DE1151661B - Process for the production of frost- and electrolyte-resistant polymer dispersions - Google Patents
Process for the production of frost- and electrolyte-resistant polymer dispersionsInfo
- Publication number
- DE1151661B DE1151661B DEB63834A DEB0063834A DE1151661B DE 1151661 B DE1151661 B DE 1151661B DE B63834 A DEB63834 A DE B63834A DE B0063834 A DEB0063834 A DE B0063834A DE 1151661 B DE1151661 B DE 1151661B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- weight
- frost
- electrolyte
- polymer dispersions
- 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.)
- Pending
Links
- 239000006185 dispersion Substances 0.000 title claims description 23
- 229920000642 polymer Polymers 0.000 title claims description 9
- 239000003792 electrolyte Substances 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 3
- 229920001567 vinyl ester resin Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 5
- -1 Vinyloctanoic acid ester Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical class CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- ZMSQRSUTMFYPLQ-UHFFFAOYSA-N 2-(8-methylnonyl)phenol Chemical class CC(C)CCCCCCCC1=CC=CC=C1O ZMSQRSUTMFYPLQ-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 1
- DLAXSFQUZITJGP-UHFFFAOYSA-N 2-methylbutan-2-yl 2-methylprop-2-enoate Chemical compound CCC(C)(C)OC(=O)C(C)=C DLAXSFQUZITJGP-UHFFFAOYSA-N 0.000 description 1
- FSVQAZDYQRQQKH-UHFFFAOYSA-N 2-methylbutan-2-yl prop-2-enoate Chemical compound CCC(C)(C)OC(=O)C=C FSVQAZDYQRQQKH-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- HPHRYEFAPDIEIZ-UHFFFAOYSA-N ethenyl 4-methylbenzoate Chemical compound CC1=CC=C(C(=O)OC=C)C=C1 HPHRYEFAPDIEIZ-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
- C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
Gegenstand des Patents 1055 239 ist ein Verfahren zur Herstellung von frost- und elektrolytbeständigen Polymerisatdispersionen aus monomeren, polymerisierbaren, ungesättigten Verbindungen in wäßrigem Medium unter Zusatz von wasserlöslichen Katalysatoren und von aus alkylierten aromatischen Oxyverbindungen mit verzweigten oder unverzweigten Kohlenstoffketten aus 6 bis 20 Kohlenstoffatomen, die pro Mol mit wenigstens 9 Mol Äthylenoxyd oder Propylenoxyd umgesetzt und anschließend sulfiert worden sind, bestehenden Emulgatoren.The subject of patent 1055 239 is a method for the production of frost- and electrolyte-resistant polymer dispersions from monomeric, polymerizable, unsaturated compounds in an aqueous medium with the addition of water-soluble catalysts and of alkylated aromatic compounds Oxy compounds with branched or unbranched carbon chains of 6 to 20 carbon atoms, which reacted per mole with at least 9 moles of ethylene oxide or propylene oxide and then sulfated have been existing emulsifiers.
Es wurde nun gefunden, daß man bei der Verwendung der vorstehend genannten Emulgatoren frost- und elektrolytbeständige Polymerisatdispersionen erhält, die besonders verseifungsfeste und wetterfeste Filme ergeben, wenn man als monomere Verbindungen Gemische ausIt has now been found that when using the abovementioned emulsifiers, frost-free and electrolyte-resistant polymer dispersions that are particularly saponification-resistant and weather-resistant Films result if mixtures of monomeric compounds are used
A. 29,5 bis 95 Gewichtsteilen eines aliphatischen oder aromatischen Vinylesters,A. 29.5 to 95 parts by weight of an aliphatic or aromatic vinyl ester,
B. 4,5 bis 70 Gewichtsteilen eines Acryl- oder Methacrylsäureesters von einem in a- oder /J-Stellung verzweigten Alkohol, der mindestens 4 Kohlenstoffatome hat, undB. 4.5 to 70 parts by weight of an acrylic or methacrylic acid ester of an alcohol which is branched in the a- or / J-position and has at least 4 carbon atoms, and
C. 0,5 bis 8 Gewichtsteilen einer α, ^-ungesättigten polymerisierbaren CarbonsäureC. 0.5 to 8 parts by weight of an α, ^ -unsaturated polymerizable carboxylic acid
verwendet, wobei A, B und C zusammen 100 Gewichtsteile ausmachen.used, where A, B and C together 100 parts by weight turn off.
