EP0000161B1 - Procédé pour réduire la teneur en monomères résiduels lors de la polymérisation de lactames vinyliques et d'esters vinyliques - Google Patents

Procédé pour réduire la teneur en monomères résiduels lors de la polymérisation de lactames vinyliques et d'esters vinyliques Download PDF

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Publication number
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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EP
European Patent Office
Prior art keywords
polymerization
vinyl
tert
butyl
carried out
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EP78100179A
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German (de)
English (en)
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EP0000161A1 (fr
Inventor
Ferdinand Dr. Straub
Herbert Dr. Spoor
Hans-Uwe Dr. Schenck
Wolfgang Dr. Schwarz
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BASF SE
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BASF SE
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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
    • 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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  • 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)
  • Polymerization Catalysts (AREA)
  • Polymerisation Methods In General (AREA)

Claims (4)

1. Procédé pour réduire la teneur en monomères restants lors de l'homopolymérisation de N-vinyllactamen ou de la copolymérisation de N-vinyllactames et d'esters vinyliques dans un solvent par addition d'initiateurs de polymérisation à la suite de la polymérisation principale et postpolymérisation du mélange de réaction, caractérisé par le fait que l'on effectue la polymérisation principale à des températures de 40 à 160°C, on ajoute au mélange de réaction, après achèvement de la polymérisation principale, 0,05 à 0,5% en poids rapporté aux monomères introduits, de di-tert.-butyl- peroxyde, di-tert.-amylperoxyde, dicumylperoxyde, 2,5-diméthyl-2,5-bis-(tert.-butylperoxy)hexane, 2,2- bis-tert.-butylperoxy)-butane, 1,1-bis-(tert.-butylperoxy)-3,3,5-triméthylcyclohexane ou 4,4-di-(tert.- butylperoxy)-butylvalerate et on effectue la postpolymérisation à une température plus élevée que le polymérisation principale dans les limites de 100 à 200°C.
2. Procédé selon la revendication 1, caractérisé par le fait que l'on effectue la polymérisation principale sous pression normale et la post-polymérisation à des températures de 110 à 160°C sous une pression de 1 à 50 bars.
3. Procédé selon l'une des revendications 1 et 2, caractérisé par le fait que l'on introduit, comme vinyllactame, de la N-vinylpyrrolidone.
4. Procédé selon l'une des revendications 1 à 3, caractérisé par le fait qu'on copolymérise du N-vinylpyrrolidone et de l'ester vinylique.
EP78100179A 1977-07-02 1978-06-16 Procédé pour réduire la teneur en monomères résiduels lors de la polymérisation de lactames vinyliques et d'esters vinyliques Expired EP0000161B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2730017 1977-07-02
DE19772730017 DE2730017A1 (de) 1977-07-02 1977-07-02 Verfahren zur reduzierung der restmonomerengehalte bei der polymerisation von vinyllactamen und vinylestern

Publications (2)

Publication Number Publication Date
EP0000161A1 EP0000161A1 (fr) 1979-01-10
EP0000161B1 true EP0000161B1 (fr) 1981-05-20

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EP78100179A Expired EP0000161B1 (fr) 1977-07-02 1978-06-16 Procédé pour réduire la teneur en monomères résiduels lors de la polymérisation de lactames vinyliques et d'esters vinyliques

Country Status (4)

Country Link
US (1) US4182851A (fr)
EP (1) EP0000161B1 (fr)
JP (1) JPS6059923B2 (fr)
DE (2) DE2730017A1 (fr)

Families Citing this family (23)

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Publication number Priority date Publication date Assignee Title
DE2942657A1 (de) * 1979-10-22 1981-04-30 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von polyvinylpyrrolidon, dessen waessrige loesung eine hohe viskositaet aufweist, durch waermebehandlung von waessrigen loesungen von ueblichem polyvinylpyrrolidon
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 (de) * 1986-07-05 1988-01-14 Basf Ag Bindemittel fuer den transferdruck
DE3629933A1 (de) * 1986-09-03 1988-03-10 Basf Ag Verfahren zur entfernung von vinylpyrrolidon aus vinylpyrrolidon-polymerisaten
DE4031912A1 (de) * 1990-10-08 1992-04-09 Basf Ag Terpolymerisate, ihre verwendung in haarfestigungsmitteln mit erhoehter festigungswirkung und diese enthaltende haarfestigungsmittel
US5130388A (en) * 1991-05-06 1992-07-14 Isp Investments Inc. Precipitation polymerization process
AU1692392A (en) * 1991-04-01 1992-11-02 Isp Investments Inc. Precipitation polymerization process
DE4139963A1 (de) * 1991-12-04 1993-06-09 Basf Ag, 6700 Ludwigshafen, De Redispergierbares dispersionspulver aus n-vinylpyrrolidon-vinylacetat-copolymerisat, dessen herstellung und verwendung
DE4140086C2 (de) * 1991-12-05 1994-08-25 Basf Ag Verfahren zur Herstellung hochreiner N-Vinylpyrrolidon-Polymerisate
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 (de) 1994-06-23 1996-01-04 Basf Ag Verfahren zur Herstellung von in Wasser klar löslichen, restmonomerenarmen Copolymerisaten aus N-Vinylpyrrolidon und Vinylacetat
JP3510003B2 (ja) * 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 反射防止コーティング用組成物
US6673892B2 (en) 2002-04-29 2004-01-06 Eastman Chemical Company Process for reducing residual free radical polymerizable monomer content of polymers
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
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
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
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
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
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
DE102006056203B4 (de) * 2005-12-23 2017-01-26 Basf Se Verfahren zur Herstellung von wasserlöslichen trübungsfreien Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren
DE102007052412A1 (de) 2006-11-29 2008-06-05 Basf Se Verfahren zur Herstellung von wasserlöslichen trübungsfreien Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren
DE102009013152A1 (de) 2009-03-06 2010-09-09 Schunk Gmbh & Co. Kg Spann- Und Greiftechnik Dämpfungssystem zur Anschlagdämpfung
CN102898563B (zh) * 2012-10-24 2014-06-18 四川化工控股（集团）有限责任公司 一种降低聚乙烯吡咯烷酮中n-乙烯基吡咯烷酮的催化剂及其制备方法与应用

Family Cites Families (6)

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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

Also Published As

Publication number Publication date
JPS6059923B2 (ja) 1985-12-27
DE2730017A1 (de) 1979-01-18
JPS5414492A (en) 1979-02-02
US4182851A (en) 1980-01-08
DE2860710D1 (en) 1981-08-27
EP0000161A1 (fr) 1979-01-10

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