JP2005536600A - New polyvinyl ester - Google Patents

Abstract

The present invention relates to polymers having geometric specificity based on polyvinyl esters, initiator systems for preparing them and polymers having geometric specificity and based on polyvinyl esters. Relates to the process of preparing.

Description

DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer based on a polymer having a geometric specificity and a polyvinyl ester, and a polymer having a geometric specificity and a polymer based on a polyvinyl ester. is there.

  Polyvinyl esters are polymers derived from monomeric vinyl esters, which have a moiety of the following formula as the basic monomer of the polymer.

Among these, polyvinyl acetate (in the case of R = CH ₃ ) is outstanding in industrial importance.

  Polyvinyl acetate is an important thermoplastic polymer, among which it is used as an adhesive component, as a raw material for lacquers, to coat packaging films and paper, foodstuffs (sausage, cheese packaging), as a concrete additive, and as a polyvinyl alcohol. (Roempp Lexikon Chemie-version 2.0 Stuttgart / New York: Georg Thieme Verlag 1999).

In the industrial field, polyvinyl acetate is prepared by free radical polymerization, which may be carried out by solution polymerization, bulk polymerization or emulsion polymerization. As initiators for free free radical polymerization, azoisobutyronitrile and dibenzole peroxide (commonly known as the former AIBN / the latter BPO) are mainly used. Once these free free radical polymerizations proceed rapidly and in a free manner, it is not possible to exclude the distinction of the three-dimensional structure of the polymer chain, and it becomes difficult to control the molecular weight and molecular weight distribution (W. Daniels). ^{in:. Kirt-Othmer Encycl.Chem.Technol,} 3 rd Ed 1983,23,817-847).

  Due to the inhibition of free radical polymerization of vinyl acetate, synthesis of polyvinyl acetate having geometric specificity, for example, star-shaped, comb-shaped or ladder-shaped polyvinyl acetate having a narrow molecular weight distribution has not been possible so far. Polymers with these geometric specificities and polymers based on other monomers can find a variety of uses, such as active materials that release controlled responses. Therefore, in the production of fibers, films and molds, it is a gel-like or rubber-like application, liquid crystals for high-precision electronic materials, and high-performance plastics. Polyvinyl acetate with a narrow geometric specificity and molecular weight distribution has not been described in the literature so far.

  One means of controlled polymerization and control of polymer properties is known as ATRP (Atom Transfer Free Radical Reaction) and is synthesized under a metal catalyst (WO9630421). In this method, the redox reaction of the metal together with the initiator reversibly takes in the monomer, thereby changing to a free radical that generates a new active species (free radical). In an ideal case, the new free radical is in equilibrium with the metal by the redox reaction. This control supplies a polymer with a narrow molecular weight distribution or a polymer with a limited molecular weight range (K, Matyjaszewski, J. Xia, Chem. Rev 2001; 101 (12), 2921-2990,).

Attempts of controlled polymerization of vinyl acetate by ATRP are still ongoing due to migration equilibrium constants even for small atoms (J. Xia, H.-J. Paik, K, Matyjaszewski, Macromolecules. 1999, 32, 8310-8314).
Only one example in the literature describes controlled free radical polymerization of vinyl acetate.
(M. Wakioka, K.-Y. Baek, T. Ando, M. Kamigaito, M. Sawamoto, Macromolecules. 2002, 35, 330-333).

  The object of the invention to develop an initiator system in this way is to avoid the disadvantages described in the prior art, and to provide novel polymers based on polyvinyl esters with geometric specificity. There is to guide.

  The use of the new initiator system is now surprisingly found to be at least two effective centers that allow the synthesis of new polyvinyl esters with geometric specificity.

  The present invention provides an initiator system for preparing a polyvinyl ester comprising at least one compound of formula I, at least one metal compound of formula II and optionally at least one additive of formula III. Is:

However, in the formula, Z is a central atom and is an atom of Group 13 to Group 16 of the periodic table of elements, preferably carbon, silicon, nitrogen, phosphorus, oxygen or sulfur, more preferably carbon or silicon.
X ¹ is the same or different in each case and is a halogen atom, preferably fluorine, chlorine, bromine or iodine. More preferred are chlorine, bromine and iodine.
R ¹ is the same or different and is hydrogen or a group having 1 to 20 carbon atoms.
R ² is the same or different and is a bridging group having 1 to 20 carbon atoms or silicon or oxygen between the central atom Z and the first (R ³ -X ¹ ) unit.
R ³ is the same or different and is carbon or silicon.
R ⁴ is the same or different and is a hydrogen atom or a group having 1 to 20 carbon atoms.
R ⁵ is the same or different and is hydrogen and a group having 1 to 20 carbon atoms.
l is a natural number and 0, 1, 2 or 3.
m is the same or different in each case, and is a natural number of 0, 1, 2, 3, 4, and 5.
n is the same or different in each case, and is a natural number 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20.
o is the same or different in each case and is 1 or 2.
p is the same or different in each case and is a natural number of 1, 2, 3, 4 and 5.
q is a natural number of 2, 3 or 4.
M ¹ is the same or different in each case and is a transition metal of group 3 to group 12 of the periodic table of elements, preferably chromium, molybdenum, ruthenium, iron, rhodium, nickel, palladium or copper, more preferably iron or ruthenium It is.
X ² is the same or different in each case, and is oxygen or a halogen atom, more preferably fluorine, chlorine, bromine or iodine.
L is the same or different in each case and is a ligand, preferably a carbon ligand such as methyl, phenyl, cymene, cumene, tolyl, mesityl, xylyl, indenyl, benzylidene, cyclopentadienyl, or carbonyl. For example, triethylamine, tetramethylethylenediamine, pyridine, 2,2′-bipyridyl, substituted 2,2′-bipyridyl, 1,10-phenanthroline, phenylpyridin-2-ylmethyleneamine, acetonitrile, Substituted imidazolidine or terpyridyl, and phosphorus ligands are for example triphenylphosphine, tricyclohexylphosphine, bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane or BINAP.
r is the same or different in each case, and is a natural number of 1, 2, 3, 4, and 5.
s is the same or different in each case, and is a natural number of 0, 1, 2, 3, 4, and 5.
t is the same or different in each case, and is a natural number of 0, 1, 2, 3, 4, and 5.
u is a natural number of 1, 2, 3, 4, and 5.
M ² is the same or different and is an element of Groups 1 to 15 of the periodic table of elements, and more preferably Li, Mg, Ti, B, Al, P, or N.
R ⁶ is the same or different and is a hydrogen atom, a halogen atom or a group having 1 to 20 carbon atoms, more preferably methoxy, ethoxy, n-propoxy or i-propoxy.
v is the same or different and is a natural number of 1, 2, 3, 4, 5, 6, 7 and 8.
w is the same or different and is a natural number of 1, 2, 3, 4, 5, 6, 7 and 8.
x is a natural number of 1, 2, 3, 4, 5, 6, 7 and 8.

