DK156579B - Aqueous SOLUTION OR DISPERSION OF A HYDROLYCIZED COPOLYMER FROM THE STEERING AND MALEIC ACID ANHYDRID, ITS PREPARATION AND USE - Google Patents
Aqueous SOLUTION OR DISPERSION OF A HYDROLYCIZED COPOLYMER FROM THE STEERING AND MALEIC ACID ANHYDRID, ITS PREPARATION AND USE Download PDFInfo
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Description
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Den foreliggende opfindelse angâr en vandig opl0s-ning eller dispersion af en styren/maleinsyreanhydrid-co-polymer, en fremgangsmâde til dens fremstilling samt dens anvendelse.The present invention relates to an aqueous solution or dispersion of a styrene / maleic anhydride copolymer, a process for its preparation, and its use.
5 Fremstillingen af copolymere af maleinsyreanhydrid med vinylforbindelser, sâsom styren, har vaeret kendt i længere tid, se f.eks. Ind. Eng. Chem 41^ (1949), side 1509.5 The preparation of copolymers of maleic anhydride with vinyl compounds, such as styrene, has been known for a long time, see e.g. Ind. Meadow. Chem. 41 (1949), page 1509.
Disse copolymere opl0ses i vand under alkalitilsætning, da deres virkning som pigmentdispergeringsmiddel, beskyttelses-10 kolloid, fortykningsmiddel eller slettemiddel forudsætter en saltdannelse.These copolymers dissolve in water under alkali addition, as their action as pigment dispersant, protective colloid, thickening agent or erasing agent requires a salt formation.
Endvidere kendes copolymere ud fra styren og maleinsyreanhydrid, som har et molforhold mellem styren og maleinsyreanhydrid pâ fra 1:1 til 4:1, en gennemsnitlig molekyl-15 vægt pâ fra 400 til 100.000 og et smeltepunkt fra 80°C til 300°C, se f.eks. US-PS nr. 3.444.151. Disse copolymere om-sættes med aminer til nitrogenholdige copolymere, som er næsten uopl0selige i vand eller i vandige alkaliske medier, og de anvendes som emulgatorer ved emulsionspolymerisation 20 af vinylmonomere.Furthermore, copolymers are known from styrene and maleic anhydride having a molar ratio of styrene to maleic anhydride of from 1: 1 to 4: 1, an average molecular weight of from 400 to 100,000, and a melting point of 80 ° C to 300 ° C. see e.g. U.S. Patent No. 3,444,151. These copolymers are reacted with amines to nitrogen-containing copolymers which are virtually insoluble in water or in aqueous alkaline media and are used as emulsifiers in emulsion polymerization 20 of vinyl monomers.
Endvidere er det kendt, at der ved fremstillingen af klæbestoffer pâ stivelsebasis anvendes styren/maleinsyre-- copolymere, hvis molforhold mellem styren og maleinsyreanhydrid er fra 1:1 til 3:1, og hvis molekylvægt varierer 25 mellem 1600 og 50.000, se US-PS nr. 3.939.108. Disse copolymere fremstilles sædvanligvis ved opl0sningspolymerisation i et aromatisk carbonhydrid i nærværelse af en radikaldan-ner som katalysator ved en temperatur fra 75°C til 300°C.Furthermore, it is known that in the preparation of starch-based adhesives, styrene / maleic acid copolymers are used, whose molar ratio of styrene to maleic anhydride is from 1: 1 to 3: 1, and whose molecular weight varies between 1600 and 50,000, see U.S. Pat. PS No. 3,939,108. These copolymers are usually prepared by solution polymerization in an aromatic hydrocarbon in the presence of a radical dancer as catalyst at a temperature of 75 ° C to 300 ° C.
De kan efter tilsætning af ammoniak eller alkalimetal-30 hydroxid til en pH-værdi pâ fra 8 til 11 opl0ses i vand under opvarmning.After adding ammonia or alkali metal hydroxide to a pH of from 8 to 11, they can be dissolved in water under heating.
Den foreliggende opfindelse har til opgave at til-vejebringe en vandig opl0sning eller dispersion af en sty-ren/maleinsyreanhydrid-copolymer, som ikke har nogen alka-35 lisk reaktion, og som er egnet som emulgatoropl0sning eller -dispersion til kunststofdispersioner.The object of the present invention is to provide an aqueous solution or dispersion of a styrene / maleic anhydride copolymer which has no alkaline reaction and is suitable as an emulsifier solution or dispersion for plastic dispersions.
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Den foreliggende opfindelse angâr i overensstemmel-se hermed en vandig opl0sning eller dispersion af en hydro-lyseret copolymer ud fra styren og maleinsyreanhydrid med et molforhold mellem styren og maleinsyre pâ over 1:1 og 5 en molekylvægt (gennemsnit efter antal) pâ over 400, hvil-ken opl0sning eller dispersion er ejendommelig ved, at mol-forholdet ligger i omrâdet fra 1,5:1 til 6:1, molekylvægten er fra 500 til 80.000, fra 1 til 60% af carboxylgrupperne i den copolymere er neutraliserede, og opl0sningens eller 10 dispersionens pH-værdi er under 7.Accordingly, the present invention provides an aqueous solution or dispersion of a hydrolyzed copolymer from styrene and maleic anhydride having a molar ratio of styrene to maleic acid of greater than 1: 1 and 5 having a molecular weight (average by number) of more than 400. which solution or dispersion is peculiar in that the molar ratio is in the range of 1.5: 1 to 6: 1, the molecular weight is from 500 to 80,000, from 1 to 60% of the carboxyl groups of the copolymer are neutralized, and or the pH of the dispersion is below 7.
Endvidere angâr den foreliggende opfindelse ..en frem-gangsmâde til fremstilling af en vandig opl0sning eller dispersion af en hydrolyseret copolymer ud fra styren og maleinsyreanhydrid, som har et molforhold mellem styren og malein-15 syreanhydrid pâ over 1:1 og en molekylvægt (gennemsnit efter antal) pâ over 400, ved hydrolyse af en styren/maleinsyre-anhydrid-copolymer og delvis neutralisation med et uorganisk neutralisationsmiddel, hvilken fremgangsmâde er ejendomme-lig ved, at en copolymer med et molforhold mellem styren 20 og maleinsyreanhydrid pâ fra 1,5:1 til 6:1 og en molekylvægt pâ fra 500 til 80.000 opvarmes til en temperatur pâ fra 75°C til 250°C i nærværelse af vand og i nærværelse af sâ meget ammoniak eller et alkalimetalhydroxid eller et jordalkalimetalhydroxid eller zinkoxid, at fra 1 til 60% 25 af carboxylgrupperne i den copolymere neutraliseres.Furthermore, the present invention relates to a process for preparing an aqueous solution or dispersion of a hydrolyzed copolymer from styrene to maleic anhydride having a molar ratio of styrene to maleic anhydride of greater than 1: 1 and a molecular weight (average by number of over 400, by hydrolysis of a styrene / maleic anhydride copolymer and partial neutralization with an inorganic neutralizing agent, characterized in that a copolymer having a molar ratio of styrene 20 to maleic anhydride of 1.5 : 1 to 6: 1 and a molecular weight of 500 to 80,000 is heated to a temperature of 75 ° C to 250 ° C in the presence of water and in the presence of so much ammonia or an alkali metal hydroxide or an alkaline earth metal hydroxide or zinc oxide that from 1 to 60% 25 of the carboxyl groups in the copolymer are neutralized.
