JP2002539280A - Catalyst composition and method for producing polymer or copolymer - Google Patents

Abstract

(57) Abstract: A catalyst composition that is solid at room temperature comprises a transition metal or transition metal compound having an average of more than one ligand coordinated thereto, wherein each ligand is a divalent group. R (where, R represents a straight-chain optional substituted C ₁ -C _20, branched or cyclic alkylene group, an arylene, a is alkarylene or aralkylene group) is supported by a support via a. Preferably, M is Cu (I), Y is Cl or Br, and each ligand is an organic diimine group, such as 1,4-diaza-1,3-butadiene, 2,2′-. It contains bipyridine, pyridine-2-carboxaldehyde imine, oxazolidone or quinoline carbaldehyde groups, and the support is an organic or siloxane polymer or network. Also disclosed is a method of making a polymer or copolymer by controlled polymerization, comprising polymerizing a vinyl-containing monomer in the presence of an initiator and a catalyst composition according to the present invention.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a catalyst composition and a method for producing a polymer or a copolymer, and more particularly to a catalyst composition and a method for producing a polymer or a copolymer by controlled polymerization of a vinyl-containing monomer.

[0002] Controlled polymerization systems are of considerable importance in macromolecular chemistry because they allow the controlled preparation of polymers having a particular desired morphology. 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.

For many years, free radical polymerization has been a commercially important method for the preparation of high molecular weight polymers. A wide variety of monomers, in bulk, solution, emulsion, suspension or dispersion, can be polymerized or copolymerized by free radical polymerization under relatively simple conditions. However, a disadvantage of conventional free radical polymerization is the lack of control over the morphology of the resulting polymer.

[0004] Controlled radical polymerization methods have been proposed. For example, WO96 / 30421, WO
97/18247 and WO 98/01480 disclose polymerization processes based on atom transfer radical polymerization (ATRP) which provide controlled radical polymerization of styrene, (meth) acrylate and other radically polymerizable monomers. The disclosed method comprises: (i) an initiator having a radically transferable atom or group, such as 1-phenylethyl halide, alkyl 2-halopropionate,
an initiator system comprising p-halomethylstyrene or α, α′-dihaloxylene, (ii.
) Transition metals or transition metal compounds such as Cu (I) Cl, Cu (I) Br, N
i (O), FeCl ₂ or RuCl _2, and (iii) capable of coordinating with a transition metal C-, N-, O-, S- or P- containing ligand, for example bipyridine or (alkoxy) ₃ P in Include use. However, these methods suffer from the disadvantage that the transition metal complex formed by the initiating system is only partially soluble in the polymerization system, thus resulting in heterogeneous polymerization. A method for providing homogeneous atom transfer radical polymerization has been proposed in WO 97/47661, where a diimine ligand containing catalyst such as 1,4-diaza-1,3-butadiene and 2-pyridinecarbaldehyde is used. Can be However, the residual amount of catalyst in the resulting polymer is unacceptably high using this latter method, making it difficult to remove the catalyst from the polymer product. Therefore, the process can be expensive and produce undesirable colored polymer products due to residual catalyst in the product. Therefore,
There is a need for a catalyst composition that can be recovered from a polymer product.

Haddleton et al. In Chem. Commun., 1999, 99-100 claim that they are easy to remove from the polymer product for reuse, as well as their use in atom transfer polymerization of methyl methacrylate. A solid supported copper catalyst is disclosed.
However, the results show a lack of control of the polymerization reaction indicated by a large difference between the theoretical and experimental molecular weights of the polymer product.

[0006] The inventors have prepared catalyst compositions that include a supported transition metal compound and exhibit improved performance over the prior art compositions described above.

[0007] The term "comprising" as used herein means the terms "comprising,""including," and "consisting of," and is used in the broadest sense to encompass.

According to the present invention, in a first aspect, each of the coordination compounds is a solid at room temperature and comprises a transition metal or transition metal compound having an average of more than one ligand coordinated thereto. Is supported by the support via a divalent group R, wherein R is an optionally substituted C ₁ -C ₂₀ straight, branched or cyclic alkylene group, arylene, alkarylene or aralkylene group. A catalyst composition is provided.

[0009] 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 those 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,
It can be SePh or triflate (CF ₃ SO ₃ ), most preferably Cl or Br.

