DE697481C - Process for the production of high molecular weight polymerisation products which are soluble in cold water - Google Patents
Process for the production of high molecular weight polymerisation products which are soluble in cold waterInfo
- Publication number
- DE697481C DE697481C DE1936I0055120 DEI0055120D DE697481C DE 697481 C DE697481 C DE 697481C DE 1936I0055120 DE1936I0055120 DE 1936I0055120 DE I0055120 D DEI0055120 D DE I0055120D DE 697481 C DE697481 C DE 697481C
- Authority
- DE
- Germany
- Prior art keywords
- water
- polymerization
- soluble
- cold water
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 150000003839 salts Chemical group 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 4
- 150000003857 carboxamides Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims 2
- 150000001408 amides Chemical class 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- -1 maleic acid Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J135/00—Adhesives based on homopolymers or 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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J135/04—Homopolymers or copolymers of nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
Verfahren zur Herstellung von in kaltem Wasser löslichen hochmolekularen Polymerisationsprodukten Beim Erhitzen von ungesättigten polymerisierbaren Säureamiden über ihren Schmelzpunkt in An- oder Abwesenheit von Katalysatoren erhält man meist unter Abspaltung von Ammoniak Polymerisate, die in kaltem Wasser unlöslich oder nur quellbar sind. Führt man die Polymerisation in wäßriger Lösung durch, so sind die Polymerisationsprodukte nur dann in kaltem Wasser löslich, wenn sie einen sehr niedrigen Polymerisationsgrad besitzen. Sie liefern dann sehr niedr bgviscose Lösungen. Alle höherm.olekularen Polymerisationsprodukte der Säureamidesind, auch wenn man in Gegenwart von Wasser polymerisiert, in kaltem Wasser nur quellbar; .sie fallen beim Abkühlen oder beim Verdünnen der heißen Reaktionsmischungzeit kaltem Wasser gallertartig aus.Process for the preparation of high molecular weight soluble in cold water Polymerization products When unsaturated polymerizable acid amides are heated Their melting point in the presence or absence of catalysts is usually obtained with elimination of ammonia polymers that are insoluble in cold water or are only swellable. If the polymerization is carried out in aqueous solution, so are the polymerization products are only soluble in cold water if they are very have a low degree of polymerization. They then provide solutions with a very low viscosity. All higher molecular weight polymerisation products of the acid amides are, even if one polymerized in the presence of water, only swellable in cold water; .They fall when cooling or when diluting the hot reaction mixture time cold water gelatinous.
Es wurde nun gefunden, daß man in kaltem Wasser gut lösliche Polymerisationsprodukte von hohem Polymerisationsgrad aus ungesättigten Säureamiden herstellen kann, wenn man diese in solchem Maße mit Carboxylgruppen versieht, die in Salzform eine Wasserlöslichkeit herbeiführen, daß sie bis zu 5% Carbonsäuren (berechnet auf mononiere Säuren) enthalten. Dies kann man dadurch bewirken, daß man den Säureamiden vor der Polymerisation polymerisationsfähige, ungesättigte Säuren bzw. deren wasserlösliche Salze zusetzt und die Stoffe gemeinsam polymerisiert. Bei Verwendung der freien Säuren müssen diese zur Überführung in wäßrige Lösung während oder nach der PolymerisatiGn in die entsprechenden Salze unigewandelt werden. Man kann weiterhin auch die wasserunlöslichen Polymerisate der reinen Säureamide teilweise verseifest oder schon während der Polymerisation der reinen Anude eine solche teilweise Verseifung durchführen.It has now been found that polymerization products which are readily soluble in cold water are obtained of a high degree of polymerization from unsaturated acid amides, if these are provided with carboxyl groups to such an extent that they are soluble in water in salt form bring about that they contain up to 5% carboxylic acids (calculated on mononier acids). This can be achieved by adding the acid amides polymerizable, unsaturated acids or their water-soluble salts added and the substances together polymerized. If the free acids are used, they must be converted into aqueous solution during or after the polymerization into the corresponding salts to be unconverted. You can also use the water-insoluble polymers of the pure acid amides partially saponified or already during the polymerization of pure anude carry out such a partial saponification.
