EP1539842A1 - Nouveaux esters polyvinyliques - Google Patents

Nouveaux esters polyvinyliques

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Publication number
EP1539842A1
EP1539842A1 EP03792316A EP03792316A EP1539842A1 EP 1539842 A1 EP1539842 A1 EP 1539842A1 EP 03792316 A EP03792316 A EP 03792316A EP 03792316 A EP03792316 A EP 03792316A EP 1539842 A1 EP1539842 A1 EP 1539842A1
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EP
European Patent Office
Prior art keywords
different
same
integer
carbon
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03792316A
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German (de)
English (en)
Inventor
Jörg Ludwig SCHULTE
Jörg SCHOTTEK
Tim Dickner
Werner Wiltschka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Celanese Ventures GmbH
Original Assignee
Celanese Ventures GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2003127511 external-priority patent/DE10327511A1/de
Application filed by Celanese Ventures GmbH filed Critical Celanese Ventures GmbH
Publication of EP1539842A1 publication Critical patent/EP1539842A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/04—Vinyl esters
    • C08F18/08—Vinyl acetate
    • 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
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/04—Vinyl esters
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • 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
    • C08F2438/00—Living radical polymerisation

Definitions

  • the present invention relates to polymers with special geometries based on polyvinyl esters and a method for producing polymers with special geometries based on polyvinyl esters.
  • Polyvinyl esters are polymers with the grouping that are accessible from vinyl esters
  • Polyvinyl acetate is an important thermoplastic polymer and is used, among other things, as an adhesive (component), paint raw material, for packaging films, for the coating of paper and food (sausage and cheese coatings), as an additive for concrete and as a raw material for the production of polyvinyl alcohols and polyvinyl acetals used (Römpp Lexikon Chemie - Version 2.0, Stuttgart / New York: Georg Thieme Verlag 1999).
  • polyvinyl acetate is produced by free radical polymerizations, the polymerization being able to be carried out in solution, in bulk and in emulsion.
  • Azoisobutyronitrile and dibenzoyl peroxide (AIBN / BPO) are mainly used as radical initiators. Since these radical polymerization proceed rapidly and uncontrollably, a stereodifferentiation is ruled out and control the molecular weight and molecular weight distribution very difficult (W. Daniels in. Kirk-Othmer encycl Chem Technol, 3rd Ed 1983, 23, 817-... 847).
  • polyvinyl acetates Due to the restriction to free radical polymerization of vinyl acetate, it has not yet been possible to use polyvinyl acetates with special To synthesize geometries such as star-shaped, comb-shaped or ladder-shaped polyvinyl acetate with a narrow molecular weight distribution. Polymers with these special geometries based on other monomers are used, for example, in the production of fibers, films and moldings, as gel formers, as rubber, for the controlled release of active ingredients, as
  • Polymer properties consist of the so-called "ATRP” (Atom Transfer Radical Polymerization) of monomers, which can be carried out metal-catalyzed (WO9630421).
  • a redox reaction of a metal with an initiator reversibly forms a radical which a monomer incorporates to form a new radical Ideally, the newly formed radical is in equilibrium with the metal again through a redox reaction.
  • This control gives defined polymers with narrow molecular weight distributions and a defined molecular weight (K. Matyjaszewski, J. Xia, Chem. Rev. 2001; 101 ( 12), 2921-2990.).
  • the present invention relates to initiator systems for the preparation of polyvinyl esters containing at least one compound of the formula I, at least one metal compound of the formula II and optionally at least one additive of the formula III:
  • Formula III wherein: represents a central atom and an atom of the 13th to 16th group of the
  • Periodic table of the elements preferably carbon, silicon, nitrogen,
  • Phosphorus oxygen or sulfur, particularly preferably carbon or
  • X 1 is in each case the same or different, and a halogen atom, preferably fluorine,
  • R ⁇ is the same or different and is a bridging C-, - C 20 carbon-containing
  • R ⁇ is the same or different and means carbon or silicon
  • R 4 is the same or different and is a hydrogen atom or a Ci - C 20 carbon-containing group
  • R 5 is the same or different and represents hydrogen or a Ci - C 2 o - carbon-containing group
  • I is a whole natural number and represents zero, 1, 2 or 3, and m is in each case identical or different and is a whole natural number and stands for zero, 1, 2, 3, 4 and 5, and n is in each case identical or different and is an integer and is zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20, and o is the same or different and 1 or 2
  • p is the same or different and is an integer and stands for 1, 2, 3, 4 and 5, and q is an integer and stands for 2, 3 and 4, and M 1 is in each case identical or different and a transition metal of the 3rd to 12th
