EP0000161B1 - Process for reducing the amount of residual monomers during the polymerisation of vinyl lactams and vinyl esters - Google Patents
Process for reducing the amount of residual monomers during the polymerisation of vinyl lactams and vinyl esters Download PDFInfo
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- EP0000161B1 EP0000161B1 EP78100179A EP78100179A EP0000161B1 EP 0000161 B1 EP0000161 B1 EP 0000161B1 EP 78100179 A EP78100179 A EP 78100179A EP 78100179 A EP78100179 A EP 78100179A EP 0000161 B1 EP0000161 B1 EP 0000161B1
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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
- C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
- C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
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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
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
Definitions
- the invention relates to a process for reducing the residual monomer contents in the polymerization of vinyl esters and vinyl lactams in a solvent by adding polymerization initiators after the main polymerization and post-polymerization of the reaction mixture.
- powdery polymers which are obtained for example by spray drying the polymer solutions, generally contain only small amounts of residual monomers.
- a powdery polymer can indeed be obtained from the polymer solution by spray drying and then dissolved again in the pure solvent.
- this process is cumbersome and, for example in the case of polyvinyl lactams, does not lead to polymers which have a very low residual monomer content.
- N-vinyl lactams are first polymerized as initiators by known processes with the aid of inorganic or organic peroxides which decompose under the reaction conditions, and the reaction mixture Postpolymerization subjects as soon as the monomer content remains constant.
- the post-polymerization is carried out by adding further peroxide to the reaction mixture and heating it.
- the monomer content after the main polymerization is about 6% and can be reduced to about 0.9% by post-polymerization of the reaction mixture.
- the object of the invention is to provide a process for reducing the residual monomer contents in the polymerization of vinyl esters and vinyl lactams in a solvent by adding polymerization initiators after the main polymerization and post-polymerization of the reaction mixture, in which polymer solutions are obtained which have a very low residual content Have monomers.
- the object is achieved in that the main polymerization is carried out at from 40 to 160 ° C., the reaction mixture after the end of the main polymerization is 0.05 to 0.5% by weight, based on the monomers used, of di-tert-butyl peroxide , Di-tert-amyl peroxide, dicumyl peroxide, 2,5-dimethyi-2,5-bis- (tert-buty!
- the advantage of the process according to the invention is that the desired degree of polymerization and the color of the products are not adversely affected. It is surprising that the choice of dialkyl peroxides and perketals as the polymerization initiator in the post-polymerization gives polymer solutions in which the residual monomer content is 10 to 20 times lower than in polymer solutions which are prepared by known processes.
- N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam are particularly suitable as vinyl lactams.
- the process according to the invention makes it possible to prepare polymer solutions with a low residual monomer content of homo- and copolymers of N-vinyl lactams.
- the process is of particular importance for the production of copolymers of vinyl lactams, in particular of copolymers of N-vinylpyrrolidone.
- Suitable monomers which are copolymerizable with N-vinylpyrrolidone are, for example, vinyl esters saturated fatty acids containing 2 to 20 carbon atoms, e.g.
- Acrylic esters and methacrylic acid esters derived from alcohols having 1 to 12 carbon atoms e.g. Acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid isobutyl ester and 2-ethylhexyl acrylate as well as acrylic ester or methacrylic ester, which are derived from basic monomers, e.g. Derive aminoethanol or aminopropanol and acrylamide as well as N-methylolacrylamide and N-methylolmethacrylamide.
- Copolymers which are of particular technical interest contain 10 to 90% by weight of vinyl lactam and 90 to 10% by weight of a vinyl ester, preferably vinyl acetate or vinyl propionate.
- the vinyl lactams can also be copolymerized with several comonomers, for example with vinyl acetate and vinyl isobutyrate or with vinyl acetate and ethyl acrylate.
- Copolymers of N-vinylpyrrolidone which contain 80 to 20% by weight of vinyl acetate are preferably produced.
- the monomers are polymerized in the known solvents. These are solvents in which the monomers or monomer mixtures are soluble. Suitable solvents are, for example, water, alcohols, hydrocarbons, halogenated hydrocarbons, esters, ketones and ethers.
- Examples of individual representatives from the classes mentioned are, for example, methanol, ethanol, n- and isopropanol, cyclopentanol, cyclohexanol, methylene chloride and 1,1,1-trichlor ethane, 1,1,2-trifluoroethane, 1,1,2-trichloroethane, ethylene glycol, propanediol, butanediol, hexylene glycol, methyl acetate, ethyl acetate, benzyl acetate, acetone, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. It is of course also possible to use mixtures of the solvents mentioned, for example mixtures of water and isopropanol or mixtures of isopropanol and acetone.
