DK150905B - ALKALI-SOLUBLE HARPIXES BASED ON COPOLYMERISATES OF MONOOLEFINICALLY UNSATURATED CARBOXYLIC ACIDS AND WITH AROMATIC GROUPS SUBSTITUTED ALFA-OLEPHINES AND THEIR USE AS HARPISPERSON HARPERS - Google Patents
ALKALI-SOLUBLE HARPIXES BASED ON COPOLYMERISATES OF MONOOLEFINICALLY UNSATURATED CARBOXYLIC ACIDS AND WITH AROMATIC GROUPS SUBSTITUTED ALFA-OLEPHINES AND THEIR USE AS HARPISPERSON HARPERS Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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Abstract
Description
150905150905
Opfindelsen angår nye, alkaliopløselige, i polymerdispersioner anvendelige harpikser på basis af statistisk opbyggede copolymerisater, af den i indledningen til krav 1 angivne art, samt en anvendelse af disse 5 harpikser som harpikskomponenter i polymerdispersioner.The invention relates to new, alkali-soluble, polymer dispersions, resins useful on the basis of statistically constructed copolymers of the kind set forth in the preamble of claim 1, and to the use of these resins as resin components in polymer dispersions.
Alkaliopløselige harpikser, der egner sig som harpikskomponenter til polymerdispersioner af denne art, og som for eksempel er opbygget af styren og (meth)acrylsyre som comonomer e, og som har molvægte mellem 700 og 5000, er kendt 10 fra DE-AS 15 19 201 og GB-PS 1 107 249. De udviser syretal på 140 til 300 og fremstilles ved opløsningspolymerisation i nærværelse af radikaldannende initiatorer og regulerende midler ved en diskontinuerlig metode. Ulempen ved sådanne harpikser består i, at de ikke meddeler de 15 selvskinnende film, der dannes ud fra de selvskinnende emulsioner, nogen yderligere stabilitet over for begyndende genopløsning ved påføring af den anden film. Når en selvskinnende emulsion har manglende stabilitet over for begyndende genopløsning, bliver den første film ved påfø-20 ringen af det andet filmlag selv begyndende opløst af den selvskinnende emulsion, og der opstår uæstetiske pletter, der nødvendiggør en fjernelse og nypåføring af den selvskinnende emulsion. Det er fremfor alt økonomiske grunde, der stiller sig i vejen for hyppige fornyelser af filmene, 25 og det er derfor opfindelsens formål at udvikle en alkali opløselig harpikskomponent, der gør de film, der dannes af de selvskinnende emulsioner, stabile mod begyndende genopløsning. Ansøgningen angår således alkaliopløselige, i polymerdispersioner anvendelige harpikser, og disse harpikser 30 er ejendommelige ved det i krav l's kendetegnende del angivne.Alkali-soluble resins, which are suitable as resin components for polymer dispersions of this kind, which are, for example, made up of styrene and (meth) acrylic acid as comonomer e, and having molecular weights between 700 and 5000, are known from DE-AS 15 19 201 and GB-PS 1,107,249. They exhibit acid numbers of 140 to 300 and are prepared by solution polymerization in the presence of radical-forming initiators and regulators by a discontinuous method. The disadvantage of such resins is that they do not give the 15 self-shining films formed from the self-shining emulsions any additional stability to the initial redissolution upon application of the second film. When a self-shining emulsion has a lack of stability against initial resolution, the first film, upon application of the second film layer, is itself initially dissolved by the self-shining emulsion, and aesthetic stains are required which necessitate removal and re-application of the self-shining emulsion. Above all, economic reasons stand in the way of frequent renewal of the films, and it is therefore the object of the invention to develop an alkali soluble resin component which makes the films formed by the self-shining emulsions stable against initial redissolution. Thus, the application relates to alkali-soluble resins useful in polymer dispersions, and these resins 30 are characterized by the characterizing part of claim 1.
