NO136152B - MONOMER EMULSION STABILIZER. - Google Patents

MONOMER EMULSION STABILIZER. Download PDF

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NO136152B
NO136152B NO415669A NO415669A NO136152B NO 136152 B NO136152 B NO 136152B NO 415669 A NO415669 A NO 415669A NO 415669 A NO415669 A NO 415669A NO 136152 B NO136152 B NO 136152B
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chloride
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Carlos Miguel Samour
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Kendall & Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)

Description

Foreliggende oppfinnelse angår en monomer emulsjons-s.tabilisator som er i stand til å stabilisere polymerisering av etylenisk umettede monomerer og danne en kopolymer med en slik monomer, hvorved den blir en del av polymeren. The present invention relates to a monomer emulsion stabilizer which is capable of stabilizing polymerization of ethylenically unsaturated monomers and forming a copolymer with such a monomer, whereby it becomes part of the polymer.

Polymerlatexer av etylenisk umettede monomere benyttes for. en rekke formål som f .eks.. Icleb.emasser og bindmidler i ikke-vevede t-ekstiler. Slike polymere latexer fremstilles vanligvis ved emulsjonspolymerisasjon., dvs. ved å polymerisere monomere forbindelser mens disse- er dispergert i et vandig medium, ved hjelp av -et overf lateakt.ivt middel. Det overflateaktive middel ican være anionisk, f . eks ., såpe eller natriumlaurylsuifat. Eventuelt kan midlet være ikke-ionisk-, f.eks. et etylenoksydderivat eller en polyhydroksylforbindelse, eller kan være kationisk, f.eks. et alkylammoniumhalogenid. Kationiske overflateaktive midler brukes-fortrinnsvis sammen med et ikke-ionisk middel for å oppnå bedre resultater. Polymerisasjon av.monomere forbindelser foretas også ofte i nærvær av et vannopploselig beskyttelseskolloid eller stabiliseringsmiddel. Bruken av overflateaktivt eller stabili-serende middel gir.opphav til vannomfindtlig ingrediens i den ferdigfremstilte polymerlatex. Når latexen- skal brukes under forhold hvor våtstyrke og bestandighet overfor vann er onskelige egenskaper, f.eks. som belegg på papir eller under fremstilling av ikke-vevede tekstiler og visse trykkfolsomme klebebånd, er nærvær av disse vannomfindtlige bestanddeler i polymermassen uonsket. Polymer latexes of ethylenically unsaturated monomers are used for. a number of purposes such as e.g. Icleb.emasses and binders in non-woven t-extiles. Such polymeric latexes are usually produced by emulsion polymerization, i.e. by polymerizing monomeric compounds while these are dispersed in an aqueous medium, with the help of a surface-active agent. The surfactant can be anionic, e.g. e.g., soap or sodium lauryl sulfate. Optionally, the agent can be non-ionic, e.g. an ethylene oxide derivative or a polyhydroxy compound, or may be cationic, e.g. an alkylammonium halide. Cationic surfactants are preferably used together with a non-ionic agent to achieve better results. Polymerization of monomeric compounds is also often carried out in the presence of a water-soluble protective colloid or stabilizer. The use of a surface-active or stabilizing agent gives rise to a water-sensitive ingredient in the ready-made polymer latex. When the latex is to be used under conditions where wet strength and resistance to water are undesirable properties, e.g. as a coating on paper or during the production of non-woven textiles and certain pressure-sensitive adhesive tapes, the presence of these water-soluble components in the polymer mass is undesirable.

Man har nå oppnådd nye kvaternære organiske salter som samtidig tjener som stabiliseringsmidler for emulsjonspolymerisa-sj.on av etylenisk umettede monomere og som en monomer reaktant under polymerisasjonen, slik at saltene blir en tilhorende del av den polymere, og derved selv-stabiliseres uten bruk av overflateaktive stoffer og uten nevnte -vannomfindtlige ingredienser. New quaternary organic salts have now been obtained which simultaneously serve as stabilizers for the emulsion polymerization of ethylenically unsaturated monomers and as a monomeric reactant during the polymerization, so that the salts become an integral part of the polymer, and are thereby self-stabilized without the use of surface-active substances and without mentioned water-soluble ingredients.

Ifolge foreliggende oppfinnelse er det således til-veiebragt en monomer.emulsjonsstabilisator som er i stand til å stabilisere polymerisering av etylenisk umttede monomerer og- danne en kqpolymer.med en slik monomer, hvorved den blir en del av polymeren,.og denne monomer er kjennetegnet ved at den har formelen: According to the present invention, a monomer emulsion stabilizer is thus provided which is capable of stabilizing the polymerization of ethylenically unsaturated monomers and forming a kqpolymer with such a monomer, whereby it becomes part of the polymer, and this monomer is characterized in that it has the formula:

hvor V er en maleoyloksy-, citrakonoyloksy-, vinyl- eller metylvinylgruppe, A er en alkylengruppe som inneholder 1-3 C-atomer og utgjor en metylengruppe når V er en vinyl- eller en metylvinylgruppe, R^, R2 og FU er uavhengig av hverandre enverdige organiske grupper som hver inneholder under 8 C-atomer, eller R^ er et uav-henig enverdig organisk radikal som inneholder under 8 C-atomer og R2 og R^ utgjor sammen med nitrogenatomet en pyrrolidin-, piperidin-, morfolin- eller tetrahydro-S-triazin-2-on-gruppe, eller R^, R2 og R-j utgjor sammen med nitrogenatomet en pyridin- eller substituert where V is a maleoyloxy, citraconoyloxy, vinyl or methylvinyl group, A is an alkylene group containing 1-3 C atoms and constitutes a methylene group when V is a vinyl or a methylvinyl group, R^, R2 and FU are independent of mutually monovalent organic groups each containing less than 8 C atoms, or R^ is an independent monovalent organic radical containing less than 8 C atoms and R2 and R^ together with the nitrogen atom form a pyrrolidine, piperidine, morpholine or tetrahydro-S-triazin-2-one group, or R^, R2 and R-j form together with the nitrogen atom a pyridine- or substituted

pyridingruppe, Y betegner en sulfonat-, sulfat-, sulfitt- eller, fosfatgruppe, og R^ er et lipofilt radikal_som inneholder minst en hydrokarbonkjede på 8-28 C-atomer. pyridine group, Y denotes a sulphonate, sulphate, sulphite or phosphate group, and R^ is a lipophilic radical containing at least one hydrocarbon chain of 8-28 C atoms.

R^, R2 og R^, når disse utgjor uavhengige grupper kan være alkylgrupper, alkoksyalkylgrupper, aralkylgrupper som benzyl, amidogrupper som -RCONHR'-, hvor R' betegner hydrogen eller en alkylgruppe, karboksylsyre- eller estergrupper, eller alkylnitrilradi-kaler som -RCN-. Når R-^, R2 og R^ alle betegner uavhengige grupper, utgjores de fortrinnsvis alle av metylgrupper. Når R^ betegner en uavhengig gruppe og R2 og R-j. danner en del av en ringstruktur, foretrekkes igjen at R-^ er en metylgruppe. R^, R2 and R^, when these form independent groups can be alkyl groups, alkoxyalkyl groups, aralkyl groups such as benzyl, amido groups such as -RCONHR'-, where R' denotes hydrogen or an alkyl group, carboxylic acid or ester groups, or alkylnitrile radicals such as - RCN-. When R 1 , R 2 and R 1 all denote independent groups, they are preferably all made up of methyl groups. When R 1 denotes an independent group and R 2 and R 1 . forms part of a ring structure, it is again preferred that R-^ is a methyl group.