Die aus den drei verschiedenartigen Comonomeren hergestellten Polymerisatdispersionen sind außerordentlich frost- und elektrolytbeständig und lassen sich darum mit wäßrigen Salzlösungen, insbesondere mit Salzlösungen von mehrwertigen Metallen, in jedem Verhältnis mischen, ohne daß die Dispersion zerstört wird. Ebenso können die Polymerisatdispersionen mehrmals schnell oder langsam auf tiefe Temperaturen, z. B. auf — 20° C, abgekühlt werden, ohne zu koagulieren. Ein besonderes Charakteristikum der nach den erfindungsgemäßen Verfahren hergestellten Polymerisatdispersionen ist jedoch, daß die daraus hergestellten Filme sehr verseifungs- und wetterfest sind. Sie sind darum ganz besonders gut für den Oberflächenschutz, z.B. für Anstrichzwecke, geeignet.The polymer dispersions produced from the three different types of comonomers are extraordinary Resistant to frost and electrolytes and can therefore be used with aqueous salt solutions, especially with Mix salt solutions of polyvalent metals in any ratio without destroying the dispersion will. Likewise, the polymer dispersions can quickly or slowly to low temperatures several times, z. B. to - 20 ° C, can be cooled without coagulating. A special characteristic of the polymer dispersions prepared by the process according to the invention, however, is that the therefrom The films produced are very resistant to saponification and weathering. They are therefore especially good for him Surface protection, e.g. suitable for painting purposes.
Als Vinylester, die am Aufbau des Mischpolymerisats mit 29,5 bis 95 Gewichtsteilen beteiligt sein sollen, kommen beispielsweise Vinylformiat, Vinylacetat, Vinylpropionat, Vinyl-n-butyrat, Vinylisobutyrat, Vinylhexoat, Vinyl-2-äthyl-n-hexoat, Vinylcyclohexoat, Vinyloctansäureester, Vinyllaurat, Vinylstearat, Vinylbenzoat oder Vinyl-p-methylbenzoat in Frage.As vinyl esters, which are involved in the structure of the copolymer with 29.5 to 95 parts by weight are, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, Vinyl hexoate, vinyl 2-ethyl-n-hexoate, vinyl cyclohexoate, Vinyloctanoic acid ester, vinyl laurate, vinyl stearate, vinyl benzoate or vinyl p-methylbenzoate in Question.
Als Acryl- oder Methacrylsäureester von Alkoholen mit mindestens 4 Kohlenstoffatomen, die in α- oder Verfahren zur HerstellungAs acrylic or methacrylic acid esters of alcohols with at least 4 carbon atoms in α- or Method of manufacture
von frost- und elektrolytbeständigenof frost and electrolyte resistant
PolymerisatdispersionenPolymer dispersions
Zusatz zum Patent 1 055 239Addendum to patent 1,055,239
Anmelder:Applicant:
Badische Anilin- & Soda-Fabrik
Aktiengesellschaft, Ludwigshafen/RheinAniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhein
Dr. Heinz Pohlemann, Limburgerhof (Pfalz),Dr. Heinz Pohlemann, Limburgerhof (Palatinate),
und Dr. Gerhard Floras, Ludwigshafen/Rhein,and Dr. Gerhard Floras, Ludwigshafen / Rhine,
sind als Erfinder genannt wordenhave been named as inventors
/i-Stellung des Alkoholrestes verzweigt sind, sind beispielsweise tert.-Butylacrylat, tert.-Butylmethacrylat, tert.-Amylacrylat, tert-Amylmethacrylat oder auch Acrylate oder Methacrylate von cyclischen Alkoholen, beispielsweise von Cyclohexylalkohol, 2-Äthylhexylalkohol, 2-Methylpentylalkohol oder Tridecylalkohol, geeignet./ i-position of the alcohol radical are, for example, tert-butyl acrylate, tert-butyl methacrylate, tert-amyl acrylate, tert-amyl methacrylate or acrylates or methacrylates of cyclic alcohols, for example of cyclohexyl alcohol, 2-ethylhexyl alcohol, 2-methylpentyl alcohol or Tridecyl alcohol, are suitable.