Væsentligst for egenskaberne i henhold til opfindelsen er ved disse harpikser de talmæssige forhold af comonomeren-hederne, syretallet, molvægten og polymerisationsmetoden.Most important for the properties of the invention in these resins are the numerical ratios of the comonomer units, the acid number, the molecular weight and the polymerization method.
2 1509052 150905
Fra DE-OS 25 02 172 kender man harpikser, der blandt andet fremstilles ved termisk copolymerisation - altså ligeledes uden radikaldannende initiatorer - af 2 til 35 vægtprocent acrylsyre, styren og maleinsyreanhydrid ved ca. 150 til 5 300°C. Disse harpikser indeholder altså væsentligt mindre acrylsyre i indpolymeriseret tilstand, er vanskeligere eller overhovedet ikke alkaliopløselige og anbefales i henhold til den angivne publikation som papirlimemiddel.DE-OS 25 02 172 discloses resins which are produced, inter alia, by thermal copolymerization - ie also without radical-forming initiators - of 2 to 35% by weight acrylic acid, styrene and maleic anhydride at approx. 150 to 5 300 ° C. Thus, these resins contain substantially less acrylic acid in the polymerized state, are more difficult or not at all alkali soluble and are recommended according to the disclosed publication as a paper adhesive.
De egner sig ikke som harpikskomponent i polymerdispersi-10 oner og anbefales heller ikke på noget sted i det angivne offentliggørelsesskrift til dette formål.They are not suitable as a resin component in polymer dispersions and are also not recommended at any place in the disclosed publication for this purpose.
Med henblik på det før angivne DE-AS 15 19 201 er det overraskende, at det højere syretal og den termiske polymerisationsmetode ved temperaturer mellem 200 og 400°C 15 fører til produkter med en i og for sig lignende opbygning, men som dog meddeler de selvskinnende film den væsentligt forbedrede egenskab: hvad angår stabilitet over for begyndende genopløsning i sammenligning med filmene af kendte, selvskinnende emulsioner.In view of the aforementioned DE-AS 15 19 201, it is surprising that the higher acid number and the thermal polymerization method at temperatures between 200 and 400 ° C 15 lead to products of a similar structure but which nevertheless disclose the self-shining film has the substantially improved property: in terms of stability to initial resolution compared to the films of known self-shining emulsions.
20 Derudover har det overraskende vist sig, at disse nye harpikser meddeler de selvskinnende film en yderligere højere glans, større hårdhed, forbedret trædestyrke og forbedret resistens mod påvirkning fra et viskelæder, sorte gummistreger og snavs. Desuden forbedrer de befugtningsvirknin-25 gen af de selvskinnende emulsioner.20 In addition, it has been surprisingly found that these new resins give the self-shining films a further higher gloss, greater hardness, improved tensile strength and improved resistance to impact from an eraser, black rubber bars and dirt. In addition, they enhance the wetting effect of the self-shining emulsions.
Ansøgningen angår også anvendelsen af de alkaliopløselige harpikser ifølge krav 1 som harpikskomponenter i polymerdispersioner, jævnfør krav 4.The application also relates to the use of the alkali-soluble resins of claim 1 as resin components in polymer dispersions, according to claim 4.
Udgangsmonomere (a) til fremstilling af harpikserne iføl-30 ge opfindelsen er styren eller vinyltoluen. De er ind- 3 150905 polymeriseret i copolymerisaterne i en mængde af 55 til 45 vægtprocent.Starting monomer (a) for preparing the resins of the invention is styrene or vinyl toluene. They are polymerized in the copolymers in an amount of 55 to 45% by weight.
Udgangsmonomere (b) er acrylsyre eller methacrylsyre.Starting monomer (b) is acrylic acid or methacrylic acid.
De er indpolymeriseret i mængder mellem 45 og 55 5 vægtprocent.They are polymerized in amounts between 45 and 55% by weight.
Desuden kan der som comonomere (c) være indpolymeriseret indtil 10, fortrinsvis mellem 2 og 10 vægtprocent af maleinsyre eller maleinsyreanhydrid, beregnet i forhold til (a) + (b).In addition, as comonomers (c), there may be polymerized up to 10, preferably between 2 and 10% by weight of maleic or maleic anhydride, calculated in relation to (a) + (b).
