse omsetninger lar seg altså gjennomføre i vandig-alkalisk medium i heterogen fase, eventuelt under tilsetning av et organisk oppløsningsmiddel som isopropanol som fortynner, These reactions can therefore be carried out in an aqueous-alkaline medium in a heterogeneous phase, possibly with the addition of an organic solvent such as isopropanol which dilutes,
og - et på grunn av den jevnere substitusjonsmulighet vesentlige fremskritt f.eks. overfor betingelser til fremstilling av celluloseetere - også i homogen fase. Polyhydroksymetylen er uoppløselig i de vandige oppløsningsmidler som vann, alkoholer, estere, aceton, dimetylformamid, etere, benzen, toluen, kloroform, dimetylsulfoksyd og svelles bare i noen tilfeller litt av dem: den oppløser seg imidlertid i alkaliske oppløsninger, som f.eks. i 25-50 vekt-%-ige NaOH-oppløsninger allerede ved værelsestemperatur, ved and - a significant advance due to the more even possibility of substitution, e.g. against conditions for the production of cellulose ethers - also in homogeneous phase. Polyhydroxymethylene is insoluble in the aqueous solvents such as water, alcohols, esters, acetone, dimethylformamide, ethers, benzene, toluene, chloroform, dimethylsulphoxide and is only slightly swollen by them in some cases: it does, however, dissolve in alkaline solutions, such as e.g. in 25-50% by weight NaOH solutions already at room temperature, at
ca. 8 0°C er det hertil allerede tilstrekkelig ved en 20 vekt-%-ig NaOH-oppløsning. about. 80°C, a 20% by weight NaOH solution is already sufficient for this purpose.
Ved fortynning av oppløsningene eller annen nedsettelse When diluting the solutions or other reduction
av NaOH-konsentrasjonen kan ved fremadskridende foretring ifølge metode 2 en del av polyhydroksymetylenet igjen falle ut, er imidlertid en oppløselighet av den dannede eter i vann gitt, så kan også her omsetningen videreføres i homogen fase. of the NaOH concentration, with progressive etherification according to method 2, part of the polyhydroxymethylene may again precipitate out, however, if a solubility of the formed ether in water is given, then the reaction can also be continued in a homogeneous phase.
Alkyleringsmidlet som skal anvendes må, på grunn av de ione-utveksleregenskaper som skal oppnås, ved siden av en eller flere til eterdanning egnede grupper minst ha en funksjonell gruppe som er ionisk eller ioniserbar, hertil hører en karboksyl-, sulfo-, fosfo-, kvarternær ammonium- eller substi-tuert aminorest. For denne oppgave er det egnet stoffer som de følgende: N,N-dialkylamino-g-kloralkaner The alkylating agent to be used must, due to the ion exchange properties to be achieved, next to one or more groups suitable for ether formation at least have a functional group that is ionic or ionizable, this includes a carboxyl, sulfo, phospho, quaternary ammonium or substituted amino residue. Substances such as the following are suitable for this task: N,N-dialkylamino-g-chloroalkanes
N,N-diarylamino-3-kloralkaner N,N-diarylamino-3-chloroalkanes
3-klor-2-hydroksypropyl-trimetylammqniumhydroklorid 2,3-epoksypropyl-trimetylammonium-hydroklorid etylenimin 3-chloro-2-hydroxypropyl-trimethylammonium hydrochloride 2,3-epoxypropyl-trimethylammonium hydrochloride ethyleneimine
kloreddiksyre chloroacetic acid
dikloreddiksyre dichloroacetic acid
trikloreddiksyre trichloroacetic acid
^-kloretansulfonsyre ^-chloroethanesulfonic acid
vinylsulfonsyre vinyl sulfonic acid
kloretanfosforsyre chloroethane phosphoric acid
vinylsulfonsyre vinyl sulfonic acid
kloretanfosfonsyre chloroethanephosphonic acid
vinylfosfonsyre vinylphosphonic acid
N,N-diklor-etyl-alkylaminer N,N-dichloro-ethyl-alkylamines
N,N-diklor-etyl-arylaminer N,N-dichloro-ethyl-arylamines
Produktene oppnådd ifølge oppfinnelsen kan være vannoppløse-lige eller for en stor del vannuoppløselige. Å påvirke disse sistnevnte egenskaper er mulig ved valg av substituenter, av substitusjonsgraden eller ved nettdannelse med minst bifunksjonelle reagenser. The products obtained according to the invention can be water-soluble or largely water-insoluble. Influencing these latter properties is possible by choosing substituents, by the degree of substitution or by network formation with at least bifunctional reagents.