Blandinger av kvaterniserte monomere emulsjonsstabilisatorer med ovenstående formel kan også brukes til polymerisasjonsprosessen. Mixtures of quaternized monomeric emulsion stabilizers of the above formula can also be used for the polymerization process.

Monomere emulsjonsstabilisatorer med ovenstående Monomeric emulsion stabilizers with the above

formel kan fremstilles ved forst å fremstille et kvaternaert ammoniumhalogenid med formelen: formula can be prepared by first preparing a quaternary ammonium halide with the formula:

hvor V, A, R-^, R2 og R^ har tidligere angitte betydninger, og deretter omsetter det kvaternære ammoniumhalogenid med et lipofilt salt med formel R^YX,. hvor R^ er en lipofil gruppe som inneholder minst én åpenkjedet hydrokarbongruppe på 8-28 C-atomer, Y betegner anion-gruppen og X er et alkalimetall eller en ammoniumgruppe, hvorved reaksjonen følges av eliminering av et molekyl alkalimetall eller ammoniumhalogenid. where V, A, R-^, R 2 and R^ have previously indicated meanings, and then reacts the quaternary ammonium halide with a lipophilic salt of formula R^YX,. where R^ is a lipophilic group containing at least one open-chain hydrocarbon group of 8-28 C atoms, Y denotes the anion group and X is an alkali metal or an ammonium group, whereby the reaction is followed by the elimination of a molecule of alkali metal or ammonium halide.

Kvaternære ammoniumhalogenider med ovenstående formel kan fremstilles ved omsetning av et egnet etylenisk-umettet alkylen-halogenid med et tertiært amin eller med en egnet ringforbindelse som inneholder nitrogen i ringen, eller ved omsetning av en halogenert forbindelse inneholdende aktivt halogen med et substituert etylenisk- Quaternary ammonium halides of the above formula can be prepared by reacting a suitable ethylenically unsaturated alkylene halide with a tertiary amine or with a suitable ring compound containing nitrogen in the ring, or by reacting a halogenated compound containing active halogen with a substituted ethylenic-

umettet amin. unsaturated amine.

Typiske reaksjoner er reaksjoner mellom allylklorid og pyridin eller metylmorfolin, mellom allylklorid og dimetylbenzylamin, mellom allylbromid og trietylamin og mellom klormetylbutyleter og dimetylallylamin. Typical reactions are reactions between allyl chloride and pyridine or methylmorpholine, between allyl chloride and dimethylbenzylamine, between allyl bromide and triethylamine and between chloromethylbutyl ether and dimethylallylamine.

Andre kvaternære ammoniumhalogenider av ovenstående formel kan fremstilles via en totrinnsprosess, f.eks. kondensasjon av maleinsyréanhydrid eller citrakonsyreanhydrid med en aminoalkohol under dannelse av en nitrogenholdig halvester, fulgt av kvaterni-sering av nitrogenet med en egnet forbindelse som inneholder aktivt halogen. Eksempler på fremstilling av halvestere er omsetninger mellom citrakonsyreanhydrid og en disubstituert aminoalkohol som dimetylaminoetanol. Det således formede aminoderivat overfores til et kvaternært ammoniumhalogenid ved omsetning med en aktiv halogenfor-bindelse som kloracetonitril, en halogenmetylalkyleter som klormetylbutyleter, en halogenester med formel XCHgCOOR, hvor X betegner halogen og R et alifatisk hydrokarbonradikal som inneholder hbyst 7 C-atomer som etylkloracetat,eller et halogenacetamid med formel XCHgCONHR, hvor X og R har samme betydninger som for estere ovenfor, eksempelvis kloracetamid. Alternativt kan aminoalkoholen forst kvaterniseres og deretter omsettes med anhydridet. En annen totrinns-reaksjon for fremstilling av det kvaternære ammoniumhalogenid er om-setningen mellom et syreanhydrid som maleinsyre- eller citrakonsyreanhydrid og en alkanol som inneholder aktivt halogen, som brometa-nol, hvoretter produktet omsettes med et tertiært amin som tri-metylamin. Other quaternary ammonium halides of the above formula can be prepared via a two-step process, e.g. condensation of maleic anhydride or citraconic anhydride with an amino alcohol to form a nitrogenous half-ester, followed by quaternization of the nitrogen with a suitable compound containing an active halogen. Examples of the production of half-esters are reactions between citraconic anhydride and a disubstituted amino alcohol such as dimethylaminoethanol. The amino derivative thus formed is transferred to a quaternary ammonium halide by reaction with an active halogen compound such as chloroacetonitrile, a halogen methyl alkyl ether such as chloromethyl butyl ether, a halogen ester of the formula XCHgCOOR, where X denotes halogen and R an aliphatic hydrocarbon radical containing at least 7 C atoms such as ethyl chloroacetate, or a haloacetamide of formula XCHgCONHR, where X and R have the same meanings as for esters above, for example chloroacetamide. Alternatively, the amino alcohol can first be quaternized and then reacted with the anhydride. Another two-step reaction for producing the quaternary ammonium halide is the reaction between an acid anhydride such as maleic or citraconic anhydride and an alkanol containing an active halogen, such as bromethanol, after which the product is reacted with a tertiary amine such as trimethylamine.

Eksempler på egnede lipofile salter for overforing av de kvaternære ammoniumhalogenider til den monomere emulsjonsstabilisator er natriumlaurylsulfat, di-tridecyinatrium-sulfosuccinat, di-oktyl-natriumsulfosuccinat, natrium-2-etylheksylsulfat, natrium-dodecyl-fenylsulfonat, natrium-di-2-etylheksylfosfat, og ammonium-salter av sulfatestere av alkylfenoksypolyetylenoksy-etanoler. Sist-nevnte har generell formel, cn<H>(2n+i)_C6<H>4<->°<*>(CH2*CH2'°'^mCH2*S04~ ~NH^+ og forhandles under varemerket "Alipal" Examples of suitable lipophilic salts for transferring the quaternary ammonium halides to the monomeric emulsion stabilizer are sodium lauryl sulfate, di-tridecy sodium sulfosuccinate, di-octyl sodium sulfosuccinate, sodium 2-ethylhexyl sulfate, sodium dodecyl phenyl sulfonate, sodium di-2-ethylhexyl phosphate, and ammonium salts of sulfate esters of alkylphenoxypolyethyleneoxyethanols. The latter has the general formula, cn<H>(2n+i)_C6<H>4<->°<*>(CH2*CH2'°'^mCH2*S04~ ~NH^+ and is sold under the trademark "Alipal "

Reaksjonen mellom det lipofile salt og det kvaternære ammoniumhalogenid er rask og fullstendig, slik at den monomere emulsjonsstabilisator ikke behpver å* isoleres og renses. The reaction between the lipophilic salt and the quaternary ammonium halide is rapid and complete, so that the monomeric emulsion stabilizer does not need to be* isolated and purified.

