KR20010112306A - Catalyst composition and method for making a polymer or copolymer - Google Patents

Abstract

The present invention is directed to a support via a divalent group R, wherein R is an unsubstituted or substituted C ₁ -C ₂₀ straight, branched or cyclic alkylene group, arylene, alkaryl or aralkylene group. It relates to a catalyst complex comprising a transition metal or transition metal compound having an average of one or more coordination ligands supported by the ligand. Preferably, M is Cu (I) and Y is Cl or Br and each ligand is an organic diimine group such as 1,4-diaza-1,3-butadiene, 2,2'-ratio Pyridine, pyridine-2-carboxaldehyde imine, oxazolidone or quinoline carbaldehyde group, and the support is an organic or siloxane polymer or network structure. The present invention also relates to a process for preparing a polymer or copolymer by controlling the polymerization, characterized in that the vinyl containing monomer is polymerized in the presence of an initiator and a catalyst composite according to the invention.

Description

Catalyst composites and methods for preparing polymers or copolymers

The present invention relates to a catalyst composite and a process for producing a polymer or copolymer, in particular a method for producing a polymer or copolymer by controlling the polymerization of a catalyst composite and a vinyl containing monomer.

Control of the polymerization system is of great importance in the field of macromolecular chemistry because such controlled polymerization systems can control the preparation of polymers having certain desirable aspects. For example, by controlling the ratio of monomer to initiator concentration, the molecular weight, molecular weight distribution, functionality, topology, and / or dimensional structure of the resulting polymer can be controlled.

In preparing high molecular weight polymers, free radical polymerization has long been a commercially important process. A wide range of monomers can be polymerized or copolymerized without solvent or under free radical polymerization in solutions, emulsions, suspensions or dispersions under relatively simple conditions. However, a disadvantage of the existing free radical polymerization is that it is difficult to control the aspect of the resulting polymer.

A method of controlling radical polymerization has been proposed. For example, in WO 96/30421, WO 97/18247 and WO 98/01480, polymerization based on atom transfer radical polymerization (ATRP) which controls radical polymerization of styrene, (meth) acrylates and other radically polymerizable monomers The method is described. The process comprises (i) an initiator system having an radical or radically transferable atom or group, for example 1-phenylethyl halide, alkyl 2-halopropionate, or α, α-dihaloxylene, ii) a transition metal or transition metal compound, for example Cu (I) Cl, Cu (I) Br, Ni (0), FeCl ₂ , or RuCl ₂ and (iii) a C capable of coordinating with the transition metal, N, O, S or P containing ligands such as bipyridine or (alkoxy) ₃ P are used. However, this method has the disadvantage that the transition metal complex formed by the initiating system is only partially soluble in the polymerization system, resulting in heterogeneous polymerization. A homogeneous atom transfer radical polymerization method is proposed in WO 97/47661, in which diimine ligand containing catalysts are used, for example 1,4-diaza-1,3-butadiene and 2-pyridinecarb-aldehyde. However, in this method the residual amount of catalyst in the resulting polymer is unacceptably high and it is difficult to remove the catalyst from the polymer product. Thus, the process is not only costly, but also undesirably the colored polymer product can be produced due to the presence of the residual catalyst in the product.

See Chem. Commun., 1999, 99-100 Haddleton et al, describe solid supported copper catalysts and their use in atom transfer polymerization of methyl methacrylate, which are believed to be reusable and easy to remove from polymer products. It is. However, as explained from the fact that the difference between the theoretical molecular weight of the polymer product and the experimental molecular weight is large, it was found that the control of the polymerization reaction was not performed properly.

We have prepared catalyst composites that include supported transition metal compounds and have improved performance compared to the compositions of the prior art described above.

As used herein, the term "comprises" is used in its broadest sense to encompass "contains", "consists of" and "consists of."

In embodiment 1 according to the invention, the divalent group R, wherein R is an unsubstituted or substituted C ₁ -C ₂₀ straight, branched or cyclic alkylene group, arylene, alkarylene or aralkylene group There is provided a catalyst complex comprising a transition metal or transition metal compound having an average of one or more coordination ligands supported by the support, and which is solid at room temperature.

The transition metal may be selected from, for example, copper, iron, ruthenium, chromium, molybdenum, tungsten, rhodium, cobalt, rhenium, nickel, manganese, vanadium, zinc, gold and silver. Suitable transition metal compounds include compounds of the formula MY wherein M is a transition metal cation and Y is a counter anion. M is preferably selected from Cu (I), Fe (II), Co (II), Ru (II) and Ni (II), most preferably Cu (I). Y is, for example, Cl, Br, F, I, NO ₃ , PF ₆ , BF ₄ , SO ₄ , CN, SPh, SCN, SePh or triflate (CF ₃ SO ₃ ), most preferably Cl Or Br.

The catalyst complex includes an average of one or more ligands coordinated with the transition metal or transition metal compound, and preferably includes two or more coordinated ligands. Suitable ligands include C, N, O, P, and S containing ligands that are capable of coordinating with the transition metal or transition metal compound. WO 97/47661, WO 96/30421, WO 97/18247 and WO 98/01480 describe a number of examples of suitable ligands. Preferred ligands are organic diimine groups, in particular 1,4-diaza-1,3-butadiene of formula I, 2,2'-bipyridine of formula II, pyridine-2-carboxaldehyde imine of formula III, formula IV Oxazolidone or quinoline carbaldehyde of the formula (V).