[0010] The catalyst composition comprises an average of more than one ligand coordinated with a transition metal or transition metal compound, and preferably has at least two ligands. Suitable ligands include C-, N-, O-, P- and S-containing ligands that can coordinate with a transition metal or transition metal compound. WO97 / 47661, WO96 / 3042
1, WO 97/18247 and WO 98/01480 disclose a number of examples of suitable ligands. Preferred ligands are organic diimine groups, in particular,

Formula (I):

Embedded image 1,4-diaza-1,3-butadiene of

Formula (II):

Embedded image 2,2′-bipyridine,

Formula (III):

Embedded image Pyridine-2-carboxaldehyde imine
),

Formula (IV):

Embedded image Oxazolidone, or

Formula (V):

Embedded image (Wherein R ¹ is independently a hydrogen atom, an optionally substituted C ₁ -C ₂₀ linear, branched or cyclic alkyl group, aryl, alkaryl, aralkyl group or a quinoline carbaldehyde) A halogen atom, preferably R ¹ is a hydrogen atom or an unsubstituted C ₁ -C ₁₂ alkyl group, R ² is each independently a R ¹ group, a C ₁ -C ₂₀ alkoxy group, NO ₂ — , CN- or a carbonyl group).

[0016] One or more adjacent R ¹ and R ² groups, and R ² and R ² groups, C ₅
It may form a ＣC ₈ cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl or cyclic aryl group, for example a cyclohexyl, cyclohexenyl or norbonenyl group. The 2-pyridine carbaldehyde imine compound of formula (III) may include a fused ring on the pyridine group.

Preferred organic diimine-containing groups are those having the formula (III), wherein R ² is each a hydrogen atom.

The divalent radical R is preferably a C ₁ -C ₆ unsubstituted linear or branched alkylene radical, for example a propylene radical, or an aralkylene or alkarylene radical, for example a benzylene or tolylene radical.

The support is an inorganic or organic network (network) or a polymer.
Can get. Suitable inorganic networks or polymers are Si, Zr, Al or Ti
Examples of such oxides include, for example, mixed oxides thereof, for example, Zeola.
Site. Preferred inorganic supports are of the formula (R^Three _ThreeSiO_1/2)_a(R^Three _TwoSiO _2/2 )_b(R^ThreeSiO_3/2)_c(SiO_4/2)_d(Where R^ThreeAre each independently an alkyl group
, Preferably a methyl group, a hydroxyl group or an alkoxy group, a, b, c
And d are each independently 0 or a positive integer, and a + b + c + d is at least
Is also an integer of 10).
You. Siloxane polymers and networks are composed of silicon-containing monomers or oligos.
Polymers such as organofunctional silanes, silicas, and compounds of the formula (R^Four _TwoSiO)_n(Where R^Four Is an alkyl group such as C₁~ C₆And most preferably a methyl group
Which is produced by polymerization or crosslinking of an organocyclosiloxane having
You.

Suitable organic networks or polymer supports can include any organic material that causes the catalyst composition to solidify at room temperature and does not interfere with any polymerization reactions that the catalyst composition should catalyze. Examples of suitable organic networks or polymers include polyolefins, polyolefin halides, oxides or glycols, polymethacrylates, polyarylenes or polyesters.

The ligand can be physically or chemically attached to the support via the divalent group R. However, chemical bonding of the ligand with the support via the divalent radical R is preferred.

Particularly preferred catalyst compositions of the first aspect of the present invention are those of formulas (VI) and (VI)
According to I):

Embedded image (Wherein the siloxane polymer or network structure (network), the formula (R ³ ₃ S
_{^{iO 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 described above, and n is a positive integer).

Thus, according to the present invention, two solids that are solid at room temperature and coordinated therewith
Has a lysine-2-carboxaldehyde imine ligand
Wherein each of the ligands has the formula (R^Three _ThreeSiO_1/2)_a(R^Three _TwoSiO _2/2 )_b(R^ThreeSiO_3/2)_c(SiO_4/2)_d(Where R^Three, A, b, c and d are above
A siloxane polymer or network having units of
Provided a catalyst composition dictated by a polystyrene polymer or network.
It is.

[0024] The catalyst composition of the first aspect of the present invention may be prepared by conventional methods known to those skilled in the art. The molar ratio of the reagents used to make the catalyst composition must be such that in the catalyst composition the transition metal or transition metal compound has on average more than one ligand coordinated thereto. No.

As an example, an organic diimine-containing group, diazabutadiene, is reacted with an aniline derivative of glyoxal:

Embedded image Wherein X is a leaving group, such as a hydroxy or alkoxy group, or a halogen atom, wherein the diazabutadiene reacts with a suitable support and a transition metal compound to form a catalyst composition. Can produce things. Examples are shown below:

[0026]

Embedded image (Where n is the same as above).

