WO2008090153A2 - Procédé de préparation d'homopolymères et de copolymères de l'acide vinylphosphonique - Google Patents

Procédé de préparation d'homopolymères et de copolymères de l'acide vinylphosphonique Download PDF

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WO2008090153A2
WO2008090153A2 PCT/EP2008/050705 EP2008050705W WO2008090153A2 WO 2008090153 A2 WO2008090153 A2 WO 2008090153A2 EP 2008050705 W EP2008050705 W EP 2008050705W WO 2008090153 A2 WO2008090153 A2 WO 2008090153A2
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monomers
anhydride
acid
vinylphosphonic acid
polymerization
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PCT/EP2008/050705
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German (de)
English (en)
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WO2008090153A3 (fr
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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
    • 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

Definitions

  • the present invention relates to a process for the preparation of homopolymers and copolymers of vinylphosphonic acid with a copolymerized vinylphosphonic acid content of at least 30% by weight, based on the total weight of the homo- or copolymer.
  • the invention also relates to the homo- and 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 and the like , Due to their high water solubility and biocompatibility, P (PVA) and copolymers with a high content of vinylphosphonic acid are suitable as additives in galenics, for example for the solubilization of active ingredients, as well as for orthopedic applications and for the production of synthetic cartilage and bone material.
  • P (PVA) and copolymers with a high content of vinylphosphonic acid are suitable as additives in galenics, for example for the solubilization of active ingredients, as well as for orthopedic applications and for the production of synthetic cartilage and bone material.
  • 3,297,663 describes a process for preparing homopolymers of vinylphosphonic acid or its salts in which vinylphosphonic acid or a salt of vinylphosphonic acid in an organic solvent which does not dissolve the polymer which forms is polymerized in the presence of a polymerization initiator by the precipitation polymerization method becomes.
  • 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. There are described only copolymers with a low content of copolymerized vinylphosphonic.
  • the present invention is therefore based on the object to provide a process for the preparation of homo- and copolymers of vinyl phosphonic acid with a content of copolymerized vinyl phosphonic acid of at least 30 wt .-%, which is easy to control and to produce high molecular weight 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.
  • this invention relates to a process for the preparation of homopolymers and copolymers of vinylphosphonic acid with a copolymerized vinylphosphonic acid content of more than 30 wt .-%, based on the total weight of the homo- or copolymer, comprising the radical polymerization of a monomer composition which, based on the total amount of monomers in the monomer 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, CrC 4 -Akoxy, 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.
  • 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 resulting homo- and copolymers 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 especially 100,000 to 1,000,000 daltons (weight average, determined by light scattering or viscometry).
  • the molecular weight can also be determined by 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 wt .-% solutions of the respective polymer 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 processes described in SU 174625, EP-A 2733, EP-A 15483, EP-A 32663 and US 2632768 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 procedure will generally be such that vinylphosphonic acid is reacted with the anhydride of the nonpolymerizable carboxylic acid, for example by reacting vinylphosphonic acid with the anhydride of the nonpolymerizable carboxylic acid, optionally with the addition of a inert organic solvent, mixed.
  • vinylphosphonic acid is reacted with the anhydride of the nonpolymerizable carboxylic acid, optionally with the addition of a inert organic solvent, mixed.
  • 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.
  • 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 vinylphosphonic use.
  • 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 reaction of vinylphosphonic acid with the anhydride of a nonpolymerizable carboxylic acid in the polymerization reactor, followed by homo- or copolymerization the monomers a and optionally further monomers. This procedure is particularly useful when carrying out the polymerization 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, are polymerized as such. Homopolymers of the vinylphosphonic acid or of the vinylphosphonic acid derivatives are obtained in this way, the latter being able to be converted into the polyvinylphosphonic acid by a simple hydrolytic work-up.
  • comonomers are ethylenically unsaturated monomers, in particular monoethylenically unsaturated monomers, which are also referred to below as monomers b.
