WO2008090152A1 - Procédé de préparation de copolymères de l'acide vinylphosphonique - Google Patents

Procédé de préparation de copolymères de l'acide vinylphosphonique Download PDF

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WO2008090152A1
WO2008090152A1 PCT/EP2008/050704 EP2008050704W WO2008090152A1 WO 2008090152 A1 WO2008090152 A1 WO 2008090152A1 EP 2008050704 W EP2008050704 W EP 2008050704W WO 2008090152 A1 WO2008090152 A1 WO 2008090152A1
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monomers
anhydride
acid
monomer
vinylphosphonic acid
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PCT/EP2008/050704
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German (de)
English (en)
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Rainer Klopsch
Marta Millaruelo
Volker Steinert
Brigitte Voit
Hartmut Komber
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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen

Definitions

  • the present invention relates to a process for the preparation of copolymers of vinyl phosphonic acid with at least one monoethylenically or conjugated diethyl-unsaturated monomer having a water solubility of less than 50 g / l at 25 0 C.
  • the invention also relates to the copolymers obtainable by this process.
  • Polyvinylphosphonic acid (hereinafter also P (PVA)) and copolymers of vinylphosphonic acid are of interest for numerous applications, for example as flame retardants, for the preparation of cation exchange membranes, as additives in coating compositions, as additives for dental cement, as soil improver, as adhesion improver Dispersants and the like. Due to their high water solubility and biocompatibility, copolymers with a high proportion of vinylphosphonic acid are suitable as additives in galenics, for example for the solubilization of active substances, as well as for orthopedic applications and for the production of synthetic cartilage and bone material.
  • P (PVA) Polyvinylphosphonic acid
  • copolymers with a high proportion of vinylphosphonic acid are suitable as additives in galenics, for example for the solubilization of active substances, as well as for orthopedic applications and for the production of synthetic cartilage and bone material.
  • the vinylphosphonic acid is only partially incorporated into the copolymer, so that substantial amounts of homopolymer are formed in the free-radical polymerization and part of the vinylphosphonic acid remains in the reaction mixture in unpolymerized form.
  • a further problem in the preparation of copolymers of vinylphosphonic acid is that the polymers obtained generally have only a low molecular weight. The achievable molecular weights (weight average) are regularly below 30,000 daltons.
  • the vinylphosphonic acid polymerization processes described in the prior art do not permit the preparation of higher molecular weight copolymers.
  • US 3,297,663 describes a process for the preparation of homopolymers of vinylphosphonic acid or its salts, in which vinylphosphonic acid or a Salt of the vinylphosphonic acid in an organic solvent, which does not dissolve the polymer forming, is polymerized in the presence of a polymerization initiator by the method of precipitation polymerization.
  • EP 114394 describes a process for the radical polymerization of vinylphosphonic acid, in which the vinylphosphonic acid in a protic diluent in the presence of 1, 0 to 5.5 wt .-% of aliphatic peroxide esters, diacyl peroxides and / or aliphatic azo compounds with a certain Decay characteristic polymerized.
  • the proportion of unreacted vinyl phosphonic acid in the product can be significantly reduced.
  • the molecular weights achieved are low.
  • the residual monomer content is still unsatisfactory.
  • EP 123297 A2 describes the preparation of crosslinked copolymers, wherein as crosslinking monomer, inter alia, the anhydride of vinylphosphonic acid is proposed. Only copolymers with water-soluble monomers, such as acrylamide, acrylic acid, methacrylic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylformamide, N-vinyl-N-methylacetanide, vinylpyrrolidone and the like, are described there.
  • water-soluble monomers such as acrylamide, acrylic acid, methacrylic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylformamide, N-vinyl-N-methylacetanide, vinylpyrrolidone and the like.
  • the present invention is therefore based on the object to provide a process for the preparation of copolymers of vinyl phosphonic acid with at least one hydrophobic comonomer, which is easy to control and to products having a high molecular weight, a high proportion of copolymerized vinylphosphonic and a low content of unreacted vinylphosphonic acid leads.
  • this object is achieved by a radical polymerization process in which one uses a vinylphosphonic acid, which is present at least partially in the form of its anhydride or in the form of an anhydride derivative. Accordingly, this invention relates to a process for preparing copoly the radical polymerization of a monomer mers of vinyl phosphonic acid with at least one monoethylenically or conjugated diethylenically unsaturated comonomer having a water solubility of less than 50 g / l at 25 0 C comprising composition
  • Anhydride derivatives are understood as meaning compounds of the formula I in which n has the abovementioned meaning and one or both radicals X and X 'are halogen, for example As chlorine, or an acyl radical such as Ci-C4-alkylcarbonyl, z. B. for acetyl, where one of the radicals X or X 'may also be OH.