- the concentration of the polymer in the solution is generally between 5 and 95%.
- the usual radical polymerization initiators can be used for the main polymerization phase, e.g. Azobisisobutyronitrile, diacyl peroxides such as dibenzoyl peroxide or dilauroyl peroxide, peresters, e.g. tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl peracetate or tert-butyl perbenzoate, hydrogen peroxide and hydroperoxides, e.g. tert-butyl hydroperoxide or cumene hydroperoxide.
- diacyl peroxides such as dibenzoyl peroxide or dilauroyl peroxide
- peresters e.g. tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl peracetate or tert-butyl perbenzoate
- hydrogen peroxide and hydroperoxides e
- the monomers are polymerized in a known manner at temperatures between 40 and 160, preferably 45 to 100 ° C.
- the polymerization is usually carried out at normal pressure. Polymerization is usually carried out at the boiling point of the solvent or solvent mixture.
- the polymerization temperature can easily be adjusted by a suitable choice of solvents.
- the polymerization itself can be carried out continuously or batchwise. For example, it is possible to introduce the monomer solution and meter in one or more polymerization initiators over a relatively long period of time, or to feed the monomer solution and polymerization initiator continuously or batchwise to a polymerization vessel. For the polymerization you need e.g. 0.05 to 1% by weight, based on the monomers of a polymerization initiator. The higher the use of peroxide, the lower the K values of the polymer obtained.
- the K value of the polymers prepared in this way is in the range from 10 to 90.
- the dialkyl peroxide s di-tert-butyl peroxide, di-tert-amyl peroxide, dicumyl peroxide or 2,5-dimethyl-2,5-bis (tert-butyl peroxy) hexane or the perketals 2,2- Bis- (tert-butylperoxy) -butane, 1,1-bis- (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 4,4-di- (tert-butylperoxy) -n-iso- or tert-Butylvalerat and heats the reaction mixture to a temperature which is above the temperature in the main polymerization reaction, it surprisingly succeeds in drastically reducing the residual monomer contents in the polymerate
- dialkyl peroxides and dialkyl perketals are used in an amount of 0.05 to 0.5% by weight, based on the monomers originally used. It is of course also possible to use mixtures of 2 or more of the peroxides mentioned in the postpolymerization, e.g. Mixtures of di-tert-butyl peroxide and dicumyl peroxide or of di-tert-butyl peroxide and 2,2-bis (tert-butyl peroxy) butane.
- the postpolymerization is preferably carried out at temperatures of 110 to 160 ° C .; carried out. Because of the solvents used in the main polymerization, it may be necessary to carry out the post-polymerization under pressures between 1 and about 50 bar. If the post-polymerization is carried out under increased pressure, a range between 2 and 7 bar is selected for this.
- the postpolymerization time is between 0.5 and 5 hours.
- the invention is illustrated by the following examples.
- the parts given in the examples are parts by weight, the percentages relate to the weight of the substances.
- the polymerization initiators given in the following table are added in solution in isopropanol over a period of 0.5 hours.
- the amount of the polymerization initiator added was in each case 0.2%, based on the monomers originally used in the polymerization.
- the post-polymerization is carried out at a higher temperature than the main polymerization.
- the reaction conditions and the contents of residual monomers in the polymer solution are given in the following table.
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Description
Die Erfindung betrifft ein Verfahren zur Reduzierung der Restmonomerengehalte bei der Polymerisation von Vinylestern und Vinyllactamen in einem Lösungsmittel durch Zusatz von Polymerisationsinitiatoren im Anschluß an die Hauptpolymerisation und Nachpolymerisieren des Reaktionsgemisches.The invention relates to a process for reducing the residual monomer contents in the polymerization of vinyl esters and vinyl lactams in a solvent by adding polymerization initiators after the main polymerization and post-polymerization of the reaction mixture.