Zur Herstellung dieser Produkte geeignete polymerisationsfähige, ungesättigte Säureamide sind z. B. Acrylsäureamid und seine Homologen, wie Methacrylsäureamid.Polymerizable, unsaturated ones suitable for the manufacture of these products Acid amides are z. B. Acrylic acid amide and its homologues, such as methacrylic acid amide.
Als geeignete polymerisationsfähige Carbonsäuren bzw. deren Salze seien genannt: Acrylsäure und ihre Salze sowie ihre Namologen, z. B. Methacrylsäure und deren wasserlösliche Salze., besonders die Alkali- und iNlagnesüumsalze, ferner Dicarbonsäuren, wie Maleinsäure, und deren wasserlösliche Salze. Trotz des geringen Gehaltes an ungesättigten Carbon.säuren bzw. ihren Salzen sind die erhaltenen Produkte in kaltem Wasser gut löslich. Gleichzeitig behalten sie ihren chemischen Charakter als Säureaniide praktisch unverändert bei. Neutralisiert man die zugesetzte ungesättigte Carbonsäurc während der 697 481 Polymerisation oder setzt man von vornherein das entsprechende Salz zu, so erhält man unmittelbar eine klare, hochvisco@se Lbsuiig. Führt man die Polymerisation in Gegenwart der freien ungesättigten Carbonsäuren durch, so fällt das sich bildende polymere Produkt aus; es löst sich durch Neutralisation.Suitable polymerizable carboxylic acids or their salts may be mentioned: acrylic acid and its salts and their namologues, eg. B. methacrylic acid and its water-soluble salts., Especially the alkali and inlagnesium salts, also dicarboxylic acids, such as maleic acid, and their water-soluble salts. Despite the low content of unsaturated carboxylic acids or their salts, the products obtained are readily soluble in cold water. At the same time, they retain their chemical character as acid aniides practically unchanged. If the added unsaturated carboxylic acid is neutralized during the 697,481 polymerization or if the corresponding salt is added from the start, a clear, highly viscous liquid is obtained immediately. If the polymerization is carried out in the presence of the free unsaturated carboxylic acids, the polymeric product formed precipitates; it dissolves through neutralization.
Die Polymerisation der Säureamide wird in bekannter Weise bei erhöhter Temperatur in Gegenwart von Polymerisationsbeschleunigern in wäßriger Lösung ausgeführt. Die Polymerisationstemperatur liegt etwa zwischen 4o bis 9o°, vorzugsweise bei etwa 6o bis 70°. Das Verhältnis von Säureamid zu Wasser bei der Polymexisation kann in weiten Grenzen geändert werden, z. B. von i : i o bis i : i . Im allgemeinen ist der Polymerisationsgrad um so höher, je weniger Wasser verwendet wird. Zweckmäßig polymerisiert man im Verhältnis 1:3 bis 1:5 Amid zu Wasser und setzt unmittelbar nach der Polymerisation noch in der Wärme zur Erzielung von noch fließbaren Lösungen weitere -Mengen Wasser zu.The polymerization of the acid amides is increased in a known manner Temperature carried out in the presence of polymerization accelerators in aqueous solution. The polymerization temperature is between about 4o to 9o °, preferably about 6o to 70 °. The ratio of acid amide to water in the polymexization can be in wide limits are changed, e.g. B. from i: i o to i: i. In general is The less water is used, the higher the degree of polymerization. Appropriate one polymerizes in a ratio of 1: 3 to 1: 5 amide to water and sets immediately after the polymerization still in the heat to achieve still flowable solutions additional amounts of water.
An Stelle von Wasser kann man auch mehrwertige Alkohole, wie Glycerin oder Glykol, oder deren wasserlösliche Derivate oder Mischungen dieser unter sich mit Wasser verwenden.Instead of water you can also use polyhydric alcohols, such as glycerine or glycol, or their water-soluble derivatives or mixtures of these among themselves use with water.