  • anhydrides as well as the acylated anhydrides (i.e., compounds of formula I wherein one or both of X and X 'is an acyl radical wherein one of X or X' may also be OH):
  • the use of the anhydride or anhydride derivative of the vinylphosphonic acid in the polymerization process according to the invention leads to a significantly increased rate of polymerization in comparison to the pure vinylphosphonic acid.
  • the content of unreacted vinyl phosphonic acid is significantly lower and is generally not more than 5% by weight, based on the amount of monomer a used.
  • the molecular weight of the copolymers obtained is well above 50,000 daltons and is frequently at least 80,000 daltons and more preferably at least 100,000 daltons, e.g. B. 50,000 to 50,000,000, often 80,000 to 10,000,000 and in particular 100,000 to 1,000,000 Dalton (weight average, determined by light scattering or viscometry).
  • the molecular weight can also be estimated from the relative viscosity, which is generally at least 0.6 dL / g and often at least 0.8 dL / g or at least 0.9 dL / g (determined as 1% strength by weight solutions of the respective Polymers in water (water-soluble polymers) or dimethyl sulfoxide or dimethylformamide (water-insoluble polymers)).
  • the advantages of the invention are surprisingly achieved even at low levels of anhydride or anhydride derivative in the monomers used a.
  • the content of anhydride or anhydride derivative is usually at least 5 mol%, often at least 10 mol%, especially at least 20 mol%, preferably at least 30 mol% , particularly preferably at least 40 mol% and very particularly preferably at least 50 mol%, based on the total amount of the monomers a.
  • the preparation of the anhydride or anhydride derivative of the vinylphosphonic acid can be carried out in a manner known per se, for example by the process described in EP 32663 or by use of water-dehydrating agents, for example in analogy to the process described in DE 2758580 or as described below ,
  • anhydride or anhydride derivative of the vinylphosphonic acid in a step upstream of the polymerization, for.
  • Example by reacting vinylphosphonic acid with the anhydride of a non-polymerizable carboxylic acid, wherein the anhydride or the acylated anhydride or, depending on the reaction conditions, a mixture of vinylphosphonic acid and the anhydride or acylated anhydride of the vinylphosphonic acid.
  • the product obtained in this case can then be used as monomer (e) a in the polymerization process according to the invention.
  • Suitable non-polymerizable carboxylic anhydrides are, in particular, the anhydrides of alkanecarboxylic acids having preferably 1 to 6 and in particular 2 to 4 carbon atoms, such as acetic anhydride, propionic anhydride and butyric anhydride. It is also possible to use mixed anhydrides of nonpolymerizable carboxylic acids, in particular mixed anhydrides of alkanecarboxylic acids.
  • the preparation of the anhydride or acylated anhydride of the vinylphosphonic acid will generally be carried out by reacting vinylphosphonic acid with the anhydride of the nonpolymerizable carboxylic acid, for example by reacting vinylphosphonic acid with the anhydride of the nonpolymerizable carboxylic acid, if appropriate under Addition of an inert organic solvent, mixed. Preferably, it is then subsequently to a temperature above 30 0 C, in particular above 40 0 C, z. B. to a temperature in the range of 40 to 100 0 C to accelerate the formation of the anhydride. However, heating is not required.
  • the anhydride of the non-polymerizable carboxylic acid will be present in an amount of at least 0.3 mol, often in an amount of at least 0.5 mol, e.g. B. in an amount of 0.3 to 10 mol and in particular in an amount of 0.5 to 3 mol and especially in an amount of 0.5 to 1 mol, per mole of vinyl phosphonic use. Zen.
  • This reaction product can be used immediately without further purification in the polymerization process according to the invention.
  • the anhydride can also be prepared in situ by, for example, forming the anhydride or the acylated anhydride of the vinylphosphonic acid by reacting vinylphosphonic acid with the anhydride of a nonpolymerizable carboxylic acid in the polymerization reactor, followed by copolymerization of the monomers a and b and optionally further monomers. This procedure is particularly useful when carrying out the copolymerization in the anhydride of a non-polymerizable carboxylic acid as a solvent.