Endelig angâr den foreliggende opfindelse tillige anvendelsen af ovennævnte opl0sning eller dispersion som stabilisatoropl0sning eller -dispersion for vandige dis-persioner og ved dispersionspolymerisation af vinylforbin-30 delser.Finally, the present invention also relates to the use of the above solution or dispersion as a stabilizer solution or dispersion for aqueous dispersions and in dispersion polymerization of vinyl compounds.
Den if0lge opfindelsen anvendte styren/maleinsyre-anhydrid-copolymer har en molekylvægt (gennemsnit efter antal) pâ fra 500 til 80.000, fortrinsvis fra 800 til 30.000. Molforholdet mellem styren og maleinsyreanhydrid andrager 35 fra 1,5:1 til 6:1, fortrinsvis fra 1,6:1 til 4:1.The styrene / maleic anhydride copolymer used according to the invention has a molecular weight (average by number) of from 500 to 80,000, preferably from 800 to 30,000. The molar ratio of styrene to maleic anhydride is 35 from 1.5: 1 to 6: 1, preferably from 1.6: 1 to 4: 1.
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Styren/maleinsyreanhydrid-copolymeren opvarmes og hydrolyseres if0lge opfindelsen i nærværelse af vand og i nærværelse af etuprganisk neutralisationsmiddel til en tem-peratur pâ fra 75°C til 250°C, fortrinsvis 85-180°C. De 5 derved opstâede frie carboxylgrupper i den copolymere neu-traliseres herved i en udstrækning pâ fra 1 til 60%, fortrinsvis 6—50%. Ved denne alkaliske behandling af den copolymere andrager dennes koncentration 5-50 vægtprocent, fortrinsvis 10-30 vægtprocent, baseret pâ den samlede mængde 10 vand og copolymer. Alt efter den copolymeres koncentration og sammensætning samt den anvendte temperatur varer behand-lingen fra 5 minutter til 5 timer, fortrinsvis 10-200 minut-ter. En h0j styrenandel i den copolymere, en h0j copolymer-koncentration og en lav behandlingstemperatur kræver i al-15 mindelighed en længere behandlingstid, og ved variation i de angivne paramétré kan f01gelig behandlingstiden ændres.The styrene / maleic anhydride copolymer is heated and hydrolyzed according to the invention in the presence of water and in the presence of etuprganic neutralizing agent to a temperature of 75 ° C to 250 ° C, preferably 85-180 ° C. The free carboxyl groups thus formed in the copolymer are thereby neutralized to an extent of 1 to 60%, preferably 6 to 50%. In this alkaline treatment of the copolymer, its concentration is 5-50% by weight, preferably 10-30% by weight, based on the total amount of water and copolymer. Depending on the concentration and composition of the copolymer and the temperature used, the treatment lasts from 5 minutes to 5 hours, preferably 10-200 minutes. Generally, a high styrene proportion in the copolymer, a high copolymer concentration, and a low processing temperature require a longer processing time, and, if variation in the specified parameters, the processing time can be changed.
Det er anbefalelsesværdigt at arbejde under en indifferent gas, f.eks. nitrogen.It is advisable to work under an inert gas, e.g. nitrogen.
Styren/maleinsyreanhydrid-copolymeren indeholder 20 eventuelt yderligere ën eller flere andre monomère indpoly-meriseret i en mængde pâ op til 20 molprocent, baseret pâ den samlede mængde monomer. Egnede er olefinisk umættede forbindelser, sâsom vinylestere, vinylethere og acryl-syreestere, og umættede carboxylsyrer, sâsom acrylsyre, 25 methacrylsyre, itaconsyre, crotonsyre, vinylsulfonsyre og N-methacryloylaminopropansulfonsyre.The styrene / maleic anhydride copolymer optionally contains 20 additional one or more other monomers polymerized in an amount up to 20 mole percent, based on the total amount of monomer. Suitable are olefinically unsaturated compounds, such as vinyl esters, vinyl ethers and acrylic acid esters, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, vinyl sulfonic acid and N-methacryloylaminopropane sulfonic acid.
Som uorganisk neutralisationsmiddel tjener ammoni-umhydroxid eller et alkalimetalhydroxid, f.eks. lithium-hydroxid, natriumhydroxid og kaliumhydroxid, eller et jord-30 alkalimetalhydroxid, f.eks. magnesiumhydroxid og calcium- hydroxid, samt zinkoxid. I stedet for et enkelt neutralisationsmiddel kan der ogsâ anvendes en blanding af flere neutralisationsmidler. Den mængde neutralisationsmiddel, som skal anvendes, skal vælges pâ en sâdan mâde, at der 35 opnâs den 0nskede neutralisationsgrad, og den ligger i om-râdet fra 0,02 til 1,2 baseækvivalenter, fortrinsvis 0,12-1 0 4As inorganic neutralizing agent, ammonium hydroxide or an alkali metal hydroxide, e.g. lithium hydroxide, sodium hydroxide and potassium hydroxide, or an alkaline earth metal hydroxide, e.g. magnesium hydroxide and calcium hydroxide, and zinc oxide. Instead of a single neutralizing agent, a mixture of several neutralizing agents can also be used. The amount of neutralizing agent to be used must be chosen in such a way that the desired degree of neutralization is obtained and it is in the range of 0.02 to 1.2 base equivalents, preferably 0.12-1 0 4.
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baseækvivalent, baseret pâ et mol maleinsyreanhydrid i den copolymere. Alt efter neutralisationsmidlets art og mængde fâs der en copolymeropl0sning eller -dispersion, idet der til fremstillingen af en opl0sning anvendes en st0rre mæng-5 de neutralisationsmiddel end til fremstillingen af en dispersion.base equivalent, based on one mole of maleic anhydride in the copolymer. Depending on the nature and amount of the neutralizing agent, a copolymer solution or dispersion is obtained, using a greater amount of neutralizing agent than for the preparation of a dispersion.
Til fremstilling af en sur opl0sning af en hydro-lyseret styren/maleinsyreanhydrid-copolymer er det anbe-falelsesværdigt at gennemf0re den alkaliske behandling i 10 nærværelse af en emulgator, fortrinsvis en anionisk emul-gator. Som emulgatorer egner sig især alkalimetalsalte eller ammoniumsalte af alkylsulfonsyrer, arylsulfonsyrer eller alkylarylsulfonsyrer samt de tilsvarende svovlsyrer, phosphorsyrer eller phosphonsyrer, idet de nævnte forbin-15 delser eventuelt indeholder oxyethylenenheder mellem den pâgældende carbonhydridgruppe, med fortrinsvis 10-18 car-bonatomer, og den anioniske gruppe, og de oxethylerede for-bindelser indeholder fortrinsvis 5-30 ethylenoxidenheder. Eksempler pâ egnede emulgatorer er natriumlaurylsulfat, 20 natriumoctylphenolglycolethersulfat, natriumdodecylbenzen-sulfonat, natriumlauryldiglycolsulfat samt ammoniumsaltene af oxethyleret og sulfateret tri-t-butylphenol, t-butyl-phenol og nonylphenol.To prepare an acidic solution of a hydrolyzed styrene / maleic anhydride copolymer, it is advisable to carry out the alkaline treatment in the presence of an emulsifier, preferably an anionic emulsifier. As emulsifiers, alkali metal or ammonium salts of alkylsulfonic acids, arylsulfonic acids or alkylarylsulfonic acids as well as the corresponding sulfuric acids, phosphoric acids or phosphonic acids are particularly suitable, said compounds optionally containing oxyethylene units between the relevant hydrocarbon group, preferably 10-18 carbon atoms, preferably, the oxethylated compounds contain 5-30 ethylene oxide units. Examples of suitable emulsifiers are sodium lauryl sulfate, sodium octylphenol glycol ether sulfate, sodium dodecylbenzene sulfonate, sodium lauryl digglycols sulfate, and the ammonium salts of oxethylated and sulfated tri-t-butylphenol, t-butylphenol and nonylphenol.