Als a, /S-ungesättigte polymerisierbare Carbonsäuren, die in Mengen von 0,5 bis 8 Gewichtsteilen als Comonomere am Aufbau des Mischpolymerisats beteiligt sind, kommen beispielsweise Acrylsäure, Methacrylsäure, Crotonsäure, Itaconsäure in Frage. Acrylic acid, methacrylic acid, crotonic acid, itaconic acid, for example, are suitable as α, / S-unsaturated polymerizable carboxylic acids which, in amounts of 0.5 to 8 parts by weight, are involved as comonomers in the structure of the copolymer.
Die übrigen Polymerisationsbedingungen sind die gleichen wie im Hauptpatent.The other polymerization conditions are the same as in the main patent.
Die in den Beispielen genannten Teile sind Gewichtsteile. The parts mentioned in the examples are parts by weight.
970 Teile Wasser werden unter Rühren mit 40 Teilen eines mit 25 Mol Äthylenoxyd umgesetzten und anschließend mit Schwefelsäure sulfierten Isooctylphenols versetzt. Das Gemisch wird auf etwa 80° C erhitzt, und unter gutem Rühren und Rückflußkühlung werden gleichzeitig aus zwei getrennten Gefäßen eine Mischung von 700 Teilen Vinylpropionat, 300 Teilen Acrylsäure-tert.-butylester und 15 Teilen Acrylsäure sowie eine Lösung von 3 Teilen Kaliumpersulfat in 60 Teilen Wasser zugegeben.970 parts of water are reacted with 40 parts of a 25 mol of ethylene oxide and stirred then treated with sulfuric acid sulfated isooctylphenol. The mixture is brought to about 80 ° C heated, and with good stirring and reflux cooling are simultaneously from two separate vessels a mixture of 700 parts of vinyl propionate, 300 parts of tert-butyl acrylic ester and 15 parts Acrylic acid and a solution of 3 parts of potassium persulfate in 60 parts of water were added.
Nach beendetem Zulauf hält man das Polymerisationsgemisch noch 1 Stunde auf 80° C, dampft dieWhen the addition is complete, the polymerization mixture is kept at 80 ° C. for a further hour and then evaporated
309 647/296309 647/296
restlichen Monomeren ab, kühlt auf Zimmertemperatur und stellt mit Ammoniak auf einen pH-Wert von 8,0 ein. Man erhält eine etwa 5O°/oige koagulatfreie Dispersion von guter Frost- und Elektrolytbeständigkeit. Die Dispersion liefert einen klaren Film. Sie eignet sich gut für Anstrichzwecke. Zum Vergleich der Alkalifestigkeit des hergestellten Films werden folgende Versuche durchgeführt:residual monomers, cools to room temperature and adjusted with ammonia to a pH value of 8.0. An approximately 50% coagulate-free dispersion of good frost and electrolyte resistance is obtained. The dispersion provides a clear film. It works well for painting purposes. To compare the alkali resistance of the film produced, the following tests are carried out:
Die Filme der vorstehend beschriebenen Dispersion werden bei Zimmertemperatur mit 7%iger Natronlauge behandelt. Nach 4 Stunden ist der Film erst teilweise verseift.The films of the dispersion described above are treated with 7% sodium hydroxide solution at room temperature treated. The film is only partially saponified after 4 hours.
Eine unter den gleichen Bedingungen hergestellte Dispersion, die jedoch an Stelle des tert.-Butylesters Acrylsäure-n-butylester einpolymerisiert enthält, ist bereits nach 3 Stunden verseift.A dispersion prepared under the same conditions, but instead of the tert-butyl ester Contains acrylic acid-n-butyl ester in copolymerized form saponified after 3 hours.