  • the monomers a d. H. the anhydride or anhydride derivative of the vinylphosphonic acid or a mixture of vinylphosphonic acid and its anhydride or anhydride derivative, copolymerized together with comonomers.
  • comonomers ethylenically unsaturated monomers, in particular monoethylenically unsaturated monomers, which are also referred to below as monomers b.
  • the proportion of monomers a is generally at least 0.01% by weight, frequently at least 0.1% by weight, in particular at least 0.5% by weight. and especially at least 1% by weight and may be up to 95% by weight. Frequently, however, it will not exceed 90% by weight, in particular 80% by weight and especially 50% by weight.
  • the proportion of comonomers (monomers b) is generally at least 5 wt .-%, often at least 10 wt .-%, in particular at least 20 wt .-% and especially at least 50 wt .-%, z. B. in the range of 5 to 99.99% by weight, often 10 to 99.9 wt .-%, in particular 20 to 99.5 wt .-% and especially 50 to 99 wt .-%, each based on the total amount.
  • a first preferred embodiment relates to the preparation of copolymers of vinylphosphonic acid with a low content of polymerized monomers a).
  • the monomers a make up 0.01 to 30% by weight, frequently 0.1 to 20% by weight, in particular 0.5 to 15% by weight and especially 1 to 10% by weight of the Automatmenge of the monomers in the monomer to be polymerized from.
  • the proportion of monomers b in the monomer composition is usually at least 70% by weight and often at least 80% by weight.
  • Another, likewise preferred embodiment of the invention relates to the preparation of copolymers of vinylphosphonic acid with a content of copolymerized monomers a of from 10 to 90% by weight, in particular from 20 to 80% by weight and especially from 70 to 30% by weight
  • the monomers b are usually from 10 to 90% by weight, in particular from 20 to 80% by weight and especially from 30 to 70% by weight, based on the total amount of the monomers in the monomer composition to be polymerized.
  • Suitable monomers b) are in principle all monoethylenically unsaturated compounds which are known to be free-radically polymerizable, but also conjugated diethylenically unsaturated compounds having a limited water solubility, which according to the invention not more than 50 g / L, in particular not more than 30 g / L at 25 0 C is.
  • hydrophobic monomers having a limited water solubility of typically not more than 50 g / L are:
  • vinyl aromatic monomers such as styrene, ⁇ -methylstyrene
  • Alkanols, Cs-Cs-cycloalkanols, phenyl-C 1 -C 4 -alkanols or phenoxy-C 1 -C 4 -alkanols for example esters of acrylic acid with C 1 -C 20 -alkanols, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate and stearyl acrylate, esters of acrylic acid with Cs -docycloalkanols such as cyclohexyl acrylate, esters of acrylic acid with phenyl-C 1 -C 4 -alkanols such as benzyl acrylate, 2-phenylethyl acrylate and 1-phenylethyl acryl
  • C 1 -C 4 -alkanols such as 2-phenoxyethyl acrylate, esters of methacrylic acid with C 1 -C 20 -alkanols, preferably C 1 -C 10 -alkanols, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, Ethylhexylmethacrylat, decyl methacrylate, lauryl methacrylate and stearyl methacrylate, esters of methacrylic acid with Cs-do-cycloalkanols such as cyclohexyl methacrylate, esters of methacrylic acid with phenyl Ci-C4-alkanols such as benzyl methacrylate, 2-phenylethyl methacrylate and 1-phenylethyl
  • C 1 -C 20 -alkylamides and di-C 1 -C 20 -alkylamides monoethylenically unsaturated C 3 -C 8 -monocarboxylic acids in particular the C 1 -C 20 -alkylamides and di-C 1 -C 20 -alkylamides of acrylic acid and of methacrylic acid;
  • Vinyl esters of aliphatic carboxylic acids having 1 to 20 carbon atoms for. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl laurate and vinyl stearate; C 2 -C 10 -olefins such as ethylene, propene, 1-butene, 2-butene, isobutene, 1-hexene, 1-octene, diisobutene, 1-decene or 1-dodecene; - conjugated diolefins such as butadiene and isoprene, as well
  • Halovinyl compounds such as chloroethene (vinyl chloride), 1,1-dichloroethene (vinylidene chloride), fluoroethene, 1,1-difluoroethene and tetrafluoroethene.