En med oppfinnelsen oppnådd fordel ligger deri at de ifølge oppfinnelsen anvendte stoffer er av høyere kjemisk bestandig-het, således at de ikke uten videre avbygges. De motstår spesielt også enzymatisk og andre biokjemiske avbygningspro-sesser. Deres ioneutvekslerevne med ioniske eller krypto-ioniske stoffer f.eks. under biokjemiske og fysiologisk-kjemiske betingelser er utmerket, hvorfor de kan finne brede anvendelsesmuligheter som ioneutvekslere i biokjemi, medisin og fysiologisk kjemi. An advantage achieved with the invention lies in the fact that the substances used according to the invention are of higher chemical resistance, so that they are not easily degraded. In particular, they also resist enzymatic and other biochemical degradation processes. Their ion exchange ability with ionic or crypto-ionic substances e.g. under biochemical and physiological-chemical conditions is excellent, which is why they can find wide application possibilities as ion exchangers in biochemistry, medicine and physiological chemistry.
I de følgende eksempler betyr de angitte prosentmengder vekt-prosenter og MS betyr molar substitusjonsgrad. In the following examples, the stated percentages mean weight percentages and MS means molar degree of substitution.
Eksemp_el_l Example_el_l
En mengde på 50 g polyhydroksymetylen (1,67 mol, referert til den polymeres grunnbyggesten) ble blandet i knaer med 250 ml 87%-ig isopropanol og 66,8 g av den 50%-ig vandige NaOH-oppløsning (0,84 mol) i løpet av 3 0 minutter ved 25°C. Foretringen foregikk ved tildrypning av 168 g av en 50%-ig vandig oppløsning av 3-klor-2-hydroksypropyl-trimetylammon-iumhydroklorid (0,45 mol) og etterfølgende oppvarming til 70°C i 60 minutter. Deretter ble reaksjonsblandingen fortynnet med metanol og nøytralisert mot fenolftalein med iseddik. Det etter frafiltrering dannede hvite pulver ble vasket med vandig metanol og tørket ved 60°C. Det inneholdt 0,5% N, hvilket tilsvarer en MS på ca. 0,01. An amount of 50 g of polyhydroxymethylene (1.67 mol, referred to the basic building block of the polymer) was mixed in a bucket with 250 ml of 87% isopropanol and 66.8 g of the 50% aqueous NaOH solution (0.84 mol ) within 30 minutes at 25°C. The etherification took place by dropwise addition of 168 g of a 50% aqueous solution of 3-chloro-2-hydroxypropyl-trimethylammonium hydrochloride (0.45 mol) and subsequent heating to 70°C for 60 minutes. The reaction mixture was then diluted with methanol and neutralized against phenolphthalein with glacial acetic acid. The white powder formed after filtration was washed with aqueous methanol and dried at 60°C. It contained 0.5% N, which corresponds to a MS of approx. 0.01.
Eksemp_el_2_ Example_el_2_
En mengde på 15 g polyhydroksymetylen (0,5 mol) ble innført i 120 g av en 24%-ig vandig NaOH-oppløsning (0,7 mol) i en 500 ml trehalset kolbe, oppvarmet til 70°C og omrørt i 45 minutter ved denne temperatur. Foretringen foregikk ved tildrypning av 188 g av en 50%-ig vandig oppløsning av 3-klor-2-hydroksypropyl-trimetylammonium-hydroklorid i den viskose, gelaktige oppløsning i løpet av 10 minutter. Opp-løsningen tapte derved i viskositet og en del av stoffet falt ut. Reaksjonsblandingen ble helt inn i 500 ml vann, filtrert, vasket med vann, isopropylalkohol og aceton, tørket ved 60°C og deretter malt. Det således dannede hvite pulver inneholdt 1,8% N, hvilket tilsvarer en MS på 0,05. An amount of 15 g of polyhydroxymethylene (0.5 mol) was introduced into 120 g of a 24% aqueous NaOH solution (0.7 mol) in a 500 ml three-necked flask, heated to 70°C and stirred for 45 minutes at this temperature. The etherification took place by dropping 188 g of a 50% aqueous solution of 3-chloro-2-hydroxypropyl-trimethylammonium hydrochloride into the viscous, gel-like solution over 10 minutes. The solution thereby lost viscosity and part of the substance fell out. The reaction mixture was poured into 500 ml of water, filtered, washed with water, isopropyl alcohol and acetone, dried at 60°C and then ground. The white powder thus formed contained 1.8% N, which corresponds to an MS of 0.05.