Die Säureamide können unter Beibehaltung der Wasserlöslichkeit auch andere polymerisierbare Stoffe in geringen Wengen, z. B. Acrylsäureester oder Vinylester, enthalten. Die Menge dieser Zusatzstoffe richtet sich nach ihrer Wasserverträglichkeit. So erhält man nach dem vorliegenden Verfahren z. B. beim Zusatz von bis zu 300'o Acrylsäuremethylester bzw. bis zu 2o0!o @crylsäureäthylester noch in Wasser lösliche Säureamidpolymerisate.The acid amides can also be used while maintaining the water solubility other polymerizable substances in small amounts, e.g. B. acrylic acid esters or vinyl esters, contain. The amount of these additives depends on their water tolerance. Thus, according to the present method, for. B. when adding up to 300'o Acrylic acid methyl ester or up to 2o0! O @ acrylic acid ethyl ester are still soluble in water Acid amide polymers.
Die erhaltenen Lösungen sind farblos bis schwach gelblich gefärbt und können fürähnliche Zwecke wie Lösungen von Gumrniarabicum, Britischgummi, Stärke, Dextrin, Polyvinylalkohol und polycarbonsäuren Salzen verwendet werden, z. B. zur Erhöhung der Viscosität von Wasser oder wäßrigen Lösunnen oder Emulsionen, zum Aufrahmen von Latex, zum Schiebefestmachen und Appretieren von Geweben, zum Schlichten von Fäden, als Klebmittel usw. Bei Verwendung der festen Produkte ist es häufig zweckmäßig, weichmachende Alittel, wie Glycerin oder Glykol, zuzusetzen, z. B. zur Herstellung von Ilektographenmassen aus den beschriebenen Produkten.The solutions obtained are colorless to pale yellow in color and can be used for similar purposes such as solutions of gum arabic, British gum, starch, Dextrin, polyvinyl alcohol and polycarboxylic salts can be used, e.g. B. to Increasing the viscosity of water or aqueous solutions or emulsions, for creaming of latex, for securing and finishing fabrics, for sizing Threads, as an adhesive, etc. When using solid products, it is often useful to softening agents, such as glycerine or glycol, to be added, e.g. B. for production of ilectograph masses from the products described.
Es ist bereits bekannt, tlaß man Mischpolymerisate aus Acrylsäure oder ihren Homologen und Acrylsiittreamid oder dessen homologen herstellen kann. Auch «wird bekanntlich durch Einführen von liydropliilcn Gruppen die Wasserlöslichkeit organischer Verbindungen erhöht. Man hat auch schon vorgeschlagen, die Stabilität von wäßrigen Dispersionen wasserunlöslicher Polym-erisationsprodukte dadurch zu erhöhen, daß man diese mit hydrophilen Gruppen versieht. Es ist aber überraschend, daß schon ein so geringer Gehalt an Carbonsäuregruppen wie nach der vorliegenden Erfindung die Wasserlöslichkeit von an sich wasserunlöslichen hochpolymeren Carbonsäureamiden bewirkt. Dabei bleibt der Carbonsäureamidcharakter im wesentlichen erhalten; bei der Herstellung von Mischpoly-' merisaten ist es ungewöhnlich, die eine zu polymerisierende Verbindung in so geringen Mengen wie nach der vorliegenden Erfindung anzuwenden. iblischpolymerisate aus polymerisierbaren Carbonsäureamiden und Carbonsäuren mit höherem Gehalt an Carbonsäuren besitzen aber schon in starkem Maße die chemischen Eigenschaften einer Säure, während gleichzeitig der Amidcharakter zurückgedrängt ist. Beispiel i i oo Teile acrylsäure;amid werden in .loo Teilen Wasser gelöst, mit 5 Teilen Acrylsäure und o,5 Teilen Kaliumpersulfat versetzt und mit Natronlauge bis zum pH von 6 bis 7 neutralisiert. Man erwärmt dann die Mischung auf 6o° und hält sie unter Rühren bei dieser Temperatur etwa i Stunde lang. Man