DE3005889A1 - Emulsion polymerisation with prepolymer contg. azo gps. - as catalyst and emulsifier, giving stable emulsion in water or organic solvent - Google Patents
Emulsion polymerisation with prepolymer contg. azo gps. - as catalyst and emulsifier, giving stable emulsion in water or organic solventInfo
- Publication number
- DE3005889A1 DE3005889A1 DE19803005889 DE3005889A DE3005889A1 DE 3005889 A1 DE3005889 A1 DE 3005889A1 DE 19803005889 DE19803005889 DE 19803005889 DE 3005889 A DE3005889 A DE 3005889A DE 3005889 A1 DE3005889 A1 DE 3005889A1
- Authority
- DE
- Germany
- Prior art keywords
- emulsion
- water
- emulsifier
- catalyst
- polymerisation
- 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.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title claims abstract description 9
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 9
- 239000003960 organic solvent Substances 0.000 title claims description 3
- 239000000839 emulsion Substances 0.000 title abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 3
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 229920000570 polyether Polymers 0.000 claims abstract description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 abstract description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 abstract description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001804 emulsifying effect Effects 0.000 abstract description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 abstract 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 10
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 238000013459 approach Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000205 poly(isobutyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- -1 polyazo Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
- C08F2/08—Organic solvent with the aid of dispersing agents for the polymer
-
- 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
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
Azogruppen enthaltende Polymere alsPolymers containing azo groups as
Polymerisationsinitiatoren und Emulgatoren Polymerisate ethylenisch ungesättigter Monomerer kann man herstellen, indem man das Monomer oder die Monomeren in Anwesenheit eines oder mehrerer Emulgatoren in Wasser emulgiert unddlann mit Hilfe Radikale bildender Katalysatoren polymerisiert. Im allgemeinen sind diese Katalysatoren wasserlöslich. Üblich sind Peroxide oder sogenannte Redoxkatälysat oren.Polymerization initiators and emulsifiers Ethylenic polymers Unsaturated monomers can be prepared by adding the monomer or monomers emulsified in the presence of one or more emulsifiers in water and then with Polymerizes with the help of catalysts which form free radicals. In general these are Catalysts soluble in water. Peroxides or so-called redox catalysis are common oren.
Der Erfindung liegt die Erkenntnis zugrunde, daß Azogruppen -enthaltende Polymere (azogruppenhaltige Prepolymere) der Formel I in der P1 einen Polymerblock, der aus einem ethylenisch ungesättigten Monomeren gebildet wurde, R einen aliphatischen, cycloaliphatischen oder aromatischen Rest mit bis zu 36 C-Atomen, der gegebenenfalls Heteroatome wie 0 enthält oder aber ein Polyether ist, n eine Zahl von 1 bis 104, m eine Zahl von 1 bis 100 bedeuten, sowohl die Funktion des Emulgators wie des Katalysators in einer Emulsionspolymerisation ethylenisch ungesättigter Monomerer übernehmen können. Die Azogruppen enthaltenden Polymeren werden dabei zersetzt.The invention is based on the finding that polymers containing azo groups (prepolymers containing azo groups) of the formula I in P1 a polymer block that was formed from an ethylenically unsaturated monomer, R an aliphatic, cycloaliphatic or aromatic radical with up to 36 carbon atoms, which optionally contains heteroatoms such as 0 or is a polyether, n is a number from 1 to 104 , m is a number from 1 to 100, can take over both the function of the emulsifier and the catalyst in an emulsion polymerization of ethylenically unsaturated monomers. The polymers containing azo groups are decomposed in the process.
Monomere M1, die zur Bildung von P1 eingesetzt werden können, sind beispielsweise Acrylamid, N-Vinylpyrrolidon, Acrylsäure, Methacrylsäure, Ester der Acryl- und Methacrylsäure, Vinylester, Styrol und Styrolderivat.Monomers M1 that can be used to form P1 are for example acrylamide, N-vinylpyrrolidone, acrylic acid, methacrylic acid, esters of Acrylic and methacrylic acid, vinyl ester, styrene and styrene derivative.
Die azogruppenhaltigen Prepolymeren I werden hergestellt, indem ein Polyazoinitiator der Formel II in der R die oben genannte Bedeutung besitzt, n eine Zahl von 1 bis 104 bedeuten, in Gegenwart von ethylenisch ungesättigten Monomeren partiell zersetzt wird. Dabei werden 5 bis 90 96, vorzugsweise 30 - 70 46, der Azogruppen zersetzt. Der Zerfall der Azogruppen wird durch die Wahl von Temperatur und Zeit gesteuert. Die Zeit wird dabei zwischen 10 sec. und 8 Tagen, vorzugsweise 1 Minute und 3 Tagen, und die Temperatur zwischen 30 und 1100C, vorzugsweise 40 und 800C, variiert.The prepolymers I containing azo groups are prepared by adding a polyazo initiator of the formula II in which R has the meaning given above, n is a number from 1 to 104, is partially decomposed in the presence of ethylenically unsaturated monomers. 5 to 90 96, preferably 30-70 46, of the azo groups are decomposed. The decomposition of the azo groups is controlled by the choice of temperature and time. The time is varied between 10 seconds and 8 days, preferably 1 minute and 3 days, and the temperature between 30 and 110 ° C., preferably 40 and 80 ° C.