In the context of the present invention, in a group having 1 to 20 carbon atoms (C ₁ -C ₂₀ ), preferably a C ₁ -C ₂₀ -alkyl group, and more preferably methyl, ethyl, n-propyl, i-propyl, n - butyl, i- butyl, s- butyl, t- butyl, n- pentyl, s- pentyl, cyclopentyl, cyclohexyl n- hexyl, cyclo, a n- octyl or _cyclooctyl, C 1 _{-C 20} - alkenyl in, more preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, cyclohexenyl, cyclohexenyl, octenyl, or cyclooctenyl, C 1 _-C 20 _- alkynyl, more preferably ethynyl, propynyl, butynyl, pentynyl, hexynyl, or a _octynyl, C 6 _{-C 20} - aryl, more favorable Shiino phenyl, biphenyl, naphthyl or _anthracenyl, C 1 _{-C 20} - fluoroalkyl, a more preferred are trifluoromethyl, pentafluoroethyl or 2,2,2-trifluoroethyl, _{C 6} - C ₂₀ -aryl, more preferred is phenyl, biphenyl, naphthyl, anthracenyl, triphenylenyl, [1,1 ′; 3 ′, 1 ″] terphenyl-2′-yl, binaphthyl, or phenanthrenyl, and C ₆ in -C ₂₀ fluoroaryl, more preferred is tetrafluorophenyl or _{heptafluoronaphthyl,} with C 6 _{-C 20} alkoxy, more preferred are methoxy, ethoxy, n- propoxy, i- propoxy, n- butoxy I-butoxy, s-butoxy, or t-butoxy , And _the at C 6 _{-C 20} aryloxy, more preferred are phenoxy, naphthoxy, Bifenirokishi, anthracenyl Niro alkoxy, a phenanthrenylene b _{carboxymethyl,} C 7 _{-C 20} - aryl alkyl, more preferred are o- tolyl, m-tolyl, p-tolyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-i-propylphenyl, 2,6-di-t-butylphenyl, ot-butylphenyl M-t-butylphenyl, p-t-butylphenyl, with C ₇ -C ₂₀ -alkylaryl being more preferred benzyl, ethylphenyl, propylphenyl, diphenylmethyl, triphenylmethyl, or naphthalenyl Methyl, C ₇ -C ₂₀ -aryloxyalkyl, more preferably o-me Tokishifeniru, m- phenoxymethyl, a p- _{phenoxymethyl,} C 12 _{-C 20} - The arylene Loki shear reel, more preferred is p- phenylene b _{hydroxyphenyl,} C 5 _{-C 20} - heteroaryl, more preferably the 2-pyridyl, 3-pyridyl, 4-pyridyl, quinolinyl, isoquinolinyl, acridinyl, a benzoquinolinyl or benzo _{isoquinolinyl,} C 4 _{-C 20} - heterocycloalkyl, more preferred are furyl, benzofuryl, 2 - pyrrolidinyl, 2-indolyl, 3-indolyl, 2,3-a hydro _indolyl, C 8 _{-C 20} - the arylalkenyl, more preferred are o- vinylphenyl, m- vinylphenyl, p- vinylphenyl in _and, C 8 _{-C 20} - arylalkylene Le, more preferred are o- ethynylphenyl, m- ethynylphenyl or p- ethynylphenyl, C 2 _-C 20 _- The group containing a hetero atom, more preferred are carbonyl, benzol, oxy benzol, benzoyloxy, Mention that acetyl, acetoxy, or nitrile and one or more C ₁ -C ₂₀ groups may form a cyclic circulating group.

In the context of the present invention, the bridged C ₁ -C ₂₀ group is preferably C ₁ -C ₂₀ alkyl, more preferably methylene, ethylene, propylene, butylene, pentylene, cyclopentylene, hexylene or cyclohexylene. , C ₁ -C ₂₀ -alkenyl, more preferred are ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, or cyclohexenyl, and preferred C ₁ -C ₂₀ -alkynyl is more preferred ethynyl, propynyl , Butynyl, pentynyl or hexynyl and C ₁ -C ₂₀ -aryl are more preferred o-phenylene, m-phenylene or p-phenylene, groups containing C ₁ -C ₁₀ heteroatoms, more preferred are carbonyl , Oxycarbonyl, carbonillo Shi, are mentioned as a carbamoyl or amide.

  The following illustrative examples, however, do not limit the invention, but the compounds of formula I are as follows:

The following illustrative examples, however, do not limit the invention, but the compounds of formula II are as follows:

The following illustrative examples, however, do not limit the invention, but the additive of formula III is as follows:

  The meanings of the abbreviations in this table are: M = methyl, Et = ethyl, nPr = n-propyl, iPr = isopropyl, nBu = n-butyl, sBu = sec-butyl, tBu = tert-butyl and Ph = phenyl. .

  In order to prepare polyvinyl esters, the present invention further provides an initiator system, and the invention comprises a metal compound of formula IV, formula II and optionally an additive of formula III.