  • X 2 is in each case the same or different and is oxygen or a halogen atom, particularly preferably fluorine, chlorine, bromine or iodine, and
  • L is in each case the same or different and is a ligand, preferably a carbon-containing ligand such as e.g. Methyl, phenyl, cymene, cumene, tolyl, mesityl, xylyl, indenyl benzylidene, cyclopentadienyl or carbonyl, a nitrogen-containing ligand, such as e.g.
  • Triethylamine tetramethylethylene diamine, pyridine, 2,2'-bipyridyl, substituted 2,2'-bipyridyl, 1, 10-phenanthroline, phenylpyridin-2-yl-methylenamine, acetonitrile, substituted imidazolidine or terpyridyl, a phosphorus-containing ligand, e.g. Triphenylphosphine, tricyclohexylphosphine, bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane or BINAP, and each r is the same or different and is an integer and is 1,
  • M 2 is the same or different and is an element of the 1st to 15th group of the periodic table of the elements, particularly preferably Li, Mg, Ti, B, Al, P or
  • N is and R 6 is the same or different and is hydrogen, a halogen atom or a Ci -
  • C 20 - carbon-containing group particularly preferably methoxy, ethoxy, n-
  • the C 1 -C 20 -alkyl radicals are preferred under a C 1 -C 2 -carbon-containing group, particularly preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s- Butyl, t-butyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl or cyclooctyl, Ci - C 20 - alkenyl, particularly preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl,
  • a bridging C - C 2 o -carbon-containing group is preferably CrC 2 o -alkyl, particularly preferably methylene, ethylene, propylene, butylene, pentylene, cyclopentylene, hexylene or cyclohexylene, C
  • C2o-alkenyl particularly preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl or cyclohexenyl
  • C 1 -C 20 alkynyl particularly preferably ethynyl, propynyl, butynyl, pentynyl or hexynyl
  • C 1 -C 2 o-aryl particularly preferably o-phenylene, m-phenylene or p-phenylene
  • Ci - C 2 o - heteroatom-containing group particularly preferably carbonyl, oxycarbonyl, carbonyloxy, carbamoyl or amido understood.
  • additives of formula III are:
  • Another component of the invention are initiator systems for the production of polyvinyl esters consisting of a compound of the formula IV and a metal compound of the formula II and, if appropriate, an additive of the formula III:
  • Ar is an aromatic backbone with at least four carbon atoms, in which one or more carbon atoms can be replaced by boron, nitrogen or phosphorus, and preferred aromatic or heteroaromatic backbones are derived from benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, Quinoline, pyridine, bipyridine, pyridazine,
  • X 1 has the same meaning as described above, and y is an integer and is zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 , 16, 17, 18, 19 and 20, and z is an integer and is 2, 3, 4, 5, 6, 7, 8, 9 and 10.
  • Another component of the invention are initiator systems for the production of polyvinyl esters consisting of a compound of formula V and a metal compound of formula II and optionally an additive of formula III:
  • Ap is a cyclic non-aromatic backbone with at least three carbon atoms, which can also contain heteroatoms such as nitrogen, boron, phosphorus, oxygen or sulfur, preferred aliphatic backbones from the group cycloalkyl, such as, for example
  • R 1 , R 2 , R 3 , R 4 , R 5 have the same meaning as described above, and m, n, o, p have the same meaning as described above, and
  • X 1 has the same meaning as described above, and a is an integer and for zero ,, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
  • 13, 14, 15, 16, 17, 18, 19 and 20 is , and b is an integer and is 2, 3, 4, 5, 6, 7, 8, 9 and 0, and c is an integer is a natural number and stands for zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20.
  • the initiator systems according to the invention are obtained by reacting a compound of the formula I, IV or V with a metal compound of the formula II.
  • a reaction in which a metal compound of the formula II is used stoichiometrically in relation to the radical-starting halide groups X 1 present is preferred.
  • an additive of the formula III can be present during the preparation of the catalyst system, or an additive of the formula III can optionally be introduced subsequently.
  • the concentration of additive of formula II! can be between 0.001 and 100 mol% based on the monomer used, particularly preferably the concentration of additive of the formula III is 0.01 and 20 mol% based on the monomer used.
  • the initiator system can be prepared in the presence of one or more solvents or in vinyl esters, preferably in vinyl acetate, or in another liquid monomer.
  • the present invention relates to a process for the preparation and purification of polyvinyl esters comprising the steps:
  • Formula III in which: denotes a central atom and is an atom from the 13th to 16th group of the Periodic Table of the Elements, preferably carbon, silicon, nitrogen, phosphorus, oxygen or sulfur, particularly preferably carbon or silicon, and