As a further example, an organic diimine-containing group that is a pyridine-2-carboxaldehyde imine of formula (III) above can be prepared by reaction of ethanolamine with pyridine-2-carboxaldehyde.

Embedded image

Next, pyridine-2-carboxaldehyde imine (pyridine-2-carboxaldehyde i)
mine) can be reacted with a suitable support and a transition metal compound to produce a catalyst composition as described above.

[0029] The catalyst composition of the first aspect of the present invention has particular utility in a process for producing a polymer or copolymer by catalyzing a controlled polymerization of a vinyl-containing monomer.

Thus, according to the present invention, in a second aspect, there is provided a process for the preparation of a polymer or copolymer by controlled polymerization, comprising the step of: A method is provided that includes polymerizing.

The advantage of the method of the second aspect of the present invention over the above conventional method is that the catalyst composition of the first aspect of the present invention used in the method of the second aspect is solid at room temperature, Thus, it is recoverable and reusable from the polymer product, allowing a high degree of control of the polymerization reaction. Particularly useful catalyst compositions are those that are solid at room temperature but have a melting point below the temperature at which the polymerization reaction occurs. Since the catalyst composition is a fluid in the reaction mixture at the reaction temperature, and thus the transition metal compound can be more easily formulated in the reaction mixture to perform the catalyst of the reaction,
Particularly effective polymerization reactions can be carried out in this way. The catalyst can be recovered from the reaction mixture as the temperature of the product cools below the melting point of the catalyst composition after the reaction has taken place.

[0032] The vinyl-containing monomer can 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 such as organic functional methacrylates and acrylates such as glycidyl methacrylate, trimethoxysilyl propyl methacrylate, allyl methacrylate, Hydroxyethyl methacrylate, hydroxypropyl methacrylate,
Dialkylaminoalkyl methacrylates and fluoroalkyl (meth) acrylates. 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 such as vinyl chloride and vinyl fluoride, acrylonitrile, methacrylonitrile,
(Wherein halogen is a is Cl or F) wherein CH ₂ = C (halogen) ₂ vinylidene halides, wherein ^{_{CH 2 = CR 5 -CR 5 =}} CH 2 ( wherein, R ⁵ are each independently, H, A C ₁ -C ₁₀ alkyl group, Cl or F) optionally substituted butadiene of the formula CH ₂ ＝
CHCONR ⁶ ₂ of acrylamide or a derivative thereof, and wherein _{CH 2 = C (CH 3)} CONR 6 2 ( wherein, R ⁶ is, H, an alkyl group or a Cl to C ₁ -C ₁₀₎ methacrylamide or its Derivatives. Mixtures of different monomers can also be used.

The initiator used in the method of the second aspect of the present invention may be any conventional initiator suitable for use with the catalyst composition of the first aspect of the present invention in a controlled polymerization reaction. Examples of such initiators include 1-phenylethyl chloride and bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, 2-halo-C ₁ -C ₆ carboxylic acids such as 2-chloro or 2 C ₁ -C ₆ esters of -bromopropionic acid and 2-chloro or 2-bromoisobutyric acid, 1-
Phenylethyl chloride 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 disclosed in WO 97/47661, WO 96/30421, WO 97/18247 and WO 98/01480 mentioned above.

A preferred initiator for use in the method of the second aspect of the present invention is at least one
Group of -D-CR⁸ _TwoX 'and the formula (R⁷ _ThreeSiO_1/2), (R⁷ _TwoSiO_2/2), (R ⁷ SiO_3/2) And / or (SiO_4/2Wherein D is oxygen or nitrogen
Divalent straight or branched chain containing atoms or substituted by a carbonyl group
An alkylene group;⁸Each independently represents an alkyl group or a hydrogen atom;
′ Is a halogen atom, R⁷Are each independently a group -D-CR⁸ _TwoX 'or any
Which is a substituted hydrocarbon group).

[0035] Preferred initiators can be linear, branched, cyclic or resinous siloxanes.

R ⁷ represents an alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl or hexyl group), a substituted alkyl group (eg, fluoropropyl group), an alkenyl group (eg, vinyl or hexenyl group), an aryl group (eg, phenyl group) Group), an aralkyl group (eg, a benzyl group) or an alkaryl group (eg, a tolyl group), and is preferably a C ₁ -C ₆ alkyl group.