10 Som polymerisationsapparatur kan man for eksempel an vende en trykkedel, en trykkedelkaskade, et trykrør eller en trykkedel med et efterindskudt reaktionsrør, der er forsynet med en statisk blander. Fortrinsvis polymeriserer man de monomere (a), (b) og even-15 tuelt (c) i mindst to efter hinanden indskudte polymerisationszoner. Derved kan den ene reaktionszone bestå af en tryktæt kedel, den anden af et tryktæt reaktionsrør, fortrinsvis en opvarmelig, statisk blander. Når man gennemfører polymerisationen i to 20 efter hinanden indskudte zoner, opnår man omsætninger, der ligger over 99%. Under polymerisationen må man sørge for en god gennemblanding af komponenterne.For example, as a polymerization apparatus, a pressure member, a pressure member cascade, a pressure tube, or a pressure member may be used with a post-injected reaction tube provided with a static mixer. Preferably, the monomers (a), (b) and optionally (c) are polymerized in at least two consecutive polymerization zones. Thereby, one reaction zone may consist of a pressure-tight boiler, the other a pressure-tight reaction tube, preferably a heatable static mixer. When the polymerization is carried out in two 20 successively intersected zones, the turnover is greater than 99%. During the polymerization, a good mixing of the components must be ensured.
For eksempel anvender man tryktætte kedler, der er forsynet med en rører, eller polymerisationsrør med 25 statiske blandere.For example, pressure-tight boilers fitted with a stirrer or polymerization tubes with 25 static mixers are used.
Copolymerisationen gennemføres kontinuerligt og i fravær af radikaldannende initiatorer. Et copoly-merisat af styren, acrylsyre og maleinsyreanhydrid kan for eksempel fremstilles på den måde, at man 30 kontinuerligt tilfører de monomere til en reak tor eller to efter hinanden indskudte polymerisationszoner, for eksempel en trykkedelkaskade, 4 150905 og at man kontinuerligt udsluser materialet fra reaktionszonen efter en opholdstid på 3 til 60 minutter, fortrinsvis 5 til 30 minutter, ved temperaturer mellem 200 og 400°C. Overholdelsen af disse temperaturgrænser er vigtig, fordi 5 man ved at arbejde med temperaturer derunder må konstatere, at opholdstiderne bliver for lange og molvægtene for høje, og fordi man ved at overskride temperaturgrænserne må konstatere, at der kan indtræde termiske dekompositionsprocesser.The copolymerization is carried out continuously and in the absence of radical-forming initiators. For example, a copolymer of styrene, acrylic acid and maleic anhydride can be prepared by continuously adding the monomers to a reactor or two successively inserted polymerization zones, for example, a pressure boiler cascade, and continuously removing the material from the reaction zone after a residence time of 3 to 60 minutes, preferably 5 to 30 minutes, at temperatures between 200 and 400 ° C. Compliance with these temperature limits is important because by working with temperatures below, it must be noted that the residence times become too long and the molecular weights too high, and because by exceeding the temperature limits it must be noted that thermal decomposition processes can occur.
10 Polymerisationen gennemføres ved tryk > 1 bar, fortrinsvis mellem 1 og 200 bar. Man opnår særligt gode resultater, når man gennemfører polymerisationsreaktionen ved periodiske trykvariationer med trykdifferenser mellem 5 og 120 bar og derpå afspænder, ligeledes ved periodiske trykvari-15 ationer med de samme trykdifferenser. Denne forholdsregel, der medfører en pulserende strømning af reaktionsmassen, frembringer en selvrensning af reaktoren og forhindrer produktskadelige vægbelægninger og begyndende sammenbagninger i reaktoren. Det udtagne produkt er homogent og inde-20 holder ingen uregelmæssigheder eller revner.The polymerization is carried out at pressures> 1 bar, preferably between 1 and 200 bar. Particularly good results are obtained when conducting the polymerization reaction by periodic pressure variations with pressure differences between 5 and 120 bar and then relaxing, as well as by periodic pressure variations with the same pressure differences. This precaution, which results in a pulsating flow of the reaction mass, produces a self-cleaning of the reactor and prevents product-damaging wall coverings and incipient backbacks in the reactor. The product taken out is homogeneous and contains no irregularities or cracks.