900 Teile Wasser, 60 Teile eines mit 25 Mol Äthylenoxyd oxäthylierten und anschließend sulfierten Isooctylphenols, 600 Teile Vinylpropionat, 400 Teile Acrylsäure-tert.-butylester und 20 Teile Acrylsäure werden gut emulgiert und mit verdünntem Ammoniak auf einen pH-Wert von 4,5 gestellt. Von der so erhaltenen Emulsion werden 100 Teile unter Rühren auf 75 bis 80° C erhitzt und mit 10 Teilen einer Lösung von 5 Teilen Kaliumpersulfat in 100 Teilen Wasser versetzt. Sobald die Polymerisation begonnen hat, läßt man unter weiterem Rühren bei 80° C den Rest der Monomerenemulsion und der Kaliumpersulfatlösung zulaufen. Man erhält eine etwa 5O°/oige Dispersion, die mit verdünnter Natronlauge auf einen pH-Wert von 8 bis 9 eingestellt wird. Ein aus dieser Dispersion bei 35° C hergestellter Film ist wesentlich verseifungsfester als ein Film, der aus einer Dispersion, die Acrylsäure-n-butylester an Stelle des Acrylsäure-tert-butylesters einpolymerisiert enthält, hergestellt wurde.900 parts water, 60 parts of an oxyethylated with 25 moles of ethylene oxide and then sulfated isooctylphenol, 600 parts of vinyl propionate, 400 parts of acrylic acid tert-butyl ester and 20 parts of acrylic acid are well emulsified and diluted with ammonia to a pH value of 4.5 posed. 100 parts of the emulsion thus obtained are heated to 75 ° to 80 ° C. with stirring, and 10 parts of a solution of 5 parts of potassium persulfate in 100 parts of water are added. As soon as the polymerization has begun, the remainder of the monomer emulsion and the potassium persulfate solution are allowed to run in at 80 ° C. with further stirring. An approximately 5O ° / o dispersion is adjusted with dilute sodium hydroxide to a pH value 8 to 9 A film produced from this dispersion at 35 ° C. is significantly more resistant to saponification than a film produced from a dispersion which contains acrylic acid n-butyl ester in polymerized form instead of acrylic acid tert-butyl ester.
In der nach Beispiel 2 angegebenen Weise werden 90 Teile Vinylpropionat, 10 Teile Acrylsäure-tert.-butylester, 1,5 Teile Acrylsäure, 3,5 Teile eines mit 25 Mol Äthylenoxyd oxäthylierten und anschließend sulfierten Isodecylphenols, 0,5 Teile Kaliumpersulfat und 100 Teile Wasser umgesetzt. Man stellt die erhaltene 5O«/oige Dispersion mit konzentriertem Ammoniak auf einen pg-Wert von 7,5 und erhält eine Dispersion, die sich gut für Anstrichzwecke eignet. Die mit dieser Dispersion hergestellten Filme haben einen matten Seidenglanz, eine gute Naßabriebfestigkeit und eine gute Verseifungsfestigkeit.In the manner indicated in Example 2, 90 parts of vinyl propionate, 10 parts of acrylic acid tert-butyl ester, 1.5 parts of acrylic acid, 3.5 parts of an oxyethylated with 25 moles of ethylene oxide and then sulfated isodecylphenol, 0.5 part of potassium persulfate and 100 parts of water. One puts the received 50% dispersion with concentrated ammonia to a pg value of 7.5 and receives a Dispersion that is well suited for painting purposes. The films made with this dispersion have a matt silk gloss, good wet abrasion resistance and good saponification resistance.
50 Teile Wasser, 2,5 Teile eines mit 25 Mol Äthylenoxyd oxäthylierten und anschließend sulfierten Isooctylphenols, 35 Teile Vinyl-2-äthylhexoat, 15 Teile Acrylsäure-tert.-butylester, 0,75 Teile Acrylsäure und 0,5 Teile Kaliumpersulfat werden gut emulgiert. Das Gemisch wird unter gutem Rühren auf 85° C erhitzt und 1 Stunde bei dieser Temperatur gehalten. Die restlichen Monomeren werden dann 15 Minuten abgedampft, und dann wird die Dispersion bei Zimmertemperatur mit Ammoniak auf einen pH-Wert zwischen 8 und 9 eingestellt. Man erhält eine etwa 48°/oige Polymerisatdispersion, die eine gute Verseifungsfestigkeit aufweist und sich zur Herstellung von Oberflächenbeschichtungen eignet. Eine praktisch ίο gleiche Dispersion wird erhalten, wenn man an Stelle von 0,5 Teilen Kaliumpersulfat 0,4 Teile Azo-diisobuttersäureamid verwendet.50 parts of water, 2.5 parts of an isooctylphenol which is oxyethylated with 25 moles of ethylene oxide and then sulfated, 35 parts of vinyl 2-ethylhexoate, 15 parts of tert-butyl acrylate, 0.75 parts of acrylic acid and 0.5 part of potassium persulfate are emulsified well . The mixture is heated to 85 ° C. with thorough stirring and kept at this temperature for 1 hour. The remaining monomers are then evaporated for 15 minutes and then the dispersion is adjusted at room temperature with ammonia to a pH value 8 to 9 An approximately 48% polymer dispersion is obtained which has good saponification resistance and is suitable for producing surface coatings. A practically identical dispersion is obtained if 0.4 part of azo-diisobutyric acid amide is used instead of 0.5 part of potassium persulfate.