  • X 1 is in each case the same or different, and is a halogen atom, preferably fluorine, chlorine, bromine or iodine, particularly preferably chlorine, bromine or iodine, and
  • R 1 is the same or different and is hydrogen or a Ci - C 20 carbon-containing group
  • R ⁇ is the same or different and is a bridging Ci - C 2 o - carbon-containing group between the central atom Z and the initiating unit [R 3 -X 1 j or silicon or oxygen, and
  • R 3 is the same or different and means carbon or silicon
  • R 4 is the same or different and is a hydrogen atom or a Ci - C 20 carbon-containing group
  • R ö is the same or different and is hydrogen or a Ci - C 20 carbon-containing group
  • I is a whole natural number and stands for zero
  • 1, 2 or 3 and m is in each case identical or different and is a whole natural number and stands for zero, 1, 2, 3, 4 and 5, and n each is equal to or is different and is an integer and for zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19 and
  • M 1 is in each case the same or different and a transition metal of the 3rd to 12th
  • Ruthenium, iron, rhodium, nickel, palladium or copper, particularly preferably iron or ruthenium, and X 2 is in each case the same or different and oxygen or a halogen atom, particularly preferably fluorine, chlorine, bromine or iodine, and L in each case is the same or different and is a ligand, preferably a carbon-containing ligand such as methyl, phenyl, cymene, cumene, tolyl,
  • Tricyclohexylphosphine bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane or BINAP
  • each r is the same or different and is an integer and is 1, 2, 3, 4 and 5 and s is the same or different and is an integer and is zero, 1, 2, 3, 4 and 5, and t is the same or different and is an integer and is zero, 1, 2, 3, 4 and 5, and u is an integer and stands for 1, 2, 3, 4 and 5, and M 2 is the same or different and is an element of the 1st to 15th group of the
  • Periodic table of the elements particularly preferably Li, Mg, Ti, B, Al, P or N
  • R 6 is the same or different and is hydrogen, a halogen atom or a Ci - C 2 o - carbon-containing group, particularly preferably methoxy,
  • Is ethoxy, n-propoxy or i-propoxy, and v is the same or different and is an integer and is 1, 2,
  • step D optionally separating the reaction products formed in the oxidation in step D), (F) precipitating the polymer by adding the polymer solution to one or more nonpolar aprotic solvent (s) and separating the supernatant solvent and optionally drying the polymer obtained, (G optionally redissolving the polymer obtained from step F) in one or more organic solvents,
  • step G precipitating the polymer by adding the solution from step G) to water or to an aqueous solution of an acid or an aqueous solution of a base, if appropriate with stirring and cooling, (I) isolating the precipitated polymer, preferably by filtration or decanting, optionally washing the polymer with water or one of the liquids mentioned under step H), (J) optionally repeating steps G), H) and I) (K) drying the polymer.
  • the solvents used in step C) are preferably (i) aromatic hydrocarbons, in particular toluene, benzene or xylene, (ii) ketones, in particular acetone, diethyl ketone or methyl isobutyl ketone, (iii) ethers, in particular diethyl ether, dibutyl ether, methyl tert-butyl ether , Tetrahydrofuran, anisole or dioxane, (iv) esters in particular such as methyl acetate or ethyl acetate, (v)
  • Alcohols in particular methanol, ethanol or isopropanol, (vi) halogenated hydrocarbons, in particular dichloromethane or trichloromethane, and also (vii) ethylene carbonate or (viii) N, N-dimethylformamide.
  • the oxidizing agent used in step D) is, in particular, hydrogen peroxide, sodium peroxide, sodium hypochlorite, sodium perborate, sodium peroxodisulfate, potassium peroxodisulfate, potassium permanganate, potassium chlorate, calcium peroxide, tert-butyl hydroperoxide, or m-chloroperbenzoic acid, the addition or the oxidizing agent either as the substance or in the oxidizing agent Solution can be done.
  • the solvents used in step F) are in particular aliphatic hydrocarbons, particularly preferably n-pentane, n-hexane, isohexane or n-heptane.
  • the solvents used in step G) are preferably
  • aromatic hydrocarbons in particular toluene, benzene or xylene
  • ketones in particular acetone, diethyl ketone or methyl isobutyl ketone
  • ethers in particular diethyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, anisole or dioxane
  • esters in particular such as Methyl acetate or ethyl acetate
  • alcohols in particular methanol, ethanol or isopropanol
  • Hydrocarbons in particular dichloromethane or trichloromethane, and also (vii) ethylene carbonate or (viii) N, N-dimethylformamide.
  • the acids used in step H) are preferably inorganic and / or organic acids, in particular hydrogen fluoride,
  • the bases used in step H) are preferably inorganic and / or organic bases, in particular sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, tetramethylethylenediamine, trimethylamine, triethylamine, EDTA sodium salt or hexamethylenetetramine.