Når f.eks. den monomere emulsjonsstabilisator fremstilles When e.g. the monomeric emulsion stabilizer is prepared

i opplbsning i organisk opplbsningsmiddel, formes umiddelbart en felling av alkalimetallhalogenid. Hvis stabilisatoren isoleres, in solution in an organic solvent, a precipitate of alkali metal halide is immediately formed. If the stabilizer is isolated,

er virkningen ved stabilisering av polymerisasjonens andre monomere lik den virkning som oppnås i nedenstående eksempler hvorved stabilisatoren fremstilles og- brukes in situ. is the effect of stabilizing the other monomers of the polymerization similar to the effect achieved in the examples below whereby the stabilizer is produced and used in situ.

Som eksempel ble 8,9 gram ållyltrietylammonrumklorid og 29,2 gram di-trSecylnatriumsulfosuccinat i 200 gram etylacetat rbrt sammen i 8 dager ved romtemperatur. Det dannede faste natriumklo-rid ble frafiltrert og■etylacetatet inndampet, og etterlot 34, 1 gram voksaktig fast stoff, et utbytte på over' 90 * f<> av det teoretiske. Voks-forbindelsen ble opplost i vann og man kunne ikke finne noen frie kloridioner, hvilket viser at kvaternært ammoniumhalogenid ikke var tilstede.. As an example, 8.9 grams of allyl triethylammonium chloride and 29.2 grams of di-trSecyl sodium sulfosuccinate in 200 grams of ethyl acetate were stirred together for 8 days at room temperature. The solid sodium chloride formed was filtered off and the ethyl acetate evaporated, leaving 34.1 grams of waxy solid, a yield of over 90% of theory. The wax compound was dissolved in water and no free chloride ions could be found, showing that quaternary ammonium halide was not present.

Som et ytterligere eksempel satte man 9 gram allyltri-etylammoniumklorid til 17,4 gram natriumdocecylbenzensulfonat i 200 gram etylace.tat. Etter tre dager ved romtemperatur bie det faste natriumkloridet frafiltrert og etylacetatet inndampet, og lot tilbake 23,9 gram voksaktig fast stoff. Ved- opplbsning i vann kunne man ikke finne frie kloridioner.- As a further example, 9 grams of allyltriethylammonium chloride was added to 17.4 grams of sodium docecylbenzenesulfonate in 200 grams of ethyl acetate. After three days at room temperature, the solid sodium chloride was filtered off and the ethyl acetate evaporated, leaving 23.9 grams of a waxy solid. When dissolved in water, no free chloride ions could be found.

Overforing av kvaternært ammoniumhalogenid med formel II til emulsjonsstabilisator- med' formel I foregår tilsynelatende kvantitativt, og-det- lipofile salt som anvendes f or „f remstilling av kvaternisert stabilisator bor ikke' betraktes som en forbindelse som i seg selv har' overfla-teaktiv virkning, i foreliggende oppfinnelses reaksjoner. Transfer of quaternary ammonium halide with formula II to emulsion stabilizer with formula I apparently takes place quantitatively, and the lipophilic salt used for the production of quaternized stabilizer should not be considered as a compound which in itself has surface-active effect, in the reactions of the present invention.

FREMSTILLING AV KVATERNÆRE AMMONIUMHALOGENIDER MED FORMEL II PREPARATION OF QUATERNARY AMMONIUM HALIDES OF FORMULA II

1. Maleoyloksy-etyl-carbam'oylmetyl-dimetyl-ammoniumklorid. .374 gram: av en' vandig opplbsning- inneholdende 50-vektprosent dime.tylaminoe.tylmaleinsyreester (fra maleinsyréanhydrid og dimetylaminoetanol)' ble kokt under til-bakelop i 9 timer med 95 gram kloracetamid (98,5 i° rent). Kloridanalyse ved-vandig titrering etter tilbakelopskokingen viste at- 9.7- $ av den. teoretiske mengde klorid forelå i. ioneform... 1. Maleoyloxy-ethyl-carbamoylmethyl-dimethyl-ammonium chloride. 374 grams of an aqueous solution containing 50% by weight of dimethylaminoethylmaleic acid ester (from maleic anhydride and dimethylaminoethanol) was refluxed for 9 hours with 95 grams of chloroacetamide (98.5% pure). Chloride analysis by aqueous titration after reflux showed that 9.7% of it. theoretical amount of chloride was present in ionic form...

2. Allylpyridinklorid.. 2. Allylpyridine chloride..

15, 8 gram pyridin ble satt' til 15,3 gram' allylklorid i 15.8 grams of pyridine were added to 15.3 grams of allyl chloride i

31 gram -dimetylf or.mamid og hensatt; i 9: dager ved 25°C Det kvaternære halogenidet ble isolert ved tilsetning av etylacetat, og ana-lysen viste 94 $ av teoretisk kloridinnhold.- 31 grams of -dimethylformamide and reserved; for 9 days at 25°C. The quaternary halide was isolated by addition of ethyl acetate, and analysis showed 94% of theoretical chloride content.

3.. Allyl-n-butoksymetyl-dime4;ylarnmoniumklorid. 3.. Allyl-n-butoxymethyl-dimethyl-dimethylammonium chloride.

24,7 gram klormetylbutyleter ble tilsatt til 17 gram dimetylallylamin i 32 gram etylacetat. Reaksjonen foregikk sterkt eksotermt og to sjikt dannet seg meget hurtig. Man fortsatte rbr-ingen ved 25°C i 24 timer, hvoretter opplbsningsmidlet ble .fjernet i vakuum. Kloridanalyse av det temmelig viskose flytende produkt angav 91 i° av teoretisk utbytte. 24.7 grams of chloromethylbutyl ether was added to 17 grams of dimethylallylamine in 32 grams of ethyl acetate. The reaction was highly exothermic and two layers formed very quickly. Stirring was continued at 25°C for 24 hours, after which the solvent was removed in vacuo. Chloride analysis of the rather viscous liquid product indicated 91% of theoretical yield.

4. Allyl-trietyl-ammoniumbromid. 4. Allyl triethyl ammonium bromide.

20,2 gram trietylamin- ble satt til 24,-2 gram allylbromid 20.2 grams of triethylamine were added to 24.2 grams of allyl bromide

i 44 gram etylacetat. Et krystallinsk fast'stoff begynte å felles ut etter 5 minutter. Etter 24 timer ved 25°C ble produktet frafiltrert, vasket og tbrket. Det isolerte produktet veide 41,3 gram- in 44 grams of ethyl acetate. A crystalline solid began to precipitate after 5 minutes. After 24 hours at 25°C, the product was filtered off, washed and dried. The isolated product weighed 41.3 grams-

og smeltet ved 230 - 234°C under dekomponering. Bromidanalyse viste 97,5 i° av teoretisk bromidmengde i det vannopploselige, hvite, krystallinske stoff. 5. Citrakonoyloks-etyl-karbamoylmetyl-dimetylammoniumklorid. and melted at 230 - 234°C during decomposition. Bromide analysis showed 97.5% of the theoretical amount of bromide in the water-soluble, white, crystalline substance. 5. Citraconoyloxyethylcarbamoylmethyldimethylammonium chloride.

