NO140736B - PROCEDURE FOR THE PREPARATION OF POLY-ALFA-OXYACRYLIC ACID - Google Patents
PROCEDURE FOR THE PREPARATION OF POLY-ALFA-OXYACRYLIC ACID Download PDFInfo
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- NO140736B NO140736B NO61773A NO61773A NO140736B NO 140736 B NO140736 B NO 140736B NO 61773 A NO61773 A NO 61773A NO 61773 A NO61773 A NO 61773A NO 140736 B NO140736 B NO 140736B
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- acid
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- bromine
- oxy
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- 238000000034 method Methods 0.000 title claims description 10
- 239000002253 acid Substances 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- -1 chlorine tetracarbon Chemical compound 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 235000011121 sodium hydroxide Nutrition 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 10
- 229910001424 calcium ion Inorganic materials 0.000 description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HMENQNSSJFLQOP-UHFFFAOYSA-N 2-bromoprop-2-enoic acid Chemical compound OC(=O)C(Br)=C HMENQNSSJFLQOP-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
-
- 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
- C08F8/44—Preparation of metal salts or ammonium salts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Detergent Compositions (AREA)
- Removal Of Specific Substances (AREA)
Description
Fremgangsmåte til fremstilling av poly-a-oksyakrylsyre. Process for the production of poly-a-oxyacrylic acid.
Oppfinnelsen vedrører fremgangsmåte til fremstilling av poly-oi-oksyakrylsyre som kan anvendes som kompleksdannere for flerverdige metallioner. The invention relates to a method for the production of poly-o-oxyacrylic acid which can be used as complex formers for polyvalent metal ions.
Kompleksdannere har vært kjent i stort antall i lengere tid og anvendes spesielt ved fremstilling av vaske- og rensemidler eller i tekstilindustrien. De tilkommer da den opp-gave komplekst å binde kalsium- og magnesiumioner som betinger vannets naturlige hårdhet og derved gjøre vannet bløtt. Oftest anvendes hertil natriumtripolyfosfat. Andre gode kompleksdannere er forbindelser av typen aminoeddiksyre, som f.eks. nitrilo-tri-eddiksyre eller etylendiamintetraeddiksyre og lignende. Anvendel-sen av disse kjente kompleksdannere er forbundet med den ulempe at de på grunn av deres nitrogen- eller fosforinnhold kan begunstige eutroferingen av naturlig vann eller avvann. Complex formers have been known in large numbers for a long time and are used in particular in the production of detergents and cleaning agents or in the textile industry. They then have the complex task of binding calcium and magnesium ions that condition the water's natural hardness and thereby make the water soft. Sodium tripolyphosphate is most often used for this purpose. Other good complex formers are compounds of the aminoacetic acid type, such as e.g. nitrilo-triacetic acid or ethylenediaminetetraacetic acid and the like. The use of these known complex formers is associated with the disadvantage that, due to their nitrogen or phosphorus content, they can favor the eutrophication of natural water or waste water.
Det består således et behov for erstatningsstoffer There is thus a need for replacement substances
som minst er likeverdige med de kjente kompleksdannere med hensyn til komplekseringsevnen, men som imidlertid ikke har ulempene ved de kjente komplekseringsevnen, men som imidlertid ikke har ulempene ved de kjente kompleksdannere. which are at least equivalent to the known complex formers with respect to the complexing ability, but which, however, do not have the disadvantages of the known complexing ability, but which do not, however, have the disadvantages of the known complex formers.
Som slike erstatningsstoffer omtales i tysk off.skrift 1.904.940 karboksyl- resp. karboksylat og hydroksylgruppeholdige, rettlinjede eller nettdannende i hovedkjeden C-C-bindingsholdige polymere med en polymerisasjonsgrad på 3-5000, fortrinnsvis 3 til 600, idet de polymere eksempelvis kan bestå av enheter med de generelle formler: Such substitutes are referred to in German official publication 1,904,940 carboxyl or carboxylate and hydroxyl group-containing, linear or network-forming in the main chain C-C bond-containing polymers with a degree of polymerization of 3-5000, preferably 3 to 600, as the polymers can for example consist of units with the general formulas:
I de generelle formler I, II og III betyr A hydrogen eller en valens av et- eller flerverdig metall, R og R^ betyr en alkyl-gruppe eller hydrogenatom og R1 betyr dessuten et halogenatom. In the general formulas I, II and III, A means hydrogen or a valence of a monovalent or polyvalent metal, R and R^ means an alkyl group or hydrogen atom and R 1 also means a halogen atom.