  • the proportion of monomers a based on the total amount of the monomers to be polymerized, more than 30 wt .-%, in particular at least 35 wt .-%. Accordingly, the proportion of comonomers (monomers b will not exceed 70% by weight and in particular 65% by weight.
  • a first preferred embodiment relates to the preparation of homopolymers of vinylphosphonic acid or the preparation of copolymers with a low content of comonomers.
  • the monomers a constitute 95 to 100% by weight of the total amount of the monomers in the monomer composition to be polymerized. Accordingly, the proportion of monomers b in the monomer composition is not more than 5% by weight.
  • Another, likewise preferred embodiment of the invention relates to the preparation of copolymers of vinylphosphonic acid with a content of copolymerized monomers b of from 5 to 70% by weight, in particular from 10 to 65% by weight.
  • the monomers a constitute from 30 to 95% by weight, in particular from 35 to 90% by weight, based on the total amount of the monomers in the monomer composition to be polymerized.
  • the monomers b constitute from 5 to 70% by weight, and more preferably from 10 to 65% by weight, based on the total amount of the monomers in the monomer composition.
  • Suitable monomers b are in principle all monoethylenically unsaturated compounds which, as is known, can be polymerized by free-radical polymerization, but also conjugated diethylenically unsaturated compounds.
  • the monomers b include hydrophilic monomers, ie those having an increased water solubility of generally at least 50 g / L (monomers b1), but also hydrophobic monomers having a low water solubility of generally less than 50 g / L at 25 ° C. , hereinafter monomers b2.
  • hydrophilic monomers b1 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,
  • C atoms such as maleic anhydride, hydroxyl C 2 -C 4 -alkyl esters of monoethylenically unsaturated mono- or dicarboxylic acids having 3 to 8 C atoms, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, - monoethylenically unsaturated sulfonic acids and their salts, eg.
  • the comonomers b comprise at least 80% by weight, in particular at least 90% by weight, based on the total amount of the monomers b, of at least one such hydrophilic monomer b1 having a water solubility of at least 50 g / l at 25 ° C has.
  • Preferred monomers b1 are: monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 8 C atoms, in particular acrylic acid, methacrylic acid and itaconic acid,
  • Methacrylic acid the abovementioned monoethylenically unsaturated sulfonic acids
  • Acrylonitrile and monoethylenically unsaturated compounds having a poly-C 2 -C 4 -alkylene oxide group in particular the esters of acrylic acid and methacrylic acid with poly-C 2 -C 4 -alkylene oxide
  • Ci-Cio-alkyl-poly-C2-C4-alkylene glycols are Ci-Cio-alkyl-poly-C2-C4-alkylene glycols.
  • hydrophobic monomers b2 having a limited water solubility of usually not more than 50 g / L are:
  • vinyl aromatic monomers such as styrene, ⁇ -methylstyrene
  • C 1 -C 20 -alkanols C 1 -C -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
  • 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, acrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, 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-
  • Diesters monoethylenically unsaturated C4-Cs-dicarboxylic acids with C1-C20 alkanols such as diesters of maleic acid or fumaric acid with C1-C20 alkanols, eg. Dimethyl maleate, diethyl maleate, di-n-butyl maleate, dimethyl fumarate, diethyl fumarate and di-n-butyl fumarate;
  • C 1 -C 20 -alkylamides and di-C 1 -C 20 -alkylamides monoethylenically unsaturated C 3 -C 5 -monocarboxylic acids in particular the C 1 -C 20 -alkylamides and di-C 1 -C 20 -alkylamides of acrylic acid and of methacrylic acid, eg. B. and vinyl esters of aliphatic carboxylic acids having 1 to 20 carbon atoms, for.
  • C 2 -C 10 -olefins such as ethylene, propene, 1-butene, 2-butene, isobutene, 1-hexene, 1-octene,
  • the comonomers b comprise at least 80% by weight, in particular at least 90% by weight, based on the total amount of the monomers b, of at least one such hydrophobic monomer b2 having a water solubility of less than 50 g / L at 25 0 C has.
  • preferred monomers b2 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 Cs-Cio Cycloalkanols such as cyclohexyl acrylate, esters of acrylic acid with phenyl-Ci-C4-alkanols such as benzyl acrylate, 2-phenylethyl acrylate and 1-phenylethyl acrylate, esters of acrylic acid with phenoxy-Ci-C4-alkanols such
  • 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, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate and stearyl methacrylate, 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, 2-ethy
  • Cs-Cio-cycloalkanols such as cyclohexyl methacrylate, esters of methacrylic acid with phenyl-Ci-C4-alkanols such as benzyl methacrylate, 2-phenylethyl methacrylate and 1-phenylethyl methacrylate, and esters of methacrylic acid with phenoxy-Ci-C4-alkanols such as 2-phenoxyethyl methacrylate; Vinyl esters of aliphatic carboxylic acids having 1 to 20 carbon atoms, for.
  • C2-Cio-olefins such as ethylene, propene, 1-butene, 2-butene, isobutene, 1-hexene, 1-octene, diisobutene, 1-decene