In the above formulas (I) to (V),

Each R ¹ is independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ straight chain, branched or cyclic alkyl group, aryl, alkaryl, aralkyl group or halogen atom, preferably hydrogen atom or substituted Unsubstituted C ₁ -C ₁₂ alkyl group,

Each R ² is independently an R ¹ group or a C ₁ -C ₂₀ alkoxy group, NO ₂ —, CN- or carbonyl group.

At least one contiguous R ¹ and R ² group, and two R ² are C ₅ -C ₈ cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl or cyclic aryl groups such as cyclohexyl, cyclo Hexenyl or norbornale groups may be formed. The 2-pyridinecarbaldehyde imine compound of Formula III may comprise a fused ring on a pyridine group.

Preferred organic diimine containing groups are groups of formula III wherein each R ² is a hydrogen atom.

The divalent R is preferably an unsubstituted C ₁ -C ₆ straight or branched alkylene group (eg propylene group) or an aralkylene or alxarylene group (eg benzylene or tolylene group).

The support may be an inorganic or organic network structure or polymer. Suitable inorganic networks or polymers consist of oxides of Si, Zr, Al or Ti and mixed oxides thereof (eg zeolites). Preferred inorganic supports are siloxane polymers or networks having units of the formula (R ³ ₃ SiO _1/2 ) _a (R ³ ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d . [Wherein R ³ is each independently an alkyl group (preferably a methyl group), a hydroxy group or an alkoxy group, a, b, c and d are each independently 0 or a positive integer and a + b + c + d is an integer of 10 or more]. Such siloxane polymers and networks can include silicon-containing monomers or oligomers, such as organic functional silanes, silica and organic cyclosiloxanes of formula (R ⁴ ₂ Si) _e , wherein R ⁴ is an alkyl group, for example C _1- C ₆ alkyl group, most preferably methyl group).

Suitable organic network or polymer supports can include any organic material that can maintain the catalyst composite in a solid state at room temperature and does not interfere with any polymerization reaction in which the catalyst composite acts as a catalyst. Examples of suitable organic networks or polymers include polyolefins, polyolefin halides, oxides and glycols, polymethacrylates, polyarylenes and polyesters.

The ligand may be physically or chemically bound to the support via a divalent group R, but the ligand is preferably chemically bound to the support via a divalent bond R.

Particularly preferred catalyst composites of embodiment 1 of the present invention are those according to formulas VI and VII.

In the above formulas VI and VII,

The siloxane polymer or network structure is a unit of formula (R ³ ₃ SiO _1/2 ) _a (R ³ ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d , wherein R ³ , a, b, c and d are as defined above and n is a positive integer).

Thus, according to the present invention there is provided a catalyst complex comprising a Cu (I) compound that is solid at room temperature and is coordinated with two pyridine-2-carboxaldehyde imine ligands, each of which is a (R ³ ₃ SiO). _1/2 ) _a (R ³ ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d , where R ³ , a, b, c and d are as defined above Is supported by a siloxane polymer or network, or a polystyrene polymer or network.

The catalyst composite of Embodiment 1 of the present invention may be prepared by conventional methods known to those skilled in the art. The reagents used to prepare the catalyst complex should be used in a molar ratio such that in the catalyst complex the transition metal or transition metal compound is coordinated with an average of one or more ligands.

For example, an organic diimine-containing group, which is a diazabutadiene, can be prepared by reacting glyoxal with an aniline derivative, as shown in Scheme 1.

In Scheme 1 above,

X is a leaving group, for example a hydroxy group, an alkoxy group or a halogen atom.

The diazabutadiene thus prepared is subsequently reacted with a suitable support material and transition metal compound to form a catalyst complex, for example as shown in Scheme 2:

In Scheme 2 above,

n is as defined above.

As another example, an organic diimine containing group, which is pyridine-2-carboxaldehyde imine of Formula III, can be prepared by reacting ethanolamine with pyridine-2-carboxaldehyde, as shown in Scheme 3:

The pyridine-2-carboxaldehyde imine thus prepared is subsequently reacted with a suitable support material and transition metal compound to form a catalyst complex, as shown above.

Catalyst composites according to embodiment 1 of the present invention are particularly useful in the process for preparing polymers or copolymers by controlling the polymerization of vinyl containing monomers with a catalyst.

Thus, in embodiment 2 according to the present invention, a method is provided for producing a polymer or copolymer by controlling the polymerization, including the step of polymerizing a vinyl containing monomer in the presence of an initiator and a catalyst according to embodiment 1 of the present invention.

An advantage of the method of embodiment 2 of the present invention is that the catalyst composite of embodiment 1 of the present invention used in the method of embodiment 2 is a solid at room temperature and can therefore be recovered and reused from the polymer product for a high degree of control over the polymerization reaction. Can be. Particularly advantageous catalyst composites are those which are not only solid at room temperature but also have a melting point below the temperature at which the polymerization reaction takes place. Particularly effective polymerization can be carried out in such a way that the catalyst complex is a liquid in the reaction mixture at room temperature so that the transition metal compound is more easily mixed into the reaction mixture to effectively carry out the catalysis of the reaction. As the temperature of the product is cooled after the reaction is carried out below the melting point of the catalyst composite, the catalyst can be recovered from the reaction mixture.

