NL193088C - Process for the preparation of aqueous solutions of unsaturated quaternary ammonium salts. - Google Patents
Process for the preparation of aqueous solutions of unsaturated quaternary ammonium salts. Download PDFInfo
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- NL193088C NL193088C NL8920072A NL8920072A NL193088C NL 193088 C NL193088 C NL 193088C NL 8920072 A NL8920072 A NL 8920072A NL 8920072 A NL8920072 A NL 8920072A NL 193088 C NL193088 C NL 193088C
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- reaction
- water
- quaternary ammonium
- unsaturated quaternary
- ammonium salts
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- 238000000034 method Methods 0.000 title claims description 18
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims description 12
- 239000007864 aqueous solution Substances 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 20
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229940050176 methyl chloride Drugs 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 3
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VMEZXMFPKOMWHR-UHFFFAOYSA-N (dimethylamino)methyl prop-2-enoate Chemical compound CN(C)COC(=O)C=C VMEZXMFPKOMWHR-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- 241001104043 Syringa Species 0.000 description 1
- 235000004338 Syringa vulgaris Nutrition 0.000 description 1
- -1 air or pure oxygen Chemical compound 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- USFMMZYROHDWPJ-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound CC(=C)C(=O)OCC[N+](C)(C)C USFMMZYROHDWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/38—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
1 1930881 193088
Werkwijze voor de bereiding van waterige oplossingen van onverzadigde quaternaire ammonium· zoutenProcess for the preparation of aqueous solutions of unsaturated quaternary ammonium salts
De uitvinding heeft betrekking op een werkwijze voor de bereiding van waterige oplossingen van onverza-5 digde quaternaire ammoniumzouten (I) volgens de volgende formule: H2C = CH - C(O) - A - R3 - N+(R,) (R2) (R), X~ waarin: - A een zuurstofatoom of een NH-groep is, - R3 een lineaire of vertakte alkyleengroep met van 1 tot 6 koolstofatomen is, 10 - R,, R2, R verschillend of gelijk elk een alkyl- of arylgroep zijn, - X" gekozen wordt uit Cl, Br, I, CH3-C03 en CH3-S04 vanuit ten minste één acrylzuurmonomeer (II) van de formule: H2C = CH - C(O) - A - R3 - N^) (R2), en ten minste één quaterniserend middel (III) met de formule RX, waarin R, R1t R2, R3, A en X de 15 voornoemde betekenissen hebben, in aanwezigheid van ten minste één polymerisatieremmer, welke werkwijze de volgende stappen omvat: - in een eerste stap (a) laat men onder verhoogde druk ten minste één van het acrylzuurmonomeer (II) met tot 30 gew.% van de hoeveelheid vereist voor de reactie van, ten minste één quaterniserend middel (lil), evenals 5 tot 50 gew.% van een waterige oplossing van onverzadigde quaternaire ammoniumzouten (I) 20 welke 50 tot 85 gew.% van genoemde zouten bevat, reageren, - en, in een tweede stap (b) voegt men continu water en het quatemiserende middel (III) toe tot men de gewenste concentratie van onverzadigde quaternaire ammoniumzouten in het water verkregen heeft toe, - wordt de reactie, tijdens de stappen (a) en (b) bewerkstelligd in aanwezigheid van zuurstof, bij een temperatuur gelegen tussen 10 en 90°C, 25 - en, aan het eind van de reactie vermindert men geleidelijk de druk tot atmosferische druk, en tegelijkertijd brengt men een verhouding van de volumetrische capaciteit van het totale gas bij de uitgang van de reactor ten opzichte van de volumetrische zuurstofcapaciteit, die in de reactor geleid wordt, aan onder 100.The invention relates to a process for the preparation of aqueous solutions of unsaturated quaternary ammonium salts (I) according to the following formula: H2C = CH - C (O) - A - R3 - N + (R,) (R2) ( R), X ~ wherein: - A is an oxygen atom or an NH group, - R 3 is a linear or branched alkylene group having from 1 to 6 carbon atoms, 10 - R 1, R 2, R different or the same as an alkyl or aryl group - X "is selected from Cl, Br, I, CH 3 -CO 3 and CH 3 -SO 4 from