Emulgatoren anvendes i en mængde fra 3-100 vægt-25 procent, fortrinsvis 5-25 vægtprocent, baseret pâ styren/” maleinsyreanhydrid-copolymer.The emulsifier is used in an amount of 3-100% by weight, 25%, preferably 5% to 25% by weight, based on styrene / maleic anhydride copolymer.
Den her omhandlede copolymerdispersion kan ogsâ overf0res i en opl0sning, idet den efter tilsætning af en emulgator af ovennævnte art opvarmes til en temperatur inden-30 for det ovenfor anf0rte behandlingstemperaturomrâde.The present copolymer dispersion can also be transferred into a solution, after the addition of an emulsifier of the above kind is heated to a temperature within the above-mentioned treatment temperature range.
Den her omhandlede, vandige opl0sning eller dispersion af en hydrolyseret copolymer ud fra styren og maleinsyreanhydrid udviser sur reaktion. Dens pH-værdi er under 7 og fortrinsvis under 6, og særlig fordelagtig er 35 en opl0sning eller dispersion med en pH-værdi pâ fra 2,0 til 5,7. Qpl0sningens eller dispersionens indhold af co-The present aqueous solution or dispersion of a hydrolyzed copolymer from styrene and maleic anhydride exhibits an acidic reaction. Its pH is less than 7 and preferably below 6, and particularly advantageous is a solution or dispersion having a pH of 2.0 to 5.7. The content of the solution or dispersion of the co-solution
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0 5 polymer ligger i omrâdet fra 5 til 50 vægtprocent, fortrins-vis 10-30 vægtprocent. Viskositeten af opl0sningen eller dispersionen er fra 20 til 20.000 mPa-s, fortrinsvis 50--3.000 mPa*s (malt if0lge Epprecht).The polymer is in the range of 5 to 50% by weight, preferably 10-30% by weight. The viscosity of the solution or dispersion is from 20 to 20,000 mPa · s, preferably 50–3,000 mPa · s (painted according to Epprecht).
5 Den her omhandlede copolymeropl0sning eller -dis persion anvendes som emulgerings-, dispergerings-, slette-, limnings-, fortyknings-, flokkulerings- og hydrophoberings-middel og' 1 tekstil-, malings-, klæbestof- og papirsek-toren som belægnings- og bindemiddel. Pâ sâdanne materialer 10 som træ, papir, keramik, métal eller kunststof anbringes den opl0ste eller dispergerede copolymer efter pâf0ring af op-l0sningen eller dispersionen ved fjernelse af vandet eller ved elektrokemisk udskillelse.The copolymer solution or dispersion of the present invention is used as the emulsifying, dispersing, erasing, sizing, thickening, flocculating and hydrophobic agents and the '1 Textile, Paint, Adhesive and Paper Sector as coating material. and binder. On such materials as wood, paper, ceramics, metal or plastics, the dissolved or dispersed copolymer is applied after application of the solution or dispersion by removal of the water or by electrochemical separation.
Opl0sningen eller dispersionen egner sig fortrin-15 ligt til stabilisering af vandige dispersioner af naturlige eller syntetiske, uorganiske eller organiske materialer, f.eks. cellulose, kunststoffer, pigmenter og fyldstoffer. Copolymeropl0sningen eller -dispersionen anvendes èndvidere ved suspensions- eller emulsionspolymerisation af vinylfor-20 bindelser, især vinylestere og acrylsyreestere. De pâ den-ne mâde stabiliserede kunststofdispersioner udviser en forh0jet stabilitet overfor forskydningskræfter og pigmenter. Tidspunktet for tilsætningen af stabilisatoropl0snin-gen eller -dispersionen er i denne forbindelse uvæsentligt, 25 og tilsætningen kan med samme gode résultat ske under frem-stillingen af den dispersion, som skal stabiliseres, eller efter fremstillingen.The solution or dispersion is preferably suitable for stabilizing aqueous dispersions of natural or synthetic, inorganic or organic materials, e.g. cellulose, plastics, pigments and fillers. The copolymer solution or dispersion is further used in suspension or emulsion polymerization of vinyl compounds, especially vinyl esters and acrylic acid esters. In this way, the plastic dispersions stabilized exhibit increased stability to shear forces and pigments. In this connection, the timing of the addition of the stabilizer solution or dispersion is immaterial, and the addition may be carried out with the same good result during the preparation of the dispersion to be stabilized or after preparation.
Den her omhandlede copolymeropl0sning eller -dispersion anvendes f0rst og fremmst ved polymerisationen af 30 vinylforbindelser, som polymeriseres i vandigt medium under sure betingelser. Særligt egnede monomère er olefinisk umæt-tede forbindelser med den almene formel H9C=C-R1 Δ ' 2The present copolymer solution or dispersion is first and foremost used in the polymerization of 30 vinyl compounds which are polymerized in aqueous medium under acidic conditions. Particularly suitable monomers are olefinically unsaturated compounds of the general formula H9C = C-R1 Δ '2
35 R35 R
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hvor R1 betyder et hydrogenatom eller en methylgruppe, og 2 R betyder (a) en alkylcarboxygruppe med 2-18, fortrinsvis 2-12 carbonatomer, (b) en alkoxygruppe med 1-4 carbonatom-er, (c) en nitrilgruppe, (d) et halogenatom, fortrinsvis 5 et chloratom, (e) en carboxylgruppe eller sulfogruppe, (f) en alkoxycarbonylgruppe med 2-12, fortrinsvis 2-9 carbonatomer, (g) en aminocarbonylgruppe, (h) et hydrogenatom, (i) en phenylgruppe eller (k) en vinylgruppe. Som eksempler pâ sâdanne, olefinisk umættede forbindelser skal nævnes 10 (a) vinylestere af aliphatiske carboxylsyrer med 2-18, for- trinvis 2-12, carbonatomer, f.eks. vinylacetat, vinyl-propionat, vinylbutyrat, vinylpivalat, vinylisononat, vinyllaurat og vinyldecanat, samt vinylestere af en blan-ding af monocarboxylsyrer med 9-11 carbonatomer, 15 (b) vinylethere, f.eks. vinylmethylether, vinylethylether, og vinyl-n-butylether, (c) acrylonitril og methacrylonitril, (d) vinylhalogenider, f.eks. vinylchlorid og allylchlorid,wherein R 1 represents a hydrogen atom or a methyl group and 2 R represents (a) an alkyl carboxy group of 2-18, preferably 2-12 carbon atoms, (b) an alkoxy group of 1-4 carbon atoms, (c) a nitrile group, (d) a halogen atom, preferably a chlorine atom, (e) a carboxyl group or sulfo group, (f) an alkoxycarbonyl group of 2-12, preferably 2-9 carbon atoms, (g) an aminocarbonyl group, (h) a hydrogen atom, (i) a phenyl group or (k) a vinyl group. Examples of such olefinically unsaturated compounds are 10 (a) vinyl esters of aliphatic carboxylic acids having 2-18, preferably 2-12, carbon atoms, e.g. vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl isonate, vinyl laurate and vinyl decanate, as well as vinyl esters of a mixture of monocarboxylic acids of 9-11 carbon atoms; vinyl methyl ether, vinyl ethyl ether, and vinyl n-butyl ether, (c) acrylonitrile and methacrylonitrile, (d) vinyl halides, e.g. vinyl chloride and allyl chloride,
Ce) umættede monocarboxylsyrer, f.eks. acrylsyre, methacryl- 20 syre og vinylsulfonsyre, (f) acrylsyreestere eller methacrylsyreestere af monovalente alkanoler med 1-11, fortrinsvis 1-8, carbonatomer, f.eks. methylacrylat, ethylacrylat, butylacrylat, 2-ethylhexyl-acrylat, methylmethacrylat, ethylmethacrylat, butylmeth-25 acrylat, hexylmethacrylat, oxtylmethacrylat og 2-ethyl- hexylmethacrylat, fg) acrylsyreamider og methacrylsyreamider, f.eks. acrylsyre-amid, N-methylolacrylsyreamid, methacrylsyreamid og N--methylolmethacrylsyreamid, 30 (h)’ethylen, (i) styren og methylstyren, og (k) butadien og isopren.Ce) unsaturated monocarboxylic acids, e.g. acrylic acid, methacrylic acid and vinylsulfonic acid; (f) acrylic acid esters or methacrylic acid esters of monovalent alkanols having 1-11, preferably 1-8, carbon atoms, e.g. methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, oxtylmethacrylate and 2-ethylhexylmethacrylate, fg) acrylic acid amides and methacrylic acid amides, e.g. acrylic acid amide, N-methylolacrylic acid amide, methacrylic acid amide, and N - methylol methacrylic acid amide, (h) ethylene, (i) styrene and methyl styrene, and (k) butadiene and isoprene.