  • the polymer purified by the process according to the invention is colorless and contains no solvent and no residual monomer.
  • a preferred embodiment of the process according to the invention comprises steps A) and B) as described above, dissolving the reaction mixture according to step C) in acetone, toluene and / or methanol, precipitation of the polymer according to
  • Step F) by adding the solution from step C) to n-heptane and subsequent removal of the solvent, redissolving the polymer in acetone according to step G), adding the solution, preferably with stirring, to an inorganic acid according to step H), isolation the precipitated polymer and washing the polymer with water and then drying the polymer.
  • a particularly preferred embodiment of the process according to the invention comprises steps A) and B) as described above, dissolving the reaction mixture according to step C) in acetone, precipitating the polymer according to step F) by adding the solution from step C) to n-heptane and subsequently
  • step G Removing the solvent, redissolving the polymer in acetone according to step G), adding the solution, preferably with stirring, to a 1 molar hydrochloric acid according to step H), isolating the precipitated polymer and washing the polymer with water and subsequently drying the polymer.
  • Another object of the present invention is a process for the production and purification of polyvinyl esters comprising the steps:
  • step B dissolving the reaction mixture from step B) in one or more organic solvents as described above, (D) optionally oxidation of the catalyst in the mixture by stirring in the presence of atmospheric oxygen or addition of oxidizing agents as described above,
  • step F optionally precipitating the polymer by adding the polymer solution to one or more non-polar aprotic solvent (s) and separating off the supernatant solvent and optionally drying the polymer obtained as described above, (G) optionally redissolving the polymer obtained from step F) in one or more organic solvents as described above, (L) adding the solution from C) to water or an aqueous solution of an acid or to an aqueous solution of a base, optionally with stirring, (M) stirring the mixture of L) for the extraction of impurities, separation of the phases and separation of the aqueous phase,
  • the acids used in step L) are preferably inorganic and / or organic acids, in particular hydrogen fluoride, hydrochloric acid, hydrogen bromide, hydrogen iodide, phosphoric acid, phosphoric acid, hypophosphorous acid, sulfuric acid, sulfurous acid, acetic acid, tartaric acid, nitric acid, nitric acid Acid, ammonium chloride or citric acid.
  • the bases used in step L) are preferably inorganic and / or organic bases, in particular sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, tetramethylethylene diamine, trimethylamine, triethylamine, EDTA sodium salt or hexamethylene tetramine.
  • the solvents used in step N) are preferably (i) aromatic hydrocarbons, in particular toluene, benzene or xylene, (ii) ketones, in particular acetone, diethyl ketone or methyl isobutyl ketone, (iii) ethers, in particular diethyl ether, dibutyl ether, methyl tert-butyl ether , Tetrahydrofuran, anisole or dioxane, (iv) esters in particular such as methyl acetate or ethyl acetate, (v)
  • Alcohols in particular methanol, ethanol or isopropanol, (vi) halogenated hydrocarbons, in particular dichloromethane or trichloromethane, and also (vii) ethylene carbonate or (viii) N, N-dimethylformamide.
  • a preferred embodiment of the further process according to the invention comprises steps A) and B) as described above, dissolving the polymer according to step C) in acetone and / or methanol, precipitating the polymer according to step F) by adding the solution from step C) to n -Heptane and subsequent separation of the solvent, redissolving the polymer in toluene, acetone and dichloromethane according to step G), adding the solution, preferably with stirring, to an inorganic acid according to step L), stirring the mixture to extract the impurities, separating the Phases and separation of the organic phase according to step M), addition of acetone to the organic phase according to step N), repetition of steps L), M) and N) according to step O), isolation and drying of the polymer by removing the solvent! in the
  • a particularly preferred embodiment of the further process according to the invention comprises steps A) and B) as described above, dissolving the polymer according to step C) in toluene, acetone and dichloromethane, adding the
  • Ar is an aromatic backbone with at least four carbon atoms, in which one or more C atoms can be replaced by boron, nitrogen or phosphorus, and where preferred aromatic or heteroaromatic backbones are derived from benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, Quinoline, pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, benzopyrrole, benzotriazole, benzopyridine,
  • Benzopyrazidine benzopyrimidine, benzopyrazine, benzotriazine, indolizine, quinolizine, carbazole, acridine, phenazine, benzoquinoline, phenoxazine, which may optionally also be substituted