at least one acrylic acid monomer (II) of the formula: H 2 C = CH - C (O) - A - R 3 - N ^) ( R2), and at least one quaternizing agent (III) of the formula RX, wherein R, R1, R2, R3, A and X have the aforementioned meanings, in the presence of at least one polymerization inhibitor, the process comprising the following steps: in a first step (a), under elevated pressure, at least one of the acrylic acid monomer (II) is left containing up to 30% by weight of the amount required for the reaction of at least one quaterni sieving agent (III), as well as 5 to 50% by weight of an aqueous solution of unsaturated quaternary ammonium salts (I) containing 50 to 85% by weight of said salts, react - and, in a second step (b) water and the quatemizing agent (III) are added continuously until the desired concentration of unsaturated quaternary ammonium salts in the water is obtained, - the reaction is effected in steps (a) and (b) in the presence of oxygen at a temperature between 10 and 90 ° C, 25 - and, at the end of the reaction, the pressure is gradually reduced to atmospheric pressure, and at the same time a ratio of the volumetric capacity of the total gas at the outlet of the reactor is made with respect to of the volumetric oxygen capacity passed into the reactor to below 100.
Een dergelijke werkwijze is bekend uit de Europese octrooiaanvrage 0.250.325. Deze bekende werkwijze dient te worden uitgevoerd bij atmosferische druk of bij verhoogde druk tot maximaal 1,6 bar. In het 30 document is aangetoond voor methacryloyloxyethyltrimethylammonium, dat reactiedrukken van 5 bar absoluut zonder doorleiden van lucht en van 3 bar absoluut met doorleiden, van lucht leidt tot een instabiel product en de verwachting is uitgesproken dat de momentane verdamping van overmaat opgelost methylchloride bij het beëindigen van de reactie polymerisatie veroorzaakt en toepassing van een druk hoger dan 1,6 bar leidt tot een instabiel product, dat de neiging kan hebben om te polymeriseren.Such a method is known from European patent application 0.250.325. This known method must be carried out at atmospheric pressure or at elevated pressure up to a maximum of 1.6 bar. In the document it has been shown for methacryloyloxyethyltrimethylammonium, that reaction pressures of 5 bar absolutely without air pass-through and of 3 bar absolute with pass-through air lead to an unstable product and it is expected that the instantaneous evaporation of excess dissolved methyl chloride upon termination of the reaction causes polymerization and application of a pressure above 1.6 bar results in an unstable product, which may tend to polymerize.
35 De werkwijze volgens de genoemde Europese octrooiaanvrage maakt het mogelijk waterige oplossingen van onverzadigde quaternaire ammoniumzouten (I) te bereiden die een stabiliteit hebben van meer dan 1 jaar bij kamertemperatuur. Men heeft echter geconstateerd dat er in deze oplossingen onzuiverheden aanwezig zijn, genoemd zijn in de voorbeelden 9 en 11 0,69 resp. 0,85% acrylzuur, 15 resp. 10 dpm methylchloride en 1,3 resp. 1,2% dimethylaminoethylacrylaat.The method according to the said European patent application makes it possible to prepare aqueous solutions of unsaturated quaternary ammonium salts (I) which have a stability of more than 1 year at room temperature. However, it has been found that impurities are present in these solutions, named in Examples 9 and 11 are 0.69, respectively. 0.85% acrylic acid, 15 resp. 10 ppm methyl chloride and 1.3 resp. 1.2% dimethylaminoethyl acrylate.
40 Het probleem dat de onderhavige uitvinding oplost, bestaat uit het voorzien in een werkwijze voor de bereiding van waterige oplossingen van onverzadigde quaternaire ammoniumzouten (I), welke werkwijze het mogelijk maakt om tegelijkertijd de vorming van onzuiverheden en de duur van de reactie van de quaterni-sering aanzienlijk te verminderen.The problem solved by the present invention consists in providing a process for the preparation of aqueous solutions of unsaturated quaternary ammonium salts (I), which process allows the formation of impurities and the duration of the reaction of the quaternium at the same time. significantly reduce lilac.