Disse polymeres kompleksbindeevne overfor kalsiumioner uttrykt i kompleksbindekonstanten logK s tai, D • Ca++, utgjør 1,8 til ca. 2,3 og er ikke tilstrekkelig for mange anvendelses-former. Dessuten kan de polymere bare fremstilles med dårlig utbytte, således at deres anvendelse er uøkonomisk. The complex binding capacity of these polymers towards calcium ions, expressed in the complex binding constant logK s tai, D • Ca++, amounts to 1.8 to approx. 2.3 and is not sufficient for many forms of application. Moreover, the polymers can only be produced with a poor yield, so that their use is uneconomical.
Andre som kompleksdannere egnede karboksyl- og hydroksylgruppeholdige oligo- og/eller polymere, slik de omtales i tysk off.skrift 21 64 888 er produkter som fåes ved hydrolyse av halogenholdige blandingspolymere, hvis halogeninnhold inne-holder ca. 5-60 vekt%, idet disse halogenholdige blandingspolymere i hovedkjenden er oppbygd av i vilkårlig rekkefølge an-ordnede enheter med de generelle formler (III), (IV) resp. (III) og (V). Other carboxyl- and hydroxyl-group-containing oligo- and/or polymers suitable as complex formers, as described in German official publication 21 64 888, are products obtained by hydrolysis of halogen-containing mixed polymers, whose halogen content contains approx. 5-60% by weight, as these halogen-containing mixed polymers are mainly made up of randomly arranged units with the general formulas (III), (IV) or (III) and (V).
I de generelle formler III, IV og V betyr X, Y og Z et hydrogen- og/eller halogenatom, idet en av substituentene er et halogenatom. R betyr et karboksylhalogenradikal, en karboksyl-, ester-, nitril- eller anhydridgruppe og molbrøken m et tall hvis verdi er større enn 0 og mindre enn 1. De polymere fåes ved hydrolyse av a-halogenholdige blandingspolymere av akrylsyre og malein-syre resp. itakonsyre og deres derivater og har en kompleksbinde-konstant overfor kalsium på logKg^b Ca<++> lik 5-8. In the general formulas III, IV and V, X, Y and Z mean a hydrogen and/or halogen atom, one of the substituents being a halogen atom. R means a carboxyl halogen radical, a carboxyl, ester, nitrile or anhydride group and the mole fraction m a number whose value is greater than 0 and less than 1. The polymers are obtained by hydrolysis of α-halogen-containing mixed polymers of acrylic acid and maleic acid resp. itaconic acid and their derivatives and have a complex binding constant to calcium of logKg^b Ca<++> equal to 5-8.
Oppfinnelsens gjenstand er en ny fremgangsmåte til fremstilling av poly-a-oksy-akrylsyre, idet fremgangsmåten er karakterisert ved at man omsetter polyakrylsyre oppløst i et inert oppløsningsmiddel i nærvær av mindre mengder fosfortriklorid og spor av jod med den støkiometriske mengde av klorgass eller brom ved en temperatur fra ca. 80 til 95°C, etter avsluttet reaksjon avdriver overskytende klorgass eller brom ved oppvarming av reaksjonsblandingen under tilbakeløp og ved etterfølgende fordampning av en del av oppløsningsmidlet utfeller og utskiller poly-a-klor- resp. -bromakrylsyre, hvorpå man oppløser den dannede poly-a-klor- resp.-bromakrylsyre i vann og inndamper den fil- The object of the invention is a new process for the production of poly-a-oxy-acrylic acid, the process being characterized by reacting polyacrylic acid dissolved in an inert solvent in the presence of small amounts of phosphorus trichloride and traces of iodine with the stoichiometric amount of chlorine gas or bromine at a temperature from approx. 80 to 95°C, after completion of the reaction excess chlorine gas or bromine is driven off by heating the reaction mixture under reflux and by subsequent evaporation of part of the solvent precipitates and separates poly-a-chloro-resp. -bromoacrylic acid, after which the formed poly-a-chloro- or bromoacrylic acid is dissolved in water and the fil-
terte oppløsning til tørrhet for utvinning av poly-a-oksyakrylsyre. tert solution to dryness for recovery of poly-α-oxyacrylic acid.