The vinyl containing monomer may be methacrylate, acrylate, styrene, methacrylonitrile or diene. Examples of vinyl containing monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and other alkyl methacrylates and corresponding acrylates, including glycidyl methacrylate, tri Organic functionality including methoxysilylpropyl methacrylate, allyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dialkylaminoalkyl methacrylate, and fluoroalkyl (meth) acrylates Methacrylates and acrylates are included. Other suitable vinyl containing monomers include methacrylic acid, acrylic acid, fumaric acid and esters, itaconic acid (and esters), maleic anhydride, styrene, α-methylstyrene, vinyl halides (e.g. vinyl chloride and vinyl fluoride), acrylonitrile , Methacrylonitrile, vinylidene halide of formula CH ₂ = C (halogen) ₂ , wherein halogen is Cl or F, unsubstituted or substituted butadiene of formula CH ₂ = CR ⁵ -CR ⁵ = CH ₂ Wherein R ⁵ is each independently H, a C ₁ -C ₁₀ alkyl group, Cl or F), an acrylamide of the formula CH ₂ = CHCONR ⁶ ₂ or a derivative thereof, wherein R ⁶ is H, C ₁ -C ₁₀ Alkyl group or Cl) and methacrylamide of the formula CH ₂ = C (CH ₃ ) CONR ⁶ ₂ or a derivative thereof, wherein R ⁶ is H, a C ₁ -C ₁₀ alkyl group or Cl. Mixtures of different monomers can also be used.

The initiator used in the method of embodiment 2 of the present invention may be any conventional initiator suitable for use with the catalyst composite of embodiment 1 of the present invention controlling the polymerization. Examples of such initiators are C ₁ -C ₆ esters of 1-phenylethyl chloride and bromide, chloroform, carbon tetrachloride, 2-chloropropionnitrile, 2-halo-C ₁ -C ₆ -carboxylic acids, such as 2-chloro or 2- Bromopropionic acid and 2-chloro or 2-bromoisobutyric acid), 1-phenylethylchloride and bromide, methyl and ethyl 2-chloropropionate, methyl and ethyl 2-bromopropionate, ethyl 2-isobutyrate , α, α'-dichloro and α, α'-dibromoxylene and hexakis (α-bromomethyl) benzene. Other suitable initiators are described in WO 97/47661, WO 96/30421, WO 97/18247 and WO 98/01480 described above.

Preferred initiators used in the process of embodiment 2 of the present invention include one or more groups of the formula -D-CR ⁸ ₂ X 'wherein D contains an oxygen or nitrogen heteroatom and / or is substituted by a carbonyl group A straight or branched alkylene group, R ⁸ is each independently an alkyl group or a hydrogen atom, X ′ is a halogen atom), a chemical formula (R ⁷ ₃ SiO _1/2 ), (R ⁷ ₂ SiO _2/2 ), A unit of (R ⁷ SiO _3/2 ) and / or (SiO _4/2 ), wherein R ⁷ is each independently a group of formula —D—CR ⁸ ₂ X ′ or a substituted or unsubstituted hydrocarbon group Include.

Preferred initiators may be straight, branched, cyclic or dendritic siloxanes.

R ⁷ is an alkyl group (eg methyl, ethyl, propyl, butyl, pentyl or hexyl group), substituted alkyl group (eg fluoropropyl group), alkenyl group (eg vinyl or hexenyl group), aryl group (Eg phenyl groups), aralkyl groups (eg benzyl groups) or alkaryl groups (eg tolyl groups), with C ₁ -C ₆ alkyl groups being preferred.

Preferably, at least one of the groups R ⁸ in each group of the formula —D—CR ⁸ ₂ X ′ is an alkyl group. That is, X 'is preferably a secondary or tertiary halogen atom. More preferably, in each group of the formula -D-CR ⁸ ₂ X 'both groups R ⁸ are both alkyl groups. That is, X 'is more preferably a tertiary halogen atom. In a particularly preferred embodiment each R ⁸ is a methyl group.

X is preferably a bromine atom.

Preferred examples of divalent group D include Chemical formula and group of Wherein R ⁹ is an alkyl group, for example methyl or a hydrogen atom, R ¹⁰ is each independently a straight or branched alkylene group, and r is an integer from 1 to 4.

Preferred initiators used in the process of Embodiment 2 of the invention are compounds of the formula R ⁷ ₃ SiO (SiR ⁷ ₂ O) _q SiR ⁷ ₃ , wherein R ⁷ is as defined above and q is 0 or a positive integer, eg For example, 10 to 100).

Particularly preferred initiators have the formula

In the above formula (VIII),

R ⁷ , R ⁸ , D, X 'and q are as defined above.

Examples of initiators of formula VIII are as follows:

,

,

And

(Where s is 0 or a positive integer, for example 1 to 100, and t is a positive integer, for example 1 to 10).

Preferred initiators used in the process of Embodiment 2 of the present invention have at least one group R11 and include formulas (R ¹¹ ₃ SiO _1/2 ), (R ¹¹ ₂ SiO _2/2 ), (R ¹¹ SiO _3/2 ) and And / or units of (SiO _4/2 ), wherein at least one group R ¹¹ is an amino group, a hydroxy group or an alkoxy group or an alkyl group substituted with amino, hydroxy or alkoxy and the remaining groups R ¹¹ are each independently A siloxane (i) comprising a group R ⁷ as defined above and a compound of formula X'CR ⁸ ₂ -E, wherein E is condensed with an amino group, hydroxy group or alkoxy group, or amino, hydroxy or A group which participates in condensation reaction with an alkoxy substituted alkyl group to form a divalent straight or branched alkylene group containing an oxygen or nitrogen heteroatom and / or substituted by a carbonyl group, R ⁸ and X 'Jung from above A condensation reaction with a bar like) (ii) it may be prepared by a process comprising performing a.