Særlig egnede monomère er vinylestrene (a), vinyl-ethrene (b), vinylhalogeniderne (d) og acrylsyreestrene og 35 methacrylsyreestrene (f). De monomère anvendes hver for sig eller i blanding med hverandre. Monomerkombinationer dannesParticularly suitable monomers are the vinyl esters (a), vinyl ethers (b), vinyl halides (d) and acrylic acid esters and methacrylic acid esters (f). The monomers are used separately or in admixture with each other. Monomer combinations are formed
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0 7 f,eks. ud fra en acrylsyreester og en methacrylsyreester, en acryl- eller methacrylsyreester og en vinylester samt en blanding af forskellige vinylestere, især vinylacetat og vinylestere af en blanding af monocarboxylsyrer med 9-11 5 carbonatomer, endvidere ud fra vinylacetat og ethylen samt ud fra vinylacetat, ethylen og vinylchlorid.0 7 f, ex. from an acrylic acid ester and a methacrylic acid ester, an acrylic or methacrylic acid ester and a vinyl ester as well as a mixture of various vinyl esters, especially vinyl acetate and vinyl esters of a mixture of monocarboxylic acids having 9-11 carbon atoms, further from vinyl acetate and ethylene and from vinyl acetate, ethylene and vinyl chloride.
Polymerisationen sker pâ gængs mâde i nærværelse af en radikaldannende initiator, fortrinsvis en peroxid-forbindelse eller en aliphatisk azoforbindelse. Initiatoren 10 er olieopl0selig eller fortrinsvis vandopl0selig, og den anvendes i en mængde pâ fra 0,05 til 2 vægtprocent, fortrinsvis 0,1-1 vægtprocent, baseret pâ den samlede mængde af monomère. Særlig egnet er hydrogenperoxid, alkalimetal-eller ammoniumsalte af persvovlsyre, af peroxydisvovlsyre 15 eller af peroxydiphosphorsyre, f.eks. natriumpersulfat, kaliumperoxydisulfat og ammoniumperoxydisulfat, endvidere alkylhydroperoxider, sâsom t-butylhydroperoxid, dialkyl-peroxider, sâsom di-t-butylperoxid, diacylperoxider, sâsom diacetylperoxid, dilaurylperoxid og dibenzoylperoxid, samt 20 azodiisosm0rsyrenitril, azodicarboxamid og azo-γ,γ'-bis-(4--cyanvaleriansyre). Initiatoren anvendes eventuelt sammen med et reduktionsmiddel, især sammen med et ammoniumsalt, alkalimetal- eller jordalkalimetalsalt af en reducerende virkende, svovlholdig syre, og fortrinsvis egnede er sul-25 fiter, bisulfiter, pyrosuifiter, dithioniter, thiosulfater og formaldehydsulfoxylater. Reduktionsmiddelmængden er fra 0,05 til 20 vægtprocent, fortrinsvis 0,5-10 vægtprocent, baseret pâ styren/maleinsyreanhydrid-copolymer.The polymerization is carried out in the usual manner in the presence of a radical-forming initiator, preferably a peroxide compound or an aliphatic azo compound. The initiator 10 is oil-soluble or preferably water-soluble and is used in an amount of 0.05 to 2% by weight, preferably 0.1-1% by weight, based on the total amount of monomers. Particularly suitable are hydrogen peroxide, alkali metal or ammonium salts of persulfuric acid, peroxydisulfuric acid or peroxydiphosphoric acid, e.g. sodium peroxide, potassium peroxide disulfate and ammonium peroxide disulfate, further alkyl hydroperoxides, such as t-butyl hydroperoxide, dialkyl peroxides, such as di 4 - cyanvaleriansyre). The initiator is optionally used with a reducing agent, especially with an ammonium salt, alkali metal or alkaline earth metal salt of a reducing acting sulfuric acid, and preferably suitable are sulfites, bisulfites, pyrosulfites, dithionites, thiosulfates and formaldehyde sulfoxylates. The amount of reducing agent is from 0.05 to 20% by weight, preferably 0.5-10% by weight, based on styrene / maleic anhydride copolymer.
Til for0gelse af polymerisationshastigheden er det 30 fordelagtigt at anvende en opl0sning eller dispersion af en hydrolyseret styren/maleinsyreanhydrid-copolymer, hvis fremstilling er blevet gennemf0rt i nærværelse af et sul-fit. Egnet som suifiter er neutrale eller sure salte af svovlsyrling eller pyrosvovlsyrling, især ammoniumsalte, 35 alkalimetal- og jordalkalimetalsalte. Sulfitet anvendes eventuelt i en mængde pâ fra 0,05 til 20 vægtprocent, for- 8In order to increase the rate of polymerization, it is advantageous to use a solution or dispersion of a hydrolyzed styrene / maleic anhydride copolymer, the preparation of which has been carried out in the presence of a sulphite. Suitable as suphites are neutral or acidic salts of sulfuric acid or pyrosulfuric acid, especially ammonium salts, alkali metal and alkaline earth metal salts. Sulphity is optionally used in an amount of 0.05 to 20% by weight, for 8
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0 trinsvis 0,5-10 vægtprocent, baseret pâ styren/maleinsyre-anhydrid-copolymer.0, preferably 0.5-10% by weight, based on styrene / maleic anhydride copolymer.
