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WO2011061076A1 - Procédé de fabrication de copolymères greffés à base de polyéthers - Google Patents

Procédé de fabrication de copolymères greffés à base de polyéthers Download PDF

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Publication number
WO2011061076A1
WO2011061076A1 PCT/EP2010/066920 EP2010066920W WO2011061076A1 WO 2011061076 A1 WO2011061076 A1 WO 2011061076A1 EP 2010066920 W EP2010066920 W EP 2010066920W WO 2011061076 A1 WO2011061076 A1 WO 2011061076A1
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WO
WIPO (PCT)
Prior art keywords
reaction
polyethers
weight
polymerization
component
Prior art date
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Ceased
Application number
PCT/EP2010/066920
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German (de)
English (en)
Inventor
Jürgen DECKER
Achim Pommer
Ulrich Filges
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2011061076A1 publication Critical patent/WO2011061076A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals

Definitions

  • the present invention relates to an improved process for preparing polyether graft copolymers by reacting hydrophobic monomers and a polyether in the presence of a radical initiator system.
  • Such graft polymers are known per se. However, it has been found that in the known procedures on an industrial scale, the safety of the process is not guaranteed, because no adequate control of the reaction is possible.
  • EP-A 1 125 954 describes the reaction of vinyl carboxylic esters with polyethers in the presence of a free-radical initiator system and using a polyalkylene glycol which is liquid at room temperature as a solvent for the initiator system. The reaction takes place at constant bath temperature.
  • the object has been achieved by a process for the preparation of polyether-polyvinyl ester graft polymers by reacting polyethers and hydrophobic monomers in the presence of an organic solvent and a radical-forming polymerization initiator under reflux conditions, with a monomer composition of
  • the total amount of the components a) to c) is 100 wt .-%, which is characterized in that the control of the reaction in dependence on the amount of heat removed via the reflux condenser.
  • Suitable vinyl esters are vinyl acetate or vinyl propionate, with vinyl acetate being preferred.
  • hydrophobic vinyl ester In addition to the hydrophobic vinyl ester are suitable as further hydrophobic comonomers monoolefinically unsaturated monomers which have boiling temperatures of 65 to 80 ° C in particular at atmospheric pressure. Suitable comonomers are, for example, acrylonitrile, methyl acrylate and methyl methacrylate. Such relatively low-boiling hydrophobic comonomers reach the reflux under the conditions of the polymerization. Preference is given to using methyl acrylate as further hydrophobic monomer.
  • Polyether components which can be used according to the invention are polyethylene glycol, polypropylene oxide, polyethylene oxide-polypropylene oxide block copolymers or polytetramethylene oxide. Preference is given to using polyethylene glycol.
  • the weight average molecular weight of the polyether component may be from 1,000 to 35,000, preferably from 1,500 to 15,000, more preferably from 6,000 to 9,000.
  • composition of the starting monomer mixture is preferably chosen such that from 5 to 35% by weight of the polyether is reacted with from 65 to 95% by weight of comonomers, the percentages being based on the total amount of polyether and comonomer, which is equal to 100% by weight. % is refer.
  • 10 to 30 wt .-% polyether are reacted with 70 to 90 wt .-% comonomers.
  • Particularly preferred are graft polymers containing only vinyl acetate as a comonomer.
  • the amount of component c) is preferably 15 to 45% by weight.
  • radical-forming initiators the following polymerization initiators can be used: tert-butyl peroxy-2-ethyl-hexanoate, acetylcyclohexanesulfonyl peroxide, di- n-butyl peroxydicarbonate, tert-butyl peroxypivalate, di-octanoyl peroxide, di-tert-butyl peroxycyclohexanedicarboxylate, tert-butyl peroxy-3,5,5-trimethylhexanoate,
  • the polymerization initiators are fed to the polymerization mixture in the form of an organic solution.
  • Suitable organic solvents are preferably methanol and furthermore linear C 2 -C 4 -alcohols such as ethanol, propanol or n-butanol, and also esters such as ethyl acetate or ethers such as tetrahydrofuran or dioxane.
  • suitable at room temperature are liquid polyalkylene glycols which preferably have molecular weights of from 100 to 600, in particular polyethylene glycols.
  • the polymerization is carried out under reflux of the volatile under the reaction conditions components, ie the hydrophobic monomers b) and c) and the solvent for the initiator.
  • a suitable device is a reactor equipped with a reflux condenser.
  • the reactor is usually equipped with a jacket heating and cooling system.
  • customary measuring devices for measuring the heat of reaction are attached.
  • the reactor is equipped with conventional pressure control devices, so that a vacuum can be applied as desired or an increased pressure can be set.
  • devices for supplying inert gas are provided.
  • the polymerization takes place under a nitrogen atmosphere.
  • the polymerization is carried out as a feed process.
  • initially the polyether component can be initially charged and the template heated.