The particular reagents (i) and (ii) as defined above used in the method of preparing the initiator will of course depend on the particular initiator to be prepared. For example, to prepare an initiator wherein the divalent group D comprises a peptide bond as defined above, a condensation reaction can be performed between the aminoalkyl substituted siloxane and acyl halide, as shown in Scheme 4 below. .

For further example, if the divalent group D comprises a carboxy bond, a condensation reaction can be carried out between the hydroxyalkyl substituted siloxane and the acyl halide as shown in Scheme 5 below.

The condensation reaction can be carried out at room temperature or higher, for example 50 to 100 ° C.

The method of embodiment 2 of the invention can be carried out at a wide range of temperatures, for example from room temperature to 200 ° C., in particular from room temperature to 130 ° C., most preferably from 80 to 100 ° C.

The method of embodiment 2 can be carried out in the presence or absence of a solvent. Suitable solvents are water, propionitrile, hexane, heptane, dimethoxyethane, diethoxyethane, tetrahydrofuran, ethyl acetate, diethyl ether, N, N-dimethylformamide, anisole, acetonitrile, diphenyl ether Protic and aprotic solvents, including methyl isobutyrate, butan-2-one, toluene and xylene, with toluene and xylene being preferred.

The process can be carried out under an inert atmosphere, for example under an argon or nitrogen atmosphere.

The catalyst composite may be used in an amount of 1 to 50% by weight, preferably 1 to 20% by weight, more preferably 5 to 10% by weight of the monomers.

The method of embodiment 2 of the present invention can be used to prepare a variety of polymers and copolymers. A wide variety of monomers can be polymerized to provide homopolymers, random or gradient copolymers, periodic copolymers, block copolymers, functionalized polymers, hyperbranched and branched polymers, graft or comb polymers and polysiloxane organic copolymers. have. Polysiloxane organic copolymers have several potential uses. For example, polysiloxane-polyhydroxyalkyl acrylate blocks and graft copolymers are used in the field of soft contact lenses, and polysiloxane-aminoacrylate copolymers are useful as antifoaming and anti-inflammatory agents, and polysiloxanes with short-chain aminoacrylate blocks. -Aminoacrylate copolymers are useful as fiber treatment agents, polyalkoxysilylalkylacrylate-polysiloxanes and polyepoxyglycidylacrylate-polysiloxane copolymers are useful as additives for epoxy resins, curable powder coatings and sealants, Long chain alkyl methacrylate or acrylate-polysiloxane copolymers are useful as surface modifiers or additives for polyolefins and polyester-polyacrylate copolymers, and ABA methacrylate or acrylate-polysiloxane block copolymers Crosslinking may be useful as an oxygen barrier coating, phosphonic Phoebe other person or sulfonic Phoebe-polysiloxane ionomer as saenghon resistance, for example, it can be used in shampoos and other hair treatment agent.

The present invention will now be described by way of examples.

Example 1 Preparation of Solid Supported Copper Catalyst 1

In a 100 ml flask equipped with a magnetic stirrer and a condenser, 20.0 g (186.7 mmol) of 2-pyridine carboxyaldehyde and 10.7 g (74.6 mmol) of CuBr are mixed in 62 ml of tetrahydrofuran. Insoluble matter is dissolved by adding 33.5 g (186.8 mmol) of 3-aminopropyltrimethoxysilane. The reaction is an exothermic reaction that forms a dark red solution, cooled to room temperature and then 0.07 g (1.9 mmol) of NH ₄ F diluted in 1.7 ml of water is added. The resulting solution is then heated with stirring at 60 ° C. for 24 hours. The volatiles were evaporated under vacuum, the resulting solid was milled, washed with ether and dried under vacuum at 80 ° C. to give a reddish brown powder [Cu (% m / m) = 8.92%, insoluble in toluene, xylene and acetone) 45.5 g is obtained.

Reference Example 1 Preparation of Polydimethylsiloxane (PDMS) Macromolecular Initiators End-capped with Bromoisobutyrylamide

In a 250 ml flask equipped with a magnetic stirrer, a condenser and an addition funnel, to a solution of 9.0 g (62.9 mmol) of tetramethylazasilacyclopentane in 40 ml of toluene under N ₂ in hydroxy terminated PDMS [40 degree of polymerization (D _p) ) = 45] 100.0 g is added dropwise at room temperature. After heating at 50 ° C. for 2 hours, volatiles were removed under vacuum to yield 93.0 g of a colorless liquid. According to the results analyzed by ¹³ C, ²⁹ Si NMR and FTIR, the obtained liquid was identified as PDMS (D _p = 45) end capped with amine.

Then, a magnetic stirrer, condenser and addition funnel is bromo cattle feeders butyryl bromide 4.25g in 100ml to the terminal is capped with an amine of triethylamine in 50ml PDMS 30g in the flask, 20ml of toluene, which provided (18.5mmol) N ₂ Drop wise at room temperature. The mixture is kept at 90 ° C. for 1 hour with stirring, then the salts are filtered under vacuum and the solvent is evaporated. The polymer obtained is washed with toluene and water. The organic phase was dried over magnesium sulfate, filtered and the volatiles removed to give 27.8 g (86% yield) of a pale yellow liquid. ¹ H, ¹³ C and ²⁹ Si NMR characteristics of the obtained liquid showed that the liquid was N-bromoisobutylyl, N-methylamino, 2-methylpropyl end-blocked PDMS (Br (CH ₃ ) ₂ CCON (CH ₃ ) CH ₂ CH (CH ₃ ) CH ₂ )-).