20.1 gram dimetylaminoetyl-citrakonsyreester (fra citrakonsyreanhydrid og dimetylaminoetanol) ble tilsatt til 9,5 gram (98,5 io rent) kloracetamid i 30 gram dimetylformamid. Det kvaternære halogenid ble isolert ved tilsetning av etylacetat og inneholdt 70 io av det teoretiske kloridinnhold. 20.1 grams of dimethylaminoethyl citraconic acid ester (from citraconic anhydride and dimethylaminoethanol) was added to 9.5 grams (98.5 io of pure) chloroacetamide in 30 grams of dimethylformamide. The quaternary halide was isolated by the addition of ethyl acetate and contained 70 io of the theoretical chloride content.

6. Allylmetyl-morfolinklorid. 6. Allylmethyl morpholine chloride.

20.2 gram n-metyl-morfolin ble satt til 50 gram allylklorid. Et krystallinsk fast stoff skilte seg. ut i lopet av 2 timer. Etter 18 dager ved 25°C ble stoffet fraskilt, vasket med etylacetat og torket. Produktet smeltet ved 175 - 185°C under dekomponering og inneholdt 100,5 i° av teoretisk kloridinnhold. 20.2 grams of n-methyl-morpholine was added to 50 grams of allyl chloride. A crystalline solid separated. out in the course of 2 hours. After 18 days at 25°C, the substance was separated, washed with ethyl acetate and dried. The product melted at 175-185°C during decomposition and contained 100.5% of theoretical chloride content.

7. Allylbenzyl-dimetylammoniumklorid. 7. Allylbenzyldimethylammonium chloride.

27-gram dimetylbenzylamin ble satt til 15,4 gram allylklorid i 42,4 gram etylacetat. • Reaksjonen var endoterm, og et krystallinsk produkt dannet seg i lopet av 5 minutter. Etter 7 dagers henstand ved 25°C ble det hvite, faste stoff frafiltrert, vasket og torket. Kloridinnholdet i det kvaternære halogenid var 95,5 i av det teoretiske. 27 grams of dimethylbenzylamine was added to 15.4 grams of allyl chloride in 42.4 grams of ethyl acetate. • The reaction was endothermic, and a crystalline product formed within 5 minutes. After standing for 7 days at 25°C, the white solid was filtered off, washed and dried. The chloride content of the quaternary halide was 95.5% of the theoretical.

8. Allylacetamido-dimetylammoniumklorid. 8. Allylacetamido-dimethylammonium chloride.

17 gram. dimetylallylamin og 19,1 gram kloracetamid ble blandet sammen i 40 gram dimetylformamid. Reaksjonen var eksoterm og en homogen opplbsning dannet seg. Etter 24 timer ble reaksjons-produktet, allylacetamido-dimetylammoniumklorid, isolert ved tilsetning av metyletylketon. Omkrystallisering gav et hvitt, krystallinsk stoff som smeltet ved 110 til 114°C og som ved analyse viste 97 i av teoretisk kloridinnhold. 9. Maleoyloksy-isopropyl-karbamoylmetyl-dimetylammoniumklorid. 17 grams. dimethylallylamine and 19.1 grams of chloroacetamide were mixed together in 40 grams of dimethylformamide. The reaction was exothermic and a homogeneous solution formed. After 24 hours, the reaction product, allyl acetamido-dimethylammonium chloride, was isolated by addition of methyl ethyl ketone. Recrystallization gave a white, crystalline substance which melted at 110 to 114°C and which on analysis showed 97 µl of theoretical chloride content. 9. Maleoyloxy-isopropyl-carbamoylmethyl-dimethylammonium chloride.

20,6 gram dimetylisopropanolamin ble opplost i 40,2 gram H^O, hvortil man satt 19,6 gram pulverisert maleinsyréanhydrid, og holdt temperaturen under 40°C ved avkjbling. Etter 24 timer ved 25°C tilsatte man 18,7 gram 2-kloracetamid (98,5 % renhet). Kloridanalyse ved vandig titrering etter koking under tilbakelbp viste at 95 i av den teoretiske kloridmengde forelå i ioneform. 20.6 grams of dimethylisopropanolamine were dissolved in 40.2 grams of H2O, to which 19.6 grams of powdered maleic anhydride were added, and the temperature was kept below 40°C during cooling. After 24 hours at 25°C, 18.7 grams of 2-chloroacetamide (98.5% purity) were added. Chloride analysis by aqueous titration after boiling under reflux showed that 95% of the theoretical amount of chloride was present in ionic form.

FREMSTILLING AV MONOMER EMULS JONS S TABILISATOR MED FORMEL I, OG DERES ANVENDELSE VED KOPOLYMERISASJON MED ANDRE MONOMERE. PREPARATION OF MONOMER EMULS JONS S TABILIZER OF FORMULA I, AND THEIR USE IN COPOLYMERIZATION WITH OTHER MONOMERS.

Som nevnt ovenfor, foregår reaksjonen mellom kvaternært ammoniumhalogenid og lipofilt salt hurtig og kvantitativt. ' Når de etylenisk-umettede monomere polymeriseres i satsvis prosess, er det en fordel å fore det kvaternære ammoniumhalogenid og det lipofile salt sammen i vandig opplbsning, tilsette stbrsteparten av den monomere, som lett blir emulgert, og derpå starte polymerisasjonen. As mentioned above, the reaction between quaternary ammonium halide and lipophilic salt takes place rapidly and quantitatively. When the ethylenically unsaturated monomers are polymerized in a batch process, it is an advantage to bring the quaternary ammonium halide and the lipophilic salt together in aqueous solution, add the bulk of the monomer, which is easily emulsified, and then start the polymerization.

Når den monomere emulsjonsstabilisator fremstilles på denne måten in situ, kan det tillates et stbkiometrisk overskudd av kvaternært salt, forutsatt at det dannes tilstrekkelig kompleks (formel i) til at mengden utgjor 0,2 til 5 molprosent av den samlede monomermengde som skal polymeriseres. Et overskudd av lipofilt salt bor imidlertid unngås, siden nærvær av vesentlige mengder fritt lipofilt salt i den ferdige polymer oker vannomfindtligheten hos den polymere. When the monomeric emulsion stabilizer is prepared in this way in situ, a stoichiometric excess of quaternary salt can be allowed, provided that sufficient complex is formed (formula i) so that the amount constitutes 0.2 to 5 mole percent of the total amount of monomer to be polymerized. However, an excess of lipophilic salt should be avoided, since the presence of significant amounts of free lipophilic salt in the finished polymer increases the water sensitivity of the polymer.

Generelt er det en fordel at mengden monomer emulsjonsstabilisator utgjor 0,2 til 5 molprosent av den totale monomer som set-tes til polymerisasjonsblandingen, og at den ferdige polymer hvorav stabilisatoren utgjor en del inneholder 0,2 til 5,0 molprosent grupper som stammer fra stabilisatoren. In general, it is an advantage that the amount of monomer emulsion stabilizer constitutes 0.2 to 5 mol percent of the total monomer added to the polymerization mixture, and that the finished polymer of which the stabilizer forms a part contains 0.2 to 5.0 mol percent of groups originating from the stabilizer.

Man kan fremstille vandige polymerdispersjoner Aqueous polymer dispersions can be prepared

hvor innholdet av fast polymer er 40 - 50 vektprosent. Om bnsket kan torrstoffinnholdet fortynnes til 1 i eller mindre, under opprettholdelse av stabiliteten ved både hbyere og lavere kon-sentrasjoner. where the content of solid polymer is 40 - 50 percent by weight. If desired, the dry matter content can be diluted to 1 in or less, while maintaining stability at both higher and lower concentrations.