Det har vist seg hensiktsmessig som oppløsningsmiddel It has proven to be suitable as a solvent
å anvende iseddik eller trikloreddiksyre med karbontetraklorid. Ifølge en ytterligere foretrukket utførelsesform av fremgangsmåten ifølge oppfinnelsen, gjennomfører man halogeneringen av polyakrylsyren ved en temperatur fra 80 til 110°C. to use glacial acetic acid or trichloroacetic acid with carbon tetrachloride. According to a further preferred embodiment of the method according to the invention, the halogenation of the polyacrylic acid is carried out at a temperature from 80 to 110°C.
Fremstillingen av poly-a-oksy-akrylsyre foregår fortrinnsvis over poly-a-bromakrylsyren. Det ved bromering av polyakrylsyren dannede bromhydrogen kan opparbeides ved oksydasjon igjen til brom, således at bromet ved fremstilling av poly-a-oksyakrylsyren bare opptrer som oksydasjonsmiddel. Den ved fremgangsmåten ifølge oppfinnelsen fremstilte poly-a-oksyakrylsyre viser i IR-spektret de samme karakteristiske bånd, som den etter kjent fremgangsmåte fremstilte poly-a-oksy-akrylsyre. The production of poly-a-oxy-acrylic acid preferably takes place above the poly-a-bromoacrylic acid. The hydrogen bromine formed by bromination of the polyacrylic acid can be worked up by oxidation again to bromine, so that the bromine in the production of the poly-a-oxyacrylic acid only acts as an oxidizing agent. The poly-α-oxyacrylic acid produced by the method according to the invention shows the same characteristic bands in the IR spectrum as the poly-α-oxy-acrylic acid produced by the known method.
Poly-a-oksyakrylsyren ifølge oppfinnelsen har spesielt overfor kalsiumioner en utmerket komplekseringsevne cg har en stabilitetskonstant log , Ca<++> på 6,85 til 7,0. Stabilitets-konstanten ligger således i samme størrelsesorden som for nitrilo-trieddiksyre, som har en verdi på 6,4. Komplekseringen av kalsium-ionene ved poly-a-oksysyre foregår, bortsett fra en liten påvirk-ning av statisk fordeling, i støkiometrisk forhold på 1:3, dvs. The poly-α-oxyacrylic acid according to the invention has an excellent complexing ability especially with respect to calcium ions and has a stability constant log , Ca<++> of 6.85 to 7.0. The stability constant is thus in the same order of magnitude as for nitrilo-triacetic acid, which has a value of 6.4. The complexation of the calcium ions by poly-α-oxyacid takes place, except for a small influence of static distribution, in a stoichiometric ratio of 1:3, i.e.
at det til binding av et kalsiumion kreves tre karboksylgrupper. Kalsium-chelatkomplekset lar seg formelmessig vise på følgende måte: that three carboxyl groups are required to bind a calcium ion. The calcium chelate complex can be expressed in the following way:
Virkningen av poly-a-akrylsyren ifølge oppfinnelsen er ikke bare begrenset til dens komplekseringsevne overfor kalsiumioner eller andre ioner, men den kan dessuten i nærvær av karbonationer holde ytterligere mengder kalsiumioner i oppløs-ning. En utfelling av CaCO^ opptrer i nærvær av karbonationer først ved overskridelse av deres støkiometriske forhold mellom poly-a-oksy-akrylsyre og Ca-ioner, dvs. når det pr. kalsiumione er tilstede mindre enn to karboksylgrupper. The effect of the poly-a-acrylic acid according to the invention is not only limited to its ability to complex with calcium ions or other ions, but it can also, in the presence of carbonate ions, keep additional amounts of calcium ions in solution. A precipitation of CaCO^ occurs in the presence of carbonate ions only when their stoichiometric ratio between poly-a-oxy-acrylic acid and Ca ions is exceeded, i.e. when, per calcium ion is present less than two carboxyl groups.