However, in the formula, Ar has an aromatic basic structure having at least 4 carbon atoms, and one or more of these carbon atoms may be substituted with boron, nitrogen or phosphorus. Or the basic structure of heteroaromatic is benzene, biphenyl, naphthalene, anthracene, phenatrene, triphenylene, quinoline, pyridine, bipyridine, pyridazine, pyrimidene, pyrazine, triazine, benzopyrrole, benzotriazole, benzopyridine, benzopyrazidine, benzopyrimidine, They are derived from benzopyrazine, benzotriazine, indolizine, quinolidine, carbazole, acridine, phenazine, benzoquinoline, phenoxazine, and they are often each optionally substituted.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ are each as previously defined.
m, n, o, and p are as defined above.
Each X ¹ is as defined above.
y is a natural number of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.
z is a natural number of 2, 3, 4, 5, 6, 7, 8, 9 and 10.

  The following illustrative examples, however, do not limit the invention, but structural formula IV is:

  The invention further provides an initiator system for preparing polyvinyl esters, which consists of a compound of formula V, a metal compound of formula II and optional additives of formula III.

However, in the formula, Ap is a cyclic non-aromatic basic structure having at least 3 carbon atoms, but may contain heteroatoms such as nitrogen, boron, phosphorus, oxygen or sulfur. Preferred aliphatic basic structures are those derived from cycloalkyl groups, such as those derived from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cycloheteroalkyl groups, such as aziridine, From azetidine, pyrrolidine, piperidine, azepan, azocan, 1,3,5-triazinan, 1,3,5-trioxane, oxetane, furan, dihydrofuran, tetrahydrofuran, pyran, dihydropyran, tetrahydropyran, oxepane, oxocan, or sugars For example, there are alpha-glucose and beta-glucose.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ are each as previously defined.
m, n, o, and p are as defined above.
Each X ¹ is as defined above.
a is a natural number and is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.
b is a natural number of 2, 3, 4, 5, 6, 7, 8, 9 and 10.
c is a natural number of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.

  The following illustrative examples, however, do not limit the invention but the compounds of formula V are as follows:

The initiator system of the invention results from reacting a compound of formula I, IV or V with a metal compound of formula II. The selection is obtained by a reaction in which the metal compound of the formula II is used stoichiometrically in relation to the presence of X ¹ of the halogen radical initiated by the free radical. The additive of formula III may optionally be present when the catalyst system is prepared, in which case the additive of formula III may subsequently be determined if necessary. The additive concentration of formula III may be used between 0.001 and 100 mol% per monomer used, and the additive concentration of formula III is more preferably 0.01 to 20 mol% per monomer used. Used between. The initiator system is prepared in one or more solvents or vinyl esters, preferably in the presence of vinyl acetate or other liquid monomer.

The present invention provides a method for producing and purifying a polyvinyl ester comprising the following steps:
(A) At least one compound of formula I is reacted with at least one metal compound of formula II, optionally in the presence of at least one additive of formula III.

However, in the formula, Z is a central atom and is an atom of Groups 13 to 16 in the periodic table of elements, preferably carbon, silicon, nitrogen, phosphorus, oxygen or sulfur, more preferably carbon or silicon.
X ¹ is the same or different in each case and is a halogen atom, preferably fluorine, chlorine, bromine or iodine, more preferably chlorine, bromine or iodine.
R ¹ is the same or different and is hydrogen or a group having 1 to 20 carbon atoms.
R ² is the same or different and is a bridging group having 1 to 20 carbon atoms or silicon or oxygen between the central atom Z and the first (R ³ -X ¹ ) unit.
R ³ is the same or different and is carbon or silicon.
R ⁴ is the same or different and is a hydrogen atom or a group having 1 to 20 carbon atoms.
R ⁵ is the same or different and is hydrogen or a group having 1 to 20 carbon atoms.
l is a natural number, 0, 1, 2, or 3.
m is the same or different in each case, and is a natural number of 0, 1, 2, 3, 4, and 5.
n is the same or different in each case, and is a natural number 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20.
o is the same or different in each case and is 1 or 2.
p is the same or different in each case, and is a natural number of 1, 2, 3, 4, and 5.
q is a natural number of 2, 3 or 4.
M ¹ is the same or different in each case and is a transition metal of group 3 to group 12 of the periodic table of elements, preferably chromium, molybdenum, ruthenium, iron, rhodium, nickel, palladium or copper, more preferably iron or ruthenium It is.
X ² is the same or different in each case, and is oxygen or a halogen atom, more preferably fluorine, chlorine, bromine or iodine.
L is the same or different in each case and is a ligand, preferably a carbon ligand such as a methyl, phenyl, cymene, cumene, tolyl, mesityl, xylyl, indenylbenzylidene, cyclopentadienyl, or carbonyl group In the nitrogen ligand, for example, triethylamine, tetramethylethylenediamine, pyridine, 2,2′-bipyridyl, substituted 2,2′-bipyridyl, 1,10-phenanthroline, phenylpyridin-2-ylmethylenamine, Acetonitrile, substituted imidazolidine or terpyridyl, and as the phosphorus ligand, for example, triphenyl phosphate, tricyclohexylphosphine, bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane or BINAP.
r is the same or different in each case, and is a natural number of 1, 2, 3, 4, and 5.
s is the same or different in each case, and is a natural number of 0, 1, 2, 3, 4, and 5.
t is the same or different in each case, and is a natural number of 0, 1, 2, 3, 4, and 5.
u is a natural number of 1, 2, 3, 4, and 5.
M ² is the same or different and is an element of Groups 1 to 15 of the periodic table of elements, and more preferably Li, Mg, Ti, B, Al, P, or N.
R ⁶ is the same or different and is a hydrogen atom, a halogen atom or a group having 1 to 20 carbon atoms, more preferably methoxy, ethoxy, n-propoxy or i-propoxy.
v is the same or different and is a natural number of 1, 2, 3, 4, 5, 6, 7 and 8.
w is the same or different and is a natural number of 1, 2, 3, 4, 5, 6, 7 and 8.
x is a natural number of 1, 2, 3, 4, 5, 6, 7 and 8.
(B) Concentrate the reaction mixture from step A) to remove residual monomer and solvent.
(C) The reaction mixture from step B) is dissolved in one or more organic solvents.
(D) If necessary, the catalyst in the mixture is oxidized by stirring in the presence of an oxygen atmosphere or adding an oxidizing agent.
(E) If necessary, the reaction product obtained by oxidation in step D) is removed.
(F) The polymer solution is added to one or more non-polar aprotic solvents to precipitate the polymer, remove the supernatant solvent and, if necessary, dry the polymer.
(G) If necessary, redissolve the polymer obtained from step F) in one or more organic solvents.
(H) Reprecipitate the polymer by adding the solution from step G) to water or an acidic or basic aqueous solution, with stirring or cooling if necessary.
(I) The precipitated polymer is separated and washed with water or one of the liquids described in step H), if necessary, preferably by filtration or transfer of the supernatant solution.
(J) Repeat steps G), H) and I) if necessary.
(K) The polymer is dried.