Polymerisasjonsprosessen skal illustreres ved folgende eksempler. The polymerization process shall be illustrated by the following examples.

Eksempel 1 Example 1

75 gram (0,75 mol) etylakrylat ble emulgert ved under ror-ing å tilsette 3,10 gram maleoyloksyetyl-karbamoylmetyl-dimetylammoniumklorid og 1,5 gram natriumlaurylsulfat i 300 gram R^O, hvorved emuls j-onens pH var 4,5. 75 grams (0.75 mol) of ethyl acrylate was emulsified by adding, while stirring, 3.10 grams of maleoyloxyethylcarbamoylmethyldimethylammonium chloride and 1.5 grams of sodium lauryl sulfate in 300 grams of R2O, whereby the pH of the emulsion was 4.5 .

Den monomere emulsjonsstabilisatorens konsentrasjon var The monomeric emulsion stabilizer concentration was

1 molprosent. Emulsjonen ble kjblt til 18°C, og man tilsatte 8 1 mole percent. The emulsion was cooled to 18°C, and 8 was added

gram 3 $ig H^C^ i H20' sami: langsomt dråpevis 0,02 gram ferroammoniumsulfat og 0,5 gram askorbinsyre i 10 gram E^ 0. Man arbeidet under nitrogenatmosfære og fortsatte roringen,hvilket også gjelder for alle de nedenstående eksempler. 1,8 gram reduksjonsopplosning var nbdvendig for å starte polymerisasjonen, og eksotermiteten var ca. 16°C på 6 minutter. Etterat reaksjonsblandingen var avkjblt til romtemperatur, tilsatte man 1 gram til av reduksjonsopplosning, gram 3 $ig H^C^ in H20' sami: slowly drop by drop 0.02 gram ferroammonium sulfate and 0.5 gram ascorbic acid in 10 gram E^ 0. Work was done under a nitrogen atmosphere and the stirring was continued, which also applies to all the examples below. 1.8 grams of reducing solution were required to start the polymerization, and the exothermic rate was approx. 16°C in 6 minutes. After the reaction mixture had cooled to room temperature, 1 gram more of reducing solution was added,

uten at ytterligere eksoterm reaksjon satte inn. Polymerutbyttet var over 90 i° av teoretisk, og det dannet seg ikke noe koagulat. without further exothermic reaction setting in. The polymer yield was over 90% of theoretical, and no coagulum formed.

Man gjentok dette eksempel med 75 gram etylakrylat, men satte til denne opplbsning 2,25 gram av det voksaktige faste stoff isolert fra en reaksjonsblanding av etyl-trietylammoniumklorid og di-tridecyl-natriumsulfosuccinat som beskrevet ovenfor, i 290 gram R^O. Polymerisasjonen ble startet og gjennomført som i eksempel 1 med lignende resultater. This example was repeated with 75 grams of ethyl acrylate, but to this solution was added 2.25 grams of the waxy solid isolated from a reaction mixture of ethyl triethylammonium chloride and ditridecyl sodium sulfosuccinate as described above, in 290 grams of R2O. The polymerization was started and carried out as in Example 1 with similar results.

Man gjentok igjen eksempel 1 med 75 gram etylakrylat, Example 1 was repeated again with 75 grams of ethyl acrylate,

men med 2,3 g av ovenstående voksaktige reaksjonsprodukt mellom allyl-trietylammoniumklorid og natrium-dodecyl-benzensulfonat, i 290 gram H^O, som monomer emulsjonsstabilisator. Polymerisasjonen ble igjen startet og'gjennomført som i eksempel 1, og atter med i det vesentlige likt resultat. but with 2.3 g of the above waxy reaction product between allyl triethylammonium chloride and sodium dodecyl benzene sulfonate, in 290 grams of H^O, as monomer emulsion stabilizer. The polymerization was again started and carried out as in example 1, and again with essentially the same result.

Eksempel 2 Example 2

10 gram etylakrylat og 73,6 gram 2-etylheksylakrylat ble emulgert ved å tilsette disse under omroring til 2,52 gram natriumlaurylsulfat og 2,52-gram maleoyloksyetyl-karbamoylmetyl-dimetyl-'ammoniumklorid i 350 gram HgO. Innholdet av monomer emulsjonsstabilisator var 1,8 og emulsjonens pH lik 4,5. Tilsetninger av red-ox-forbindelse var som i eksempel 1. Polymerisasjonen ble satt igang ved tilsetning av 2,4 gram reduksjonsopplosning og eksotermiteten var 28°C etter 4,5 minutter. Etter avkjoling til romtemperatur tilsatte man 2 gram ytterligere reduksjonsmiddel uten videre eksoterm reaksjon. Utbytte av brukbar polymer var over 90 $ av teoretisk-, og den polymere var egnet som trykkfblsomt klebestoff. 10 grams of ethyl acrylate and 73.6 grams of 2-ethylhexyl acrylate were emulsified by adding these with stirring to 2.52 grams of sodium lauryl sulfate and 2.52 grams of maleoyloxyethylcarbamoylmethyldimethylammonium chloride in 350 grams of HgO. The content of monomeric emulsion stabilizer was 1.8 and the pH of the emulsion equal to 4.5. Additions of red-ox compound were as in example 1. The polymerization was initiated by the addition of 2.4 grams of reduction solution and the exotherm was 28°C after 4.5 minutes. After cooling to room temperature, 2 grams of further reducing agent were added without further exothermic reaction. The yield of usable polymer was over 90% of theoretical, and the polymer was suitable as a pressure sensitive adhesive.

Eksempel 3 Example 3

100 gram etylakrylat ble emulgert ved å tilsette disse under omrbring til 3 gram natriumdi-2-etylheksylfosfat og 3 gram maleoyloksy-etyl-karbamoylmetyl-dimetylammoniumklorid i 290 gram vann. Emulsjonens pH var 4,5. Den monomere emulsjonsstabilisator holdt en konsentrasjon på 0,9 molprosent. Red-ox-opplbsningene og polymerisasjonsprosessen var som angitt i eksempel 1. 100 grams of ethyl acrylate were emulsified by adding these while stirring to 3 grams of sodium di-2-ethylhexyl phosphate and 3 grams of maleoyloxy-ethyl-carbamoylmethyl-dimethylammonium chloride in 290 grams of water. The pH of the emulsion was 4.5. The monomeric emulsion stabilizer maintained a concentration of 0.9 mole percent. The red-ox solutions and polymerization process were as indicated in Example 1.

Utbytte av brukbar polymer var over 90 i av den teoretiske. Eksempel 4 The yield of usable polymer was over 90% of the theoretical. Example 4

100 gram etylakrylat ble emulgert ved å tilsette denne forbindelse under rbring til 3 gram "ALIPAL CO 436" og 3 gram maleoyloksy-etyl-karbamoylmetyl-dimetylammoniumklorid i 270 gram H^O. Emulsjonens pH var 4,5. Polymerisasjonen ble startet og fullfort under samme forhold og med samme reagenser som i eks. 1. Utbytte var over 90 i av det teoretiske av brukbar polymer. 100 grams of ethyl acrylate was emulsified by adding this compound with stirring to 3 grams of "ALIPAL CO 436" and 3 grams of maleoyloxyethylcarbamoylmethyldimethylammonium chloride in 270 grams of H₂O. The pH of the emulsion was 4.5. The polymerization was started and completed under the same conditions and with the same reagents as in ex. 1. Yield was over 90% of the theoretical amount of usable polymer.