  • R 1 , R 2 , R 3 , R 4 , R 5 have the same meaning as described under formula (I)
  • m, n, o, p have the same meaning as described under formula (I)
  • X 1 has the same meaning as described under formula (I)
  • y is an integer and stands for zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20, and z is a completely natural one Number is and stands for 2, 3, 4, 5, 6, 7, 8, 9 and 10.
  • Ap is a cyclic non-aromatic backbone with at least three
  • Is carbon atoms which may also contain heteroatoms such as nitrogen, boron, phosphorus, oxygen or sulfur, preferred aliphatic backbones being selected from the group cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or from Cycloheteroalkyl group, such as
  • Another component of the present invention is a process for the polymerization of vinyl esters using a catalyst system according to the invention, polymerization being understood to mean both the homopolymerization of vinyl esters and the copolymerization of vinyl esters with other olefins.
  • olefins having 2 to 20, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-decene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1, 3-butadiene, 1, 4-hexadiene, vinyl norbornene, norbornadiene, ethylnorbornadiene and cyclic olefins such as norbornene, cyclopentadiene, tetracyclododecene or methylnorbornene, and polar monomers such as
  • Methyl acrylate methyl methacrylate, acrylic acid, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
  • vinyl acetate is preferably homopolymerized, or vinyl acetate with one or more 1-olefins having 4 to 20 carbon atoms, such as
  • copolymers are vinyl acetate, methyl methacrylate copolymers or vinyl acetate / methyl methacrylate / styrene terpolymers.
  • the polymerization is carried out at a temperature of 0 to 300 ° C., preferably 50 to 200 ° C., very particularly preferably 50 to 80 ° C.
  • the pressure is 0.5 to 2000 bar, preferably 1 to 64 bar.
  • the polymerization can be carried out in solution, in bulk, in suspension or in emulsion, continuously or batchwise, in one or more stages.
  • Suitable solvents for the polymerization are, for example, ethers, such as.
  • Initiator systems for the production of polyvinyl acetate consisting of a compound of the formulas I, IV or V, cyclopentadienyl iron dicarbonyl dimer (formula II) and aluminum triisopropoxide (formula III) are very particularly preferred.
  • Another object of the present invention are the polymers with special geometries based on polyvinyl esters of the formulas VI, VII and VIII, which from the reaction of a central unit of the formulas I, IV or V with vinyl esters, or vinyl esters with one or more 1-olefins, the following are obtained:
  • R 1 , R 2 , R 3 , R 4 , R 5 have the same meaning as described above, and I, m, n, o, p, q, y, z, a, b, c have the same meaning as above and X 1 has the same meaning as described above, and d can be the same or different, and is zero or one, and Pol stands for a polymer based on a polyvinyl ester, particularly preferably for a homo- or copolymer based of polyvinyl acetate.
  • the chain length of the polymer Pol can be determined by the reaction parameters (time, temperature, pressure, concentrations).
  • the chain length is particularly preferred from 3 to 10,000. In example 3:
  • polymers according to the invention are:
  • polymers based on polyvinyl esters with special geometries can be chemically modified.
  • the polymers can be saponified, whereby polyvinyl alcohols with special geometries are obtained. These can be converted, for example, with butyraldehyde to polyvinyl butyrals with special geometries.
  • the polymers of the formulas VI, VII and VIII are particularly suitable as additives for fuels and motor oils, as additives for concrete, as additives in paper production as an adhesive (component), as a lubricant, as a coating component, as high-performance plastics and as a starting material for new materials based on polyvinyl alcohol and polyvinyl butyral with special geometries.
  • the invention is illustrated by the following examples which, however, do not restrict the invention.
  • Example 4 Preparation of a polyvinyl acetate star polymer according to DE10238659
  • Example 5 Purification of the polyvinyl acetate star polymer produced in example 4
  • the solvent and residual vinyl acetate are removed in vacuo at 70 ° C.
  • the reaction mixture is dissolved in 800 ml of acetone and added to 1.25 l of n-heptane. The mixture is allowed to sit for one hour and the supernatant n-heptane is decanted off.
  • the dark brown polymer thus obtained is dried in vacuo for two hours and again taken up in 800 ml of acetone.
  • the dark polymer solution is added dropwise to 2 l of an ice / 2 M hydrochloric acid mixture (1 kg of ice / 1 l of 2M HCl) with vigorous stirring using a KPG stirrer.
  • the polymer powder obtained in this way is filtered off, washed neutral twice with 250 ml of water each time and freeze-dried in vacuo.
  • the polymer thus obtained (yield: 270 g) is colorless and no longer contains anisole.
  • Example 6 Purification of the polyvinyl acetate star polymer produced in Example 4 by extraction