Die Polyazoinitiatoren II können durch Umsetzung von Azobisisobutyronitril mit Diolen hergestellt werden. Die Diole haben die Formel III H O - R - O H (iii) worin R die oben genannte Bedeutung besitzt.The polyazoinitiators II can be obtained by reacting azobisisobutyronitrile be made with diols. the Diols have the formula III H O - R - O H (iii) in which R has the meaning given above.
Geeignete Diole sind insbesondere: 1.3-Propandiol, 1. 4-Butandiol, 1.6-Hexandiol, Di-, Tri-, Tetraethylenglykol, Polyethylenglykol mit mittleren Molekulargewichten von 200 bis 2000 und Polytetrahydrofurane mit mittleren Molekulargewichten von 200 bis 2000.Suitable diols are in particular: 1,3-propanediol, 1,4-butanediol, 1.6-hexanediol, di-, tri-, tetraethylene glycol, polyethylene glycol with medium molecular weights from 200 to 2000 and polytetrahydrofurans with average molecular weights of 200 until 2000.
Gegenstand der Erfindung ist ein Verfahren zur Emulsionspolymerisation ethylenisch ungesättigter Monomerer an Radikale bildenden Katalysatoren und in Gegenwart von Emulgatoren, das d a d u r c h g e k e n n z e i c h -n e t ist, daß man als Katalysator und Emulgator 0,1 bis 50 Gew.-Teile pro 100 Gew.-Teile Monomer eines Polymerisats der Formel I verwendet. Dieses Verfahren ist verwendbar zur Polymerisation ethylenisch ungesättigter Monomerer wie Vinylacetat, Acrylnitril, Styrol, Methylmethacrylat, Ethylacrylat, Acrylamid, N-Vinylpyrrolidon, Butadien.The invention relates to a process for emulsion polymerization ethylenically unsaturated monomers on catalysts which form free radicals and in the presence of emulsifiers, which is d u r c h g e n n n z e i c h -n e t that one as Catalyst and emulsifier 0.1 to 50 parts by weight per 100 parts by weight of one monomer Polymer of the formula I used. This method is useful for polymerization ethylenically unsaturated monomers such as vinyl acetate, acrylonitrile, styrene, methyl methacrylate, Ethyl acrylate, acrylamide, N-vinylpyrrolidone, butadiene.
Es können Homopolymerisate oder auch Copolymerisate mehrerer Monomerer hergestellt werden.It can be homopolymers or copolymers of several monomers getting produced.
Bei Emulsionspolymerisationen werden üblicherweise ionische Tenside eingesetzt. Die Stabilisierung der emulgierten Teilchen erfolgt dabei durch die Anhäufung von Ladung an der Oberfläche dieser Teilchen. Bei dem hier beschriebenen Verfahren werden Polymerblöcke P1 des Prepolymeren I an der Oberfläche der emulgierten Teilchen angereichert.Ionic surfactants are usually used in emulsion polymerizations used. The emulsified particles are stabilized by the Accumulation of charge on the surface of these particles. With the one described here Process are polymer blocks P1 of the prepolymer I. on the surface enriched in the emulsified particles.
Die Stabilisierung der emulgierten Teilchen erfolgt durch Solvatisierung der Polymerblöcke P1 durch das umgebende Lösungsmittel. Deshalb können nach dem hier beschriebenen Verfahren Emulsionen sowohl in Wasser als auch in organischen Lösungsmitteln hergestellt werden. Das Prepolymere I rmzß dabei so gewählt werden, daß P1 in der emulgierenden Flüssigkeit löslich ist. Zur Emulsionspolymerisation in Wasser ist P1 beispielsweise Polyacrylamid, in Alkoholen ist P1 beispielsweise Poly-N-vinylpyrrolidon, in Petrolether (Kohlenwasserstoffen) ist P1 beispielsweise Poly-i-octylmethacrylat.The emulsified particles are stabilized by solvation the polymer blocks P1 by the surrounding solvent. Therefore, after the Process described here emulsions both in water and in organic Solvents are produced. The prepolymer I must be chosen so that that P1 is soluble in the emulsifying liquid. For emulsion polymerization in water, for example, P1 is polyacrylamide; in alcohols, for example, P1 is For example, poly-N-vinylpyrrolidone in petroleum ether (hydrocarbons) is P1 Poly-i-octyl methacrylate.