Eksempel 5 Example 5

100 gram etylakrylat ble emulgert ved å tilsette forbindelsen under rbring til 3 gram natriumlaurylsulfat og 3 gram allylpyridinklorid i 290 gram vann. 100 grams of ethyl acrylate was emulsified by adding the compound under stirring to 3 grams of sodium lauryl sulfate and 3 grams of allylpyridine chloride in 290 grams of water.

Emulsjonens pH var 5,0. Den monomere emulsjonsstabilisatorkonsentrasjon var 1,3 molprosent. Polymerisasjonen ble startet og fullfort med samme reagenser og under samme betingelser som i eksempel 1. Utbytte av polymer var over 90 i av teoretisk. The pH of the emulsion was 5.0. The monomeric emulsion stabilizer concentration was 1.3 mole percent. The polymerization was started and completed with the same reagents and under the same conditions as in example 1. The yield of polymer was over 90% of theoretical.

Eksempel 6 Example 6

100 gram etylakrylat ble emulgert ved tilsetning under omrbring til 3 gram natriumlaurylsulfat og 3 gram allyl-n-butoksy-metyl-dimetylammoniumklorid i 290 gram R^O. Emulsjonens pH var 3»5, og den monomere emulsjonsstabilisatorkonsentrasjon var 1,1 molprosent. Polymerisasjonen ble satt igang og fullfort med samme reagenser og under samme forhold som i eksempel 1, og utbytte av brukbar polymer var over 90 i» av det teoretiske. 100 grams of ethyl acrylate was emulsified by adding with stirring to 3 grams of sodium lauryl sulfate and 3 grams of allyl-n-butoxy-methyl-dimethylammonium chloride in 290 grams of R₂O. The pH of the emulsion was 3.5, and the monomeric emulsion stabilizer concentration was 1.1 mole percent. The polymerization was started and completed with the same reagents and under the same conditions as in example 1, and the yield of usable polymer was over 90% of the theoretical.

Eksempel 7 Example 7

100 gram etylakrylat ble emulgert ved tilsetning under omroring til 3 gram "ALIPAL CO 436" og 3 gram allyl-trietylammonium-bromid i 290 gram H^O. Emulsjonens pH var 5,0. Polymerisasjonen ble startet og fullfort med samme reagenser og forhold som i eksempel 1. Utbytte av polymer var over 90 i av det teoretiske. 100 grams of ethyl acrylate was emulsified by adding with stirring to 3 grams of "ALIPAL CO 436" and 3 grams of allyl triethylammonium bromide in 290 grams of H₂O. The pH of the emulsion was 5.0. The polymerization was started and completed with the same reagents and conditions as in example 1. Yield of polymer was over 90% of the theoretical.

Eksempel 8 Example 8

100 gram etylakrylat ble emulgert ved tilsetning under om- 100 grams of ethyl acrylate was emulsified by addition under stirring

rbring til 3 gram "ALIPAL CO 436" og 3 gram allyl-metyl-morfolinklorid i 290 gram H^O. Emulsjonens pH var 5,0. Polymerisasjonen ble satt igang og fullfort med samme reagenser og under samme forhold som i eksempel 1. Utbytte av brukbar polymer var over 90 % rbring to 3 grams of "ALIPAL CO 436" and 3 grams of allyl-methyl-morpholine chloride in 290 grams of H^O. The pH of the emulsion was 5.0. The polymerization was initiated and completed with the same reagents and under the same conditions as in example 1. The yield of usable polymer was over 90%

av teoretisk. of theoretical.

Eksempel 9 Example 9

50 gram etylakrylat ble emulgert ved tilsetning under omrbring til 1,5 gram natriumlaurylsulfat og 2,1 gram citraconoyloksy-etyl-karbamoylmetyl-dimetylammoniumklorid i 145 gram H"20. Emulsjonens pH var 4,5. Konsentrasjonen av monomer emulsjonsstabilisator var 2 molprosent. Emulsjonen ble avkjblt til 17°C og 5 gram 3 foig H20250 grams of ethyl acrylate was emulsified by addition under stirring to 1.5 grams of sodium lauryl sulfate and 2.1 grams of citraconoyloxyethylcarbamoylmethyldimethylammonium chloride in 145 grams of H"20. The pH of the emulsion was 4.5. The concentration of monomeric emulsion stabilizer was 2 mole percent. The emulsion was cooled to 17°C and 5 grams 3 foig H 2 O 2

tilsatt. Dråpevis tilsetning av 1 gram av den vanlige ferroammoniumsulfat-askorblnsyre-reduktant startet polymerisasjonen, som ble fullfort som i eksempel 1. Utbytte av brukbar polymer var over 90 $ added. Dropwise addition of 1 gram of the common ferrous ammonium sulfate-ascorbic acid reductant initiated the polymerization, which proceeded as in Example 1. Yields of usable polymer were over $90

av teoretisk. of theoretical.

Eksempel 10 Example 10

10 gram etylakrylat og 77 gram butylakrylat ble emulgert ved under omrbring å tilsette disse til 3 gram natriumlaurylsulfat og 3 gram allylbenzyl-dimetylammoniumklorid i 290 gram H"20. Emulsjonens -pH var lik 5,5. Konsentrasjonen av monomer emuls jonsstabi-lisator var 2 molprosent. Med 10 gram 3 $ig H202-opplosning og den vanlige reduktantopplbsning ble polymerisasjonen satt igang og fullfort som i eksempel 1. Utbytte av brukbar polymer var over 90 % av teoretisk. 10 grams of ethyl acrylate and 77 grams of butyl acrylate were emulsified by adding these with stirring to 3 grams of sodium lauryl sulfate and 3 grams of allylbenzyldimethylammonium chloride in 290 grams of H"20. The -pH of the emulsion was equal to 5.5. The concentration of monomer emulsion stabilizer was 2 With 10 grams of 3% H 2 O 2 solution and the usual reductant solution, the polymerization was initiated and completed as in example 1. The yield of usable polymer was over 90% of theoretical.

Eksempel 11 Example 11

100 gram av vinylacetat "ble emulgert ved under omrbring 100 grams of vinyl acetate were emulsified with stirring

å tilsette forbindelsen til 3 gram natriumlaurylsulfat og 3 gram allyl-trietyl-ammoniumbromid i 290 gram HgO. Emulsjonens pH var 5,0. Emulsjonen ble avkjolt til 18°C, og polymerisasjonen startet og fullfort med hydrogenperoksyd, ferroammoniumsulfat og askorbinsyre som i eksempel 1. Utbytte av brukbar polymer var 95 $ av teoretisk. adding the compound to 3 grams of sodium lauryl sulfate and 3 grams of allyl triethyl ammonium bromide in 290 grams of HgO. The pH of the emulsion was 5.0. The emulsion was cooled to 18°C, and polymerization started and completed with hydrogen peroxide, ferrous ammonium sulfate, and ascorbic acid as in Example 1. Yield of usable polymer was $95 of theoretical.