Example 2 Polymerization of Methyl Methacrylate

5.39 g (53.9 mmol) of methyl methacrylate (MMA) in 11.5 mL of anhydrous p-xylene are added to 0.66 g of the catalyst prepared in Example 1 above in a Schlenk tube. The resulting mixture is deoxygenated by one freeze-pump-thaw cycle, and then 1.0 g of the macromolecular initiator prepared in Reference Example 1 above is added at room temperature. The resulting solution is heated at 90 ° C. for 6 hours under N ₂ and samples are taken at timed intervals to conduct ¹ H NMR analysis. The final polymer and catalyst are separated by simple filtration with paper. The final polymer is dried under vacuum to yield 3.9 g of a pale yellow solid. The conversion of monomers as observed by ¹ H NMR is 59%. The catalyst is washed with toluene and ether and dried in vacuo to give 0.51 g of active copper catalyst which can be reused in further polymerization. The results are presented in Table 1, which shows that a very good correlation was established between the theoretical molecular weight and the experimental value to control the polymerization.

Hour % Conversion Mn _th (g / mol) Mn (g / mol) PDMS% 0 0 3710 3710 100 2 10 5710 5480 68 3 27 9110 8590 43 4 42 12160 11470 32 5 52 14130 14090 26 6 59 15450 15200 24

Mn = number average molecular weight

Mn _th = number average molecular weight theory

Example 3 Polymerization of MMA Using Recycled Catalyst

4.01 g (40.1 mmol) of MMA in 8.6 ml of dry p-xylene is added to 0.49 g of the copper catalyst recycled from Example 2 above in a Schlenk tube. After the resulting mixture is deoxygenated by one freeze-pump-thaw cycle, 0.744 g of the macromolecular initiator prepared in Reference Example 1 above are added. The resulting solution is heated at 90 ° C. for 24 h under N ₂ and samples are taken at timed intervals to conduct ¹ H NMR analysis. The results are shown in Table 2, which shows that a very good correlation between molecular weight theory and experimental value was established, indicating that polymerization was controlled.

Hour % Conversion Mn _th (g / mol) Mn (g / mol) PDMS% 0 0 3710 3710 100 4 9 5510 5350 70 6 13 6310 5990 62 24 84 20500 18700 20

Example 4 Preparation of Solid Supported Copper Catalyst 2

In a 1 L flask equipped with a magnetic stirrer and condenser, 100.4 g (560.0 mmol) of 3-aminopropyltrimethoxysilane and 63.0 g (558.2 mmol) of 2-pyridine carboxyaldehyde are mixed. After stirring for 10 minutes, 26.8 g (186.8 mmol) CuBr, 170.4 g (1119.4 mmol) tetramethoxysilane, 45.2 g (2511.1 mmol) water and 0.6 g (16.2 mmol) NH ₄ F are added continuously to the flask. . A strong exothermic reaction is observed and a homogeneous dark solution is obtained at room temperature. After 48 hours, the solution gels with a soft gel. After aging this solid for one week, the volatiles are removed by evaporation under vacuum. The resulting solid is milled, washed with ether and dried under vacuum at 80 ° C. for 8 hours to give 202.5 g of reddish brown powder.

Reference Example 2 Preparation of PDMS Macromolecular Initiators End-capped with Bromoisobutyrate

Into a 100 ml flask with 20 ml of toluene and a magnetic stirrer, condenser and addition funnel, -Si (CH ₃ ) _2- (CH ₂ ) ₂ -o- (CH ₂ ) ₃ CH ₂ OH terminal units 51 g PDMS with an average molecular weight of 2084 (OH 0.049 mol) is loaded. 12.37 g (0.053 mol) of bromobutyrate bromide is added dropwise at room temperature, the reaction is allowed to react overnight at room temperature, the salts are filtered off and the solvent is evaporated. The polymer is washed with toluene and water. The organic phase is dried over magnesium sulfate, filtered and the volatiles are removed under reduced pressure. Analysis of ¹ H NMR spectra revealed that all carbinol functional groups (δ = 3.56 ppm) disappeared and -Si (CH ₃ ) _2- (CH ₂ ) ₂ -o- (CH ₂ ) ₃ CH ₂ OCOC (CH ₃ ) at 4.19 ppm ₂ Br appears.

Example 5-Polymerization of MMA

190 g (1.9 mmol) of MMA in 300 ml of dry p-xylene are added to 10 g of the catalyst prepared in Example 5 (pre-extracted with p-xylene for 6 hours in a soxhlet) in a 500 ml Schlenk tube. The resulting mixture is deoxygenated by one freeze-pump-thaw cycle and heated at 90 ° C., followed by the addition of 10 g of the macromolecular initiator prepared in Example 6. The reaction is continued for 30 hours at 90 ° C. Samples are taken at timed intervals to perform ¹ H NMR analysis. During the polymerization, the viscosity of the solution becomes very high but remains transparent, and the catalyst remains visible in the polymer solution. After the polymerization, the solid catalyst is removed by filtration. The conversion of monomers observed by ¹ H NMR is 44% and Mn measured by ¹ H NMR is 20,900. The catalyst can be extracted with p-toluene for 6 hours in a soxhlet and reused for further polymerization. GPC analysis of the polymer showed a narrower molecular weight distribution (Mn _th / Mn = 1.29) compared to the molecular weight distribution of the starting polysiloxane macromolecular initiator (Mn _th / Mn = 1.5).