Bei Polymerisationsreaktionen bleiben bekänntlich geringe Mengen an Monomeren unumgesetzt. Besonders die Polymeren, die im kosmetisch-pharmazeutischen Anwendungsbereich eingesetzt werden, sollten aber extrem niedrige Restmonomerengehalte haben. Pulverförmige Polymerisate, die beispielsweise durch Sprühtrocknen der Polymerisatlösungen erhalten werden, enthalten im allgemeinen nur geringe Mengen an Restmonomeren. Wenn man aber für die Anwendung bereits Polymerisatlösungen einsetzen möchte, so ist es beispielsweise nicht möglich, die nicht polymerisierten Monomeren durch Destillation weitgehend zu entfernen. Aus der Polymerisatlösung kann zwar ein pulverförmiges Polymerisat durch Sprühtrockung gewonnen und anschließend wieder im reinen Lösungsmittel gelöst werden. Dieses Verfahren ist jedoch umständlich und führt beispielsweise bei Polyvinyllactamen nicht zu Polymerisaten, die einen sehr geringen Restmonomerengehalt aufweisen.As is known, small amounts of monomers remain unreacted in polymerization reactions. In particular, the polymers used in the cosmetic-pharmaceutical field of application should have extremely low residual monomer contents. Powdery polymers, which are obtained for example by spray drying the polymer solutions, generally contain only small amounts of residual monomers. However, if one already wants to use polymer solutions for the application, it is not possible, for example, to largely remove the unpolymerized monomers by distillation. A powdery polymer can indeed be obtained from the polymer solution by spray drying and then dissolved again in the pure solvent. However, this process is cumbersome and, for example in the case of polyvinyl lactams, does not lead to polymers which have a very low residual monomer content.
Aus der US-PS 2 665 271 ist ein Verfahren zum Polymerisieren von N-Vinyllactamen bekannt, bei dem man N-Vinyllactame zunächst nach bekannten Verfahren mit Hilfe von anorganischen oder organischen Peroxiden, die unter den Reaktionsbedingungen zerfallen, als Initiatoren polymerisiert und das Reaktionsgemisch einer Nachpolymerisation unterwirft, sobald der Monomerengehalt konstant bleibt. Die Nachpolymerisation wird in der Weise durchgeführt, daß man dem Reaktionsgemisch weiteres Peroxid zusetzt und es erhitzt. Der Monomerengehalt beträgt nach der Hauptpolymerisation etwa 6% und kann durch Nachpolymerisieren des Reaktionsgemisches auf einen Wert von etwa 0,9% gesenkt werden.From US Pat. No. 2,665,271 a process for polymerizing N-vinyl lactams is known, in which N-vinyl lactams are first polymerized as initiators by known processes with the aid of inorganic or organic peroxides which decompose under the reaction conditions, and the reaction mixture Postpolymerization subjects as soon as the monomer content remains constant. The post-polymerization is carried out by adding further peroxide to the reaction mixture and heating it. The monomer content after the main polymerization is about 6% and can be reduced to about 0.9% by post-polymerization of the reaction mixture.
Aufgabe der Erfindung ist es, ein Verfahren zur Reduzierung der Restmonomerengehalte bei der Polymerisation von Vinylestern und Vinyllactamen in einem Lösungsmittel durch Zusatz von Polymerisationinitiatoren im Anschluß an die Hauptpolymerisation und Nachpolymerisation des Reaktionsgemisches aufzuzeigen, bei dem man Polymerisatlösungen erhält, die einen sehr niedrigen Gehalt an restlichen Monomeren aufweisen.The object of the invention is to provide a process for reducing the residual monomer contents in the polymerization of vinyl esters and vinyl lactams in a solvent by adding polymerization initiators after the main polymerization and post-polymerization of the reaction mixture, in which polymer solutions are obtained which have a very low residual content Have monomers.
Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß man die Hauptpolymerisation bei Temperaturen von 40 bis 160°C durchführt, dem Reaktionsgemisch nach Beendigung der Hauptpolymerisation 0,05 bis 0,5 Gew.%, bezogen auf die eingesetzten Monomeren, Di-tert.-butylperoxid, Di- tert.-amylperoxid, Dicumylperoxid, 2,5-Dimethyi-2,5-bis-(tert.-buty!peroxy)-hexan, 2,2-Bis-(tert.- butylperoxy)-butan, 1,1-Bis-(tert.-Liutylperoxy)-3,3,5-trimethylcyclohexan oder 4,4-Di-(tert.-butyl- peroxy)-butylvalerat zusetzt, und die Nachpolymerisation bei höherer Temperatur als die Hauptpolymerisation im Bereich von 100 bis 200°C durchführt.The object is achieved in that the main polymerization is carried out at from 40 to 160 ° C., the reaction mixture after the end of the main polymerization is 0.05 to 0.5% by weight, based on the monomers used, of di-tert-butyl peroxide , Di-tert-amyl peroxide, dicumyl peroxide, 2,5-dimethyi-2,5-bis- (tert-buty! Peroxy) -hexane, 2,2-bis- (tert-butyl peroxy) -butane, 1, 1-bis- (tert-Liutylperoxy) -3,3,5-trimethylcyclohexane or 4,4-di- (tert-butyl-peroxy) -butylvalerate, and the post-polymerization at a higher temperature than the main polymerization in the range of 100 up to 200 ° C.