  • Examples of preferred monomers b are:
  • esters of acrylic acid with C 1 -C 20 -alkanols such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate and stearyl acrylate, esters of acrylic acid with C 2 -C 10 cycloalkanols such as cyclohexyl acrylate, esters of acrylic acid with phenyl-C 1 -C 4 -alkanols such as benzyl acrylate, 2-phenylethyl acrylate and 1-phenylethyl acrylate, esters of acrylic acid with phenoxy-C 1 -C 4 -alkanols such as 2-phenoxyethyl acrylate, esters of me
  • C 1 -C 4 -alkanols such as 2-phenoxyethyl methacrylate
  • Vinyl esters of aliphatic carboxylic acids having 1 to 20 carbon atoms for. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl laurate and vinyl stearate; C2-C olefins such as ethylene, propene, 1-butene, 2-butene, isobutene, 1-hexene, 1-octene, diisobutene, 1-decene; and conjugated diolefins such as butadiene and isoprene.
  • C2-C olefins such as ethylene, propene, 1-butene, 2-butene, isobutene, 1-hexene, 1-octene, diisobutene, 1-decene
  • conjugated diolefins such as butadiene and isoprene.
  • the vinylaromatic monomers the abovementioned esters of acrylic acid and of methacrylic acid, in particular the esters of acrylic acid and of methacrylic acid with C 1 -C 20 -alkanols, are particularly preferred.
  • the monomers to be polymerized may also comprise hydrophilic monomers, ie those having an increased water solubility of generally at least 50 g / L at 25 ° C., in particular at least 80 g / L (monomers c). Examples of hydrophilic monomers c having an increased water solubility of generally at least 50 g / L at 25 ° C. are:
  • monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 8 C atoms such as acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, - amides of monoethylenically unsaturated carboxylic acids, such as acrylamide or methacrylamide,
  • Anhydrides monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 8 carbon atoms such as maleic anhydride, hydroxyl C 2 -C 4 -alkyl esters of monoethylenically unsaturated mono- or dicarboxylic acids having 3 to 8 carbon atoms, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
  • N-vinyl heterocycles such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole and monoethylenically unsaturated compounds having a poly-C 2 -C 4 -alkylene oxide group, for example vinyl and allyl ethers of poly-C 2 -C 4 -alkylene glycols or C 1 -C 10 -alkyl
  • Poly-C2-C4-alkylene glycols esters of monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 8 carbon atoms with poly-C2-C4-alkylene glycols or Ci-Cio-alkyl-poly-C2-C4-alkylene glycols.
  • Preferred monomers c are:
  • monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 8 C atoms in particular acrylic acid, methacrylic acid and itaconic acid, amides of monoethylenically unsaturated carboxylic acids having 3 to 8 C atoms, in particular acrylamide and methacrylamide, Hydroxy-C 2 -C 4 -alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 8 carbon atoms, in particular hydroxy-C 2 -C 4 -alkyl esters of acrylic acid and of methacrylic acid, the abovementioned monoethylenically unsaturated sulfonic acids, - acrylonitrile and monoethylenically unsaturated compounds having a poly-C 2 -C 4 -alkyl ester C4-alkylene oxide group, in particular the esters of acrylic acid and methacrylic acid with poly-C 2 -C 4 -alkylene glycols,
  • the monomers to be polymerized comprise 0.01 to 30 wt .-%, in particular 0.1 to 20 wt .-% or 0.5 to 15 wt .-% of such monomers c), each based on the total amount of monomer.
  • the total amount of monomers a + c will not exceed 90% by weight, especially 80% by weight and especially 70% by weight and at least 0.02% by weight, often at least 0.2% by weight and specifically at least 1 wt .-% amount.
  • the monomers b from 10 to 99.98 wt .-%, often 20 to 99.8 wt .-%, in particular 30 to 99 wt .-%, each based on the total amount of monomer, from.
  • a further preferred embodiment relates to the preparation of copolymers of vinylphosphonic acid with a low content of polymerized monomers a and c.
  • the monomers a + c from 0.02 to 30 wt .-%, often 0.2 to 20 wt .-%, in particular 0.5 to 15 wt .-% and especially 1 to 10 wt .-% of Total amount of monomers in the monomer composition to be polymerized from.
  • the proportion of monomers b in the monomer composition is generally 70 to 99.98% by weight, frequently at least 80 to 99.8% by weight, in particular 85 to 99.5% by weight and especially 90 to 99% by weight.