  • the temperature at which the original is heated depends, among other things, on the initiator selected. Furthermore, the melting point of the polyether has an influence on the template temperature to be selected. The temperature must be high enough that an easily stirrable melt is present so that a uniform mixing of the reactor contents is ensured when the vinyl acetate and the initiator are added.
  • the original can be heated to 75 to 120 ° C, preferably 80 to 100 ° C.
  • the addition of the vinyl acetate, the initiator system and, if desired, component c) can be carried out in the feed process.
  • the liquid vinyl acetate and the liquid components c) are preferably added via feeds separated from the feed of the initiator solution.
  • the internal temperature of the reactor, after the polymerization reaction has started adjusts to the boiling point of the monomer / solvent mixture, depending on the starting materials and the reaction pressure set.
  • further vinyl acetate can be added via an inlet after completion of the feed of radical initiator.
  • the control of the reaction can be carried out as described below.
  • the temperature of the system is advantageously chosen so that the temperature of the reactor jacket after the heating phase to start the reaction substantially (+/- 3 ° C) corresponds to the temperature inside the reactor (the reaction mixture). This can be achieved in a particularly simple manner by switching off the heating or cooling of the jacket after the reaction has started, and merely circulating the cooling medium.
  • the heat of reaction is removed by means of a reflux condenser.
  • the amount of heat dissipated at the cooler serves to monitor the reaction and allows a good follow-up of the conversion of the polymerization.
  • the reaction temperature of the polymerization is given by the boiling point of the volatile components (unreacted monomer, solvent). The boiling point can be adjusted precisely by the pressure.
  • the reaction temperature can be adjusted by the pressure as described above.
  • the measurement of the heat of reaction removed at the reflux condenser can be carried out in a simple manner with the aid of customary measuring technology. In each case, the temperature of the inflowing cooling medium and of the outflowing cooling medium is measured.
  • the conversion of the polymerization by comparison with the supplied amount of monomer can be easily determined.
  • the conversion should not fall below a defined range, since otherwise the danger of a runaway reaction of accumulated monomers arises.
  • the desired reaction temperature is set above the boiling point of the monomer / solvent mixture.
  • the boiling point can be controlled very effectively via the reaction pressure.
  • the reactor is equipped with a device for pressure control, which includes a pressure-maintaining valve in the exhaust gas of the radiator and the required IM2 and vacuum ports.
  • the polymerization is carried out at internal temperatures between 50 and 120 ° C, preferably between 60 and 80 ° C.
  • pressures between 500 mbar (absolute, corresponds to 0.05 MPa) and 5000 mbar (absolute, corresponds to 0.5 MPa) are required for this, preferably between 500 mbar (absolute, corresponds to 0.05 MPa) and 2500 mbar (absolute, corresponds to 0.25 MPa).
  • the reaction pressure is between 750 mbar (absolute, corresponds to 0.075 MPa) and 1500 mbar (absolute, corresponds to 0.15 MPa).
  • the polymerization mixture can be heated by heating the reactor jacket to 70-120 ° C., particularly preferably to 70-100 ° C.
  • the ester or nitrile groups of the polymers can subsequently be saponified partially or completely.
  • bases are, for example, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide or alkali metal alkoxides such as sodium methoxide.
  • the bases are preferably added in the form of their aqueous or alcoholic solutions.
  • alcoholic solvents are methanol, ethanol, preferably methanol is used. It may also be advisable to remove unreacted components b) and c) before adding the base.
  • Preferred degrees of saponification range from .5 to 100 mol%, more preferably between 70 and 100 mol%.
  • the K values of the polymers can be from 20 to 50 (measured .1% by weight in water).
  • the method according to the invention offers the following advantages:
  • the control on the basis of the amount of heat removed at the cooler allows a particularly secure monitoring of the reaction and a very good control of sales.
  • the molecular weight can be controlled very well over the polymerization temperature, which is adjusted via the reaction pressure.
  • the reactor had a reflux condenser (with pressure-maintaining valve in the exhaust gas), a heating or cooling bath and several regulated inlets.
  • the feed rates of the starter solution (feed 1) and of the monomer mixture (feed 2) were varied independently of one another (see Table 1).
  • the internal temperature of the reactor was adjusted by the incipient reflux cooling of the solvent / monomer mixture and kept approximately constant throughout the feed.
  • the temperature of the reactor jacket adjusted to temperatures in the range of 5 ° C below the internal temperature.
  • reaction mixture was first 2.5 l of methanol and then at a temperature of about 55 - 60 ° C, a solution of 10 g of a base (NaOH, KOH or NaOMe) added in 100 ml of methanol. After a gel phase had formed (noticeable increase in viscosity), the reaction mixture was maintained at 55-60 ° C for a further 30 min. Then 5 l of water were added in several portions and the solvent was removed by means of a steam distillation from the reaction mixture. A solution of the polymer in water was obtained.
  • a base NaOH, KOH or NaOMe
  • the K values (measured .1 wt .-% in water) were between 25.0 and 45.0