Ved emulsionspolymerisationen anvendes opl0snin-gen eller dispersionen af den hydrolyserede styren/malein-5 syreanhydrid-copolymer i en sâdan mængde, at den copoly-mere foreligger i en mængde pâ fra 0,1 til 10 vægtprocent, fortrinsvis 0,5-5 vægtprocent, baseret pâ den samlede mængde monomère. Ved suspensionspolymerisation er det tilstræk-keligt med 0,01-2 vægtprocent, fortrinsvis 0,05-1 vægtpro-10 cent, af den comonomere, baseret pâ den samlede mængde monomère. Polymerisationen sker ved en temperatur fra 25°C til 90°C, fortrinsvis 40-75°C. Alt efter arten og mængden af de deltagende monomère ligger polymerisationstiden i omrâdet fra 2 til 8 timer, fortrinsvis 2,5-5 timer.In the emulsion polymerization, the solution or dispersion of the hydrolyzed styrene / maleic anhydride copolymer is used in such an amount that the copolymer is present in an amount of from 0.1 to 10 weight percent, preferably 0.5 to 5 weight percent. based on the total amount of monomers. In suspension polymerization, 0.01-2% by weight, preferably 0.05-1% by weight, of the comonomer is sufficient, based on the total amount of monomer. The polymerization occurs at a temperature from 25 ° C to 90 ° C, preferably 40-75 ° C. Depending on the nature and amount of the monomers involved, the polymerization time ranges from 2 to 8 hours, preferably 2.5-5 hours.
15 De resulterende polymerdispersioner er i h0j ud- strækning stabile overfor forskydningskræfter og udviser en særdeles god pigmentbindeevne. De finder derfor f0rst og fremmest anvendelse som bindemiddeldispersioner i mid-ler, som skal udstryges, især dispersionsfarver og papir-20 udstrygningsmasser. Det dermed behandlede papir udmærker sig ved h0j rivestyrke og stregvâdstyrke.The resulting polymer dispersions are highly stable to shear forces and exhibit a very good pigment bonding ability. Therefore, they find, first and foremost, use as binder dispersions in agents to be ironed out, especially dispersion inks and paper smears. The paper thus treated is characterized by high tear strength and tensile strength.
Den foreliggende opfindelse belyses ved hjælp af de f0lgende eksempler. Procentangivelser er efter vægt.The present invention is illustrated by the following examples. Percentages are by weight.
25 Eksempel 1 150 g Af en copolymer ud fra styren og maleinsyre-anhydrid (molforhold 2:1), som har en gennemsnitsmolekyl-vægt pâ 1700, opvarmes sammen med 790 g vand og 7,05 g æstnatron i en beholder med omr0rer og tilbagesvaler i 30 2 timer til en temperatur pâ 95-100°C og afk0les derefter til stuetemperatur. Der fâs en klar opl0sning med en pH--værdi pâ 4,7 og et polymerindhold pâ 16,5%. Carboxylgrup-perne i den hydrolyserede copolymer er neutraliseret i en udstrækning pâ 18%.Example 1 150 g of a copolymer based on styrene and maleic anhydride (2: 1 molar ratio) having an average molecular weight of 1700 are heated together with 790 g water and 7.05 g estrogen in a stirred and reflux container. for 2 hours to a temperature of 95-100 ° C and then cooled to room temperature. A clear solution with a pH of 4.7 and a polymer content of 16,5% is obtained. The carboxyl groups in the hydrolyzed copolymer are neutralized to an extent of 18%.
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Eksempel 2 a) Eksempel 1 gentages, idet der dog i stedet for 7,05 g ætsnatron kun indsættes 3,52 g ætsnatron og i stedet for 790 g vand kun 720 g vand. Desuden filtreres reaktions- 5 blandingen efter afk0ling til stuetemperatur, og derved bliver en remanens pâ 30,9 g (efter t0rring) tilbage.Example 2 a) Example 1 is repeated, however, instead of 7.05 g of ethanol, only 3.52 g of ethanol is added and instead of 790 g of water only 720 g of water. In addition, the reaction mixture is filtered after cooling to room temperature, leaving a residue of 30.9 g (after drying).
Soin filtrat fâs en dispersion med en pH-værdi pâ 4,1 og et polymerindhold pâ 14,9%.Soil filtrate obtains a dispersion having a pH of 4.1 and a polymer content of 14.9%.
b) 8 g af den if01ge a) fremstillede dispersion opvarmes 10 sairanen med 2 g af en 15%'s vandig opl0sning af natrium- laurylsulfat til 70°C, hvorved den copolymere gâr i op-l0sning.b) 8 g of the dispersion prepared in (a) are heated to 2 g of a 15% aqueous solution of sodium lauryl sulphate to 70 ° C, whereupon the copolymer dissolves.
c) 8 g af den if0lge a) fremstillede dispersion opvarmes til 80°C sammen med 2 g af en 15%'s vandig opl0sning af 15 ammoniumsaltet af en med 25 mol ethylenoxid oxethyler- et og derpâ sulfateret nonylphenol som emulgator, hvorved den copolymere gâr i opl0sning.c) 8 g of the dispersion prepared according to (a) are heated to 80 ° C together with 2 g of a 15% aqueous solution of the 15 ammonium salt of a 25 mole ethylene oxide oxyl ether and then sulfated nonylphenol as an emulsifier, whereby the copolymer dissolves.
Eksempel 3 20 300 g af en copolymer ud fra styren og maleinsyre- anhydrid (molforhold 3:1) med en gennemsnitsmolekylvægt pâ 1900 opvarmes sammen med 1680 g vand og 29,3 g ætsnatron i en beholder med omr0rer og tilbagesvaler i 2 timer til en temperatur pâ 96°C og afk0les derefter til stuetempera-25 tur. Der fâs en opl0sning med en pH-værdi pâ 6,8 og et polymerindhold pâ 16,7%. Carboxylgrupperne i den hydrolyserede copolymer er neutraliseret i en udstrækning pâ 50%.EXAMPLE 3 300 g of a copolymer from styrene and maleic anhydride (3: 1 molar ratio) having an average molecular weight of 1900 are heated together with 1680 g of water and 29.3 g of ethanol in a stirred and reflux container for 2 hours. temperature of 96 ° C and then cooled to room temperature. A solution with a pH of 6.8 and a polymer content of 16.7% is obtained. The carboxyl groups in the hydrolyzed copolymer are neutralized to an extent of 50%.
Eksempel 4 30 I en beholder med omr0rer og tilbagesvaler opvarmes 150 g af en copolymer ud fra styren og maleinsyreanhydrid (molforhold 3:1) med en gennemsnitsmolekylvægt pâ 1900 sammen med 790 g vand og 25 g af en 25%'s vandig ammoniakop-l0sning i 2 timer til en temperatur pâ 100°C og afk0les 35 derefter til stuetemperatur. Der fâs en opl0sning med en pH-værdi pâ 6,8 og et polymerindhold pâ 16,1%. Carboxylgrupperne i den hydrolyserede copolymer er neutraliseret i en udstrækning pâ 50%.Example 4 In a stirred and reflux container, 150 g of a styrene and maleic anhydride copolymer (molar ratio 3: 1) with an average molecular weight of 1900 are heated together with 790 g of water and 25 g of a 25% aqueous ammonia solution. for 2 hours to a temperature of 100 ° C and then cooled to room temperature. A solution with a pH of 6.8 and a polymer content of 16.1% is obtained. The carboxyl groups in the hydrolyzed copolymer are neutralized to an extent of 50%.