  The solvents used in step C) are preferably (i) aromatic hydrocarbons, in particular toluene, benzene, 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 and ethyl acetate, (v) alcohols, in particular methanol, ethanol or isopropanol, (Vi) halogenated hydrocarbons, in particular dichloromethane or trichloromethane, and (vii) ethylene carbonate or (viii) N, N-dimethylformamide.

  The oxidizing agents used in step D) are in particular hydrogen peroxide, sodium peroxide, sodium hypochlorite, sodium perborate, sodium peroxide disulfate, potassium peroxide disulfate, potassium permanganate, potassium chlorate. , Calcium peroxide, tert-butyl hydroperoxide, or m-chloroperbenzoic acid, which is added to either the substance or the solution.

  The solvents used in step F) are in particular aliphatic hydrocarbons, more preferably n-pentane, n-hexane, n-isohexane or n-heptane.

  The solvents used in stage G) are preferably (i) aromatic hydrocarbons, in particular toluene, benzene, 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 and ethyl acetate, (v) alcohols, in particular methanol, ethanol or isopropanol, (Vi) halogenated hydrocarbons, in particular dichloromethane or trichloromethane, (vii) ethylene carbonate or (viii) N, N-dimethylformamito.

  The acids used in step H) are preferably inorganic and / or organic acids, in particular hydrogen fluoride, hydrochloric acid, hydrogen bromide, hydrogen iodide, phosphoric acid, phosphorous acid, hypophosphorous acid, sulfuric acid Sulfurous acid, acetic acid, tartaric acid, nitric acid, nitrous acid, ammonium chloride or citric acid. The salts used in step H) are preferably inorganic and / or organic salts, in particular sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, tetramethylethylenediamino, trimethylamine, triethylamine, EDTA sodium salt Or hexamethylenetetraamine.

  According to the present invention, the polymer purified by the method of the present invention is colorless and free of any solvent or any residual monomer.

  According to the invention, a preferred embodiment of the process of the invention comprises steps A) and B) as described above, the dissolution of the reaction mixture being carried out with acetone, toluene and / or methanol of step C), and with step F) The precipitation of the coalescence is accomplished by adding the solution from step C) to n-heptane, then removing the solvent and re-dissolving the polymer from step G) in acetone, preferably with stirring, step H. ) Is added to the inorganic acid to separate the precipitated polymer, the polymer is washed and the polymer is dried.

  According to the present invention, a particularly preferred embodiment is the step C) of dissolving the reaction mixture shown in steps A) and B), further in step C) in acetone, the polymer shown in step F) in n-heptane. Precipitation by addition of the solution shown below and subsequent removal of the solvent, redissolution of the weight body shown in step G) into acetone, preferably 1 mol of hydrochloric acid as shown in step H) under stirring, precipitation Consists of separation of the polymer and washing of the polymer with water followed by drying of the polymer.

The present invention further provides a method for producing and purifying a polyvinyl ester, and includes the following steps.
(A) As described above, at least one compound of formula I is reacted with at least one metal compound of formula II, optionally in the presence of at least one additive of formula III.
(B) As described above, the reaction mixture from step A) is concentrated to remove the remaining monomer and solvent.
(C) As described above, the reaction mixture from step B) is dissolved in one or more organic solvents.
(D) As described above, the catalyst is oxidized in the mixture by stirring in the presence of an oxygen atmosphere or adding an oxidizing agent as necessary.
(E) removing the reactants obtained by oxidation in step D) as necessary, as described above;
(F) As described above, the polymer solution is added to one or more nonpolar aprotic solvents to precipitate the polymer, and the supernatant solvent is removed to dry the polymer obtained as necessary. Let
(G) As described above, the polymer obtained from step F) is redissolved in one or more organic solvents as necessary.
(L) The polymer is reprecipitated by adding the solution from C) to water or an acidic or basic aqueous solution.
(M) Stir the mixture from L) to remove impurities, phase separate and remove the aqueous phase.
(N) If necessary, add one or more organic solvents to dissolve the polymer from M).
(O) Repeat steps L), M) and / or N) if necessary.
(P) The polymer is separated by distilling off the solvent and dried, if necessary under reduced pressure.

  The solvents and reagents used in steps A), C), D), E) and F) have already been described above in steps A), C), D), E) and F).

  The acids used in step L) are preferably inorganic and / or organic acids, in particular hydrogen fluoride, hydrochloric acid, hydrogen bromide, iodic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, sulfuric acid, sulfurous acid, Acetic acid, tartaric acid, nitric acid, nitrous acid, ammonium chloride or citric acid. The bases used in step L) are preferably inorganic and / or organic salts, in particular sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, tetramethylethylenediamino, trimethylamine, triethylamine, sodium EDTA Salt or hexamethylenetetraamine.

  The solvents used in stage N) are preferably (i) aromatic hydrocarbons, in particular toluene, benzene, 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 and ethyl acetate, (v) alcohols, in particular methanol, ethanol or isopropanol, (Vi) halogenated hydrocarbons, in particular dichloromethane or trichloromethane, (vii) ethylene carbonate or (viii) N, N-dimethylformamide.