Zur Durchführung der Emulsionspolymerisation in Wasser kann man ein Azogruppen enthaltendes Polymerisat der Formel I mit P1 = Polyacrylamid in Wasser zu einer 0,1 bis 20%gen Lösung auflösen. In dieser Lösung emulgiert man dann das oder die Monomeren in einer solchen Menge, daß die Emulsion 5 bis 50 Gew.-% Monomer enthält. Die Polymerisation wird gestartet durch Erwärmen des Polymerisationsansatzes. Die Polymerisationsdauer und -temperatur werden so gewählt, daß sie mindestens einer Halbwertszeit des Initiatorzerfalls entsprechen.To carry out the emulsion polymerization in water, one can use a Azo group-containing polymer of the formula I with P1 = polyacrylamide in water dissolve to a 0.1 to 20% solution. This is then emulsified in this solution or the monomers in an amount such that the emulsion contains 5 to 50% by weight of monomer contains. The polymerization is started by heating the polymerization batch. The polymerization time and temperature are chosen so that they are at least one Correspond to the half-life of the initiator decay.
Ausführungsbeispiele Herstellung der Azogruppen enthaltenden Polymeren 1. Initiator/Monomer-Verhältnis 1:6 Die Reaktionsapparatur, bestehend aus 500 ml Dreihalskolben mit Teflon-Flügelrührer, Innenthermometer, Rückflußkühler mit Blasenzähler und Stickstoffeinleitung, wurde vor Reaktionsbeginn 1 Stunde bei 780C mit Stickstoff gespült. Anschließend wurde eine Lösung von 5 g Polyinitiator in 90 ml t-Butanol im Stickstoffgegenstrom zugegeben. Eine Lösung von 30 g Acrylamid in 250 ml t-Butanol wurde mit einer Kolbenpumpe im Verlauf von einer Stunde zugepumpt. Die Reaktionstemperatur wurde noch weitere 15 Minuten auf 78"C gehalten, dann wurde die Reaktion durch Kühlen mit Eis abgebrochen, das während der Reaktion ausgefallene Polymere abgesaugt und bei Zimmertemperatur im blpumpenvakuum getrocknet. Die Rührgeschwindigkeit betrug 600 U/min; die 75-minütige Reaktionszeit entspricht 37 %igem Initiatorzerfall. Viskosimetrische Molekulargewichtsbestimmung ergab Werte zwischen 60 000 und 70 000 g/mol bei verschiedenen Ansätzen.EXEMPLARY EMBODIMENTS Production of the polymers containing azo groups 1. Initiator / monomer ratio 1: 6 The reaction apparatus, consisting of 500 ml Three-necked flask with Teflon paddle stirrer, internal thermometer, reflux condenser with bubble counter and nitrogen introduction, before the start of the reaction was 1 hour at 780C with nitrogen flushed. A solution of 5 g of polyinitiator in 90 ml of t-butanol was then added added in a countercurrent of nitrogen. A solution of 30 g of acrylamide in 250 ml of t-butanol was pumped in with a piston pump over the course of one hour. The reaction temperature was held at 78 "C for an additional 15 minutes, then the reaction was stopped by cooling broken off with ice, sucked off the precipitated polymer during the reaction and dried at room temperature in a pump vacuum. The stirring speed was 600 rpm; the 75-minute reaction time corresponds to 37% initiator decomposition. Viscometric Molecular weight determination gave values between 60,000 and 70,000 g / mol for various Approaches.
2. Initiator/Monomer-Verhältnis 1:50 Reaktionsapparatur, -zeit und -temperatur wie oben beschrieben. Initiator- und Monomerlösung in t-Butanol wurden direkt zu Beginn der Reaktion in die Apparatur gefrlt. Die Lösung war 10 %ig an Acrylamid. Die viskosimetrisch bestimmten mittleren Molekulargewichte verschiedener Ansätze lagen bei ca. 180 000 g/mol.2. Initiator / monomer ratio 1:50, reaction apparatus, time and temperature as described above. Initiator and monomer solution in t-butanol were poured into the apparatus directly at the beginning of the reaction. The solution was 10% Acrylamide. The viscometrically determined average molecular weights of various approaches were around 180,000 g / mol.
Beispiel 1 2 g prepolymeres Acrylamid werden mit 10 g Vinylacetat und 100 ml Wasser gemischt und unter Rühren zunächst 4 Stunden bei 700C, dann 1 Stunde bei 900C polymerisiert. Es entsteht eine dünnflüssige Emulsion, die auch nach mehreren Gefrier-Auftaucyclen keinen Bodenkörper zeigt.Example 1 2 g of prepolymer acrylamide are mixed with 10 g of vinyl acetate and 100 ml of water and mixed with stirring for 4 hours at 70 ° C, then 1 Polymerized at 900C for an hour. The result is a thin emulsion, which also shows no sediment after several freeze-thaw cycles.