  • Another, likewise preferred embodiment of the invention relates to the preparation of copolymers of vinylphosphonic acid with a content of polymerized monomers a + c of from 10 to 90% by weight, in particular from 20 to 80% by weight and especially from 70 to 30% by weight. -%.
  • the monomers b are usually from 10 to 90 wt .-%, in particular 20 to 80 wt .-% and especially 30 to 70 wt .-%, based on the total amount of the monomers in the monomer composition to be polymerized from ,
  • crosslinkers or monomers d
  • these are diesters and triesters of ethylenically unsaturated carboxylic acids, in particular the bis- and trisacrylates of diols or polyols having 3 or more OH groups, eg. Eg the bi sacrylate and the bismethacrylates of ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol or polyethylene glycols.
  • Such crosslinkers are, if desired, used in an amount of generally 0.01 to 10 wt .-% based on the total amount of the monomers to be polymerized.
  • the polymerization is carried out as a solution or precipitation polymerization.
  • the polymerization process in a solvent or diluent as a polymerization medium.
  • precipitation polymerization it is an organic solvent or diluent in which the copolymer is insoluble.
  • solution polymerization it is typically an organic solvent in which the copolymer is soluble.
  • Suitable solvents or diluents are, in particular, those solvents or solvent mixtures which contain no or only small amounts of water.
  • the amount of water is preferably not more than 2% by weight, often not more than 1% by weight, especially not more than 0.5% by weight and especially not more than 0.1 wt .-%.
  • the amount of water, based on the monomer a is not more than 10 wt .-%, often not more than 5 wt .-%, in particular not more than 2 wt .-% and especially not more than 1 wt. -%.
  • Suitable solvents or diluents are in particular those in which the monomers to be polymerized are soluble. It is also possible to polymerize in organic solvents in which monomers are not soluble. The polymerization is then carried out as an oil-in-oil emulsion or suspension polymerization wherein, depending on the proportions of polymer and organic solvent, the monomers form the coherent phase or preferably the disperse phase.
  • Preferred solvents and diluents are aprotic organic solvents and non-polymerizable aliphatic carboxylic acids having preferably 1 to 4 carbon atoms such as formic acid, acetic acid and propionic acid and mixtures thereof with aprotic organic solvents.
  • Suitable solvents include in particular aliphatic and cycloaliphatic hydrocarbons and halogenated hydrocarbons such as hexane, heptane, cyclohexane, dichloromethane, dichloroethane, aromatic hydrocarbons and aromatic halogenated hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, the abovementioned anhydrides of aliphatic, non-polymerizable carboxylic acids such as acetoanhydride , C 1 -C 6 -alkyl esters and C 5 -C 6 -cycloalkyl esters of aliphatic monocarboxylic acids having 1 to 4 C atoms, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl propionate,
  • butyl ether, dioxane and tetrahydrofuran and mixtures of the aforementioned aprotic solvents are also suitable.
  • non-polymerizable aliphatic carboxylic acids having 1 to 4 carbon atoms such as formic acid, acetic acid and propionic acid and mixtures thereof with the abovementioned aprotic organic solvents.
  • the organic solvent will be such that the monomers to be polymerized, based on the total amount of monomer plus solvent, in the range of 10 to 65 wt .-%, in particular in the range of 20 to 60% by weight. lies.
  • a solution polymerization accordingly, polymer solutions having solids contents in the range from 10 to 80% by weight and in particular from 20 to 60% by weight are obtained.
  • the polymerization is carried out as so-called suspension polymerization.
  • an aqueous monomer emulsion i. H. an emulsion of the monomers a, b and optionally further monomers in water, subjected to a radical polymerization in the presence of suitable stabilizers.
  • Diluent here is water or a mixture of water with up to 10 vol .-%, preferably not more than 1 vol .-% or 0.1 vol .-%, based on the amount of water, of organic solvents.
  • the polymerization takes place in the monomer droplets of the monomer emulsion.
  • the monomer droplets are dissolved in the monomer emulsion by suitable surfactants, i. H. Emulsifiers, protective colloids or mixtures thereof, stabilized.
  • Suitable surface-active substances are the emulsifiers and protective colloids customarily used for the suspension polymerization and also so-called pickering systems.
  • this suspension polymerization is carried out in the presence of at least one organic protective colloid and / or suspending agent such as pickering systems.
  • Surface-active substances are typically used in amounts of 0.2 to 15% by weight, preferably 0.5 to 10% by weight, based on the monomers to be polymerized.