  A further method of a preferred embodiment according to the invention comprises steps A) and B) as described above, the dissolution of the polymer in acetone and / or methanol by step C), the precipitation of the polymer by step F). Add the solution from C) to n-heptane, then remove the solvent, redissolve the polymer in toluene, acetone and dichloromethane by step G), step L), preferably while stirring, In step M) to stir the mixture to remove impurities, phase separate to remove the aqueous phase, step N) to add the asctone to the organic phase, steps O) to steps L), M) and N ), Separation of the polymer under reduced pressure and drying to remove the solvent in step P).

  A particularly preferred embodiment of the further process according to the invention comprises steps A) and B) as described above, and the dissolution of the polymer in toluene, acetone and dichloromethane according to step C), preferably with stirring by step L). While adding the solution to 1 mol hydrochloric acid, stirring the mixture according to step M) to remove impurities, phase separation to remove the organic phase, adding N to the organic phase according to step N), step from O) Repetition of L), M) and N) consists of separation and drying of the polymer under reduced pressure by removing the solvent in step P).

  As one variation of the method of the present invention, instead of the compound of formula (I), the following may be used for the compound of formula (IV).

However, in the formula, Ar is an aromatic basic structure having at least 4 carbon atoms, but one or more carbon atoms may be substituted with boron, nitrogen, phosphorus, and preferred aromatics. And the basic structure of heteroaromatics are benzene, biphenyl, naphthalene, anthracene, phenatrene, triphenylene, quinoline, pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, benzopyrrole, benzotriazole, benzopyridine, benzopyrazidine, benzopyrimidine, It is derived from benzopyrazine, benzotriazine, indolizine, quinolidine, carbazole, acridine, phenazine, benzoquinoline, phenoxazine, benzoquinoline, phenoxazine, and may be optionally substituted.
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each as defined in (I).
m, n, o, and p are as defined in (I).
X ¹ is as defined in (I).
y is a natural number of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.
z is a natural number of 2, 3, 4, 5, 6, 7, 8, 9 and 10.

  As a further variation of the method of the present invention, instead of the compound of formula (I), the compound of formula (V) may be used as follows:

Where Ap is a cyclic non-aromatic basic structure and has at least three carbons, but may contain heteroatoms such as nitrogen, boron, phosphorus, oxygen or sulfur, and is also preferred aliphatic The basic structure is derived from a cycloalkyl group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or a cycloheteralkyl group, such as aziridine, azetidine, pyrrolidine, From piperidine, azepane, azocane, 1,3,5-triazinan, 1,3,5-trioxane, oxetane, furan, dihydrofuran, tetrahydrofuran, pyran, dihydropyran, tetrahydropyran, oxepane, oxocane, or sugars Alpha-glucose, ba - there is glucose.
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each as defined in formula (I).
m, n, o, and p are as defined in (I).
X ¹ is as defined in (I).
a is a natural number and is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.
b is a natural number of 2, 3, 4, 5, 6, 7, 8, 9 and 10.
c is a natural number of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.

  The present invention further provides a method of polymerizing vinyl esters using either the catalyst system of the present invention and polymerizing either vinyl ester homopolymerization or copolymerization of vinyl esters with other olefins.

  Examples of other olefins are 1-olefins having 2 to 20 carbon atoms, 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 are 1,3-butadiene, 1,4-hexadiene, vinylnorbornene, norbornadiene, ethylnorbornadiene, and cyclic olfines are norbornene, cyclopentadiene, tetra Cyclododecene or methylnorbornene, polar monomers are methyl acrylate, methyl methacrylate, acrylic acid, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate.

  In the method of the present invention, preferred embodiments include homopolymerization of vinyl acetate and vinyl acetate and one or more olefins having 1 to 20 carbon atoms, such as styrene, norbornene, methyl acrylate, methyl methacrylate, acrylic acid, ethyl acrylate, It can be obtained by copolymerization with n-butyl acrylate or 2-ethylhexyl acrylate. Examples of such copolymers are vinyl acetate / methyl methacrylate copolymers or vinyl acetate / methyl methacrylate / styrene terpolymers.

  The polymerization is carried out at a temperature of 0 ° C. to 300 ° C., preferably 50 ° C. to 200 ° C., and even more preferably 50 ° C. to 80 ° C. The pressure is 0.5 to 2000 bar, preferably 1 to 64 bar. The polymerization may be carried out in one or more stages continuously or batchwise by solution polymerization, bulk polymerization, suspension polymerization or emulsion polymerization. Solvents suitable for polymerization are, for example, diethyl ether, dibutyl ether, methyl ter-butyl ether, tetrahydrofuran, dioxane, anisole, diphenyl ether, ethyl phenyl ether for ethers, pentane, hexane, etc. for aliphatic hydrocarbons, and aromatic hydrocarbons There are benzene, toluene, xylene and the like, and ethyl acetate, acetone, N, N-dimethylformamide, ethylene carbonate, methanol, ethanol, pronol, i-propanol or water. In accordance with the present invention, mixtures of different ratios of different solvents may be used.

  A further particular advantage is obtained from the initiator system for the preparation of polyvinyl acetate consisting of compounds of the formula I, IV or V, cyclopentadienylone dicarbonyl dimer (formula II) and aluminum triisopropoxide (formula III). It is done.

  The present invention further provides polymers based on polymers with geometric specificity and polyvinyl esters of the formulas VI, VII and VIII, and vinyl esters or vinyl esters having one or more 1-olefins. Also provided is a polymer resulting from the reaction of a class with a central unit of formula I, IV or V.

However, in the formula, Z, Ar and Ap are as defined above.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ are each as defined above.
l, m, n, o, p, q, y, z, a, b, and c are as defined above.
X ¹ is as previously defined.
d may be the same or different and may be 0 or 1.
Pol is a polymer based on polyvinyl ester, more preferably a homopolymer or copolymer based on polyvinyl acetate.

  The chain length of the polymer Pol may depend on the reaction factor (time, temperature, pressure, concentration). The chain length is more preferably 3 to 1000. They are described, for example, in Example 3.