Der Vorteil des erfindungsgemäßen Verfahrens besteht darin, daß der gewünschte Polymerisationsgrad und die Farbe der Produkte nicht nachteilig beeinflußt werden. Es ist überraschend, daß durch die Auswahl von Dialkylperoxiden und Perketalen als Polymerisationsinitiator bei der Nachpolymerisation Polymerisatlösungen erhalten werden, bei denen der Restmonomerengehalt um den Faktor 10 bis 20 niedriger liegt als bei Polymerisatlösungen, die nach bekannten Verfahren hergestellt werden.The advantage of the process according to the invention is that the desired degree of polymerization and the color of the products are not adversely affected. It is surprising that the choice of dialkyl peroxides and perketals as the polymerization initiator in the post-polymerization gives polymer solutions in which the residual monomer content is 10 to 20 times lower than in polymer solutions which are prepared by known processes.
Als Vinyllactame kommen vor allem N-Vinylpyrrolidon, N-Vinylpiperidon und N-Vinylcaprolactam in Betracht. Nach dem erfindungsgemäßen Verfahren ist es möglich, Polymerisatlösungen eines niedrigen Restmonomerengehaltes von Homo- und Copolymerisaten von N-Vinyllactamen herzustellen. Das Verfahren hat besondere Bedeutung für die Herstellung von Copolymerisaten von Vinyllactamen, insbesondere von Copolymerisaten des N-Vinylpyrrolidons. Geeignete Monomere, die mit N-Vinylpyrrolidon copolymerisierbar sind, sind beispielsweise Vinylester gesättigte Fettsäuren, die 2 bis 20 Kohlenstoffatome enthalten, z.B. Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylisobutyrat, Vinyllactat, Vinylcaproat, Vinylcaprylat, Vinyloleat und Vinylstearat, Acrylester und Methacrylsäureester, die sich von Alkoholen mit 1 bis 12 Kohlenstoffatomen ableiten, z.B. Acrylsäuremethylester, Acrylsäureäthylester, Acrylsäureisobutylester und 2-Äthylhexyl-acrylat sowie Acrylester oder Methacrylester, die sich von basischen Monomeren, z.B. Aminoäthanol oder Aminopropanol ableiten und Acrylamid sowie N-Methylolacrylamide und N-Methylolmethacrylamid.N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam are particularly suitable as vinyl lactams. The process according to the invention makes it possible to prepare polymer solutions with a low residual monomer content of homo- and copolymers of N-vinyl lactams. The process is of particular importance for the production of copolymers of vinyl lactams, in particular of copolymers of N-vinylpyrrolidone. Suitable monomers which are copolymerizable with N-vinylpyrrolidone are, for example, vinyl esters saturated fatty acids containing 2 to 20 carbon atoms, e.g. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl lactate, vinyl caproate, vinyl caprylate, vinyl oleate and vinyl stearate, acrylic esters and methacrylic acid esters derived from alcohols having 1 to 12 carbon atoms, e.g. Acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid isobutyl ester and 2-ethylhexyl acrylate as well as acrylic ester or methacrylic ester, which are derived from basic monomers, e.g. Derive aminoethanol or aminopropanol and acrylamide as well as N-methylolacrylamide and N-methylolmethacrylamide.
Technisch besonders interessante Copolymerisate enthalten beispielsweise 10 bis 90 Gew.% Vinyllactam und 90 bis 10 Gew.% eines Vinylesters, vorzugsweise Vinylacetat oder Vinylpropionat. Die Vinyllactame können auch mit mehreren Comono-meren copolymerisiert werden, beispielsweise mit Vinylacetat und Vinylisobutyrat oder mit Vinylacetat und Acrylsäureäthylester. Vorzugsweise werden Copolymerisate aus N-Vinylpyrrolidon hergestellt, die 80 bis 20 Gew.% Vinylacetat enthalten.Copolymers which are of particular technical interest contain 10 to 90% by weight of vinyl lactam and 90 to 10% by weight of a vinyl ester, preferably vinyl acetate or vinyl propionate. The vinyl lactams can also be copolymerized with several comonomers, for example with vinyl acetate and vinyl isobutyrate or with vinyl acetate and ethyl acrylate. Copolymers of N-vinylpyrrolidone which contain 80 to 20% by weight of vinyl acetate are preferably produced.