Example 6-Polymerization of MMA with Recycled Catalyst

30 g (0.3 mmol) of MMA in 30 ml of anhydrous p-xylene are added to 2.3 g of the catalyst (extracted with p-xylene for 6 hours in a soxhlet) collected in Example 7 above in a 100 ml Schlenk tube. The resulting mixture is deoxygenated by one freeze-pump-thaw cycle and heated at 90 ° C., followed by addition of 3 g of the macromolecular initiator prepared in Example 6 above at room temperature. The reaction is continued for 44 hours at 90 ° C. Samples are taken at timed intervals to perform ¹ H NMR analysis. During the polymerization, the viscosity of the solution becomes very high but remains transparent, and the catalyst remains visible in the polymer solution. After the polymerization, the solid catalyst is removed by filtration. The results are presented in Table 3, which shows that a very good correlation between the molecular weight theory and the experimental value was established to control the polymerization.

Hour % Conversion Mn _th (g / mol) Mn (g / mol) PDMS% 0 0 2400 2400 100 28 22 7800 7800 31 44 33.5 10400 10400 23

Example 7 Preparation of Solid Supported Copper Catalyst 3

5 g of aminomethylpolystyrene (0.01 mol-NH ₂ ) and 1.2 g (0.012 mol) of pyridinecarboxyaldehyde are added to 100 ml of a flask containing 50 ml of diethyl ether at room temperature and reacted under nitrogen overnight. After the reaction, the pale yellow powder is collected, washed with dichloromethane and toluene and dried at 65 ° C. for 2 hours. 4.5 g of powder are mixed with 1.02 g of CuBr in 50 ml of acetone and stirred until all the powder turns black. The reaction is continued for 3 hours under acetone reflux. After the reaction, the powder is washed with water and extracted with methanol in soxhlet for 7 hours. ¹³ C NMR analysis in the solid state confirms the presence of imine groups and the absence of amine groups.

Example 8-Polymerization of MMA

20 ml of dry p-xylene and 10 g (1.9 mol) of MMA are added to a 100 ml Schlenk tube containing 5.3 g of a copper catalyst prepared according to Example 9 above. The resulting mixture was deoxygenated by one freeze-pump-thaw cycle and heated at 90 ° C., followed by addition of 1.01 g of the macromolecular initiator prepared in Example 6 above. The reaction is continued at 90 ° C. for 5 hours and samples are taken at timed intervals. During the polymerization, the viscosity of the solution becomes very high but remains transparent. The catalyst particles remain visually identifiable in the polymer solution. After polymerization for 5 hours, the conversion of monomers observed by ¹ H NMR is 33% and Mn is 7,100.

Example 9-Polymerization of MMA

47.4 g (0.47 mmol) of MMA in 50 ml of dry p-xylene are added to 19.4 g of the copper catalyst prepared according to Example 5 above in a 250 ml Schlenk tube. The resulting mixture is deoxygenated by one freeze-pump-thaw cycle and heated at 90 ° C., followed by addition of 5.0 g of the macromolecular initiator prepared according to Example 6. The reaction is continued under N ₂ at 90 ° C. for 4 hours. Samples are taken at timed intervals to perform ¹ H NMR analysis. During the polymerization, the viscosity of the solution becomes very high and the catalyst remains visible in the polymer solution. The results are presented in Table 4, which shows that a very good correlation between the molecular weight theory and the experimental value was established, indicating that the polymerization was controlled.

Hour % Conversion Mn _th (g / mol) Mn (g / mol) PDMS% 0 0 960 960 100 60 21 2850 2960 32 120 65 6810 7760 13 180 84 8520 9360 10 240 95 9510 10760 9

Reference Example 3 Preparation of PDMS Macromolecular Initiators Having Side Chain Bromoisobutyrate Groups

80.5 g of dimethylmethyl (aminopropyl) siloxane, terminated with dimethoxyethoxy, having a polymerization degree of 100 and NH ₂ 0.018 mol in a 500 ml three-necked reaction flask equipped with a dropping funnel, a thermometer and a magnetic stirrer, and p- Load 100 ml of xylene. After homogenization, 3.35 ml (0.024 mol) of triethylamine are added and 5.53 g (0.024 mol) of bromoisobutyryl bromide is slowly injected at room temperature. The reaction is carried out with stirring at 50 ° C. for 3 hours. After the reaction, p-xylene is evaporated and triethylammonium salt is precipitated by adding 300 ml of n-hexane. Following this step, the hexanes are evaporated after filtration. The product is a clear yellow high viscosity polymer. According to the ¹ H NMR spectrometer, the amine functionality disappears, the peak of CH ₂ C H ₂ NH ₂ shifts from 3.99 ppm to 3.30 ppm, and a new signal corresponding to -N H -COC (CH ₃ ) ₂ Br at 6.99 ppm It is confirmed to appear. Although some terminal ethoxy groups are hydrolyzed, the bromination yield is 100%.