Under the conditions described in the description (solvent: anisole, 4.8 mmol vinyl acetate, 5 mol% iron catalyst based on vinyl acetate, 5 mol% aluminum isopropoxide, pressure = 1 bar, T = 70 ° C.) Polyvinyl acetate with a geometric specificity of 12 units vinyl acetate chain length per bond is obtained in 12 hours and polyvinyl acetate with a vinyl acetate chain length and geometric specificity of 12 units per bond Is obtained in 24 hours. The polymer exhibits the following properties:
Tg = 41 ° C. (Cp = 0.42 J / (g * K); Mw = 7200 g / mol; Mn = 2200 g / mol, Mw / Mn = 3.2) The glass transition temperature is a commercially available polyvinyl acetate (Tg = 28 ° C) is clearly higher.

    The following illustrative examples, however, do not limit the invention, but the polymers of the invention are as follows:

However, in the formula, Pol, Xi and d are as defined previously.

  Polymers based on polyvinyl esters and having geometric specificity may be chemically modified. For example, it may be hydrolyzed to obtain polyvinyl alcohol with geometric specificity. These react, for example, with butyraldehyde to obtain polyvinyl butyral with geometric specificity.

  Polymers of the formulas VI, VII and VIII are in particular additives for fuels and motor oils, additives for concrete, additives in paper manufacture, adhesives (components), lubricants, It is suitable as a raw material as a new material based on lacquer components, high-performance plastics and the geometrical specificity of polyvinyl alcohol and polyvinyl butyral.

  The present invention is illustrated by the examples described below, however, these examples are not intended to limit the invention.

  General description: Organometallic compounds were prepared and handled under conditions of argon protection gas (Schlenk technology or globebox), excluding air and moisture. All solvents were completely purified using molecular sieves and also required purification by argon flow.

Example 1:
4- {1,1-bis [4- (2-bromo-2-methylpropionyloxy) phenyl] ethyl} phenyl 2-bromo-2-methyl-propionate

In a 1 L 2-neck round bottom flask, 25 g (82 mmol) of tris (p-hydroxyphenyl) -ethane is suspended in 500 ml of dichloromethane. Add 26 g (36 ml, 261 mmol) of triethylamine and 1 mol% of 4-N, N-dimethylaminopyridine (100 mg, 0.82 mmol). Thereafter, 60 g (261 mmol) of 2-bromoisobutyric acid in 250 ml of dichloromethane is added dropwise within 15 minutes at 0 ° C. After the addition is complete, the mixture is refluxed for 2.5 hours and stirred at room temperature overnight. The reaction mixture is washed three times, each with 350 ml of water and dry magnesium sulfate. The solvent is distilled off by drying under reduced pressure to recover a white powder product.
Yield: 61 g (100%). ¹ H NMR (500 MHz, CDCl ₃ ): δ = 7.10, 7.03 (2 × m, 12H, H of aromatic ring), 2.16 (s, 3H, CH ₃ ), 2.05 (s , _18H, CH 3) ppm.
Example 2:
4- {1,1-bis [4- (2-iodo-2-methylpropionyloxy) phenyl] ethyl} phenyl 2-iodo-2-methyl-propionate

Dissolve 20 g (26.5 mmol) of trisbromide from Example 1 in 500 ml of degassed acetone in a 2 L 2-neck round bottom flask. After the addition of 59.7 g (398 mmol, 15 eq.) Sodium iodide, the compound is refluxed for 24 hours. 700 ml of water are added to the brown suspension solution and the mixture is stirred for 30 minutes at room temperature. The mixture is extracted four times with 400 ml each of diethyl ether and the organic phase is washed twice with 500 ml of water each time. After drying with magnesium sulfate, the solvent is distilled off under reduced pressure to recover a brown semi-crystalline solid (22.4 g). The solid is taken up in 100 ml of methanol, heated briefly and stirred for 0.5 hour. The product is filtered by suction and washed, and the filtration is performed until the color disappears (approx. 50 ml of methanol), and a light camel-colored solid is recovered.
Yield: 14.1 g (15.8 mmol / 60%). In some cases, the product compound is recrystallized with a mixed solution of CHCl ₃ / heptane for further purification. ¹ H NMR (500 MHz, CDCl ₃ ): δ = 7.11, 7.04 (2 × m, 12H, H of aromatic ring), 2.19 (s, 18H, CH ₃ ), 2.16 (s , _3H, CH 3) ppm.
Example 3
Polymerization of vinyl acetate using the initiator of Example 2

A 50 ml Schlenk tube containing a stir bar is initially charged with 85 mg (0.24 mmol) of cyclopentadiel iron dicarbonyl dimer. The following reagents are added sequentially to the iron complex:
1) Anisole 0.19ml
2) 4.42 ml of vinyl acetate (4.13 g, 4.8 mmol)
3) Trisiodide solution from Example 2 (corresponding to 0.16 mmol) 0.0391M 4 ml
4) A solution of aluminum triisopropoxide in anisole (equivalent to 0.24 mmol) 0.25M 0.96 ml
Next, the reaction mixture is stirred at 70 ° C. for 24 hours in a sealed Schlenk tube. After cooling at room temperature, the solvent is completely distilled off by drying under reduced pressure. Add 20 ml of toluene to the residue. The organic phase is washed 3 times with 10 ml of 2M hydrochloric acid each time; the aqueous phase of the compound is extracted twice with 20 ml of toluene each time. The organic phase of the compound is dried over magnesium sulfate and the solvent is completely distilled off under reduced pressure (yield: 2.5 g, 60%). The following steps may be carried out for further purification:
The residue was taken up in a small amount of acetone and purified by column chromatography packed with silica gel (eluent: acetone). The eluent was prepared to 3 ml, and 30 ml of pentane was added. The pentane is removed and discarded and the product compound is then once more dissolved in 3 ml of acetone and added to 30 ml of pentane. After removing the pentane, the pale yellow residue can be recovered as a foamy solid by drying with a vacuum oil pump.
Yield: 1.8 (44%). ¹ H NMR (500 MHz, CDCl ₃ ):
δ = 7.19-6.85 (m, aromatic ring H), 4.83 (s, br, PVAc), 2.13, 1.98, 1, 82, 1.72 (4x s, brPVAc) ) Ppm
¹³ C-NMR (125 MHz, CDCl ₃ )
δ = 170.4, 170.3, 149.2, 131.4, 131.4, 129.46, 128.46, 120.8, 120.6, 113.8, 67.7, 66.9, 66, 7, 66.6, 66.5, 66.3, 66.0, 55.1, 51.5, 39.5, 38.7, 38.6, 21.1, 20.9, 20. 8 ppm.
Tg = 41 ° C. (ΔCp = 0.42 J / (g * K); Mw = 7200 g / mol; Mn = 2200 g / mol, Mw / Mn = 3.2.
Example 4: Polyvinyl acetate star polymer according to DE 10238659