Die Monomeren werden in den bekannten Lösungsmitteln polymerisiert. Es handelt sich hierbei um Lösungsmittel, in denen die Monomeren bzw. Monomerengemische löslich sind. Geeignet sind als Lösungsmittel beispielsweise Wasser, Alkohole, Kohlenwasserstoff, Halogenkohlenwasserstoffe, Ester, Ketone und Äther. Beispiele für einzelne Vertreter aus den genannten Klassen sind beispielsweise Methanol, Äthanol, n- und iso-Propanol, Cyclopentanol, Cyclohexanol, Methylenchlorid, 1,1,1-Trichloräthan, 1,1,2-Trifluoräthan, 1,1,2-Trichloräthan, Athylenglykol, Propandiol, Butandiol, Hexylenglykol, Methylacetat, Äthylacetat, Benzylacetat, Aceton, Äthylenglykolmonomethyläther und Äthylenglykolmonoäthyläther. Man kann selbstverständlich auch Mischungen der genannten Lösungsmittel einsetzen, z.B. Mischungen aus Wasser und Isopropanol oder Mischungen aus Isopropanol und Aceton. Die Konzentration des Polymerisats in der Lösung beträgt im allgemeinen zwischen 5 und 95%.The monomers are polymerized in the known solvents. These are solvents in which the monomers or monomer mixtures are soluble. Suitable solvents are, for example, water, alcohols, hydrocarbons, halogenated hydrocarbons, esters, ketones and ethers. Examples of individual representatives from the classes mentioned are, for example, methanol, ethanol, n- and isopropanol, cyclopentanol, cyclohexanol, methylene chloride and 1,1,1-trichlor ethane, 1,1,2-trifluoroethane, 1,1,2-trichloroethane, ethylene glycol, propanediol, butanediol, hexylene glycol, methyl acetate, ethyl acetate, benzyl acetate, acetone, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. It is of course also possible to use mixtures of the solvents mentioned, for example mixtures of water and isopropanol or mixtures of isopropanol and acetone. The concentration of the polymer in the solution is generally between 5 and 95%.
Für die Hauptpolymerisationsphase können die üblichen radikalischen Polymerisationsinitiatoren verwendet werden, z.B. Azobisisobuttersäurenitril, Diacylperoxide, wie Dibenzoylperoxid oder Dilauroylperoxid, Perester, z.B. tert.-Butylperpivalat, tert.-Butylperoktoat, tert.-Butylperacetat oder tert.-Butylperbenzoat, Wasserstoffperoxid und Hydroperoxide, z.B. tert.-Butylhydroperoxid oder Cumolhydroperoxid.The usual radical polymerization initiators can be used for the main polymerization phase, e.g. Azobisisobutyronitrile, diacyl peroxides such as dibenzoyl peroxide or dilauroyl peroxide, peresters, e.g. tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl peracetate or tert-butyl perbenzoate, hydrogen peroxide and hydroperoxides, e.g. tert-butyl hydroperoxide or cumene hydroperoxide.
Die Monomeren werden in bekannter Weise bei Temperaturen zwischen 40 und 160, vorzugsweise 45 bis 100°C polymerisiert. Die Polymerisation wird in der Regel bei Normaldruck vorgenommen. Gewöhnlich polymerisiert man beim Siedepunkt des Lösungsmittels bzw. der Lösungsmittelmischung. Die Polymerisationstemperatur kann dabei leicht durch eine geeignete Auswahl von Lösungsmitteln eingestellt werden. Die Polymerisation selbst kann kontinuierlich oder diskontinuierlich durchgeführt werden. Es ist beispielsweise möglich, die Monomerenlösung vorzulegen und einen oder mehrere Polymerisationsinitiatoren über einen längeren Zeitraum zuzudosieren oder Monomerenlösung und Polymerisationsinititiator kontinuierlich oder absatzweise einem Polymerisationsgefäß zuzuführen. Für die Polymerisation benötigt man z.B. 0,05 bis 1 Gew.%, bezogen auf die Monomeren eines Polymerisationsinitiators. Je Höher der Einsatz an Peroxid, desto niedriger sind die K-Werte des erhaltenen Polymerisats. Der K-Wert der so hergestellten Polymerisate liegt in dem Bereich von 10 bis 90.The monomers are polymerized in a known manner at temperatures between 40 and 160, preferably 45 to 100 ° C. The polymerization is usually carried out at normal pressure. Polymerization is usually carried out at the boiling point of the solvent or solvent mixture. The polymerization temperature can easily be adjusted by a suitable choice of solvents. The polymerization itself can be carried out continuously or batchwise. For example, it is possible to introduce the monomer solution and meter in one or more polymerization initiators over a relatively long period of time, or to feed the monomer solution and polymerization initiator continuously or batchwise to a polymerization vessel. For the polymerization you need e.g. 0.05 to 1% by weight, based on the monomers of a polymerization initiator. The higher the use of peroxide, the lower the K values of the polymer obtained. The K value of the polymers prepared in this way is in the range from 10 to 90.