erhält so eine klare, hochviscose Lösung. Beispiel 2 ioo Teile Methacrylsäureamid werden mit o,8 Teilen Methacrylsäure und o,25 Teilen Kaliumpersulfat 'in Zoo Teilen Wasser gelöst und bei 6o° polymerisiert. Nach 2 Stunden wird die Lösung so hochviscos, daß sie sich kaum mehr rühren läßt. Man fügt noch zoo Teile heißes Wasser und die zur Neutralisation erforderliche Menge Natronlauge unter Rühren hinzu und erhält so eine 2o@Ioi11;e hochviscose Lösung, die leicht auch in der Kälte mit Wasser weiter zu verdünnen ist. Beispiel 3 4o Teile unlösliches Polymerisat aus A'Iethacrylsiiurcamid «-erden mit i 6o Tcileii Wasser und 4. Teilen io%iger Natronlauge versetzt. Man läßt zuerst bei 3o° 2 Stunden lang quellen und erwärmt dann 3 Stunden lang auf 6o°. mach dieser Zeit ist das Polymerisat völlig @elOSC.It is already known that copolymers of acrylic acid are allowed or their homologues and acrylicsite dreamid or its homologues. It is also known that the introduction of hydrochloric groups increases the solubility in water organic compounds increased. It has also been suggested that stability of aqueous dispersions of water-insoluble polymerization products as a result increase that they are provided with hydrophilic groups. But it is surprising that even such a low content of carboxylic acid groups as according to the present one Invention the water solubility of water-insoluble high-polymer carboxamides causes. The carboxamide character is essentially retained; at in the production of copolymers, it is unusual to use the one to be polymerized Compound to be used in such small amounts as in the present invention. iblischpolymerisate from polymerizable carboxamides and carboxylic acids with However, the chemical ones already have a higher content of carboxylic acids to a large extent Properties of an acid, while at the same time suppressing the amide character is. Example 100 parts of acrylic acid; amide are dissolved in 100 parts of water, mixed with 5 parts of acrylic acid and 0.5 parts of potassium persulfate and with sodium hydroxide solution Neutralized to pH 6 to 7. The mixture is then heated to 60 ° and keep it at this temperature for about 1 hour with stirring. You get one like that clear, highly viscous solution. Example 2 100 parts of methacrylic acid amide are mixed with 0.8 Parts of methacrylic acid and 0.25 parts of potassium persulfate dissolved in zoo parts of water and polymerized at 60 °. After 2 hours, the solution is so highly viscous that it can hardly be moved anymore. Add zoo parts of hot water and that for neutralization Add the required amount of sodium hydroxide solution while stirring and thus obtain a 2o @ Ioi11; e highly viscous solution that can be easily diluted with water even in the cold is. EXAMPLE 3 40 parts of insoluble polymer of A'Iethacrylsiiurcamid'-earth mixed with 60 parts of water and 4 parts of 10% sodium hydroxide solution. One lets first Swell at 30 ° for 2 hours and then heat to 60 ° for 3 hours. do this Time the polymer is completely @elOSC.
Beispiel q.Example q.
5o Teile Methacrylsäureamid, i Teil Maleinsiiure und o,5 Teile Kaliumpersulfat werden in Zoo Teilen Wasser gelöst, mit Natronlauge neutralisiert und 2 Stunden lang auf 70° erhitzt. Man erhält so eine hochviscose Losung.50 parts of methacrylic acid amide, 1 part of maleic acid and 0.5 parts of potassium persulfate are dissolved in zoo parts of water, neutralized with sodium hydroxide and 2 hours heated to 70 ° for a long time. A highly viscous solution is obtained in this way.