Eksempel 12 Example 12

20 gram styren og 80 gram metylmetacrylat ble emulgert under omrbring ved tilsetning til 3 gram allyl-trietyl-ammoniumbromid og 3 gram natriumlaurylsulfat i 290 gram H^O. Oppløsning-ens pH var 5,0. Polymerisasjonen ble startet og fullfort ved 26 C med samme reagenser som i eksempel 1. Utbytte av brukbar polymer var over 90 $ av teoretisk. 20 grams of styrene and 80 grams of methyl methacrylate were emulsified under stirring by adding 3 grams of allyl triethyl ammonium bromide and 3 grams of sodium lauryl sulfate in 290 grams of H₂O. The pH of the solution was 5.0. The polymerization was started and completed at 26 C with the same reagents as in Example 1. The yield of usable polymer was over 90$ of theoretical.

Eksempel 13 Example 13

70 gram etylakrylat, 20 gram laurylmetakrylat, 8 gram acrylsyre og 2 gram N-metylolakrylamid ble emulgert ved under ror-, ing å tilsette dem til 3 gram allyl-trietyl-ammonium'bromid og 4 gram "ALIPAL CO 436" i 280 gram H20. Emulsjonens pH var 4,0.. Emulsjonen ble avkjblt til 17 C, hvoretter polymerisasjonen ble startet og fullfort med samme reagenser som i eksempel 1. Utbytte av brukbar polymer var over 90 i av teoretisk. 70 grams of ethyl acrylate, 20 grams of lauryl methacrylate, 8 grams of acrylic acid and 2 grams of N-methylolacrylamide were emulsified by adding them with stirring to 3 grams of allyl triethyl ammonium bromide and 4 grams of "ALIPAL CO 436" in 280 grams of H20 . The pH of the emulsion was 4.0. The emulsion was cooled to 17 C, after which the polymerization was started and completed with the same reagents as in example 1. The yield of usable polymer was over 90% of theoretical.

Eksempel 14 Example 14

100 gram etylakrylat ble emulgert under omrbring med tilsetning til 3-gram maleoyloksy-etyl-karbamoylmetyl-dimetylammoniumklorid og 3 gram natrium-bis(tridecyl)-sulfosuccionat i 290 gram H"20. Emulsjonens pH var 4,5. Polymerisasjonen ble startet og fullfort med samme reagenser som i eksempel 1. Utbytte av brukbar polymer var over 90 i av teoretisk. 100 grams of ethyl acrylate was emulsified under stirring with the addition of 3 grams of maleoyloxyethylcarbamoylmethyldimethylammonium chloride and 3 grams of sodium bis(tridecyl) sulfosuccinate in 290 grams of H"20. The pH of the emulsion was 4.5. The polymerization was started and completed with the same reagents as in example 1. Yield of usable polymer was over 90 in of theoretical.

Eksempel 15 Example 15

100 gram etylakrylat ble emulgert under omrbring ved tilsetning til 3 gram maleoyloksy-etyl-karbamoylmetyl-dimetylammoniumklorid og 3 gram natrium-2-etylheksylsulfat i 290 gram HgO. Emulsjonens pH var 4,3- Polymerisasjonen ble startet og fullfort med samme reagenser som i eksempel 1. Utbytte av brukbar polymer var over 90 i av teoretisk. 100 grams of ethyl acrylate was emulsified with stirring by adding 3 grams of maleoyloxyethylcarbamoylmethyldimethylammonium chloride and 3 grams of sodium 2-ethylhexyl sulfate in 290 grams of HgO. The pH of the emulsion was 4.3 - The polymerization was started and completed with the same reagents as in example 1. The yield of usable polymer was over 90% of theoretical.

Eksempel 16 Example 16

Man gjentok eksempel 15, bortsett fra at man istedet for natrium-2-etylheksylsulfat benyttet en ekvivalent mengde natrium-dodecyl-benzensulfonat. Resultater og utbytter var de samme som i eksempel 15. Example 15 was repeated, except that instead of sodium 2-ethylhexyl sulfate, an equivalent amount of sodium dodecyl benzene sulfonate was used. Results and yields were the same as in Example 15.

Eksempel 17 Example 17

100 gram etylakrylat ble emulgert under omrbring ved tilsetning' til 3 gram natriumlaurylsulfat og 3 gram allyl-acetamido-dimetylammoniumklorid i 290 gram H"20. Emulsjonens pH var 5,0. Polymerisasjonen ble startet og fullfort med hydrogenperoksyd, ferroammoniumsulfat og askorbinsyre som i eksempel 1. Utbytte av brukbar polymer var over 90 i av teoretisk. 100 grams of ethyl acrylate was emulsified under stirring by the addition of 3 grams of sodium lauryl sulfate and 3 grams of allyl-acetamido-dimethylammonium chloride in 290 grams of H"20. The pH of the emulsion was 5.0. The polymerization was started and completed with hydrogen peroxide, ferroammonium sulfate and ascorbic acid as in Example 1. Yield of usable polymer was over 90% of theoretical.

Eksempel 18 Example 18

15 gram vinylacetat og 60 gram etylakrylat ble emulgert ved under omrbring å tilsette dem til 2 gram natriumlaurylsulfat og 2,25.gram maleoyloksy-isopropyl-karbamoylmetyl-dimetylammoniumklorid i 290 gram H"20. Emulsjonens pH var 4,0. Polymerisasjonen ble startet og fullfort ved hjelp av hydrogenperoksyd, ferro-ammonium-sulfat og askorbinsyre som i eksempel 1. Utbytte av brukbar polymer var over 89 i av teoretisk. 15 grams of vinyl acetate and 60 grams of ethyl acrylate were emulsified by adding them with stirring to 2 grams of sodium lauryl sulfate and 2.25 grams of maleoyloxy-isopropyl-carbamoylmethyl-dimethylammonium chloride in 290 grams of H"20. The pH of the emulsion was 4.0. The polymerization was started and completed using hydrogen peroxide, ferrous ammonium sulfate and ascorbic acid as in example 1. Yield of usable polymer was over 89% of theoretical.

Ovenfor beskrevne nye monomere emulsjonsstabilisatorer er særlig' effektive, og befordrer en glatt og jevn polymerisasjon av mange forskjellige etylenisk-umettede monomere. The new monomeric emulsion stabilizers described above are particularly effective and promote a smooth and uniform polymerization of many different ethylenically unsaturated monomers.

Eksempler på etylenisk-umettede monomere som kan kopolymeri-seres med monomere.emulsjonsstabilisatorer i henhold til oppfinnel-sen er vinylacetat, vinylklorid, akrylnitril og akryl- eller met-akrylester-monomere som inneholder 1 til 14 C-atomer i estergruppens alkyldel, idet alkyl-grupper med 1 til 4 C-atomer foretrekkes. Som kjent vil mykheten hos en polymer og vanskelighetsgraden med start-ing -eller initiering av polymerisasjonen oke etterhvert som antall karbonatomer i estergruppen oker. Når akrylmonomere inneholder over 8 C-atomer i estergruppen, er det en fordel å blande disse med minst 20 io akrylester som har færre enn 4 C-atomer i estergruppen for å initiere polymerisasjonen og oke dispersjonens stabilitet. Examples of ethylenically unsaturated monomers which can be copolymerized with monomeric emulsion stabilizers according to the invention are vinyl acetate, vinyl chloride, acrylonitrile and acrylic or methacrylate monomers containing 1 to 14 C atoms in the alkyl part of the ester group, where alkyl -groups with 1 to 4 C atoms are preferred. As is known, the softness of a polymer and the degree of difficulty with starting - or initiating the polymerization will increase as the number of carbon atoms in the ester group increases. When acrylic monomers contain more than 8 C atoms in the ester group, it is advantageous to mix these with at least 20 io acrylic esters that have fewer than 4 C atoms in the ester group to initiate the polymerization and increase the stability of the dispersion.