  • conjugated diolefins such as butadiene and isoprene.
  • crosslinker examples thereof are diesters and triesters of ethylenically unsaturated carboxylic acids, in particular the bis- and tris-acrylates of diols or polyols having 3 or more OH groups, eg.
  • crosslinkers are used in an amount of generally 0.01 to 10% by weight, based on the total amount of monomers to be polymerized.
  • the polymerization process is carried out in a non-aqueous solvent or diluent as the polymerization medium.
  • the polymerization is carried out in a solvent or diluent in the sense of a solution or precipitation polymerization which contains 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 monomers a is not more than 10% by weight, frequently not more than 5% by weight, in particular not more than 2% by weight and especially not more than 1% by weight.
  • 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.
  • 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.
  • 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 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 3 -C 6 -cycloalkyl esters of aliphatic monocarboxylic acids having 1 to 4 carbon atoms, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl propionate,
  • 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 wt .-% 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 inventive radical polymerization of the monomer composition containing at least 30 wt .-% of the monomers a can be carried out by conventional methods of radical homo- or copolymerization.
  • the monomer composition containing the monomers a and optionally other monomers will polymerize under reaction conditions in which radicals form.
  • the formation of the radicals is generally carried out by using a so-called polymerization initiator, ie a compound which forms radicals on decomposition, which can be initiated 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 (2-methylpropioamidine), N- (3-hydroxy-1,1-bis-hydroxymethylpropyl) -2- [1- (3-hydroxy-1,1-bis-hydroxymethyl-propylcarbamoyl) -1-methyl-ethylazo]
  • 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 comprise an oxidizing agent, for example a salt of peroxodisulfuric acid, hydrogen peroxide or an organic peroxide such as tert-butyl hydroperoxide and a reducing agent.
  • oxidizing agent for example a salt of peroxodisulfuric 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 can contain additions 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 the monomers to be polymerized are placed in the polymerization vessel, and the monomer feed, wherein 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.
  • the reactors generally have one or more devices for supplying the starting materials and devices for removing the products and, if appropriate, means for supplying and removing the heat of reaction and, if appropriate, 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 for example solvents, can also be removed by distillation.
  • a solution poly- Merisation can also bring about a precipitation of the resulting polymer, for example by adding an organic solvent in which the polymer is insoluble.
  • 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 a variety of ways. Due to the use of the monomers a, the polymers according to the invention, unlike the homopolymers and copolymers of the vinylphosphonic acid known from the prior art, have only small amounts of unpolymerized vinylphosphonic acid after the polymerization reaction, which are typically less than 5% by weight. , in particular less than 2 wt .-%, based on the total amount of monomers used a. Since vinylphosphonic acid can generally not be removed from the resulting polymers or can only be removed with great difficulty, the process according to the invention leads overall to homopolymers 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.
  • the 31 P NMR spectra were recorded using a Bruker DRX 500 NMR spectrometer.
  • Relative viscosities were recorded using an Ubbelohde viscometer at 25 ° C. using capillaries 0a and 0c. 1% strength by weight solutions of the respective polymer in 0.5 N aqueous NaCl solution (homopolymers) or dimethyl sulfoxide (copolymers) were used, which were filtered before the measurement. Examination of the molecular weight by light scattering was carried out using a Sica 50 apparatus using a laser having a wavelength of 632 nm at an angle of 15 ° to 145 °.
  • Example 2 Copolymer of vinylphosphonic acid and n-butyl acrylate in a molar ratio of 1: 1
  • the product was subsequently dried in vacuo at 60 ° C. for 14 hours.
  • Example 3 Copolymer of vinylphosphonic acid and acrylic acid in the molar ratio 3: 7
  • vinylphosphonic acid was polymerized in water at a monomer concentration of 43% by weight and worked up. Instead of AIBN, an equimolar amount of 2,2'-azobis (2-methylpropioamidine) was used. The conversion of vinylphosphonic acid was 79%, the viscosity of the product obtained was 0.09 dL / g.
  • vinylphosphonic acid was polymerized in water at a monomer concentration of 70% by weight and worked up. Instead of AIBN, an equimolar amount of 2,2'-azobis (2-methylpropioamidine) was used. The conversion of vinylphosphonic acid was 94%, the viscosity of the product obtained was 0.40 dL / g.