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Eksempel 5 a) 150 g af en copolymer ud fra styren og maleinsyreanhydrid (molforhold 3:1) med en gennemsnitsmolekylvægt pâ 1900 opvarmes sammen med 720 g vand og 7/3 g ætsnatron i en 5 beholder med omr0rer og tilbagesvaler i 3 timer til en temperatur pâ 97°C og afk0les derefter til stuetempera-tur. Der fâs en dispersion med en pH-værdi pâ 5,6 og et polymerindhold pâ 17,6%. Carboxylgrupperne i den hydro-lyserede copolymer er neutraliseret i en udstrækning pâ 10 25%. Gennemsnitsdiametren af de dispergerede polymer- partikler er 0,038 pn.Example 5 a) 150 g of a styrene-maleic anhydride copolymer (molar ratio 3: 1) having an average molecular weight of 1900 are heated together with 720 g of water and 7/3 g of ether sodium in a 5 stirred and reflux container for 3 hours. temperature of 97 ° C and then cooled to room temperature. A dispersion with a pH of 5.6 and a polymer content of 17.6% is obtained. The carboxyl groups in the hydrolyzed copolymer are neutralized to an extent of 10 25%. The average diameter of the dispersed polymer particles is 0.038 µm.
b) 8 g af den if0lge a) fremstillede dispersion opvarmes med 2 g af en 15%1 s vandig opl0sning af natriumlauryl-sulfat til 85°C, og derved gâr den copolymere i opl0s- 15 ning.b) 8 g of the dispersion prepared according to (a) is heated with 2 g of a 15% 1 s aqueous solution of sodium lauryl sulfate to 85 ° C, thereby making the copolymer in solution.
c) 8 g af den if0lge a) fremstillede dispersion opvarmes med 2 g af en 15%'s vandig opl0sning af emulgatoren fra eksempel 2 c) til 90°C, og derved gâr den copolymere i opl0sning.c) 8 g of the dispersion prepared according to a) is heated with 2 g of a 15% aqueous solution of the emulsifier of Example 2 c) to 90 ° C, thereby making the copolymer in solution.
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Eksempel 6-8 I hvert enkelt tilfælde opvarmes 150 g af en copolymer ud fra styren og maleinsyreanhydrid (molforhold 3:1) med en gennemsnitsmolekylvægt pâ 1900 sammen med i 25 hvert enkelt tilfælde 720 g vand og forskellige mængder lithiumhydroxid i en beholder med omr0rer og tilbagesvaler i forskellig tid til en temperatur pâ 97°C og afk01es derefter til stuetemperatur. Enkelthederne og egenskaberne af den i hvert enkelt tilfælde fremstillede opl0sning el-30 1er dispersion fremgâr af tabel I.Examples 6-8 In each case, 150 g of a copolymer from styrene and maleic anhydride (molar ratio 3: 1) with an average molecular weight of 1900 are heated together with, in each case, 720 g of water and various amounts of lithium hydroxide in a stirrer container and reflux at various times to a temperature of 97 ° C and then cool to room temperature. The details and properties of the solution or dispersion prepared in each case are shown in Table I.
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Tabel ITable I
Eksempel 6 78 5 Mængde LiOH (g) 4,4 3,3 2,2Example 6 78 5 Amount of LiOH (g) 4.4 3.3 2.2
Behandlingstid (h) 2 23 Résultat opl0sning dispersion dispersion pH-værdi 5,3 5,1 4,7Processing time (h) 2 23 Result solution dispersion dispersion pH 5.3 5.3 5.1 4.7
Polymerindhold (%) 17,6 17,3 16,9 neutraliserede 25 18,7 12,5 carboxylgrupper (%)Polymer content (%) 17.6 17.3 16.9 neutralized 18.7 12.5 carboxyl groups (%)
Eksempel 9 15 150 g af en copolymer ud fra styren og maleinsyre- anhydrid (molforhold 3:1) med en gennemsnitsmolekylvægt pâ 1900 opvarmes sammen med 1300 g vand, 7,3 g ætsnatron, 125 g af en 30%'s opl0sning af emulgatoren fra eksempel 2c) og 12 g natriumpyrosulfit under nitrogenatmosfære i 20 en heholder med omr0rer og tilbagesvaler i 2 timer til en temperatur pâ 96°C og afk0les derefter til stuetempera-tur. Der fâs en opl0sning med en pH-værdi pâ 5,3 og et polymerindhold pâ 13,3%. Carboxylgrupperne i den hydroly-serede copolymere er neutraliseret i en udstrækning pâ 25 25%.Example 9 150 g of a copolymer based on styrene and maleic anhydride (3: 1 molar ratio) with an average molecular weight of 1900 are heated together with 1300 g of water, 7.3 g of ethanol, 125 g of a 30% solution of the emulsifier. from Example 2c) and 12 g of sodium pyrosulfite under a nitrogen atmosphere in a stirrer and reflux container for 2 hours to a temperature of 96 ° C and then cooled to room temperature. A solution with a pH of 5.3 and a polymer content of 13.3% is obtained. The carboxyl groups of the hydrolyzed copolymer are neutralized to an extent of 25%.
Til anvendelse ved polymérisation af vinylacetat indstilles opl0sningen med vand til en koncentration pâ 7,8%.For use in the polymerization of vinyl acetate, the solution is adjusted with water to a concentration of 7.8%.
30 Eksempel 10 150 g af en copolymer ud fra styren og maleinsyre-anhydrid (molforhold 2:1) med en gennemsnitsmolekylvægt pâ 1700 opvarmes sammen med 1300 g vand, 7,3 g ætsnatron, 125 g af en 30%'s vandig opl0sning af emulgatoren fra 35 eksempel 2 c) og 12 g natriumpyrosulfit under nitrogenatmosfære i en beholder med omr0rer og tilbagesvaler i 2 timer 0 12Example 10 150 g of a copolymer from styrene and maleic anhydride (2: 1 molar ratio) having an average molecular weight of 1700 are heated together with 1300 g of water, 7.3 g of ethanol, 125 g of a 30% aqueous solution of the emulsifier of Example 2 c) and 12 g of sodium pyrosulfite under nitrogen atmosphere in a stirred and reflux container for 2 hours 0 12
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til en temperatur pâ 96°C og afk0les derefter til stuetem-peratur. Der fâs en opl0sning med en pH-værdi pâ 4,3 og et polymerindhold pâ 13%. Carboxylgrupperne i den hydro-lyserede copolymere er neutraliseret i en udstrækning pâ 5 18,6%.to a temperature of 96 ° C and then cooled to room temperature. A solution with a pH of 4.3 and a polymer content of 13% is obtained. The carboxyl groups of the hydrolyzed copolymer are neutralized to an extent of 18.6%.
Til anvendelse ved polymérisation af vinylacetat indstilles opl0sningen med vand til en koncentration pâ 7,8%.For use in the polymerization of vinyl acetate, the solution is adjusted with water to a concentration of 7.8%.