1030 Teile Wasser werden unter Rühren mit 40 Teilen eines mit 25 Mol Äthylenoxyd umgesetzten und anschließend mit Schwefelsäure sulfierten Isooctylphenols versetzt. Dazu gibt man unter Rühren und Rückflußkühlung gleichzeitig aus zwei getrennten Gefäßen eine Mischung aus 800 Teilen Vinylpropionat, 200 Teilen Acrylsäurecyclohexylester und 10 Teilen Acrylsäure sowie eine Lösung von 4 Teilen Kaliumpersulfat in 50 Teilen Wasser. Das Gemisch wird bei etwa 80° C polymerisiert. Sobald der Zulauf aus den beiden Gefäßen beendet ist, wird noch etwa 1 Stunde bei 80° C nachgerührt. Die gegebenenfalls noch vorhandenen restlichen Monomeren werden abgedampft und die Polymerisatdispersion bei Zimmertemperatur mit Ammoniak auf einen pH-Wert von 9 eingestellt. Man erhält eine koagulatfreie Dispersion, die hervorragend frost- und elektrolytbeständig ist. Aus der Dispersion hergestellte Filme sind sehr alkalifest. 1030 parts of water are mixed with 40 parts of an isooctylphenol which has reacted with 25 moles of ethylene oxide and then sulfated with sulfuric acid, while stirring. A mixture of 800 parts of vinyl propionate, 200 parts of cyclohexyl acrylate and 10 parts of acrylic acid and a solution of 4 parts of potassium persulfate in 50 parts of water are added simultaneously from two separate vessels with stirring and reflux. The mixture is polymerized at about 80 ° C. As soon as the feed from the two vessels has ended, stirring is continued at 80 ° C. for about 1 hour. The optionally remaining rest of the monomers are evaporated and set the polymer at room temperature with ammonia to a pH value of. 9 A coagulate-free dispersion is obtained which is extremely resistant to frost and electrolytes. Films made from the dispersion are very alkali-resistant.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB63834A DE1151661B (en) | 1961-08-30 | 1961-08-30 | Process for the production of frost- and electrolyte-resistant polymer dispersions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB63834A DE1151661B (en) | 1961-08-30 | 1961-08-30 | Process for the production of frost- and electrolyte-resistant polymer dispersions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1151661B true DE1151661B (en) | 1963-07-18 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB63834A Pending DE1151661B (en) | 1961-08-30 | 1961-08-30 | Process for the production of frost- and electrolyte-resistant polymer dispersions |
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| Country | Link |
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| DE (1) | DE1151661B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1570484A1 (en) * | 1965-01-05 | 1970-04-02 | Dow Chemical Co | Latices and paper coating and coating slips and processes for their production |
| EP0009731A1 (en) * | 1978-10-03 | 1980-04-16 | Bayer Ag | Terpolymers of acrylic esters, vinyl esters and unsaturated nitriles, and their preparation |
| US4278727A (en) * | 1977-10-20 | 1981-07-14 | Wacker-Chemie Gmbh | Alkai-soluble, water-resistant binders for non-woven materials |
| US4898787A (en) * | 1987-07-02 | 1990-02-06 | Mobil Oil Corporation | Emulsion polymerized cohesive polymer latex useful as cold seal coating and improved sealable articles treated with the same |
| US5070164A (en) * | 1987-07-02 | 1991-12-03 | Mobil Oil Corporation | Cold sealable cohesive terpolymers |
-
1961
- 1961-08-30 DE DEB63834A patent/DE1151661B/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1570484A1 (en) * | 1965-01-05 | 1970-04-02 | Dow Chemical Co | Latices and paper coating and coating slips and processes for their production |
| US4278727A (en) * | 1977-10-20 | 1981-07-14 | Wacker-Chemie Gmbh | Alkai-soluble, water-resistant binders for non-woven materials |
| EP0009731A1 (en) * | 1978-10-03 | 1980-04-16 | Bayer Ag | Terpolymers of acrylic esters, vinyl esters and unsaturated nitriles, and their preparation |
| US4898787A (en) * | 1987-07-02 | 1990-02-06 | Mobil Oil Corporation | Emulsion polymerized cohesive polymer latex useful as cold seal coating and improved sealable articles treated with the same |
| US5070164A (en) * | 1987-07-02 | 1991-12-03 | Mobil Oil Corporation | Cold sealable cohesive terpolymers |
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