Bei der Herstellung von Copolymerisaten aus N-Vinylpyrrolidon und Vinylacetat ist es besonders schwierig, den Restmonomerengehalt an Vinylacetat nach Beendigung der Hauptpolymerisation erheblich zu erniedrigen. Setzt man jedoch gemäß Erfindung die Dialkylperoxide Di-tert.-butylperoxid, Di- tert.-amylperoxid, Dicumylperoxid oder 2,5-Dimethyl-2,5-bis-(tert.-butylperoxy)-hexan oder die Perketale 2,2-Bis-(tert.-butylperoxy)-butan, 1,1-Bis-(tert.-butylperoxy)-3,3,5-trimethylcyclohexan, 4,4-Di-(tert.-butylperoxy)-n-iso- oder tert.-butylvalerat ein und erhitzt das Reaktionsgemisch auf eine Temperatur, die oberhalb der Temperatur bei der Hauptpolymerisationsreaktion liegt, so gelingt es überraschenderweise, die Restmonomerengehalte in der Polymersatlösung drastisch zu senken. Die Dialkylperoxide und Dialkylperketale werden in einer Menge von 0,05 bis 0,5 Gew.%, bezogen auf die ursprünglich eingesetzten Monomeren, verwendet. Es ist selbstverständlich auch möglich, Mischungen von 2 oder mehreren der genannten Peroxide bei der Nachpolymerisation einzusetzen, z.B. Mischungen aus Di-tert.-butylperoxid und Dicumylperoxid oder aus Di-tert.-butylperoxid und 2,2-Bis-(tert.-butyl- peroxy)-butan.In the production of copolymers from N-vinylpyrrolidone and vinyl acetate, it is particularly difficult to significantly reduce the residual monomer content of vinyl acetate after the main polymerization has ended. However, according to the invention, the dialkyl peroxides di-tert-butyl peroxide, di-tert-amyl peroxide, dicumyl peroxide or 2,5-dimethyl-2,5-bis (tert-butyl peroxy) hexane or the perketals 2,2- Bis- (tert-butylperoxy) -butane, 1,1-bis- (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 4,4-di- (tert-butylperoxy) -n-iso- or tert-Butylvalerat and heats the reaction mixture to a temperature which is above the temperature in the main polymerization reaction, it surprisingly succeeds in drastically reducing the residual monomer contents in the polymerate solution. The dialkyl peroxides and dialkyl perketals are used in an amount of 0.05 to 0.5% by weight, based on the monomers originally used. It is of course also possible to use mixtures of 2 or more of the peroxides mentioned in the postpolymerization, e.g. Mixtures of di-tert-butyl peroxide and dicumyl peroxide or of di-tert-butyl peroxide and 2,2-bis (tert-butyl peroxy) butane.
Die Nachpolymerisation wird vorzugsweise bei Temperaturen von 110 bis 160°C; durchgeführt. Aufgrund der bei der Hauptpolymerisation verwendeten Lösungsmittel kann es erforderlich sein, die Nachpolymerisation unter Drücken zwischen 1 und etwa 50 bar durchzuführen. Falls die Nachpolymerisation unter erhöhtem Druck vorgenommen wird, wählt man hierfür einen Bereich zwischen 2 und 7 bar. Die Zeit für die Nachpolymerisation beträgt zwischen 0,5 und 5 Stunden.The postpolymerization is preferably carried out at temperatures of 110 to 160 ° C .; carried out. Because of the solvents used in the main polymerization, it may be necessary to carry out the post-polymerization under pressures between 1 and about 50 bar. If the post-polymerization is carried out under increased pressure, a range between 2 and 7 bar is selected for this. The postpolymerization time is between 0.5 and 5 hours.
Die Erfindung wird anhand der folgenden Beispiele näher erläutert. Die in den Beispielen angegebenen Teile sind Gewichtsteile, die Angaben in Prozent beziehen sich auf das Gewicht der Stoffe. Die K-Werte, die in der Beschreibung und in den Beispielen angegeben sind, wurden nach H. Fikentscher, Cellulosechemie, 13, 58-64 und 71-74 (1932), in 5%igen Dimethylformamidlösungen bei 20°C bestimmt; dabei bedeutet K = k ..103.The invention is illustrated by the following examples. The parts given in the examples are parts by weight, the percentages relate to the weight of the substances. The K values given in the description and in the examples were determined according to H. Fikentscher, Cellulosechemie, 13, 58-64 and 71-74 (1932), in 5% dimethylformamide solutions at 20 ° C; where K = k ..103.