Eksempel_3 Example_3
En mengde på 10 g polyhydroksymetylen (0,33 mol) ble oppløst i 75 g av en 40%-ig vandig NaOH-oppløsning (0,75 mol) og om-rørt 45 minutter ved 70°C. Foretringen foregikk ved tilsetning av 65 g glycidyl-trimetyl-ammoniumklorid (0,43 mol) og etterfølgende oppvarming og omrøring ved 7 0°C i 4 5 minutter. Reaksjonsblandingen ble helt inn i 500 ml vann, filtrert, vasket nøytral med vann, tørket ved 60°C og deretter malt. Det etter dialysen i vandig suspensjon overfor vann og en etterfølgende frysetørkning dannet vannuoppløselig pulver inneholdt 1,0% N, hvilket tilsvarer en MS på 0,02. An amount of 10 g of polyhydroxymethylene (0.33 mol) was dissolved in 75 g of a 40% aqueous NaOH solution (0.75 mol) and stirred for 45 minutes at 70°C. The etherification took place by adding 65 g of glycidyl-trimethyl-ammonium chloride (0.43 mol) and subsequent heating and stirring at 70°C for 45 minutes. The reaction mixture was poured into 500 ml of water, filtered, washed neutral with water, dried at 60°C and then ground. The water-insoluble powder formed after the dialysis in aqueous suspension against water and a subsequent freeze-drying contained 1.0% N, which corresponds to an MS of 0.02.
Eksempel_4 Example_4
Det ble gått fram som i eksempel 3, men benyttet 100 g 2-kloretan-sulfonsyre-Na-salt (0,6 mol) som foretringsmiddel. Det vannuoppløselige pulver inneholdt 3,0% S, hvilket tilsvarer en DS (substitusjonsgrad) på 0,03. The procedure was as in example 3, but 100 g of 2-chloroethane-sulfonic acid Na salt (0.6 mol) was used as etherification agent. The water-insoluble powder contained 3.0% S, which corresponds to a DS (degree of substitution) of 0.03.
Eksemp_el_5 Example_el_5
Det ble gått fram som i eksempel 3, men med 58 g 2-klor-etyl-dietylamin (0,43 mol) som foretringsmiddel. Det vannuoppløselige pulver inneholdt 4,3% N, hvilket tilsvarer en DS på 0,13. The procedure was as in example 3, but with 58 g of 2-chloro-ethyl-diethylamine (0.43 mol) as etherification agent. The water-insoluble powder contained 4.3% N, which corresponds to a DS of 0.13.
Eksemp_el_6 Example_el_6
En mengde på 15 g polyhydroksymetylen (0,5 mol) ble oppløst i en natronlut, som inneholdt 44 g NaOH (1,1 mol) i 200 g vann og den viskose masse oppvarmes i 45 minutter ved 80-90°C. Foretringen foregikk ved tildrypning av 59 g av en 80%-ig vandig monokloreddiksyreoppløsning (0,5 mol) og etterfølgende oppvarming til 80-9 0°C i løpet av en time. Etter avkjøling og nøytralisering med iseddik mot fenolftalein ble det fortynnet med vann til 500 ml og utfelt ved innhélling i ca. 4 liter metanol. Det etter frafiltreringen dannede hvite pulver ble vasket tre ganger med ren metanol, hvoretter pulveret var fritt for klorider. Deretter ble det tørket ved 60°C og pulverisert i morter. Utbytte 17,6 g. Det vannoppløselige produkt inneholdt 8,85% Na, hvilket tilsvarer en DS på 0,175. A quantity of 15 g of polyhydroxymethylene (0.5 mol) was dissolved in caustic soda, which contained 44 g of NaOH (1.1 mol) in 200 g of water and the viscous mass was heated for 45 minutes at 80-90°C. The etherification took place by dropwise addition of 59 g of an 80% aqueous monochloroacetic acid solution (0.5 mol) and subsequent heating to 80-90°C over the course of one hour. After cooling and neutralization with glacial acetic acid against phenolphthalein, it was diluted with water to 500 ml and precipitated by infusing for approx. 4 liters of methanol. The white powder formed after filtration was washed three times with pure methanol, after which the powder was free of chlorides. It was then dried at 60°C and pulverized in a mortar. Yield 17.6 g. The water-soluble product contained 8.85% Na, which corresponds to a DS of 0.175.
Eksempel_7 Example_7
Det ble gått fram som i eksempel 3, men med 84 g dikloreddiksyre (0,66 mol) som foretringsmiddel. Det vannuoppløselige pulver inneholdt 1,5% Na. The procedure was as in example 3, but with 84 g of dichloroacetic acid (0.66 mol) as etherification agent. The water-insoluble powder contained 1.5% Na.