10 Anvendelseseksempel 1 I en beholder med omr0rer fyldes 510 g vand, 1,77 g af en 6%'s vandig natriumalkylsulfonatopl0sning (alkyl-gruppernes gennemsnitlige kædelængde er 12-14 carbonatomer) og 2 g af en 30%'s vandig opl0sning af ammoniumsaltet af 15 en med 25 mol ethylenoxid oxethyleret og derefter sulfater-et nonylphenol, og der skylles med nitrogen. Efter tilsaet-ning af en opl0sning af 2,25 g ammoniumpersulfat i 20 g vand opvarmes blandingen til en temperatur pâ 50°C. Under bibeholdelse af denne temperatur sættes der til blandingen 20 samtidig i l0bet af 3 timer adskilt fra hinanden 750 g vinylacetat og en opl0sning af 0,39 g natriumformaldehyd-sulfoxylat i 50 g vand. I 10bet af den f0rste time tilsæt-tes der desuden endnu en gang samme mængde af den ifyldte emulgatorkombination, og i I0bet af de derpâ f0lgende 2 25 timer tildoseres yderligere 100 g af den if0lge eksempel 9 fremstillede copolymeropl0sning samt 1,87 g af ovennævnte alkylsulfonatopl0sning og 21,2 g af ovennævnte 30%'s ammoni-umsaltopl0sning. Derefter blandes blandingen med en opl0s-ning af 0,75 g ammoniumpersulfat i 30 g vand og opvarmes i 30 30 minutter til en temperatur pâ 75°C og afk0les dernæst til stuetemperatur.Use Example 1 In a stirrer container, 510 g of water, 1.77 g of a 6% aqueous sodium alkyl sulfonate solution (the average chain length of the alkyl groups are 12-14 carbon atoms) and 2 g of a 30% aqueous solution of the ammonium salt are charged. of 15 one with 25 moles of ethylene oxide oxethylated and then sulfates-a nonylphenol and rinsed with nitrogen. After adding a solution of 2.25 g of ammonium persulfate in 20 g of water, the mixture is heated to a temperature of 50 ° C. While maintaining this temperature, 750 g of vinyl acetate and a solution of 0.39 g of sodium formaldehyde sulfoxylate in 50 g of water were added simultaneously to the mixture 20 simultaneously. In addition, in the 10th of the first hour, the same amount of the filled emulsifier combination is added again, and in the course of the following 25 hours, an additional 100g of the copolymer solution prepared according to Example 9 and 1.87g of the above alkyl sulfonate solution are added. and 21.2 g of the above 30% ammonium salt solution. Then the mixture is mixed with a solution of 0.75 g of ammonium persulfate in 30 g of water and heated for 30 minutes to a temperature of 75 ° C and then cooled to room temperature.
Der fâs en koagulatfri polyvinylacetatdispersion, som med 3,2 g 12,5%'s ammoniakopl0sning indstilles pâ en pH-værdi pâ 6. Dispersionens indhold af fast stof er 50,8%, 35 og polymerpartiklerne har en gennemsnitsdiameter pâ 0,22 jjm. Dispersionen er forskydningsstabil, idet der efter 2 minut-A coagulate-free polyvinyl acetate dispersion is obtained which is adjusted to a pH of 6. With 3.2 g of 12.5% ammonia solution, the solids content of the dispersion is 50.8%, and the polymer particles have an average diameter of 0.22 µm. . The dispersion is shear stable, after 2 minutes
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0 13 ters omr0ring med en hurtigtgâende omr0rer (5.000 omdrejnin-ger pr. minut) ingen koagulatdannelser optræder, og den polymères gennemsnitspartikelst0rrelse ændrer sig ikke.0 13 hours of stirring with a fast stirrer (5,000 rpm) no clotting occurs and the average particle size of the polymer does not change.
5 Anvendelseseksempel 25 Application Example 2
Anvendelseseksempel 1 gentages, idet der dog i ste-det for den if01ge eksempel 9 fremstillede copolymeropl0s-ning anvendes den lf0lge eksempel 10 fremstillede copoly-meropl0sning. Den fremstillede polyvinylacetatdispersion er 10 koagulatfri. Dispersionens indhold af fast stof er 50,4%, og polymerpartiklerne har en gennemsnitsdiameter pâ 0,18 ^im. Dispersionen er forskydningsstabil (afpr0vning som i anvendelseseksempel 1) .Use Example 1 is repeated, but instead of the copolymer solution prepared according to Example 9, the copolymer solution prepared according to Example 10 is used. The polyvinyl acetate dispersion produced is 10 clot free. The solids content of the dispersion is 50.4% and the polymer particles have an average diameter of 0.18 µm. The dispersion is shear stable (test as in Application Example 1).
15 Sammenligningseksempel 1 1620 g af den i eksempel 3 anvendte styren/malein-syreanhydrid-copolymere omr0res i 8024 g vand under tilsæt-ning af 316 g ætsnatron i 6 3/4 timer ved en temperatur pâ 80°C. Den efter afk0ling til stuetemperatur fremkomne sus-20 pension filtreres, og derved fâs en fast remanens pâ 47 g. Filtratet har en pH-værdi pâ 10,0 og et polymerindhold pâ 18,7%. Carboxylgrupperne i den hydrolyserede copolymere er neutraliseret i en udstrækning pâ 100%.Comparative Example 1 1620 g of the styrene / maleic anhydride copolymers used in Example 3 are stirred in 8024 g of water with the addition of 316 g of etching sodium for 6 3/4 hours at a temperature of 80 ° C. The suspension obtained after cooling to room temperature is filtered to give a solid residue of 47 g. The filtrate has a pH of 10.0 and a polymer content of 18.7%. The carboxyl groups in the hydrolyzed copolymer are neutralized to an extent of 100%.
25 Sammenligningseksempel 2Comparative Example 2
Eksempel 4 gentages, idet dog opvarmningstempera-turen kun er 70°C. Derved gâr kun 50% af styren/maleinsyre-anhydrid-copolymeren i opl0sning, og opl0sningen har en pH-værdi pâ 5,2.Example 4 is repeated, however, the heating temperature is only 70 ° C. Thus, only 50% of the styrene / maleic anhydride copolymer dissolves, and the solution has a pH of 5.2.
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Sammenligningseksempel 3Comparative Example 3
Eksempel 4 gentages, idet dog opvarmningstempera-turen kun er 70°C, og idet der anvendes den dobbelte mæng-de ammoniakopl0sning. Den fremkomne opl0sning har en pH-35 -værdi pâ 9,3.Example 4 is repeated, however, the heating temperature is only 70 ° C and the double amount of ammonia solution is used. The resulting solution has a pH-35 value of 9.3.
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Sammenligningseksempel 4Comparative Example 4
Anvendelseseksempel 1 gentages, idet den if01ge eksempel 9 fremstillede copolymeropl0sning erstattes af vand. Den fremkomne polyvinylacetatdispersion koagulerer 5 ved afpr0vningen for forskydningsstabilitet.Application Example 1 is repeated, replacing the copolymer solution prepared according to Example 9 with water. The resulting polyvinyl acetate dispersion coagulates in the shear stability test.
Sainmenligningseksenipel 5Comparative equation nipple 5
Anvendelseseksempel 1 gentages, idet den if01ge eksempel 9 fremstillede copolymeropl0sning erstattes af 10 en tilsvarende fremstillet opl0sning af en styren/malein- syreanhydrid-copolymer (molforhold 1:1) med en gennemsnits-molekylvægt pâ 1600, hvis carboxylgrupper efter hydrolysen er neutraliseret i en udstrækning pâ 12,3%. Den fremkomne polyvinylacetatdispersion koagulerer ved afpr0vningen for 15 forskydningsstabilitet.Application Example 1 is repeated, replacing the copolymer solution prepared according to Example 9 with a correspondingly prepared solution of a styrene / maleic anhydride copolymer (1: 1 molar ratio) having an average molecular weight of 1600 whose carboxyl groups are neutralized to a degree after at 12.3%. The resulting polyvinyl acetate dispersion coagulates upon testing for shear stability.