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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)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne un procédé de fabrication de polymères greffés à base de polyéthers et d'ester de vinyle. Ce procédé consiste à prendre des polyéthers, un ester de vinyle et d'autres monomères hydrophobes en conditions de reflux, et à les faire réagir en présence d'un solvant organique et d'un initiateur de polymérisation formateur de radicaux. Ce procédé met en œuvre une composition de monomères réunissant a) de 5 à 50 % en poids de polyéther, b) de 40 à 95 % en poids d'ester de vinyle, et c) de 0 à 50 % en poids d'un autre monomère hydrophobe, la quantité totale des constituants a) à c) représentant les 100 % en poids. L'invention est caractérisée en ce que la régulation de la réaction se fait en fonction de la quantité de chaleur évacuée par l'intermédiaire du condenseur à reflux.
PCT/EP2010/066920 2009-11-17 2010-11-05 Procédé de fabrication de copolymères greffés à base de polyéthers Ceased WO2011061076A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09176244 2009-11-17
EP09176244.3 2009-11-17

Publications (1)

Publication Number Publication Date
WO2011061076A1 true WO2011061076A1 (fr) 2011-05-26

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PCT/EP2010/066920 Ceased WO2011061076A1 (fr) 2009-11-17 2010-11-05 Procédé de fabrication de copolymères greffés à base de polyéthers

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WO (1) WO2011061076A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013132042A1 (fr) * 2012-03-09 2013-09-12 Basf Se Procédé continu de synthèse de polymères greffés basé sur des polyéthers