  • Suitable protective colloids for stabilizing the monomer droplets in the suspension polymerization are organic, water-soluble polymers, including partially saponified polyvinyl acetates, starch and cellulose derivatives, carboxyl group-containing polymers such as homo- and copolymers of acrylic acid and / or methacrylic acid with comonomers such as styrene, olefins or hydroxyalkyl esters, vinylpyrrolidone-containing homopolymers and copolymers, caseins, hydroxymethylcellulose, polyethers such as polyethylene oxides, ethylene oxide / propylene oxide block copolymers.
  • organic, water-soluble polymers including partially saponified polyvinyl acetates, starch and cellulose derivatives, carboxyl group-containing polymers such as homo- and copolymers of acrylic acid and / or methacrylic acid with comonomers such as styrene, olefins or hydroxyalkyl esters, vinylpyrrol
  • Protective colloids unlike conventional emulsifiers, typically have a molecular weight above 2000 g / mol (number average). A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart 1961, pp. 411-420. Mixtures of emulsifiers and / or protective colloids can also be used.
  • So-called Pickering systems which stabilize the oil-in-water emulsion are fine solid particles, typically inorganic particles, which are insoluble in water but dispersible or are neither soluble nor dispersible in water, but are wettable by the lipophilic substance.
  • the inorganic solid particles may be metal salts such as sulfates, carbonates, sulfates, silicates, oxalates, phosphates, oxides and hydroxides of calcium, magnesium, iron, zinc, nickel, titanium, aluminum, silicon, barium and manganese. Mention may be made of magnesium hydroxide, magnesium carbonate, magnesium oxide, calcium oxalate, calcium carbonate, barium carbonate, barium sulfate, titanium dioxide, silicon dioxide, aluminum oxide, aluminum hydroxide and zinc sulfide. Silicates, bentonite, hydroxyapatite and hydrotalcites are also mentioned.
  • the size data relate to the z-average of the colloid dispersion used, determined by means of light scattering.
  • a Pickering system can consist of the solid particles alone or in addition of auxiliaries which improve the dispersibility of the particles in water or the wettability of the particles by the lipophilic phase.
  • auxiliaries which improve the dispersibility of the particles in water or the wettability of the particles by the lipophilic phase.
  • These aids are e.g. nonionic, anionic, cationic or zwitterionic surfactants (emulsifiers) or polymeric protective colloids, as described above.
  • buffer substances can be added in order to set specific, respectively advantageous pH values of the water phase. This can reduce the water solubility of the fine particles and increase the stability of the emulsion.
  • Common buffer substances are phosphate buffer, acetate buffer and citrate buffer.
  • the Pickering systems are usually used in amounts of 0.5 to 15 wt .-%, calculated as a solid and based on the water phase.
  • the inventive radical polymerization of the monomer composition which comprises the monomers a, b and optionally further monomers (monomers c and / or d). holds, can be carried out by conventional methods of radical homo- or copolymerization.
  • the monomer composition comprising the monomers a and the monomers b, and, if appropriate, further monomers are polymerized under reaction conditions in which free radicals are formed.
  • radicals are usually carried out by using a so-called polymerization initiator, d. H. a compound that forms radicals on decomposition, which can be triggered thermally or photochemically.
  • Suitable polymerization initiators include organic azo compounds, organic peroxides and hydroperoxides, inorganic peroxides and so-called redox initiators.
  • the organic peroxide compounds include, for example, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxy-isobutyrate, caproyl peroxide.
  • the hydroperoxides also include organic hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide and the like.
  • the azo compounds include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 1, 1 'Azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) 2,2'-azobis (N, N'-dimethyleneisobutyro - amidine), 2,2'-azobis (2-methylpropioamidine), N- (3-hydroxy-1, 1-bis-hydroxymethyl-propyl) -2- [1 - (3-hydroxy-1, 1-bis) hydroxymethyl-propylcarbamoyl) -1-methyl-ethylazo] -2-methyl-propionamide, and N- (1-ethyl-3-hydroxypropyl) -2- [1-
  • the inorganic peroxides include peroxodisulfuric acid and its salts, such as ammonium, sodium and potassium peroxodisulfate.
  • Redox initiator system is understood to mean initiator systems which contain an oxidizing agent, for example a salt of peroxydisulphuric acid, hydrogen peroxide or an organic peroxide such as tert-butyl hydroperoxide and a reducing agent.