In einem 40 I-Kessel, der mit Rührer, Rückflußkühler und einem Zulaufgefäß ausgestattet ist, werden 10% einer Lösung aus 6 kg N-Vinylpyrrolidon, 6 kg Vinylacetat, 12 kg Isopropanol und 36 g Azobisisobuttersäurenitrii vorgelegt und auf eine Temperatur von 80°C erhitzt. Nach dem Beginn der Polymerisation gibt man die restliche Monomerenlösung in einem Zeitraum von etwa 5 Stunden zu. Die Hauptpolymerisation der Monomeren wird in einem Temperaturbereich von 72 bis 85°C unter schwachem Sieden durchgeführt. Nach einer Zeit von 5,5 Stunden liegt eine Polymerlösung vor, die 12,6% Vinylacetat und 2,4% N-Vinylpyrrolidon enthält.10% of a solution of 6 kg of N-vinylpyrrolidone, 6 kg of vinyl acetate, 12 kg of isopropanol and 36 g of azobisisobutyric acid nitride are placed in a 40 liter kettle equipped with a stirrer, reflux condenser and an inlet vessel and brought to a temperature of 80 ° C. heated. After the start of the polymerization, the remaining monomer solution is added over a period of about 5 hours. The main polymerization of the monomers is carried out in a temperature range from 72 to 85 ° C. with low boiling. After a period of 5.5 hours, a polymer solution is present which contains 12.6% vinyl acetate and 2.4% N-vinylpyrrolidone.
Um den Restmonomerengehalt der erhaltenen Polymerisatlösung zu senken, werden die in der folgenden Tabelle angegebenen Polymerisationsinitiatoren gelöst in Isopropanol innerhalb einer Zeit von 0,5 Stunden zugegeben. Die Menge des zugesetzten Polymerisationsinitiators betrug jeweils 0,2%, bezogen auf die ursprünglich bei der Polymerisation eingesetzten Monomeren. Die Nachpolymerisation wird bei einer höheren Temperatur durchgeführt als die Hauptpolymerisation. Die Reaktionsbedingungen sowie die Gehalte an Restmonomeren in der Polymerisatlösung sind in der folgenden Tabelle angegeben.In order to reduce the residual monomer content of the polymer solution obtained, the polymerization initiators given in the following table are added in solution in isopropanol over a period of 0.5 hours. The amount of the polymerization initiator added was in each case 0.2%, based on the monomers originally used in the polymerization. The post-polymerization is carried out at a higher temperature than the main polymerization. The reaction conditions and the contents of residual monomers in the polymer solution are given in the following table.
Die Vergleichsbeispiele repräsentieren den Stand der Technik, der sich aus der US-PS 2 665 271 ergibt.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772730017 DE2730017A1 (en) | 1977-07-02 | 1977-07-02 | PROCESS FOR REDUCING THE RESIDUAL MONOMER CONTENTS DURING THE POLYMERIZATION OF VINYLLACTAMEN AND VINYLESTERS |
| DE2730017 | 1977-07-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000161A1 EP0000161A1 (en) | 1979-01-10 |
| EP0000161B1 true EP0000161B1 (en) | 1981-05-20 |
Family
ID=6013042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100179A Expired EP0000161B1 (en) | 1977-07-02 | 1978-06-16 | Process for reducing the amount of residual monomers during the polymerisation of vinyl lactams and vinyl esters |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4182851A (en) |
| EP (1) | EP0000161B1 (en) |
| JP (1) | JPS6059923B2 (en) |
| DE (2) | DE2730017A1 (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2942657A1 (en) * | 1979-10-22 | 1981-04-30 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING POLYVINYLPYRROLIDONE, WHOSE AQUEOUS SOLUTION HAS A HIGH VISCOSITY, THROUGH HEAT TREATMENT OF AQUEOUS SOLUTIONS OF COMMON POLYVINYLPYRROLIDONE |
| US4520179A (en) * | 1982-09-20 | 1985-05-28 | Gaf Corporation | Preparation of vinylpyrrolidone/vinyl acetate copolymers of various molecular weights using a single initiator system consisting essentially of t-Butylperoxypivalate |
| DE3622602A1 (en) * | 1986-07-05 | 1988-01-14 | Basf Ag | BINDERS FOR TRANSFER PRINTING |
| DE3629933A1 (en) * | 1986-09-03 | 1988-03-10 | Basf Ag | METHOD FOR REMOVING VINYLPYRROLIDONE FROM VINYLPYRROLIDONE POLYMERISATS |
| DE4031912A1 (en) * | 1990-10-08 | 1992-04-09 | Basf Ag | TERPOLYMERS, THEIR USE IN HAIR FASTENERS WITH INCREASED FIXING EFFECT, AND THEIR HAIR FASTENERS CONTAINING THEM |