Ved kontinuerlig polymerisation inden for opfindelsens rammer skal man også forstå en arbejdsmåde, ved hvilken man først i en polymerisationszone, f.eks. i en kedel, bringer ca. 10% af monomerblandingen til at foreligge, og ved 25 hvilken man derpå i løbet af 30 til 300 minutter kontinuerligt lader resten af monomerblandingen løbe til. Ved denne fremgangsmådevariant ligger imidlertid rumtidsudbytterne ikke så højt som ved den kontinuerlige polymerisation i to efter hinanden indskudte reaktionszoner. I mod-30 sætning til de kendte metoder polymeriserer man fortrinsvis i fravær af et opløsningsmiddel; man kan dog også anvende ikke regulerende opløsningsmidler, såsom f.eks. di-oxan, toluen, dimethylformamid, tetrahydrofuran, benzen eller 5 150905 xylen-Continuous polymerization within the scope of the invention is also understood to mean a mode of operation in which one is first in a polymerization zone, e.g. in a kettle, bring approx. 10% of the monomer mixture to be present, and at which time the remainder of the monomer mixture is allowed to run continuously for 30 to 300 minutes. However, with this process variant, the space-time yields are not as high as in the continuous polymerization in two successive reaction zones. Contrary to the known methods, the polymer is preferably polymerized in the absence of a solvent; however, non-regulatory solvents such as e.g. dioxane, toluene, dimethylformamide, tetrahydrofuran, benzene or xylene
De således fremkomne copolymerisater kan anvendes i polymerdispersioner til fremstilling af selvskinnende emulsioner til overtrækning af gulve eller andre overflader. Så-5 danne polymerdispersioner beror på additionspolymerisater, sådan som disse for eksempel er kendt fra DE-AS 15 19 316 eller det allerede anførte DE-AS 15 19 201. De består for eksempel af methyl(meth)acrylat, butylacrylat og indtil 20 vægtprocent acrylsyre eller methacrylsyre. Til fremstil-10 ling af de selvskinnende emulsioner kombineres de hyppigt med en voks af naturlig eller kunstig oprindelse, for eksempel i form af polyethylenvoks-emulsioner, ved hvilke molvægtene af polyethylenvoksen ligger mellem 1500 og 30.000.The copolymers thus obtained can be used in polymer dispersions to prepare self-shining emulsions for coating floors or other surfaces. Such polymer dispersions depend on addition polymerisates, such as are known, for example, from DE-AS 15 19 316 or the already mentioned DE-AS 15 19 201. They consist, for example, of methyl (meth) acrylate, butyl acrylate and up to 20% by weight. acrylic acid or methacrylic acid. To prepare the self-shining emulsions, they are frequently combined with a wax of natural or artificial origin, for example in the form of polyethylene wax emulsions, in which the molecular weight of the polyethylene wax is between 1500 and 30,000.
De alkaliopløselige harpikser ifølge opfindelsen tilsæt-15 tes som nævnt til polymerdispersionerne i mængder på ca. 0,2 til 10 vægtprocent, beregnet i forhold til tørstofindholdet, fortrinsvis mellem 0,5 og 2 vægtprocent.The alkali-soluble resins of the invention are added, as mentioned, to the polymer dispersions in amounts of approx. 0.2 to 10% by weight, calculated in relation to the dry matter content, preferably between 0.5 and 2% by weight.
De øvrige komponenter og deres talmæssige mængdeforhold hører til fagmandens viden. Der skal udtrykkeligt henvi-20 ses til DE-AS 15 19 316 og 15 19 201.The other components and their numerical proportions belong to one of ordinary skill in the art. Reference should be made explicitly to DE-AS 15 19 316 and 15 19 201.