Claims (3)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1936I0055120 DE697481C (en) | 1936-05-29 | 1936-05-29 | Process for the production of high molecular weight polymerisation products which are soluble in cold water |
| GB16746/36A GB475671A (en) | 1936-05-29 | 1936-06-16 | Improvements in the manufacture and production of polymerisation products |
| BE421689D BE421689A (en) | 1936-05-29 | 1937-05-22 | |
| FR822263D FR822263A (en) | 1936-05-29 | 1937-05-26 | Process for preparing water-soluble polymerization products |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1936I0055120 DE697481C (en) | 1936-05-29 | 1936-05-29 | Process for the production of high molecular weight polymerisation products which are soluble in cold water |
| GB16746/36A GB475671A (en) | 1936-05-29 | 1936-06-16 | Improvements in the manufacture and production of polymerisation products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE697481C true DE697481C (en) | 1940-10-15 |
Family
ID=25981936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1936I0055120 Expired DE697481C (en) | 1936-05-29 | 1936-05-29 | Process for the production of high molecular weight polymerisation products which are soluble in cold water |
Country Status (4)
| Country | Link |
|---|---|
| BE (1) | BE421689A (en) |
| DE (1) | DE697481C (en) |
| FR (1) | FR822263A (en) |
| GB (1) | GB475671A (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1049871B (en) * | 1959-02-05 | Badische Anilin- &. Soda-Fabrik Aktiengesellschaft, Ludwigshafen/Rhein | Dispersant with protective colloid properties | |
| US2732358A (en) * | 1956-01-24 | N-benzylacrylamide | ||
| DE749587C (en) * | 1941-01-11 | 1944-11-28 | Process for the production of polyacrylic acid amide | |
| DE763830C (en) * | 1942-09-02 | 1954-02-15 | Roehm & Haas G M B H | Adhesive |
| BE465267A (en) * | 1944-04-24 | |||
| BE476083A (en) * | 1946-07-22 | |||
| US2486190A (en) * | 1946-07-22 | 1949-10-25 | Eastman Kodak Co | Imidized polyacrylamides |
| US2486192A (en) * | 1947-02-08 | 1949-10-25 | Eastman Kodak Co | Gel-type imidized polyacrylamide |
| US2616818A (en) * | 1948-11-18 | 1952-11-04 | Hercules Powder Co Ltd | Paper coating |
| US2718497A (en) * | 1950-11-03 | 1955-09-20 | Union Oil Co | Drilling muds |
| DE942352C (en) * | 1951-01-23 | 1956-05-17 | Hoechst Ag | Process for the production of copolymers |
| US2764504A (en) * | 1952-08-28 | 1956-09-25 | Du Pont | Coating process and products therefrom |
| US2764503A (en) * | 1952-08-28 | 1956-09-25 | Du Pont | Coating fabrics |
| DE1037128B (en) * | 1956-03-17 | 1958-08-21 | Basf Ag | Process for the preparation of copolymers containing amide and ester groups which are soluble in water |
| DE1265116B (en) * | 1957-12-03 | 1968-04-04 | Basf Ag | Process for the production of stable, aqueous dispersions containing water repellants |
| DE1214880B (en) * | 1958-07-21 | 1966-04-21 | Goodrich Co B F | Process for the production of aqueous solutions of copolymers |
| DE1068013B (en) * | 1958-08-22 | 1959-10-29 | Henkel 6. Cie. G.m.b.H., Düsseldorf -Holthausen | Process for the preparation of concentrated aqueous polyacrylamide solutions |
| US3085853A (en) * | 1958-12-23 | 1963-04-16 | Dow Chemical Co | Method of employing dextrans |
| DE1204411B (en) * | 1959-04-07 | 1965-11-04 | Hercules Powder Co Ltd | Process for the production of water-soluble polymers |
| US2992943A (en) * | 1959-06-19 | 1961-07-18 | Eastman Kodak Co | Sizing compositions for textile yarns |
| DE1124244B (en) * | 1959-09-08 | 1962-02-22 | Bayer Ag | Process for the production of solid, water-soluble polyacrylamides with high molecular weights by precipitation polymerization |
| DE1220610B (en) * | 1961-03-04 | 1966-07-07 | Hoechst Ag | Process for carrying out reactions on water-soluble polymers and copolymers of acrylic acid amide |
| US3087890A (en) * | 1961-03-07 | 1963-04-30 | Dow Chemical Co | Method of applying acrylamide polymer flocculants |
| US3516932A (en) * | 1962-06-04 | 1970-06-23 | Monsanto Co | Clarification of water |
| US3418237A (en) * | 1963-12-22 | 1968-12-24 | American Cyanamid Co | Settling of non-argillaceous ore pulps and mineral suspensions by use of water-soluble acrylic polymers |
| US3637491A (en) * | 1969-11-03 | 1972-01-25 | Monsanto Co | Clarification of water |
-
1936
- 1936-05-29 DE DE1936I0055120 patent/DE697481C/en not_active Expired
- 1936-06-16 GB GB16746/36A patent/GB475671A/en not_active Expired
-
1937
- 1937-05-22 BE BE421689D patent/BE421689A/xx unknown
- 1937-05-26 FR FR822263D patent/FR822263A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB475671A (en) | 1937-11-24 |
| FR822263A (en) | 1937-12-24 |
| BE421689A (en) | 1937-06-30 |
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