Poly-a-akrylsyren ifølge oppfinnelsen er teknisk overlegen overfor de vanlige kompleksdannere, da den på den ene side er nitrogen-og fosforfri og ikke forårsaker noen eutrofering av vann og på den annen side overfor kalsium har en kompleks-bindingskonstant i den teknisk krevede størrelsesorden fra 5-8. The poly-a-acrylic acid according to the invention is technically superior to the usual complex formers, as it is, on the one hand, nitrogen- and phosphorus-free and does not cause any eutrophication of water and, on the other hand, has a complex-binding constant in relation to calcium in the technically required order of magnitude from 5-8.
Ved hydrolysen av poly-a-halogenakrylsyre fåes som omtalt i Marvel i J.Am.Soc. 62.3495 (1940) delvis laktonisert poly-a-oksy-akrylsyre, som alt etter typen av fremstilling resp. tilsvarende graden av kjedenettdannelsen i vann er mer eller mindre godt, vanligvis imidlertid dårlig, oppløselig, således at den på enkel måte kan adskilles, eksempelvis ved filtrering. In the hydrolysis of poly-a-halo-acrylic acid, as discussed in Marvel in J.Am.Soc. 62.3495 (1940) partially lactonized poly-a-oxy-acrylic acid, which depending on the type of preparation or the corresponding degree of chain network formation in water is more or less well, but usually poorly, soluble, so that it can be easily separated, for example by filtration.
De ved nøytralisering av poly-a-oksy-akrylsyre med ekvivalente mengder alkali dannede alkalisalter er meget godt oppløselig i vann og foretrekkes for anvendelse som kompleksdannere . The alkali salts formed by neutralizing poly-a-oxy-acrylic acid with equivalent amounts of alkali are very soluble in water and are preferred for use as complexing agents.
Eksempel 1. Example 1.
a) I en med rørverk og tilbakeløpskjøler utrustet rund-kolbe ble en blanding av 100 g a-klorakrylsyre, 400 ml benzen og 1 g benzoylperoksyd oppvarmet til koking i 3 timer under nitrogen-atmosfære. Den utfelte polymer ble adskilt og tørket ved 40°C i vakuum. Utbytte av poly-a-klorakrylsyre utgjorde 100% av det teoretiske . a) In a round flask equipped with piping and a reflux condenser, a mixture of 100 g of α-chloroacrylic acid, 400 ml of benzene and 1 g of benzoyl peroxide was heated to boiling for 3 hours under a nitrogen atmosphere. The precipitated polymer was separated and dried at 40°C in vacuum. Yield of poly-a-chloroacrylic acid was 100% of the theoretical.
b) Det fremstilles en ved 30°C mettet vandig oppløsning av poly-a-klorakrylsyre og denne oppløsning oppvarmes i to timer b) A saturated aqueous solution of poly-α-chloroacrylic acid is prepared at 30°C and this solution is heated for two hours
til koking. Det utfelte hydrolysat ble vasket kloridfritt og tørket ved 6 0°C i vakuum. Utbytte av til omtrent 1/3 laktonisert poly-a-oksy-akrylsyre utgjorde 77 g eller 100% av det teoretiske. Hydrolysatet hadde følgende egenskaper: for cooking. The precipitated hydrolyzate was washed free of chloride and dried at 60°C in vacuum. Yield of approximately 1/3 lactonized poly-a-oxy-acrylic acid was 77 g or 100% of the theoretical. The hydrolyzate had the following properties:
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19722211256 DE2211256C2 (en) | 1972-03-09 | 1972-03-09 | Process for the preparation of poly-α-oxy-acrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO140736B true NO140736B (en) | 1979-07-23 |
| NO140736C NO140736C (en) | 1979-10-31 |
Family
ID=5838332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO61773A NO140736C (en) | 1972-03-09 | 1973-02-15 | PROCEDURE FOR THE PREPARATION OF POLY-ALFA-OXYACRYLIC ACID |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS5756510B2 (en) |