De følgende eksempler belyser opfindelsen. De angivne dele er vægtdele.The following examples illustrate the invention. The parts indicated are parts by weight.
EKSEMPEL 1 47 dele styren, 50 dele acrylsyre og 3 dele maleinsyrean-25 hydrid tildoseres, kontinuerligt til en 1 liter trykkedel med efterindskudt trykrør med det dobbelte volumen med trykregulator. Systemet opvarmedes til 310°C. Trykket blev holdt i området mellem 5 og 50 bar, og det varieredes en gang inden for et minut ved en periodisk trykregulering 30 inden for dette område. Opholdstiden androg 11 minutter; copolymersmelten udtoges, hvad angår mængden, i samme omfang, som der blev tilført frisk monomerblanding. Copoly- 6 150905 molekylvægt på 650.EXAMPLE 1 47 parts of styrene, 50 parts of acrylic acid and 3 parts of maleic anhydride are dosed continuously into a 1 liter double-section pressure tube with double volume pressure regulator. The system was heated to 310 ° C. The pressure was kept in the range between 5 and 50 bar, and it was varied once within a minute by a periodic pressure control 30 within this range. The residence time was 11 minutes; the copolymer melt was withdrawn, as far as the amount is concerned, to the same extent as fresh monomer mixture was added. Copoly- molecular weight of 650.
EKSEMPEL 2 50 dele styren og 50 dele acrylsyre copolymeriseredes i henhold til eksempel 1. Temperaturen var 290°C, opholds-5 tiden 15 minutter og trykket mellem 5 og 60 bar.EXAMPLE 2 50 parts of styrene and 50 parts of acrylic acid were copolymerized according to Example 1. The temperature was 290 ° C, the residence time 15 minutes and the pressure between 5 and 60 bar.
Det fremkomne copolymerisat udviste en gennemsnitlig molekylvægt på 670 og et syretal på 380.The resulting copolymer exhibited an average molecular weight of 670 and an acid number of 380.
EKSEMPEL 3 40 dele styren, 54 dele acrylsyre og 6 dele maleinsyrean-10 hydrid copolymeriseredes i henhold til eksempel 1. Temperaturen var 300°C, trykket 10 til 80 bar og opholdstiden 9 minutter.EXAMPLE 3 40 parts styrene, 54 parts acrylic acid and 6 parts maleic anhydride were copolymerized according to Example 1. The temperature was 300 ° C, the pressure 10 to 80 bar and the residence time 9 minutes.
Det fremkomne copolymerisat udviste en gennemsnitlig molekylvægt på 720 og et syretal på 420.The resulting copolymer exhibited an average molecular weight of 720 and an acid number of 420.
15 ANVENDELSESTEKNISKE EKSEMPLER15 APPLICATION TECHNICAL EXAMPLES
Man undersøgte to selvskinnende emulsioner, der udviser følgende sammensætninger:Two self-shining emulsions were tested, showing the following compositions:
Selvskinnende emulsion A (ifølge opfindelsen); 40 vægtdele af en 40 vægtprocent vandig dispersion 20 af et copolymerisat af 38 vægtdele styren 8 vægtdele methacrylsyre 24 vægtdele methacrylsyremethylester 24 vægtdele acrylsyrebutylester 25 1 vægtdel zink i form af et amin- kompleks (tetraminacetat) 1 vægtdel af en harpiks i henhold til eksempel 1 47 vægtdele vand 30 4 vægtdele ca. 34% emulsion af et oxideret poly- ethylen 5.5 vægtdele ethyldiglycol (tempoært blødgørings- middel) 2.5 vægtdele tributoxyethylphosphat (permanent 35 blødgøringsmiddel) 1 vægtdel af et fluoreret tensid (sprednings- 7 150905 giver 100,00 dele selvskinnende emulsion.Self-shining emulsion A (according to the invention); 40 parts by weight of a 40 weight percent aqueous dispersion 20 by a copolymer of 38 parts by weight styrene 8 parts by weight methacrylic acid 24 parts by weight methacrylic acid methyl ester 24 parts by weight acrylic acid butyl ester 25 parts by weight of zinc in the form of an amine complex (tetramine acetate) 1 part by weight of a resin according to Example 1 47 parts by weight of water 30 4 parts by weight approx. 34% emulsion of an oxidized polyethylene 5.5 parts by weight of ethyl diglycol (temporary softener) 2.5 parts by weight of tributoxyethyl phosphate (permanent 35 softener) 1 part by weight of a fluorinated surfactant (dispersion 7) gives 10000 parts of self-shining emulsion.