Beispiel 2 5 g prepolymeres Acrylamid werden in 100 ml Wasser gelöst und 50 g Vinylacetat in die gerührte, auf 700C erwärmte Mischung im Verlauf von 3 Stunden eingetropft.Example 2 5 g of prepolymer acrylamide are dissolved in 100 ml of water and 50 g of vinyl acetate in the stirred, heated to 700C mixture over the course of Dripped in for 3 hours.
Man erhitzt insgesamt 4 Stunden auf 70"C und 1 Stunde auf 900C und erhält eine Emulsion mit pastenförmiger Konsistenz.The mixture is heated to 70 ° C. for a total of 4 hours and to 90 ° C. for 1 hour receives an emulsion with a paste-like consistency.
Beispiel 3 5 g prepolymeres Acrylamid werden in 100 ml Wasser gelöst, mit 30 g i-Butylmethacrylat gemischt und 4 Std. bei 70 0C polymerisiert. Zur Vervollständigung der Polymerisation wird die Reaktionsmischung 1 Std. bei 90 0C geruhrt. Man erhält eine stabile Emulsion von Polyisobutylmethacrylat in Wasser.Example 3 5 g of prepolymer acrylamide are dissolved in 100 ml of water, mixed with 30 g of i-butyl methacrylate and polymerized at 70 ° C. for 4 hours. To complete After the polymerization, the reaction mixture is stirred at 90 ° C. for 1 hour. You get a stable emulsion of polyisobutyl methacrylate in water.
Beispiel 4 1 gprepolymeres Vinylpyrrolidon wird in 49 g tert.-Butanol gelöst und unter Rühren bei 600C im Verlauf von 76 Stunden 25 g Acrylnitril zugepumpt. Nach 96 Stunden wird die Polymerisation abgebrochen. Man erhält eine Polyacrylnitrilemulsion in tert.-Butanol.Example 4 1 g of prepolymer vinylpyrrolidone is dissolved in 49 g of tert-butanol dissolved and 25 g of acrylonitrile are pumped in with stirring at 60.degree. C. in the course of 76 hours. The polymerization is terminated after 96 hours. A polyacrylonitrile emulsion is obtained in tert-butanol.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803005889 DE3005889A1 (en) | 1980-02-16 | 1980-02-16 | Emulsion polymerisation with prepolymer contg. azo gps. - as catalyst and emulsifier, giving stable emulsion in water or organic solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803005889 DE3005889A1 (en) | 1980-02-16 | 1980-02-16 | Emulsion polymerisation with prepolymer contg. azo gps. - as catalyst and emulsifier, giving stable emulsion in water or organic solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE3005889A1 true DE3005889A1 (en) | 1981-09-03 |
| DE3005889C2 DE3005889C2 (en) | 1988-08-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19803005889 Granted DE3005889A1 (en) | 1980-02-16 | 1980-02-16 | Emulsion polymerisation with prepolymer contg. azo gps. - as catalyst and emulsifier, giving stable emulsion in water or organic solvent |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3005889A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4123223A1 (en) * | 1991-07-11 | 1993-01-21 | Dainippon Ink & Chemicals | METHOD FOR PRODUCING AZO MACRO INITIATORS FOR SYNTHESISING BLOCK COPOLYMERS AND AQUEOUS BLOCK COPOLYMER DISPERSIONS AND EMULSIONS AND THE USE THEREOF |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2841033A1 (en) * | 1978-09-21 | 1980-04-03 | Bayer Ag | METHOD FOR PRODUCING AQUEOUS POLYMER DISPERSIONS |
-
1980
- 1980-02-16 DE DE19803005889 patent/DE3005889A1/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2841033A1 (en) * | 1978-09-21 | 1980-04-03 | Bayer Ag | METHOD FOR PRODUCING AQUEOUS POLYMER DISPERSIONS |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4123223A1 (en) * | 1991-07-11 | 1993-01-21 | Dainippon Ink & Chemicals | METHOD FOR PRODUCING AZO MACRO INITIATORS FOR SYNTHESISING BLOCK COPOLYMERS AND AQUEOUS BLOCK COPOLYMER DISPERSIONS AND EMULSIONS AND THE USE THEREOF |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3005889C2 (en) | 1988-08-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8110 | Request for examination paragraph 44 | ||
| 8125 | Change of the main classification |
Ipc: C08F 2/22 |
|
| D2 | Grant after examination | ||
| 8364 | No opposition during term of opposition | ||
| 8339 | Ceased/non-payment of the annual fee |