Verrassenderwijs is gevonden dat genoemd probleem wordt opgelost door de werkwijze bij hogere druk 45 uit te voeren dan tot nog toe gebruikelijk was, nl. bij 3-10 bar absoluut in plaats van 1,6 bar absoluut of lager. Derhalve wordt volgens de uitvinding de werkwijze van de in de aanhef genoemde aard gekenmerkt, doordat de reactie bewerkstelligd wordt onder een absolute druk gelegen tussen 3 en 10 bar.Surprisingly, it has been found that said problem is solved by carrying out the process at a higher pressure 45 than hitherto customary, i.e. at 3-10 bar absolute instead of 1.6 bar absolute or lower. According to the invention, the method of the preamble mentioned above is therefore characterized in that the reaction is effected under an absolute pressure of between 3 and 10 bar.
De aanwezigheid van zuurstof tijdens de reactie wordt verzekerd, overeenkomstig de praktijk volgens de 50 Europese octrooiaanvrage 250.325: - danwel door het reactiemengsel onder de druk van een zuurstofgas zoals lucht of zuivere zuurstof te handhaven, - danwel door het aanbrengen van een veegzuurstofgas zodanig dat de verhouding van de totale volumetrische gascapaciteit aan de uitgang van de reactor ten opzichte van de volumetrische capaciteit van 55 de zuurstof, die wordt binnengeleid in de reactor, onder 100 en bij voorkeur onder 50 is.The presence of oxygen during the reaction is ensured, in accordance with the practice of European patent application 250,325: - either by maintaining the reaction mixture under the pressure of an oxygen gas such as air or pure oxygen, or - by applying a sweeping oxygen gas such that the ratio of the total volumetric gas capacity at the reactor outlet to the volumetric capacity of 55 the oxygen introduced into the reactor is below 100 and preferably below 50.
Aan het einde van de reactie, wanneer het reactiemengsel op atmosferische druk is, verwijdert men op bekende wijze de sporen van quatemiserende middelen (III) die vluchtig zijn met behulp van een veeggasAt the end of the reaction, when the reaction mixture is at atmospheric pressure, the traces of quatemizing agents (III) which are volatile using a wipe gas are removed in a known manner.
Iiaauöö ϋ met een grote zuurstofcapaciteit, zoals lucht.Iiaauöö ϋ with a large oxygen capacity, such as air.
In het algemeen is de reactieduur niet langer dan 10 uur.In general, the reaction time is no longer than 10 hours.
Bij voorkeur worden tijdens stap (b), de water en de quaterniserende middel (III) -capaciteiten geregeld op een wijze zodanig dat in het reactiemengsel een waterige verzadigde oplossing of een oplossing dichtbij 5 de verzadiging van onverzadigde quaternaire ammoniumzouten (I) gehandhaafd blijft. Dit wordt gewoonlijk verkregen door een molaire verhouding water/quaterniserend middel te kiezen genomen tussen 1,5 en 3, waarbij deze verhouding des te hoger is, wanneer de reactietemperatuur lager is en wanneer de hoeveelheid van het quaterniserend middel, binnengeleid in stap (a), hoger is.Preferably, during step (b), the water and the quaternizing agent (III) capacities are controlled in such a way that in the reaction mixture an aqueous saturated solution or a solution close to saturation of unsaturated quaternary ammonium salts (I) is maintained. This is usually achieved by choosing a molar water / quaternizing agent ratio between 1.5 and 3, this ratio being all the higher when the reaction temperature is lower and when the amount of the quaternizing agent introduced in step (a) is higher.