Introduce 5.25 g (15 mmol) (I) dimer of cyclopentadienyldicarbonyliron into a baked 1 L 3-neck flask equipped with a reflux condenser, precision stirrer and pressure equalizer (argon line). To do. The apparatus is then evacuated three times and filled with argon. 12 ml of anisole (anhydrous and degassed) is added to dissolve the iron catalyst.
Thereafter, 552 ml of vinyl acetate (distilled) as an 82 ml solution of anisole (anhydrous and degassed), 5 g (10 mmol) of 1,3,5-trisiodomethylbenzene and anisole (Al (O-iPr in anisole)) ) ₃ 15 mmol concentration 0.25 mol / l) 60 ml of aluminum trisisopropoxide as a solution is added. Then, it heats to 70 degreeC with a precision glass stirrer (150 rpm), and stirs a reaction mixture for 18 hours.

Example 5:
Purification of the polyvinyl acetate star polymer prepared in Example 4 The solvent and vinyl acetate residue are distilled off at 70 ° C. under reduced pressure. The reaction mixture is dissolved in 800 ml of acetone and 1.25 L of n-heptane is added. The mixture is allowed to stand for 1 hour to remove the upper n-heptane. As a result, the obtained brown polymer was dried under reduced pressure for 2 hours and taken out again in 800 ml of acetone. This dark polymer solution is added dropwise to an ice / 2M hydrochloric acid (ice 1 kg / hydrochloric acid 2M 1L) mixture using a KPG stirrer with very high stirring speed. Thereafter, the collected powdery polymer is filtered, washed twice with 250 ml of neutral water, and freeze-dried under reduced pressure. The polymer recovered as a result (yield: 270 g) is colorless and contains no anisole.

Example 6:
Purification by extraction of the polyvinyl acetate star polymer prepared in Example 4 The solvent and the residual vinyl acetate are distilled off at 70 ° C. under reduced pressure. 50 g of the reaction mixture are dissolved in 1000 ml of acetone, 500 ml of toluene and 20 ml of dichloromethane and added to 1.25 L of 1M hydrochloric acid. After stirring for 1 hour, the mixture is allowed to stand until phase separation and the aqueous phase is removed. The volume of the aqueous phase is measured and it is added to the organic phase (V acetone = V measured-V used aqueous phase) as much as acetone so that it dissolves in the aqueous phase. Add the organic phase to 1.25 L of water and stir again. The aqueous phase is also removed from the organic phase, allowing for polymers to be isolated using a motorized evaporator, concentrating the organic phase, and subsequent drying. The polymer recovered as a result (yield: 48 g) is colorless and free of anisole.

Claims (10)

Formulas VI, VII and VIII

In the formula, Pol is a polymer based on polyvinyl ester, more preferably a homopolymer or copolymer based on polyvinyl acetate,
Z is a central atom which is a group 13 to group 16 atom of the periodic table of elements, preferably carbon, silicon, nitrogen, phosphorus, oxygen or sulfur, more preferably carbon or silicon,
X ¹ is the same or different in each case, and is a halogen atom, preferably fluorine, chlorine, bromine, or iodine, more preferably chlorine, bromine, iodine,
R ¹ is the same or different and is hydrogen or a group having 1 to 20 carbon atoms;
R ² is the same or different and is a bridging group having 1 to 20 carbon atoms or silicon or oxygen between the central atom Z and the first (R ³ -X ¹ ) unit;
R ³ is the same or different and is carbon or silicon;
R ⁴ is the same or different and is a hydrogen atom or a group having 1 to 20 carbon atoms;
R ⁵ is the same or different and is hydrogen or a group having 1 to 20 carbon atoms;
l is a natural number and 0, 1, 2 or 3;
m is the same or different in each case, and is a natural number of 0, 1, 2, 3, 4 and 5.
n is the same or different in each case, and is a natural number 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20,
o is the same or different in each case and is 1 or 2,
p is the same or different in each case and is a natural number 1, 2, 3, 4 and 5;
q is a natural number 2, 3, and 4,
Ar is an aromatic basic structure having at least 4 carbon atoms, but one or more carbon atoms may be replaced by boron, nitrogen, phosphorus, and preferred aromatic and heteroaromatic basics. The structural structure is benzene, biphenyl, naphthalene, anthracene, phenatrene, triphenylene, quinoline, pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, benzopyrrole, benzotriazole, benzopyridine, benzopyrazidine, benzopyrimidine, benzopyrazine, benzotriazine, Derived from indolizine, quinolidine, carbazole, acridine, phenazine, benzoquinoline, phenoxazine, each may be optionally substituted,
y is a natural number 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20.
z is a natural number of 2, 3, 4, 5, 6, 7, 8, 9 and 10,
Ap is a cyclic non-aromatic basic structure having at least 3 carbon atoms, but may contain heteroatoms such as nitrogen, boron, phosphorus, oxygen or sulfur, and a preferred aliphatic basic structure is cyclo Those derived from alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cycloheteralkyl groups such as aziridine, azetidine, pyrrolidine, piperidine, azepan, Azocan, 1,3,5-triazinan, 1,3,5-trioxane, oxetane, furan, dihydrofuran, tetrahydrofuran, pyran, dihydropyran, tetrahydropyran, oxepane, oxocane, or sugars such as alpha-glucose, Beta There is a course,
a is a natural number 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.
b is a natural number 2, 3, 4, 5, 6, 7, 8, 9 and 10,
c is a natural number 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.
d may be the same or different and may be 0 or 1.
A polymer based on a polyvinyl ester.   The polymer according to claim 1, wherein Pol is a copolymer based on a polyvinyl ester having one or more 1-olefins having 4 to 20 carbon atoms.   The polymer according to claim 1, wherein Pol is a homopolymer based on polyvinyl acetate.   2. The polymer according to claim 1, wherein Pol is a copolymer based on polyvinyl acetate having one or more 1-olefins having 4 to 20 carbon atoms.   As an additive for fuel, motor oil, as an additive for concrete, as an additive in paper manufacturing, as an adhesive (component), as a lubricant, as a component of lacquer, 5. Polymer process according to one or more of claims 1 to 4, as a high performance plastic and as a starting material for the preparation of polymers based on polyvinyl alcohol and polyvinyl butyral. At least one compound of formula I shown below, at least one metal compound of formula II, and optionally at least one additive of formula III:

In the formula, Z is a central atom and is a group 13 to group 16 atom of the periodic table of elements, preferably carbon, silicon, nitrogen, phosphorus, oxygen or sulfur, more preferably carbon or silicon,
X ¹ is the same or different in each case and is a halogen atom, preferably fluorine, chlorine, bromine or iodine, more preferably chlorine, bromine or iodine;
R ¹ is the same or different and is hydrogen or a group having 1 to 20 carbon atoms;
R ² is the same or different and is a bridging group having 1 to 20 carbon atoms or silicon or oxygen between the central atom Z and the first (R ³ -X ¹ ) unit;
R ³ is the same or different and is carbon or silicon;
R ⁴ is the same or different and is a hydrogen atom or a group having 1 to 20 carbon atoms;
R ⁵ is the same or different and is hydrogen or a group having 1 to 20 carbon atoms;
l is a natural number 0, 1, 2 or 3,
m is the same or different in each case and is a natural number 0, 1, 2, 3, 4, and 5;
n is the same or different in each case, and is a natural number 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20,
o is the same or different in each case and is 1 or 2,
p is the same or different in each case and is a natural number 1, 2, 3, 4, and 5;
q is a natural number 2, 3, and 4,
M ¹ is the same or different in each case and is a transition metal of group 3 to group 12 of the periodic table of elements, preferably chromium, molybdenum, ruthenium, iron, rhodium, nickel, palladium or copper, more preferably iron or ruthenium And
X ² is the same or different in each case and is an oxygen or halogen atom, more preferably fluorine, chlorine, bromine or iodine;
L is the same or different in each case and is a ligand, preferably a carbon ligand such as a methyl, phenyl, cymene, cumene, tolyl, mesityl, xylyl, indenylbenzylidene, cyclopentadienyl, or carbonyl group In the nitrogen ligand, for example, triethylamine, tetramethylethylenediamine, pyridine, 2,2′-bipyridyl, substituted 2,2′-bipyridyl, 1,10-phenantrone, phenylpyridin-2-ylmethyleneamine, Acetonitrile, substituted imidazolidine or terpyridyl, for phosphorus ligands, for example triphenylphosphine, tricyclohexylphosphine, bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane or BINAP,
r is the same or different in each case and is a natural number 1, 2, 3, 4, and 5;
s is the same or different in each case and is a natural number 0, 1, 2, 3, 4, and 5;
t is the same or different in each case and is a natural number 0, 1, 2, 3, 4, and 5;
u is a natural number 1, 2, 3, 4, and 5;
M ² is the same or different and is an element of Groups 1 to 15 of the periodic table of elements, more preferably Li, Mg, Ti, B, Al, P or N,
R ⁶ is the same or different and is hydrogen, a halogen atom or a group having 1 to 20 carbon atoms, more preferably methoxy, ethoxy, n-propoxy or i-propoxy,
v is the same or different and is a natural number 1, 2, 3, 4, 5, 6, 7 and 8;
w is the same or different and is a natural number 1, 2, 3, 4, 5, 6, 7 and 8;
x is a natural number 1, 2, 3, 4, 5, 6, 7 and 8.
An initiator system for preparing a polyvinyl ester comprising: Instead of the compound of formula I, at least one compound of formula IV shown below:

In the formula, Ar has an aromatic basic structure having at least 4 carbon atoms, and one or more of these carbon atoms may be substituted with boron, nitrogen, or phosphorus. The basic structure of heteroaromatics is benzene, biphenyl, naphthalene, anthracene, phenatrene, triphenylene, quinoline, pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, benzopyrrole, benzotriazole, benzopyridine, benzopyrazidine, benzopyrimidine, benzo Derived from pyrazine, benzotriazine, indolizine, quinolidine, carbazole, acridine, phenazine, benzoquinoline, phenoxazine, each of which may be optionally substituted,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ are each as defined in claim 5;
m, n, o and p are each as defined in claim 5;
X ¹ is as defined in claim 5;
y is a natural number 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20.
z is a natural number 2, 3, 4, 5, 6, 7, 8, 9 and 10.
An initiator system according to claim 5, characterized in that Instead of the compound of formula I, at least one compound of formula V shown below:

Where Ap is a cyclic non-aromatic basic structure and has at least 3 carbon atoms, but may contain heteroatoms such as nitrogen, boron, phosphorus, oxygen or sulfur, and is also preferably an aliphatic The basic structure is derived from a cycloalkyl group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cycloheteralkyl groups, such as aziridine, azetidine, pyrrolidine, From piperidine, azepane, azocane, 1,3,5-triazinan, 1,3,5-trioxane, oxetane, furan, dihydrofuran, tetrahydrofuran, pyran, dihydropyran, tetrahydropyran, oxepane, oxocane, or sugars Alpha-glucose, ba - There is a glucose,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ are each as defined in claim 5;
m, n, o and p are as defined in claim 5 respectively.
Each X ¹ is as defined in claim 5;
a is a natural number 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.
b is a natural number 2, 3, 4, 5, 6, 7, 8, 9 and 10,
c is a natural number 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20.
An initiator system according to claim 5, characterized in that   A process of one or more initiator systems according to any one of claims 5 to 7 for preparing the polymer according to claim 1.   The process for preparing a polymer according to claim 1, characterized in that a system of one or more initiators according to any one of claims 5 to 7 is used.