Eksempel_8 Example_8
Det ble gått fram som i eksempel 3, men med 35 g trikloreddiksyre (0,22 mol) som foretringsmiddel. Det vannuoppløse-lige pulver inneholdt 3,1% Na. The procedure was as in example 3, but with 35 g of trichloroacetic acid (0.22 mol) as etherification agent. The water-insoluble powder contained 3.1% Na.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2540688A DE2540688C3 (en) | 1975-09-12 | 1975-09-12 | Process for the production of ethers of polyhydroxymethylene which can be used as ion exchangers |
Publications (3)
Publication Number | Publication Date |
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NO763099L NO763099L (en) | 1977-03-15 |
NO145976B true NO145976B (en) | 1982-03-29 |
NO145976C NO145976C (en) | 1982-07-07 |
Family
ID=5956300
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NO763099A NO145976C (en) | 1975-09-12 | 1976-09-09 | APPLICATION OF ETHERS OF POLYHYDROXYMYL METHOD AS IONE EXCHANGERS |
Country Status (18)
Country | Link |
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JP (1) | JPS5233979A (en) |
AT (1) | AT355312B (en) |
AU (1) | AU504619B2 (en) |
BE (1) | BE846006A (en) |
CA (1) | CA1071232A (en) |
CH (1) | CH599253A5 (en) |
DE (1) | DE2540688C3 (en) |
DK (1) | DK410276A (en) |
ES (1) | ES451448A1 (en) |
FI (1) | FI61495C (en) |
FR (1) | FR2323713A1 (en) |
GB (1) | GB1489865A (en) |
IE (1) | IE43427B1 (en) |
IT (1) | IT1066290B (en) |
LU (1) | LU75773A1 (en) |
NL (1) | NL7610013A (en) |
NO (1) | NO145976C (en) |
SE (1) | SE7610018L (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE2818086C2 (en) * | 1978-04-25 | 1984-11-29 | Sumitomo Chemical Co., Ltd., Osaka | Carrier material for immobilizing enzymes and process for their production |
-
1975
- 1975-09-12 DE DE2540688A patent/DE2540688C3/en not_active Expired
-
1976
- 1976-09-08 AU AU17543/76A patent/AU504619B2/en not_active Expired
- 1976-09-09 NO NO763099A patent/NO145976C/en unknown
- 1976-09-09 BE BE170480A patent/BE846006A/en not_active IP Right Cessation
- 1976-09-09 FI FI762591A patent/FI61495C/en not_active IP Right Cessation
- 1976-09-09 CH CH1145876A patent/CH599253A5/xx not_active IP Right Cessation
- 1976-09-09 NL NL7610013A patent/NL7610013A/en not_active Application Discontinuation
- 1976-09-09 IE IE2018/76A patent/IE43427B1/en unknown
- 1976-09-10 SE SE7610018A patent/SE7610018L/en not_active Application Discontinuation
- 1976-09-10 GB GB37627/76A patent/GB1489865A/en not_active Expired
- 1976-09-10 AT AT673076A patent/AT355312B/en not_active IP Right Cessation
- 1976-09-10 FR FR7627251A patent/FR2323713A1/en active Granted
- 1976-09-10 ES ES451448A patent/ES451448A1/en not_active Expired
- 1976-09-10 CA CA260,883A patent/CA1071232A/en not_active Expired
- 1976-09-10 LU LU75773A patent/LU75773A1/xx unknown
- 1976-09-10 IT IT51214/76A patent/IT1066290B/en active
- 1976-09-10 DK DK410276A patent/DK410276A/en not_active Application Discontinuation
- 1976-09-13 JP JP51109727A patent/JPS5233979A/en active Pending
Also Published As
Publication number | Publication date |
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DE2540688C3 (en) | 1979-10-31 |
BE846006A (en) | 1977-03-09 |
AU504619B2 (en) | 1979-10-18 |
ATA673076A (en) | 1979-07-15 |
DK410276A (en) | 1977-03-13 |
CA1071232A (en) | 1980-02-05 |
IE43427B1 (en) | 1981-02-25 |
FI61495B (en) | 1982-04-30 |
CH599253A5 (en) | 1978-05-31 |
NO763099L (en) | 1977-03-15 |
GB1489865A (en) | 1977-10-26 |
JPS5233979A (en) | 1977-03-15 |
AT355312B (en) | 1980-02-25 |
IE43427L (en) | 1977-03-12 |
NO145976C (en) | 1982-07-07 |
LU75773A1 (en) | 1978-05-12 |
DE2540688A1 (en) | 1977-03-17 |
FI61495C (en) | 1982-08-10 |
ES451448A1 (en) | 1978-05-01 |
AU1754376A (en) | 1978-03-16 |
NL7610013A (en) | 1977-03-15 |
IT1066290B (en) | 1985-03-04 |
FR2323713B1 (en) | 1981-05-29 |
SE7610018L (en) | 1977-03-13 |
FR2323713A1 (en) | 1977-04-08 |
FI762591A (en) | 1977-03-13 |
DE2540688B2 (en) | 1979-03-08 |
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