| AU1692392A (en) * | 1991-04-01 | 1992-11-02 | Isp Investments Inc. | Precipitation polymerization process |
| US5130388A (en) * | 1991-05-06 | 1992-07-14 | Isp Investments Inc. | Precipitation polymerization process |
| DE4139963A1 (en) * | 1991-12-04 | 1993-06-09 | Basf Ag, 6700 Ludwigshafen, De | REDISPERIBLE DISPERSION POWDER OF N-VINYLPYRROLIDONE VINYL ACETATE COPOLYMERISATE, THE PRODUCTION AND USE THEREOF |
| DE4140086C2 (en) * | 1991-12-05 | 1994-08-25 | Basf Ag | Process for the preparation of highly pure N-vinylpyrrolidone polymers |
| US5506318A (en) * | 1993-12-13 | 1996-04-09 | Air Products And Chemicals, Inc. | Process for producing N-vinyl pyrrolidone polymer having low residual monomer |
| DE4421936A1 (en) | 1994-06-23 | 1996-01-04 | Basf Ag | Process for the preparation of copolymers of N-vinylpyrrolidone and vinyl acetate which are clearly soluble in water and have a low residual monomer content |
| JP3510003B2 (en) * | 1995-05-01 | 2004-03-22 | クラリアント インターナショナル リミテッド | Composition for anti-reflective coating |
| US6673892B2 (en) | 2002-04-29 | 2004-01-06 | Eastman Chemical Company | Process for reducing residual free radical polymerizable monomer content of polymers |
| US7572870B2 (en) | 2005-12-23 | 2009-08-11 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer |
| US7449531B2 (en) | 2005-12-23 | 2008-11-11 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer |
| US7572871B2 (en) | 2005-12-23 | 2009-08-11 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer |
| US7847044B2 (en) | 2005-12-23 | 2010-12-07 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer by polymerization under increased pressure |
| DE102006056203B4 (en) * | 2005-12-23 | 2017-01-26 | Basf Se | Process for the preparation of water-soluble haze-free copolymers of at least one water-soluble N-vinyl lactam and at least one hydrophobic comonomer |
| US20070149737A1 (en) * | 2005-12-23 | 2007-06-28 | Basf Aktiengesellschaft | Method of producing water-soluble nonturbid copolymers of at least one water-soluble n-vinyllactam and at least one hydrophobic comonomer |
| US7442751B2 (en) | 2005-12-23 | 2008-10-28 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer |
| DE102007052412A1 (en) | 2006-11-29 | 2008-06-05 | Basf Se | Process for the preparation of water-soluble haze-free copolymers of at least one water-soluble N-vinyl lactam and at least one hydrophobic comonomer |
| DE102009013152A1 (en) | 2009-03-06 | 2010-09-09 | Schunk Gmbh & Co. Kg Spann- Und Greiftechnik | Damping system for stop damping |
| CN102898563B (en) * | 2012-10-24 | 2014-06-18 | 四川化工控股（集团）有限责任公司 | Catalyst for lowering N-vinyl-2-pyrrolidone in polyvinylpyrrolidone (PVP), and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2497705A (en) * | 1946-10-16 | 1950-02-14 | Du Pont | Copolymerization product of n-vinyl lactams and polymerizable esters, and process for making same |
| US2665271A (en) * | 1951-10-25 | 1954-01-05 | Gen Aniline & Film Corp | Polymerization of n-vinyl lactams |
| US2667473A (en) * | 1952-02-08 | 1954-01-26 | Monsanto Chemicals | Vinyl acetate-n-vinyl-pyrrolidone copolymers |
| US2914516A (en) * | 1956-05-07 | 1959-11-24 | Gen Aniline & Film Corp | Purification of polyvinylpyrrolidone |
| US3534009A (en) * | 1969-01-29 | 1970-10-13 | Du Pont | Method for reducing residual vinyl acetate monomer |
| US4020267A (en) * | 1974-12-16 | 1977-04-26 | The British Petroleum Company Limited | Removal of residual monomer in the presence of water by dielectric heating |
-
1977
- 1977-07-02 DE DE19772730017 patent/DE2730017A1/en not_active Withdrawn
-
1978
- 1978-06-16 EP EP78100179A patent/EP0000161B1/en not_active Expired
- 1978-06-16 DE DE7878100179T patent/DE2860710D1/en not_active Expired
- 1978-06-27 US US05/919,449 patent/US4182851A/en not_active Expired - Lifetime
- 1978-06-30 JP JP53078778A patent/JPS6059923B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0000161A1 (en) | 1979-01-10 |
| DE2730017A1 (en) | 1979-01-18 |
| JPS5414492A (en) | 1979-02-02 |
| DE2860710D1 (en) | 1981-08-27 |
| JPS6059923B2 (en) | 1985-12-27 |
| US4182851A (en) | 1980-01-08 |
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