  • oxidizing agent for example a salt of peroxydisulphuric acid, hydrogen peroxide or an organic peroxide such as tert-butyl hydroperoxide and a reducing agent.
  • reducing agents they preferably contain a sulfur compound, which is selected in particular from sodium hydrogen sulfite, sodium hydroxymethanesulfinate and the bisulfite adduct to acetone.
  • Suitable reducing agents are phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, as well as hydrazine or hydrazine hydrate and ascorbic acid.
  • redox initiator systems may contain an addition of small amounts of redox metal salts, such as iron salts, vanadium salts, copper salts, chromium salts or manganese salts, for example the redox initiator system ascorbic acid / iron (II) sulfate / sodium peroxodisulfate.
  • Particularly preferred initiators for the polymerization process according to the invention are azo compounds, especially azobisisobutyronitrile (AIBN).
  • these polymerization initiators are generally used in an amount of 0.01 to 5 wt .-%, in particular in an amount of 0.1 to 3 wt .-%, based on the monomers to be polymerized.
  • the usual polymerization techniques can be used.
  • the main amount ie at least 60 wt .-%, in particular at least 80 wt .-% and often the total amount of monomers to be polymerized in the polymerization are presented
  • the monomer feed in which the Main amount of the monomers to be polymerized, often at least 60 wt .-%, in particular at least 80% by weight and especially at least 90 wt .-% be added in the course of the polymerization in the polymerization.
  • the polymerization is often carried out as a monomer feed with larger batches.
  • the polymerization initiator can be introduced into the polymerization vessel or added during the polymerization reaction. Frequently, the procedure is to add at least part of the initiator, preferably at least 50% by weight and in particular at least 80% by weight, of the polymerization initiator in the course of the polymerization reaction.
  • a small portion of the monomers for. B. 0.1 to 20 wt .-%, based on the total amount of the monomers to be polymerized, optionally together with a partial amount or the total amount of polymerization onsinitiator, and to submit a part or the total amount of the solvent or diluent in the polymerization vessel, to start the polymerization, for example by heating the polymerization mixture, and then adding the remaining amount of the monomers and, if necessary, the remaining amount of polymerization initiator and solvent in the course of the polymerization.
  • the polymerization temperatures customarily used for the polymerization, depending on the initiator system chosen, are generally in the range from 20 to 180 ° C., in particular in the range from 40 to 130 ° C. and especially in the range from 50 to 120 ° C.
  • the polymerization pressure is of minor importance and can be in the range of atmospheric pressure or slight negative pressure, for. B.> 800 mbar or at overpressure, z. B. to 10 bar, with higher or lower pressures can also be applied.
  • the polymerization time will usually not exceed 10 hours and is often in the range of 1 to 8 hours.
  • the polymerization process according to the invention can be carried out in the reactors customary for free-radical polymerization, for example stirred tanks, in particular those with agitated wall stirring, including stirred tank cascades and tubular reactors, which optionally have dynamic and / or static mixing elements. have elements.
  • the reactors usually have one or more devices for supplying the reactants and devices for removing the products and optionally means for supplying and removing the heat of reaction and optionally means for controlling and / or controlling the reaction parameters pressure, temperature, conversion, etc.
  • the reactors can be operated batchwise or continuously.
  • the polymerization mixture can be worked up in the usual way.
  • the polymer can be filtered off.
  • Volatile components, such as solvents, can also be separated by distillation.
  • a solution polymerization can also bring about a precipitation of the resulting polymer, for example by adding an organic solvent in which the polymer is not soluble.
  • the resulting polymer is degassed to remove further volatiles.
  • the resulting polymer can be subjected to a hydrolytic work-up in order to hydrolyze optionally present anhydride groups or acylated groups in the copolymerized vinylphosphonic acid.
  • the hydrolysis can be carried out in a simple manner by treatment with water or dilute aqueous acids such as dilute aqueous hydrochloric acid, sulfuric acid or trifluoromethanesulfonic acid, or bases such as sodium or potassium hydroxide.
  • the polymers obtained according to the invention can be used in many ways. Due to the use of the monomers a, unlike the copolymers of the vinylphosphonic acid known from the prior art, the polymers according to the invention have only small amounts of unpolymerized vinylphosphonic acid after the polymerization reaction, which are typically less than 5% by weight, in particular less as 2 wt .-%, based on the total amount of monomers used a. Since vinylphosphonic acid generally can not be removed from the resulting polymers or only very poorly, the process according to the invention leads overall to homo- and copolymers of vinylphosphonic acid with lower residual monomer contents. Therefore, the homo- and copolymers of vinylphosphonic available according to the invention are particularly suitable for a variety of applications.