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne des polymères à géométries spécifiques à base d'esters polyvinyliques, des systèmes initiateurs permettant la production desdits polymères et un procédé de production de polymères à géométries spécifiques à base d'esters polyvinyliques.
EP03792316A 2002-08-23 2003-08-14 Nouveaux esters polyvinyliques Withdrawn EP1539842A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10238659 2002-08-23
DE10238659 2002-08-23
DE2003127511 DE10327511A1 (de) 2003-06-17 2003-06-17 Verfahren zur Herstellung von Polyvinylester
DE10327511 2003-06-17
PCT/EP2003/009016 WO2004018532A1 (fr) 2002-08-23 2003-08-14 Nouveaux esters polyvinyliques

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EP1539842A1 true EP1539842A1 (fr) 2005-06-15

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CN115505340A (zh) * 2022-10-09 2022-12-23 哈尔滨工程大学 一种镍铝改性硅溶胶无机胶黏剂的制备方法

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DE10343607A1 (de) * 2003-09-20 2005-04-28 Celanese Ventures Gmbh Neue Polyvinylalkohole und neue Polyvinylalkohol-Copolymere
DE10356574A1 (de) * 2003-12-04 2005-06-30 Celanese Ventures Gmbh Neue Poly(vinylester)- und Poly(vinylalkohol)-Copolymere und deren Verwendung
DE102004019504A1 (de) * 2004-04-22 2005-11-10 Celanese Ventures Gmbh Neue Hydrogele auf Basis von Polyvinylalkoholen und Polyvinylalkohol-Copolymeren
US7838609B2 (en) 2007-02-21 2010-11-23 The Nippon Synthetic Chemical Industry Co., Ltd. Polyvinyl alcohol type resin, monolayer film and laminate
CN109863138A (zh) * 2016-08-19 2019-06-07 优美科股份公司及两合公司 烯烃复分解催化剂
CN107233607B (zh) * 2017-06-27 2020-03-31 东莞御治医疗器械有限公司 一种创面保护膜材料的制备方法

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WO1998020050A2 (fr) * 1996-11-01 1998-05-14 E.I. Du Pont De Nemours And Company Polymerisation de monomeres vyniliques

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115505340A (zh) * 2022-10-09 2022-12-23 哈尔滨工程大学 一种镍铝改性硅溶胶无机胶黏剂的制备方法
CN115505340B (zh) * 2022-10-09 2023-06-27 哈尔滨工程大学 一种镍铝改性硅溶胶无机胶黏剂的制备方法

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CA2496709A1 (fr) 2004-03-04
JP2005536600A (ja) 2005-12-02
WO2004018532A1 (fr) 2004-03-04
CN1320001C (zh) 2007-06-06
CN1678645A (zh) 2005-10-05

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