| AT (2) | AT322510B (en) |
| BE (1) | BE796531A (en) |
| CA (1) | CA1014727A (en) |
| CH (1) | CH591527A5 (en) |
| DD (1) | DD104803A5 (en) |
| DE (1) | DE2211256C2 (en) |
| DK (1) | DK139524C (en) |
| FI (1) | FI57427C (en) |
| FR (1) | FR2175200B1 (en) |
| GB (1) | GB1403151A (en) |
| IT (1) | IT979741B (en) |
| NL (1) | NL172848C (en) |
| NO (1) | NO140736C (en) |
| SE (1) | SE390971B (en) |
| SU (1) | SU488395A3 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1536136A (en) * | 1975-03-03 | 1978-12-20 | Unilever Ltd | Detergent composition |
| DE2622276A1 (en) * | 1976-05-19 | 1977-12-08 | Hoechst Ag | METAL PHOSPHATING METHOD |
| DE2643422A1 (en) * | 1976-09-21 | 1978-03-30 | Kurita Water Ind Ltd | WATER TREATMENT PRODUCTS AND METHODS FOR TREATMENT OF WATER |
| FR2514746B1 (en) * | 1981-10-20 | 1985-05-31 | Coatex Sa | INHIBITOR OF INCRUSTATION AND PRECIPITATION FOR THE TREATMENT OF INDUSTRIAL AND / OR DOMESTIC WATER |
| JPS6286098A (en) * | 1985-10-11 | 1987-04-20 | 株式会社日本触媒 | Detergent builder and detergent composition containing the same |
| JPS63251410A (en) * | 1987-04-09 | 1988-10-18 | Nippon Peroxide Co Ltd | Preparation of polylactone corresponding to poly-alpha-hydroxyacrylic acid |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2327302A (en) * | 1940-07-13 | 1943-08-17 | Du Pont | Soap composition |
| US2728746A (en) * | 1952-03-08 | 1955-12-27 | Eastman Kodak Co | Alpha-hydroxy acrylic acid polymers, and salts thereof |
| LU62270A1 (en) * | 1970-12-17 | 1972-08-23 |
-
1972
- 1972-03-09 DE DE19722211256 patent/DE2211256C2/en not_active Expired
-
1973
- 1973-01-29 FI FI24673A patent/FI57427C/en active
- 1973-02-08 DD DD16875973A patent/DD104803A5/xx unknown
- 1973-02-12 NL NL7301954A patent/NL172848C/en not_active IP Right Cessation
- 1973-02-15 CA CA163,791A patent/CA1014727A/en not_active Expired
- 1973-02-15 NO NO61773A patent/NO140736C/en unknown
- 1973-02-21 SE SE7302432A patent/SE390971B/en unknown
- 1973-02-26 CH CH276573A patent/CH591527A5/xx not_active IP Right Cessation
- 1973-03-07 GB GB1097073A patent/GB1403151A/en not_active Expired
- 1973-03-07 IT IT4863673A patent/IT979741B/en active
- 1973-03-07 AT AT200773A patent/AT322510B/en not_active IP Right Cessation
- 1973-03-08 FR FR7308391A patent/FR2175200B1/fr not_active Expired
- 1973-03-08 DK DK128273A patent/DK139524C/en not_active IP Right Cessation
- 1973-03-09 JP JP48027871A patent/JPS5756510B2/ja not_active Expired
- 1973-03-09 SU SU1898132A patent/SU488395A3/en active
- 1973-03-09 BE BE128586A patent/BE796531A/en not_active IP Right Cessation
-
1974
- 1974-03-07 AT AT81574A patent/AT323420B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AT322510B (en) | 1975-05-26 |
| DK139524B (en) | 1979-03-05 |
| IT979741B (en) | 1974-09-30 |
| FI57427C (en) | 1980-08-11 |
| JPS5756510B2 (en) | 1982-11-30 |
| NO140736C (en) | 1979-10-31 |
| DE2211256A1 (en) | 1973-09-13 |
| BE796531A (en) | 1973-09-10 |
| SU488395A3 (en) | 1975-10-15 |
| NL172848C (en) | 1983-11-01 |
| NL172848B (en) | 1983-06-01 |
| FR2175200B1 (en) | 1977-12-30 |
| DE2211256C2 (en) | 1982-12-02 |
| CH591527A5 (en) | 1977-09-30 |
| DD104803A5 (en) | 1974-03-20 |
| DK139524C (en) | 1979-08-20 |
| SE390971B (en) | 1977-01-31 |
| FI57427B (en) | 1980-04-30 |
| GB1403151A (en) | 1975-08-13 |
| NL7301954A (en) | 1973-09-11 |
| CA1014727A (en) | 1977-08-02 |
| JPS48102807A (en) | 1973-12-24 |
| FR2175200A1 (en) | 1973-10-19 |
| AT323420B (en) | 1975-07-10 |
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