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1077430B (de) 1958-04-15 1960-03-10 Hoechst Ag Verfahren zur Herstellung von Pfropfpolymerisaten von Polyvinylestern
EP0230489A1 (fr) * 1984-07-27 1987-08-05 Kanegafuchi Chemical Industry Co., Ltd. Procédé de contrôle de température des réacteurs de polymérisation
WO2000018375A1 (fr) 1998-09-30 2000-04-06 Basf Aktiengesellschaft Utilisation de polymerisats hydromiscibles ou hydrodispersibles contenant des polyethers comme agent de recouvrement, liant et/ou substance auxiliaire filmogene dans des formes d'administration pharmaceutiques
EP1125954A2 (fr) 2000-02-09 2001-08-22 Basf Aktiengesellschaft Préparation et utilisation de polymères solubles ou dispersibles dans l'eau contenant contenant un polyéther
DE10055473A1 (de) 2000-11-09 2002-05-23 Siegfried Trauschke Gartengerät
JP2002327029A (ja) * 2001-04-27 2002-11-15 Nippon Shokubai Co Ltd 親水性グラフト重合体の製造方法
JP2002363204A (ja) * 2001-04-05 2002-12-18 Mitsubishi Rayon Co Ltd 重合方法およびジエン系重合体の製造方法
DE102006055473A1 (de) * 2005-12-21 2007-07-05 Basf Ag Verfahren zur Herstellung von Pfropfcopolymeren auf Basis von Polyethern
DE102006030557A1 (de) * 2006-07-03 2008-01-10 Celanese Emulsions Gmbh Verfahren zur Herstellung wässriger Vinylester-Dispersionen
US20080281057A1 (en) * 2005-01-13 2008-11-13 Vinnolit Technologie Gmbh & Co. Kg Process For the Polymerisation of Vinyl-Containing Monomers

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1077430B (de) 1958-04-15 1960-03-10 Hoechst Ag Verfahren zur Herstellung von Pfropfpolymerisaten von Polyvinylestern
EP0230489A1 (fr) * 1984-07-27 1987-08-05 Kanegafuchi Chemical Industry Co., Ltd. Procédé de contrôle de température des réacteurs de polymérisation
US4752640A (en) * 1984-07-27 1988-06-21 Kanegafuchi Chemical Industry Co., Ltd. Temperature controlling method for polymerization reactors
WO2000018375A1 (fr) 1998-09-30 2000-04-06 Basf Aktiengesellschaft Utilisation de polymerisats hydromiscibles ou hydrodispersibles contenant des polyethers comme agent de recouvrement, liant et/ou substance auxiliaire filmogene dans des formes d'administration pharmaceutiques
EP1125954A2 (fr) 2000-02-09 2001-08-22 Basf Aktiengesellschaft Préparation et utilisation de polymères solubles ou dispersibles dans l'eau contenant contenant un polyéther
DE10055473A1 (de) 2000-11-09 2002-05-23 Siegfried Trauschke Gartengerät
JP2002363204A (ja) * 2001-04-05 2002-12-18 Mitsubishi Rayon Co Ltd 重合方法およびジエン系重合体の製造方法
JP2002327029A (ja) * 2001-04-27 2002-11-15 Nippon Shokubai Co Ltd 親水性グラフト重合体の製造方法
US20080281057A1 (en) * 2005-01-13 2008-11-13 Vinnolit Technologie Gmbh & Co. Kg Process For the Polymerisation of Vinyl-Containing Monomers
DE102006055473A1 (de) * 2005-12-21 2007-07-05 Basf Ag Verfahren zur Herstellung von Pfropfcopolymeren auf Basis von Polyethern
DE102006030557A1 (de) * 2006-07-03 2008-01-10 Celanese Emulsions Gmbh Verfahren zur Herstellung wässriger Vinylester-Dispersionen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013132042A1 (fr) * 2012-03-09 2013-09-12 Basf Se Procédé continu de synthèse de polymères greffés basé sur des polyéthers
CN104271626A (zh) * 2012-03-09 2015-01-07 巴斯夫欧洲公司 用于合成基于聚醚的接枝聚合物的连续方法
EP2862884A1 (fr) * 2012-03-09 2015-04-22 Basf Se Procédé continu pour la synthèse de polymères greffés à base de polyéthers
CN104271626B (zh) * 2012-03-09 2017-03-15 巴斯夫欧洲公司 用于合成基于聚醚的接枝聚合物的连续方法

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