Wanneer het quaterniserende middel (III) een vluchtige verbinding is bij de reactieomstandigheden, wordt 10 de introductie van het quaterniserende middel in de loop van de reactie op een dergelijke manier geregeld om zijn verliezen in de gaskanalen te beperken. De verliezen zijn zo onder 10%, zelfs onder 3% van de stoechiometrie gehandhaafd. Het gas aan de uitgang van de reactor wordt naar een inrichting voor de behandeling, gericht op het uitwassen van de sporen van het quaterniserende middel (III), welke deze bevat, geleid. Bij voorkeur stuurt men het gas van de uitgang van de reactor naar een tweede reactor welke 15 acrylzuurmonomeer omvat, waarmee het quaterniserende middel reageert.When the quaternizing agent (III) is a volatile compound under the reaction conditions, the introduction of the quaternizing agent during the course of the reaction is controlled in such a way as to limit its losses in the gas channels. The losses are thus kept below 10%, even below 3% of stoichiometry. The gas at the outlet of the reactor is passed to a treatment device, which is used to wash out the traces of the quaternizing agent (III) containing it. Preferably, the gas is sent from the reactor outlet to a second reactor comprising acrylic acid monomer with which the quaternizing agent reacts.
De werkwijze volgens de uitvinding komt overeen met de quatemisatie van de acrylzuurmonomeren (II), die gevoelig zijn voor hydrolyse zoals dimethylaminomethylacrylaat, dimethylaminopropylacrylaat, en het dimethylaminopropylacrylamide.The process of the invention corresponds to the quatemization of the acrylic acid monomers (II), which are sensitive to hydrolysis such as dimethylaminomethyl acrylate, dimethylaminopropyl acrylate, and the dimethylaminopropylacrylamide.
De quaterniserende middelen (III) geschikt voor de onderhavige uitvinding zijn met name gehalogeneerde 20 koolwaterstoffen zoals methylchloride, methylbromide, methyljodide, ethylchloride, ethylbromide, ethyljodide, benzylchloride; dimethylsulfaat of dimethylcarbonaat.The quaternizing agents (III) suitable for the present invention are in particular halogenated hydrocarbons such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, benzyl chloride; dimethyl sulfate or dimethyl carbonate.
Onder de polymerisatieremmers geschikt voor de werkwijze volgens de uitvinding kan men noemen 3,5-diterbutyl-4-hydroxytolueen, de methylether van hydrochinon, fenothiazine, hydrochinon, catechol en terbutylcatechol. Bij voorkeur gebruikt men van 100 tot 5000 ppm polymerisatieremmer met betrekking tot 25 het acrylzuurmonomeer (II).Among the polymerization inhibitors suitable for the process of the invention, mention can be made of 3,5-diterbutyl-4-hydroxytoluene, the methyl ether of hydroquinone, phenothiazine, hydroquinone, catechol and terbutyl catechol. Preferably, from 100 to 5000 ppm polymerization inhibitor with respect to the acrylic acid monomer (II) is used.
De werkwijze maakt het mogelijk waterige oplossingen te bereiden van onverzadigde quaternaire ammoniumzouten (I) met concentraties in de orde van 50 tot 85 gew.% van de zouten (I) in water, die zeer lage hoeveelheden onzuiverheden bevatten, bijvoorbeeld, hoeveelheden die de 0,6 gew.% de acrylzuurmonomeren (II) en 0,4 gew.% CH2 = CH - C(O) - AH (IV), niet te boven gaan (waarbij A de hiervoor gegeven 30 betekenis bezit).The process makes it possible to prepare aqueous solutions of unsaturated quaternary ammonium salts (I) with concentrations on the order of 50 to 85% by weight of the salts (I) in water, containing very low amounts of impurities, for example, amounts containing 0 , 6% by weight of the acrylic acid monomers (II) and 0.4% by weight of CH 2 = CH - C (O) - AH (IV), do not exceed (where A has the significance given above).
Bovendien bezitten de waterige oplossingen van de onverzadigde quaternaire ammoniumzouten, bereid volgens de werkwijze volgens de uitvinding, een stabiliteit bij opslag bij kamertemperatuur boven 1 jaar.In addition, the aqueous solutions of the unsaturated quaternary ammonium salts prepared by the method of the invention have a storage stability at room temperature above 1 year.
De voorbeelden die nu volgen geven gewichtspercentages.The examples that follow now give weight percentages.