Selvskinnende smulsion B (sammenligning):Self-shining Smulsion B (comparison):
Som A, idet man dog som harpiks anvender et polymerisat, der har den samme sammensætning som det ifølge eks. 1 frem-5 stillede, men er fremstillet ved opløsningspolymerisation.As A, however, using as a resin a polymer which has the same composition as that of Example 1, but is prepared by solution polymerization.
De selvskinnende emulsioner blev påført på linoleum- og PVC-gulvbelægninger.The self-shining emulsions were applied to linoleum and PVC floor coverings.
De fremkomne film blev underkastet de laboratorieundersøgelser, der er. sædvanligt anvendt på dette område, samt en 10 i tre uger varende prøve, hvor man gik på filmene.The resulting films were subjected to the laboratory studies that are. usually used in this field, as well as a 10-week three-week trial where the films went.
Resultaterne af den foretagne visuelle bedømmelse af de la-boratoriemæssige prøver og den praktiske prøve, hvor man gik på filmene, er udtrykt i den følgende tabel. Herved betyder 1 utilstrækkelig og 5 udmærket.The results of the visual assessment of the laboratory tests and the practical tests of the films are expressed in the following table. Hereby 1 means inadequate and 5 means excellent.
15 TABELTABLE
Selvskinnende emulsionSelf-shining emulsion
Stabilitet mod begyndende genop- A BStability towards beginning resume- A B
løsning (ingen pletter efter den anden filmpåføring) 5 3 20 Vandægthed (Gardner-slidtester) 5 3solution (no stains after the second film application) 5 3 20 Waterproofness (Gardner wear tester) 5 3
Glans (reflexionsglansmåleappa- rat i henhold til Dr. Lange) 5 4 Gåprøve 5 2,5Gloss (reflection gloss measuring device according to Dr. Lange) 5 4 Walking test 5 2.5
Resistens mod afsmitsviskelæder 4,5 2,5 25 (Stregtest med gummisfsætning)Resistant to Wiping Leather 4.5 2.5 25 (Stroke test with rubber seal)
Befugtningsevne af emulsionen 5 3Wettability of the emulsion 5 3
Tensidresistens 5 3,5Density Resistance 5 3.5
Fjernelighed (Gardner-test med grundrensning) 5 5Removability (Gardner test with basic cleaning) 5 5
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803034171 DE3034171A1 (en) | 1980-09-11 | 1980-09-11 | ALKALO-SOLUBLE RESINS BASED ON COPOLYMERISATES FROM MONOOLEFINICALLY UNSATURATED CARBONIC ACIDS AND (ALPHA) -OLEFINES SUBSTITUTED BY AROMATES AND THEIR USE AS RESIN COMPONENTS IN POLYMER DISPERSIONS |
| DE3034171 | 1980-09-11 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK401681A DK401681A (en) | 1982-03-12 |
| DK150905B true DK150905B (en) | 1987-07-13 |
| DK150905C DK150905C (en) | 1988-02-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK401681A DK150905C (en) | 1980-09-11 | 1981-09-10 | ALKALI-SOLUBLE HARPIXES BASED ON COPOLYMERISATES OF MONOOLEFINICALLY UNSATURATED CARBOXYLIC ACIDS AND WITH AROMATIC GROUPS SUBSTITUTED ALFA-OLEPHINES AND THEIR USE AS HARPISPERSON HARPERS |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0047889B1 (en) |
| JP (1) | JPS5780407A (en) |