Example 10 Preparation of Solid Supported Copper Catalyst 4

In a 2000 ml three-necked reaction flask equipped with a dropping funnel, thermometer and reflux condenser, 246 g (1.37 mol) of aminopropyltrimethoxysilane and 300 ml of p-xylene were loaded. The methanol is then distilled off while 75 g (4.16 mol) of water are added over 60 minutes. After the methanol is removed, the p-xylene is removed by stripping under reduced pressure to give a white brittle solid. 84 g of solid and 300 ml of p-xylene are loaded into a 1000 ml reaction flask and slowly added 70 g (1.0 mol) of 2-pyridine carboxyaldehyde while cooling. After 2-pyridine carboxyaldehyde is added, 57 g of CuBr is added with vigorous stirring, at which time the temperature is kept below 30 ° C. Stirring is continued until the green phase of free Cu (I) disappears completely. After the reaction is complete, the resulting solid is separated from the solvent, washed with toluene and used without further extraction. Theoretical CuBr w / w% = 29.

Example 11-Polymerization of MMA

In a 250 ml Schlenk reaction flask, 2.65 g (0.76 mol) of the catalyst prepared in Example 10 and 4.85 g (1.2 mmol) of the macromolecular initiator prepared in Reference Example 3 were loaded. The contents of the flask are vacuum dried at 80 ° C. and then covered with a nitrogen blanket. Then 28 g of MMA are added under nitrogen. The resulting mixture is deoxygenated by one freeze-thaw pump cycle in liquid nitrogen. The flask is then rapidly heated to a reaction temperature of 90 ° C. in an oil bath. During the polymerization reaction, the viscosity increases and the solid particles of the catalyst remain in the polymer solution as a suspension. After polymerization, the polymer solution is filtered, the residual monomer is evaporated and the polymer is analyzed by ¹ H NMR and / or SEC to determine the number average molecular weight and polydispersity. Based on 100% monomer conversion and total molecular initiator total conversion, the theoretical degree of polymerization is 233. ^{From the 1} H NMR calculations, the experimental degree of polymerization is 113 after 4 hours.

Reference Example 4 Preparation of Bromoisobutyrylamide Functional MT Resin Macromolecular Initiators

In a 500 ml flask equipped with a magnetic stirrer, a condenser and a dropping funnel, in a solution of 100.0 g (1.45 mol) of MeSiO _3/2 resin containing 3.6% by weight of OH functionality in 200 ml of toluene under N ₂ , tetramethylaza in 50 ml of toluene 32.2 g (225.2 mmol, excess) of silacyclopentane are added dropwise at room temperature. After heating at 60 ° C. for 1 hour, volatiles are removed under vacuum to yield 114.0 g of a colorless liquid. Analysis by ¹³ C, ²⁹ Si NMR and FTIR confirmed that the obtained liquid was an amine functional MT resin containing 4.75% by weight of -NMeH functionality.

Subsequently, in a 500 ml flask equipped with a magnetic stirrer, a condenser and a dropping funnel, to 112.7 g of amine functional MT resin in 200 ml of triethylamine, 50.0 g (217.5 mmol) of bromoisobutyryl bromide in 150 ml of toluene were added under N ₂ . Dropwise at room temperature. The mixture is kept at 60 ° C. for 2 hours with stirring, then the salts are filtered under vacuum and the solvent is evaporated. The functionalized MT resin is washed with toluene and water. The organic phase is dried over magnesium sulfate, filtered and the volatiles removed to give 108.2 g of a yellow viscous liquid. The ¹ H, ¹³ C and ²⁹ Si NMR properties of the obtained liquid were analyzed to show that N-bromoisobutyryl, N-methylamino, 2-methylpropyl functional MT resin (Br containing 9.89% by weight of Br). It is confirmed that (CH ₃ ) ₂ CCON (CH ₃ ) CH ₂ CH (CH ₃ ) CH ₂ )-) is formed.

Reference Example 12 Preparation of Solid Supported Copper Catalyst 5

In a 500 ml three-necked reaction flask equipped with a dropping funnel, a thermometer and a reflux condenser, 50 g (279.3 mmol) of aminopropyltrimethoxy silane and 200 ml of p-xylene were loaded. Methanol is distilled off while 18 g (1.25 mol) of water are added over 60 minutes. After methanol is removed, p-xylene is removed under reduced pressure to give a white solid. 200 ml of toluene is then added to the solid, and the flask is equipped with a Dean & Stark apparatus. The water is azeotropically distilled from the reaction by heating the reaction at 120 ° C. for 4 hours. Removal of toluene under reduced pressure yields a white brittle solid which is extracted with p-xylene for 4 hours in a Soxhlet extractor and then dried at 120 ° C. for 4 hours in a vacuum oven.

10 g of a white solid and 50 ml of p-xylene were loaded into a 250 ml reaction flask, and slowly added 8.6 g (69.9 mol) of 2-pyridine carboxyaldehyde, followed by standing overnight for reaction. The orange solid is recovered by filtration and washed with p-xylene.

8.6 g of the orange solid, 3.5 g (24.5 mmol) of CuBr and 30 ml of p-xylene are added to a 100 ml flask and heated at 80 ° C. for 4 hours. After cooling, the solvent is colorless and the green phase indicating free CuBr disappears. Filtration of the reaction product afforded a black solid which was extracted with p-xylene for 4 hours in a Soxhlet extractor and dried for 6 hours at 50 ° C. in a vacuum oven (theoretical CuBr% (w / w) = 35).