35 Voorbeeld (vergelijkend)35 Example (comparative)
Bereiding van een 80%-ige waterige oplossing van acryloyloxyethyltrimethylammoniumchloride vanPreparation of an 80% aqueous solution of acryloyloxyethyl trimethyl ammonium chloride of
In een reactor met dubbele mantel laadt men onder roeren 515 g dimethylaminoëthylacrylaat, gestabiliseerd met behulp van 700 ppm methylether van hydrochinon.In a double jacketed reactor, 515 g of dimethylaminoethyl acrylate, stabilized with 700 ppm of methyl ether of hydroquinone, are charged with stirring.
Tijdens de volledige reactieduur spuit men continu 0,2 Nl/h lucht in in de reactor en handhaaft men: 40 - de temperatuur op 47°C, - atmosferische druk, - de capaciteit bij de uitgang van de spuigaten onder 0,7 Nl/h (hetgeen een verhouding van de volumetri-sche capaciteiten van de luchtkanalen met betrekking tot ingevoerde zuurstof in de reactor onder 17,5 is).During the entire reaction time, 0.2 Nl / h air is continuously injected into the reactor and the following is maintained: 40 - the temperature at 47 ° C, - atmospheric pressure, - the capacity at the exit of the scavengers below 0.7 Nl / h (which is a ratio of the volumetric capacities of the air channels with respect to oxygen input to the reactor below 17.5).
In de eerste stap spuit men 18 g methylchloride in de reactor in met een capaciteit van 30 g/uur (hetgeen 45 11% van de totale hoeveelheid CH3CI noodzakelijk voor de reactie is), voordat, in een tweede stap men tegelijkertijd zowel continu methylchloride als water met een gewichtsverhouding water/CH3CI gelijk aan 0,95 inspuit.In the first step, 18 g of methyl chloride are injected into the reactor at a capacity of 30 g / hour (which is 45% of the total amount of CH3CI necessary for the reaction), before, in a second step, both continuous methyl chloride and inject water with a water / CH3CI weight ratio equal to 0.95.
Bij het naderen van het eind van de reactie wordt de methylchloridecapaciteit geleidelijk verminderd tot 10 g/uur en de capaciteit van de uitgang van de luchtkanalen wordt lager dan 1 Nl/h gehandhaafd (of met 50 een verhouding van de volumetrische capaciteiten van de luchtkanalen ten opzichte van zuurstof bij de ingang van de reactor onder 25).When approaching the end of the reaction, the methyl chloride capacity is gradually decreased to 10 g / h and the air duct output capacity is maintained below 1 Nl / h (or by 50 a ratio of the air duct volumetric capacities to relative to oxygen at the reactor entrance under 25).
De reactie wordt gestopt na 15 uren reageren.The reaction is stopped after 15 hours of reaction.
Tijdens deze bewerking gebruikt men 174 g water en 196 g methylchloride en wint men 865 g acryloyl-oxyethyltrimethylammoniumchioride van 80% in water.During this operation, 174 g of water and 196 g of methyl chloride are used and 865 g of acryloyl oxyethyl trimethyl ammonium chloride of 80% in water are recovered.
55 Het eindproduct wordt vervolgens onderworpen aan een injectie van lucht met een capaciteit van 7 Nl/h gedurende 1/2 uur in de warmte (47°C) gevolgd gedurende 1/2 uur bij kamertemperatuur.The final product is then subjected to an injection of air at a capacity of 7 Nl / h for 1/2 hour in the heat (47 ° C) followed for 1/2 hour at room temperature.