Blandinger av flere enn én av disse etylenisk-umettede monomere kan benyttes, og for å oppnå spesielle egenskaper vedrør-ende stivhet, seighet eller kryssbindings-reaktivitet for den polymere, kan man erstatte en mindre del, vanligvis under 20 molprosent av den hovedmonomere med andre etylenisk-umettede monomere, vinyl-estere som vinyllaurat eller vinylstearat, vinyletere som vinyl-metyleter, vinyletyleter eller vinylbutyleter, eller en di-umettet monomer som dietylenglykol-diakrylat, etylenglykol-diitaconat, di-allylftalat eller divinylbenzen, akryl- eller metakrylsyrer, akrylamid eller met akrylamid, hydroksyetylakryl og -metakrylat, -og hy-droksypropylakrylat eller -metakrylat, eller styren. Mixtures of more than one of these ethylenically-unsaturated monomers can be used, and in order to achieve special properties regarding stiffness, toughness or cross-linking reactivity for the polymer, one can replace a smaller part, usually less than 20 mole percent, of the main monomer with other ethylenically unsaturated monomers, vinyl esters such as vinyl laurate or vinyl stearate, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether or vinyl butyl ether, or a di-unsaturated monomer such as diethylene glycol diacrylate, ethylene glycol diitaconate, diallyl phthalate or divinylbenzene, acrylic or methacrylic acids, acrylamide or met acrylamide, hydroxyethyl acrylate and methacrylate, and hydroxypropyl acrylate or methacrylate, or styrene.

Særlig egnede polymere bindemidler for ikke-vevede tekstiler er fremstilt ved som hovedmonomer å benytte en blanding av 5 ^ til 95 i vinylacetat og 95 io til 5 $ akryl- eller metakryl-ester inneholdende fra 1 til 4 Particularly suitable polymeric binders for non-woven textiles are prepared by using as the main monomer a mixture of 5% to 95% vinyl acetate and 95% to 5% acrylic or methacrylic ester containing from 1 to 4

■ C-atomer i estergruppens alkylgruppe. Egenskaper som mykhet og bbyelighet vil forandres etterhvert som forholdet mellom vinylacetat og akrylester forandres, idet storre mykhet oppnås med bkende esterinnhold og med bkende antall C-atomer i estergruppen. ■ C atoms in the alkyl group of the ester group. Properties such as softness and flexibility will change as the ratio between vinyl acetate and acrylic ester changes, as greater softness is achieved with increasing ester content and with increasing number of C atoms in the ester group.

Selv om ovenstående eksempler er henfbrt til satsvise pro-sesser, vil st-abilisatorer i henhold til foreliggende oppfinnelse også kunne brukes i forbindelse med kontinuerlige polymerisasjons-metoder. Although the above examples refer to batch processes, stabilizers according to the present invention can also be used in connection with continuous polymerization methods.

Claims (1)

Monomer emulsjonsstabilisator som er i stand til å stabilisere polymerisering av etylenisk umtettede monomerer og danne en kopolymer med en slik monomer, hvorved den blir en del av polymeren, karakterisert ved .at den har formelen:Monomeric emulsion stabilizer capable of stabilizing the polymerization of ethylenically unsaturated monomers and forming a copolymer with such a monomer, whereby it becomes part of the polymer, characterized in that it has the formula: hvor V er en maleoyloksy-, citrakonoyloksy-, vinyl- eller metylvinylgruppe, A er en alkylengruppe som inneholder 1-3 C-atomer og utgjor en metylengruppe når V er en vinyl- eller en metylvinylgruppe, R-^, R2 og R^ er uavhengig av hverandre enverdige organiske grupper som hver inneholder under 8 C-atomer, eller R-^ er et uavhengig enverdig organisk radikal som inneholder under 8 C-atomer og R2 og R^ utgjor sammen med nitrogenatomet en pyrrolidin-, piperidin-, morfolin-eller tetrahydro-S-triazin-2-on-gruppe, eller R-^, R2 og R^ utgjor sammen med nitrogenatomet en pyridin- eller substituert pyridingruppe, Y betegner en.sulfonat-, sulfat-, sulfitt-eller fosfatgruppe, og Rjj er et lipofilt radikal som inneholder minst en hydrokarbonkjede på 8-28 C-atomer.where V is a maleoyloxy, citraconoyloxy, vinyl or methylvinyl group, A is an alkylene group containing 1-3 C atoms and constitutes a methylene group when V is a vinyl or a methylvinyl group, R-^, R 2 and R^ are independently monovalent organic groups each containing less than 8 C atoms, or R-^ is an independent monovalent organic radical containing less than 8 C atoms and R2 and R^ form together with the nitrogen atom a pyrrolidine, piperidine, morpholine or tetrahydro-S-triazin-2-one group, or R-^, R2 and R^ together with the nitrogen atom form a pyridine or substituted pyridine group, Y denotes a sulphonate, sulphate, sulphite or phosphate group, and Rjj is a lipophilic radical containing at least one hydrocarbon chain of 8-28 C atoms.
NO415669A 1968-10-21 1969-10-20 MONOMER EMULSION STABILIZER. NO136152C (en)

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BR (1) BR6913505D0 (en)
CA (1) CA939668A (en)
CH (1) CH525253A (en)
DE (1) DE1952356C3 (en)
DK (1) DK130006B (en)
ES (1) ES372712A1 (en)
FI (1) FI50533C (en)
FR (1) FR2021141A1 (en)
GB (1) GB1240571A (en)
NL (1) NL158808B (en)
NO (1) NO136152C (en)
SE (1) SE384498B (en)

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GB1298099A (en) * 1969-10-20 1972-11-29 Kendall & Co Unsaturated quaternary ammonium compounds and copolymers containing them
JPS4948611A (en) * 1972-09-14 1974-05-11
DE4216314A1 (en) * 1992-05-16 1993-11-18 Basf Ag Process for the preparation of N-allyl compounds

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GB1240571A (en) 1971-07-28
NL6915891A (en) 1970-04-23
CH525253A (en) 1972-07-15
DK130006B (en) 1974-12-09
ES372712A1 (en) 1972-02-16
DK130006C (en) 1975-05-12
FR2021141A1 (en) 1970-07-17
DE1952356A1 (en) 1970-04-23
DE1952356B2 (en) 1979-06-13
FI50533C (en) 1976-04-12
BE740585A (en) 1970-04-01
NL158808B (en) 1978-12-15
NO136152C (en) 1977-07-27
DE1952356C3 (en) 1980-02-14
CA939668A (en) 1974-01-08
BR6913505D0 (en) 1973-05-03
SE384498B (en) 1976-05-10
FI50533B (en) 1975-12-31

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