Example 13-Polymerization of MMA

2.7 (1.17 mmol) of the macromolecular initiator prepared in Reference Example 4 and 3.55 g of the catalyst prepared in Example 12 were weighed, loaded into a Schlenk vessel, and deoxygenated by exposure to vacuum for 30 minutes. 23.6 g (0.236 mol) of distilled methylmethacrylate are added under nitrogen and degassed by repeating the freeze-pump-thaw cycle three times. The resulting solution is heated at 90 ° C. for 195 minutes and the sample is recovered. During the polymerization, the solution becomes highly viscous, which makes it impossible to recover the sample. After polymerization for 195 minutes, the conversion of monomer measured by ¹ H NMR is 77%.

Claims (20)

Supported by a support via a divalent group R, wherein R is an unsubstituted or substituted C ₁ -C ₂₀ straight, branched or cyclic alkylene group, arylene, alkaryl or aralkylene group A catalyst composite comprising a transition metal or transition metal compound having an average of one or more coordinating ligands and which is solid at room temperature. The compound of claim 1, wherein the transition metal compound is a compound of formula MY wherein M is a transition metal cation selected from Cu (I), Fe (II), Co (II), Ru (II) and Ni (II). , Y is a counter anion selected from Cl, Br, F, I, NO ₃ , PF ₆ , BF ₄ , SO ₄ , CN, SPh, SCN, SePh and (CF ₃ SO ₃ ). The catalyst composite of claim 2 wherein M is Cu (I) and Y is Cl or Br. The catalyst composite according to any one of claims 1 to 3, wherein two or more ligands are coordinated to the transition metal or transition metal compound. 5. The catalyst composite according to claim 1, wherein each ligand contains an organic diimine group. 6. The compound of claim 5, wherein the organic diimine groups are each independently 1,4-diaza-1,3-butadiene of formula I, 2,2'-bipyridine of formula II, pyridine-2-carbox of formula III A catalyst composite selected from aldehyde imines, oxazolidone of formula IV and quinoline carbaldehyde of formula V. Formula I Formula II Formula III Formula IV Formula V In the above formulas (I) to (V), Each R ¹ is independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ straight chain, branched or cyclic alkyl group, aryl, alkaryl, aralkyl group or halogen atom, Each R ² is independently an R ¹ group or a C ₁ -C ₂₀ alkoxy group, NO ₂ —, CN- or carbonyl group. The catalyst composite of claim 6 wherein the organic diimine groups are each pyridine-2-carboxaldehyde imine of formula III. Formula III In Formula III above, R <^2> is all hydrogen atoms. 8. The catalyst composite of claim 1 wherein R is an unsubstituted C ₁ -C ₆ straight or branched chain alkylene group or an aralkylene or alkarylene group. 9. The support according to claim 1, wherein the support is of formula (R ³ ₃ SiO _1/2 ) _a (R ³ ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _{4 / 2} ) a siloxane polymer or network having units of _d wherein R ³ is each independently an alkyl group, a hydroxy group or an alkoxy group, a, b, c and d are each independently 0 or a positive integer, a + b + c + d is an integer of at least 10]. The catalyst composite according to claim 1, wherein the support is an organic network or polymer comprising polyolefin, polyolefin halide, oxide or glycol, polymethacrylate, polyarylene or polyester. The catalyst composite according to any one of claims 1 to 9 according to formula VI or according to any one of claims 1 to 8 and 10 according to formula VII. Formula VI Formula VII In the above formulas VI and VII, The siloxane polymer or network structure is a unit of formula (R ³ ₃ SiO _1/2 ) _a (R ³ ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d , wherein R ³ , a, b, c and d are as defined above and n is a positive integer). A process for producing a polymer or copolymer by controlling the polymerization, characterized in that the vinyl-containing monomer is polymerized in the presence of an initiator and a catalyst composite according to any one of claims 1 to 11. 13. The process of claim 12 wherein the vinyl containing monomer is methacrylate, acrylate, styrene, methacrylonitrile or diene. The _divalent straight chain of claim 12 or 13, wherein the initiator is one or more groups of the formula -D-CR ⁸ ₂ X 'wherein D contains an oxygen or nitrogen heteroatom and / or is substituted by a carbonyl group Or a branched alkylene group, each R ⁸ is independently an alkyl group or a hydrogen atom, X 'is a halogen atom], and a chemical formula (R ⁷ ₃ SiO _1/2 ), (R ⁷ ₂ SiO _2/2 ), ( R ⁷ SiO _3/2 ) and / or units of (SiO _4/2 ), wherein each R ⁷ is independently a group of formula —D—CR ⁸ ₂ X ′ or a substituted or unsubstituted hydrocarbon group. How to. The method of claim 14, wherein at least one R ⁸ in each group of formula —D—CR ⁸ ₂ X ′ is an alkyl group. The method of claim 15, wherein in each group of formula —D—CR ⁸ ₂ X ′ R ⁸ is all alkyl groups. The method of claim 12, wherein the initiator is a unit of formula R ⁷ ₃ SiO (SiR ⁷ ₂ O) _q SiR ⁷ ₃ , wherein R ⁷ is as defined above and q is 0 or positive Integer]. 18. The method of claim 17, wherein the initiator has the formula: VIII. Formula VIII In the above formula (VIII), R ⁷ , R ⁸ , D, X 'and q are as defined above. _19. The compound of any one of claims 14 to 18, wherein R ⁷ is each a C ₁ -C ₆ alkyl group and D is of the formula Groups and chemical formulas of R ⁹ is an alkyl group or a hydrogen atom, R ¹⁰ is each independently a linear or branched alkylene group, and r is an integer from 1 to 4. The method of claim 19 wherein the initiator is , , And Wherein s is from 40 to 45 and t is 4.