Het eindproduct dat zo verkregen wordt heeft de volgende karakteristieken:The end product thus obtained has the following characteristics:
Claims (3)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8801636 | 1988-02-11 | ||
| FR8801636 | 1988-02-11 | ||
| PCT/FR1989/000037 WO1989007589A1 (en) | 1988-02-11 | 1989-02-02 | Quaternization process |
| FR8900037 | 1989-02-02 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NL8920072A NL8920072A (en) | 1990-12-03 |
| NL193088B NL193088B (en) | 1998-06-02 |
| NL193088C true NL193088C (en) | 1998-10-05 |
Family
ID=9363186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL8920072A NL193088C (en) | 1988-02-11 | 1989-02-02 | Process for the preparation of aqueous solutions of unsaturated quaternary ammonium salts. |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JP2773049B2 (en) |
| BE (1) | BE1006876A4 (en) |
| CA (1) | CA1333613C (en) |
| CH (1) | CH678724A5 (en) |
| DE (1) | DE3990121C2 (en) |
| ES (1) | ES2010133A6 (en) |
| GB (1) | GB2232980B (en) |
| IT (1) | IT1230445B (en) |
| NL (1) | NL193088C (en) |
| WO (1) | WO1989007589A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3938528A1 (en) * | 1989-11-21 | 1991-05-23 | Basf Ag | METHOD FOR THE PRODUCTION OF AQUEOUS SOLUTIONS OR SUSPENSIONS OF QUATERNATION PRODUCTS OF TERTIAL AMINOALKYL ESTERS OR TERTIAL AMINOALKYLAMIDES OF ACRYLIC OR METHACRYLIC ACID, FOR EXAMPLE OF DIMETHYL ACHYL ACO |
| SE0104346L (en) * | 2001-12-21 | 2003-06-22 | Akzo Nobel Nv | Process for continuous quaternization of tertiary amines with an alkyl halide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2608868A1 (en) * | 1975-03-05 | 1976-09-16 | Mitsubishi Chem Ind | METHOD OF MANUFACTURING A QUARTAR AMMONIUM SALT |
| JPS5692252A (en) * | 1979-12-27 | 1981-07-25 | Nitto Chem Ind Co Ltd | Production of unsaturated quaternary ammonium salt |
| JPS57126452A (en) * | 1981-01-28 | 1982-08-06 | Sanyo Chem Ind Ltd | Preparation of quaternary ammonium salt |
| US4745214A (en) * | 1986-06-20 | 1988-05-17 | Norsolor | Process for the preparation of an aqueous solution of unsaturated quaternary ammonium salts |
-
1989
- 1989-02-02 NL NL8920072A patent/NL193088C/en not_active IP Right Cessation
- 1989-02-02 DE DE3990121A patent/DE3990121C2/en not_active Expired - Fee Related
- 1989-02-02 WO PCT/FR1989/000037 patent/WO1989007589A1/en active Application Filing
- 1989-02-02 CH CH3591/89A patent/CH678724A5/fr not_active IP Right Cessation
- 1989-02-02 JP JP1502099A patent/JP2773049B2/en not_active Expired - Lifetime
- 1989-02-09 IT IT8947625A patent/IT1230445B/en active
- 1989-02-09 ES ES8900468A patent/ES2010133A6/en not_active Expired
- 1989-02-10 CA CA000590756A patent/CA1333613C/en not_active Expired - Fee Related
- 1989-02-10 BE BE8900135A patent/BE1006876A4/en not_active IP Right Cessation
-
1990
- 1990-07-09 GB GB9015070A patent/GB2232980B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB9015070D0 (en) | 1990-09-26 |
| GB2232980A (en) | 1991-01-02 |
| IT1230445B (en) | 1991-10-23 |
| CA1333613C (en) | 1994-12-20 |
| JP2773049B2 (en) | 1998-07-09 |
| NL193088B (en) | 1998-06-02 |
| ES2010133A6 (en) | 1989-10-16 |
| DE3990121C2 (en) | 1999-02-11 |
| NL8920072A (en) | 1990-12-03 |
| GB2232980B (en) | 1992-01-08 |
| IT8947625A0 (en) | 1989-02-09 |
| CH678724A5 (en) | 1991-10-31 |
| WO1989007589A1 (en) | 1989-08-24 |
| BE1006876A4 (en) | 1995-01-17 |
| JPH03502451A (en) | 1991-06-06 |
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| Date | Code | Title | Description |
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| A1B | A search report has been drawn up | ||
| BA | A request for search or an international-type search has been filed | ||
| BB | A search report has been drawn up | ||
| BC | A request for examination has been filed | ||
| BC | A request for examination has been filed | ||
| BN | A decision not to publish the application has become irrevocable | ||
| V1 | Lapsed because of non-payment of the annual fee |
Effective date: 20020901 |