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Abstract

La présente invention concerne un procédé de préparation d'homopolymères et de copolymères de l'acide vinylphosphonique ayant une teneur en acide vinylphosphonique monopolymérisé d'au moins 30 % en poids rapportés au poids total de l'homopolymère ou du copolymère, le procédé comprenant la polymérisation radicalaire d'une composition monomère contenant, rapportés au poids total des monomères contenus dans la composition monomère : a) > 30 % en poids d'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) < 70 % en poids d'au moins un monomère éthyléniquement insaturé, différent de l'acide vinylphosphonique (monomère b), la polymérisation étant réalisée dans un solvant ou un diluant non aqueux. L'invention se rapporte également aux homopolymères et copolymères préparés à l'aide ce procédé.
PCT/EP2008/050705 2007-01-22 2008-01-22 Procédé de préparation d'homopolymères et de copolymères de l'acide vinylphosphonique WO2008090153A2 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019167482A (ja) * 2018-03-26 2019-10-03 国立大学法人福井大学 ポリビニルホスホン酸の製造方法
EP3670553A1 (fr) * 2018-12-18 2020-06-24 Evonik Operations GmbH Copolymères greffés et leur procédé de production
CN113206252A (zh) * 2021-04-29 2021-08-03 华南理工大学 一种大豆蛋白基多功能双链交联硫正极水性粘结剂及其制备方法与应用

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019167482A (ja) * 2018-03-26 2019-10-03 国立大学法人福井大学 ポリビニルホスホン酸の製造方法
JP7075583B2 (ja) 2018-03-26 2022-05-26 国立大学法人福井大学 ポリビニルホスホン酸の製造方法
EP3670553A1 (fr) * 2018-12-18 2020-06-24 Evonik Operations GmbH Copolymères greffés et leur procédé de production
WO2020126811A1 (fr) * 2018-12-18 2020-06-25 Evonik Operations Gmbh Copolymères greffés et procédé destiné à leur fabrication
CN113206252A (zh) * 2021-04-29 2021-08-03 华南理工大学 一种大豆蛋白基多功能双链交联硫正极水性粘结剂及其制备方法与应用
CN113206252B (zh) * 2021-04-29 2022-07-26 华南理工大学 一种大豆蛋白基多功能双链交联硫正极水性粘结剂及其制备方法与应用

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