20 25 30 3520 25 30 35
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| Application Number | Priority Date | Filing Date | Title |
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| DE2938429 | 1979-09-22 | ||
| DE19792938429 DE2938429A1 (en) | 1979-09-22 | 1979-09-22 | AQUEOUS SOLUTION OR DISPERSION OF A STYRENE / MALEIC ACID ANHYDRIDE COPOLYMER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
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| DK399380A DK399380A (en) | 1981-03-23 |
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| DK156579C DK156579C (en) | 1990-01-29 |
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| ZA (1) | ZA805810B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU5017985A (en) * | 1984-11-05 | 1986-06-03 | Owens-Corning Fiberglas Corporation | Glass fiber size and impregnant compositions |
| DE3631814A1 (en) * | 1986-09-19 | 1988-03-31 | Basf Ag | LIGHTLY CROSSLINKED, WATER-SOLUBLE POLYMAL ACID, METHOD FOR THE PRODUCTION AND USE THEREOF |
| CN1048190C (en) * | 1989-06-06 | 2000-01-12 | 普拉斯-斯托弗公司 | Highly concentrated aqeous suspension of minerals and/or fillers and/or pigments |
| IT1236966B (en) * | 1989-10-25 | 1993-05-07 | Ausidet Srl | PROCESS FOR THE PRODUCTION OF AQUEOUS SOLUTIONS OF ANTI-INCRUSTATION AGENTS AND SOLUTIONS SO OBTAINED |
| JPH07157524A (en) * | 1993-11-24 | 1995-06-20 | Union Carbide Chem & Plast Technol Corp | Vinyl copolymer containing macromonomer |
| FI991295A (en) * | 1999-06-07 | 2000-12-08 | Neste Chemicals Oy | A process for preparing styrene-maleic hydride copolymers |
| EP1405865A1 (en) * | 2002-10-04 | 2004-04-07 | DSM IP Assets B.V. | Process for preparing a polymer dispersion |
| JP5207097B2 (en) * | 2006-06-16 | 2013-06-12 | 星光Ｐｍｃ株式会社 | Filler modifier, filler slurry and paper making method |
| JP5515217B2 (en) * | 2008-01-11 | 2014-06-11 | 東洋インキＳｃホールディングス株式会社 | Dispersant, and pigment composition and pigment dispersion using the same |
| JP5614786B2 (en) * | 2013-05-09 | 2014-10-29 | 株式会社Adeka | Novel polymer and non-aqueous electrolyte secondary battery using the polymer |
| JPWO2015099170A1 (en) * | 2013-12-27 | 2017-03-23 | コニカミノルタ株式会社 | Acrylic resin film and method for producing the same, polarizing plate protective film, polarizing plate including the same, and liquid crystal display device |
| KR102440479B1 (en) * | 2018-07-11 | 2022-09-05 | 아라까와 가가꾸 고교 가부시끼가이샤 | Tackifying resin emulsion, water-based adhesive composition, and adhesive sheet |
| KR20240033249A (en) * | 2021-07-15 | 2024-03-12 | 산 노프코 가부시키가이샤 | Dispersants and water-based coating compositions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2490489A (en) * | 1944-02-03 | 1949-12-06 | Du Pont | Process for copolymerizing maleic anhydride and styrene |
| US3444151A (en) * | 1965-09-07 | 1969-05-13 | Sinclair Research Inc | Styrene-maleic anhydride-amine polymers as emulsifiers in polymerization of vinyl monomers |
| US3939108A (en) * | 1974-12-16 | 1976-02-17 | National Starch And Chemical Corporation | Cold water resistant starch-based adhesive containing styrene-maleic anhydride resin and fixed alkali |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1414918A (en) * | 1973-02-14 | 1975-11-19 | Ciba Geigy Uk Ltd | Treatment of water to prevent the deposition of scale |
| US3835122A (en) * | 1973-04-25 | 1974-09-10 | Atomic Energy Commission | Novel polystyrene product having rapid-post-irradiation decay of conductivity and process of making same |
| JPS5299104A (en) * | 1976-02-17 | 1977-08-19 | Toyo Ink Mfg Co | Composition of water dispersive material |
| JPS54107945A (en) * | 1978-02-14 | 1979-08-24 | Toagosei Chem Ind Co Ltd | Aqueous dispersion of finely granulated polymer |
-
1979
- 1979-09-22 DE DE19792938429 patent/DE2938429A1/en not_active Withdrawn
-
1980
- 1980-09-16 ES ES495100A patent/ES495100A0/en active Granted
- 1980-09-18 FI FI802934A patent/FI72990C/en not_active IP Right Cessation
- 1980-09-18 DE DE8080105591T patent/DE3063516D1/en not_active Expired
- 1980-09-18 AT AT80105591T patent/ATE3555T1/en not_active Application Discontinuation
- 1980-09-18 EP EP80105591A patent/EP0025979B1/en not_active Expired
- 1980-09-19 IE IE1958/80A patent/IE50353B1/en not_active IP Right Cessation
- 1980-09-19 NO NO802786A patent/NO802786L/en unknown
- 1980-09-19 CA CA000360619A patent/CA1161581A/en not_active Expired
- 1980-09-19 ZA ZA00805810A patent/ZA805810B/en unknown
- 1980-09-19 AU AU62551/80A patent/AU537112B2/en not_active Ceased
- 1980-09-19 DK DK399380A patent/DK156579C/en active
- 1980-09-19 BR BR8005999A patent/BR8005999A/en unknown
- 1980-09-19 JP JP12939380A patent/JPS5647412A/en active Granted
- 1980-09-19 PT PT71820A patent/PT71820B/en unknown
- 1980-09-19 AR AR282593A patent/AR222101A1/en active
- 1980-09-22 MX MX184014A patent/MX156364A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2490489A (en) * | 1944-02-03 | 1949-12-06 | Du Pont | Process for copolymerizing maleic anhydride and styrene |
| US3444151A (en) * | 1965-09-07 | 1969-05-13 | Sinclair Research Inc | Styrene-maleic anhydride-amine polymers as emulsifiers in polymerization of vinyl monomers |
| US3939108A (en) * | 1974-12-16 | 1976-02-17 | National Starch And Chemical Corporation | Cold water resistant starch-based adhesive containing styrene-maleic anhydride resin and fixed alkali |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1161581A (en) | 1984-01-31 |
| JPS5647412A (en) | 1981-04-30 |
| EP0025979A1 (en) | 1981-04-01 |
| FI72990C (en) | 1987-08-10 |
| AR222101A1 (en) | 1981-04-15 |
| ES8105356A1 (en) | 1981-06-16 |
| PT71820A (en) | 1980-10-01 |
| ES495100A0 (en) | 1981-06-16 |
| FI802934A (en) | 1981-03-23 |
| IE801958L (en) | 1981-03-22 |
| DE3063516D1 (en) | 1983-07-07 |
| JPH0336854B2 (en) | 1991-06-03 |
| AU6255180A (en) | 1981-04-09 |
| EP0025979B1 (en) | 1983-05-25 |
| NO802786L (en) | 1981-03-23 |
| DK156579C (en) | 1990-01-29 |
| MX156364A (en) | 1988-08-15 |
| IE50353B1 (en) | 1986-04-02 |
| DK399380A (en) | 1981-03-23 |
| PT71820B (en) | 1981-10-23 |
| FI72990B (en) | 1987-04-30 |
| ZA805810B (en) | 1981-10-28 |
| BR8005999A (en) | 1981-03-31 |
| AU537112B2 (en) | 1984-06-07 |
| ATE3555T1 (en) | 1983-06-15 |
| DE2938429A1 (en) | 1981-04-09 |
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