| AT (1) | ATE13677T1 (en) |
| DE (2) | DE3034171A1 (en) |
| DK (1) | DK150905C (en) |
| ES (1) | ES505382A0 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3225875A1 (en) * | 1982-07-10 | 1984-01-12 | Basf Ag, 6700 Ludwigshafen | COPOLYMERISATES FROM 2 TO 3 C-ATOMAS CONTAINING MONOOLEFINICALLY UNSATURATED CARBONIC ACIDS AND STYRENE AND THE USE THEREOF FOR THE PRODUCTION OF AQUEOUS PAPER COATINGS |
| DE3225876A1 (en) * | 1982-07-10 | 1984-01-12 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING PRINTING INK BINDERS AND THE USE THEREOF FOR AQUEOUS PRINTING INKS |
| DE3800984A1 (en) * | 1988-01-15 | 1989-07-27 | Basf Ag | BINDER FOR ADHESIVE, NON-DIRTIVE, ELASTIC COATINGS |
| DE3807285A1 (en) * | 1988-03-05 | 1989-09-14 | Basf Ag | PRODUCTION OF POLYMER BINDERS FOR DISPERSION PAINTS |
| DE4202301A1 (en) * | 1992-01-28 | 1993-10-21 | Basf Ag | coating agents |
| CA2088129A1 (en) * | 1992-02-06 | 1993-08-07 | Fritz Erdmann Kempter | Continuous polymerization of vinyl monomers |
| DE4330767A1 (en) * | 1993-09-10 | 1995-03-16 | Hoechst Ag | Polymer blends with water |
| US6197879B1 (en) | 1995-10-31 | 2001-03-06 | Henkel Corporation | Methods of preparing inorganic pigment dispersions |
| EP2514775A1 (en) * | 2011-04-20 | 2012-10-24 | Evonik Röhm GmbH | Maleic anhydride copolymers as soluble support material for fused deposition modelling (FDM) printer |
| KR20210065371A (en) | 2019-11-27 | 2021-06-04 | 한화솔루션 주식회사 | alkali water soluble resin manufacturing method comprising three-component acid, and alkali water soluble resin thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1107249A (en) * | 1964-08-31 | 1968-03-27 | Johnson & Son Inc S C | Alkali-soluble resins and method of preparing the same |
| GB1528592A (en) * | 1974-12-10 | 1978-10-11 | Procter & Gamble | Floor care and cleaning composition |
| DE2502172C3 (en) * | 1975-01-21 | 1980-09-18 | Basf Ag, 6700 Ludwigshafen | Anionic paper sizing agents |
| JPS5525455A (en) * | 1978-08-11 | 1980-02-23 | Kanegafuchi Chem Ind Co Ltd | Gloss coating composition |
-
1980
- 1980-09-11 DE DE19803034171 patent/DE3034171A1/en not_active Withdrawn
-
1981
- 1981-08-26 DE DE8181106608T patent/DE3170845D1/en not_active Expired
- 1981-08-26 AT AT81106608T patent/ATE13677T1/en not_active IP Right Cessation
- 1981-08-26 EP EP81106608A patent/EP0047889B1/en not_active Expired
- 1981-09-10 JP JP56141802A patent/JPS5780407A/en active Pending
- 1981-09-10 ES ES505382A patent/ES505382A0/en active Granted
- 1981-09-10 DK DK401681A patent/DK150905C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ES8500293A1 (en) | 1984-10-01 |
| DE3034171A1 (en) | 1982-05-06 |
| DK401681A (en) | 1982-03-12 |
| ES505382A0 (en) | 1984-10-01 |
| DK150905C (en) | 1988-02-01 |
| DE3170845D1 (en) | 1985-07-11 |
| ATE13677T1 (en) | 1985-06-15 |
| EP0047889B1 (en) | 1985-06-05 |
| JPS5780407A (en) | 1982-05-20 |
| EP0047889A3 (en) | 1982-08-04 |
| EP0047889A2 (en) | 1982-03-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PBP | Patent lapsed |