  • Example 1 Copolymer of vinylphosphonic acid and n-butyl acrylate in a molar ratio of 1: 1
  • Example 2 Preparation of a copolymer of 20 mol% of vinylphosphonic acid and 80 mol% of butyl acrylate
  • Example 3 Preparation of a copolymer of 10 mol% of vinylphosphonic acid and 90 mol% of n-butyl acrylate

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un procédé de préparation de copolymères de l'acide vinylphosphonique comprenant au moins un monomère insaturé d'un point de vue monoéthylénique ou diéthylénique conjugué ayant une solubilité dans l'eau de moins de 50 g/l à 25 °C, le procédé comprenant la polymérisation radicalaire d'une composition monomère contenant : a) de l'acide vinylphosphonique sous la forme de son anhydride ou d'un dérivé d'anhydride ou sous la forme d'un mélange d'acide vinylphosphonique et de son anhydride ou dérivé d'anhydride (monomère a); et b) au moins un monomère insaturé d'un point de vue monoéthylénique ou diéthylénique conjugué qui a une solubilité dans l'eau inférieure à 50 g/l à 25 °C (monomère b). L'invention se rapporte également aux copolymères préparés à l'aide ce procédé.
PCT/EP2008/050704 2007-01-22 2008-01-22 Procédé de préparation de copolymères de l'acide vinylphosphonique WO2008090152A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3666872A1 (fr) * 2018-12-12 2020-06-17 Henkel AG & Co. KGaA Copolymères acryliques phosphonés pour hydrophilisation de surface

Citations (5)

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Publication number Priority date Publication date Assignee Title
US3297663A (en) * 1959-11-11 1967-01-10 Hoechst Ag Vinylphosphonic acid polymers and process for making them
EP0114394A2 (fr) * 1982-12-29 1984-08-01 Hoechst Aktiengesellschaft Procédé de préparation de polymères d'acide vinyl phosphonique dans des solvants
EP0123297A2 (fr) * 1983-04-22 1984-10-31 CASSELLA Aktiengesellschaft Copolymères hydrophiles réticulés, leur préparation et leur usage
EP1059316A1 (fr) * 1999-06-10 2000-12-13 Clariant GmbH Copolymères solubles dans eau et leur utilisation pour la prospection et récupération d'huile et de gaz
WO2007080152A1 (fr) * 2006-01-09 2007-07-19 Basf Se Copolymeres, procede de production de ces copolymeres et leur utilisation pour traiter des surfaces

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Publication number Priority date Publication date Assignee Title
US3297663A (en) * 1959-11-11 1967-01-10 Hoechst Ag Vinylphosphonic acid polymers and process for making them
EP0114394A2 (fr) * 1982-12-29 1984-08-01 Hoechst Aktiengesellschaft Procédé de préparation de polymères d'acide vinyl phosphonique dans des solvants
EP0123297A2 (fr) * 1983-04-22 1984-10-31 CASSELLA Aktiengesellschaft Copolymères hydrophiles réticulés, leur préparation et leur usage
EP1059316A1 (fr) * 1999-06-10 2000-12-13 Clariant GmbH Copolymères solubles dans eau et leur utilisation pour la prospection et récupération d'huile et de gaz
WO2007080152A1 (fr) * 2006-01-09 2007-07-19 Basf Se Copolymeres, procede de production de ces copolymeres et leur utilisation pour traiter des surfaces

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Title
ARCUS C L ET AL: "Solution properties of a styrene-vinylphosphonic acid copolymer", CHEMISTRY AND INDUSTRY, SOCIETY OF CHEMICAL INDUSTRY, LONDON, GB, 12 July 1958 (1958-07-12), pages 890 - 891, XP008090157, ISSN: 0009-3068 *
BAHAR BINGOL ET AL: "Synthesis, Microstructure, and Acidity of Poly(vinylphosphonic acid)", MACROMOLECULAR: RAPID COMMUNICATIONS, WILEY VCH VERLAG, WEINHEIM, DE, vol. 27, 2006, pages 1719 - 1724, XP007904477, ISSN: 1022-1336 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3666872A1 (fr) * 2018-12-12 2020-06-17 Henkel AG & Co. KGaA Copolymères acryliques phosphonés pour hydrophilisation de surface

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