[0037] Preferably, each group -D-CR ⁸ ₂ X 'at least one group R ⁸ in the alkyl group, i.e., X' is preferably a secondary or tertiary halogen atom, more preferably , each group -D-CR ⁸ ₂ X 'group R ⁸ in is either an alkyl group, i.e., 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 the divalent group D include the following:

Embedded image Wherein R ⁹ is an alkyl group, such as a methyl 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 second preferred initiators for use in the method aspect of the present invention have the formula R ⁷ ₃ SiO (S
_{^{iR 7 2 O) q SiR 7}} 3 ( wherein, R ⁷ are as defined above, q is 0 or a positive integer,
For example, it is 10-100).

Particularly preferred initiators have the general formula (VIII):

Embedded image (Wherein, R ⁷ , R ⁸ , D, X ′ and q are the same as above).

Examples of initiators of the formula (VIII) are shown below:

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

The second preferred initiators for use in the method aspect of the present invention has at least one group R ¹¹ (i), the formula _{^{(R 11 3 SiO 1/2),}} (R 11 2 SiO 2 _{/ 2} ), (R ¹¹ Si
O _3/2 ) and / or (SiO _4/2 ) wherein at least one group R ¹¹ is an amino-, hydroxy- or alkoxy group, or an amino-, hydroxy- or alkoxy-substituted alkyl group, each separately radicals R ¹¹ are, siloxane, and (ii) compound X'CR ⁸ ₂ -E (formula comprising units of an a) above groups R ^7, E is an amino -, hydroxy - or alkoxy group, Alternatively, it participates in a condensation reaction with an amino-, hydroxy- or alkoxy-substituted alkyl group to form a divalent linear or branched alkylene group containing an oxygen or nitrogen heteroatom and / or is substituted by a carbonyl group. Wherein R ⁸ and X ′ are the same as described above).

The particular reagents (i) and (ii) described above used in the method of making the initiator will, of course, depend on the particular initiator being made. For example, to prepare an initiator in which the divalent group D contains a peptide bond, a condensation reaction can be performed between an aminoalkyl-substituted siloxane and an acyl halide:

Embedded image

As a further example, if the divalent group D contains a carboxy bond, the condensation reaction can be performed between a hydroxyalkyl-substituted siloxane and an acyl halide:

Embedded image

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

The method of the second aspect of the invention may be carried out at various temperatures, for example between room temperature and 200 ° C., especially between room temperature and 130 ° C., most preferably between 80 and 100 ° C.

[0048] The method of the second aspect may be performed in the presence or absence of a solvent. Suitable solvents include water, protic and aprotic solvents such as propionitrile, hexane, heptane, dimethoxyethane, diethoxyethane, tetrahydrofuran, ethyl acetate, diethyl ether, N, N-dimethylformamide,
Anisole, acetonitrile, diphenyl ether, methyl isobutyrate, butan-2-one, toluene and xylene are preferred, with toluene and xylene being preferred.

The method may be performed under an inert atmosphere, for example under argon or nitrogen.

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

The method of the second aspect of the present invention can be used to produce various polymers and copolymers. A number of different monomers are polymerized to form homopolymers, random or gradient copolymers, periodic copolymers, block copolymers, functional polymers, hyperbranched and branched polymers, grafted or comb polymers, and polysiloxane-organic copolymers. Bring. Polysiloxane-organic copolymers have many potential uses, for example, polysiloxane-polyhydroxyalkyl acrylate block and graft copolymers are used for soft contact lens applications, and polysiloxane-amino acrylate copolymers are defoamers and Polysiloxane-aminoacrylate copolymers having short aminoacrylate blocks can be used as textile treatment agents, and polyalkoxysilylalkyl acrylate-polysiloxanes and polyepoxyglycidyl acrylate-polysiloxane copolymers can be used as anti-dye agents. It can be used as an additive for resins, curable powder coatings and sealants. Long alkyl methacrylate or acrylate-polysiloxane copolymers can be used as surface modifiers or additives for polyolefin and polyester-polyacrylate copolymers, and ABA methacrylate or acrylate-polysiloxane block copolymers can be used as plasma crosslinkable oxygen barriers. It can be used as a coating and the phosphobetaine or sulfobetaine-polysiloxane ionomer is biocompatible for use in, for example, shampoos and other hair treatments.

Now, the present invention will be described with reference to examples. Example 1-Preparation of primary solid supported copper catalyst 20.0 g (186.7 mmol) of 2-pyridinecarboxaldehyde (2-p
yridine carboxyaldehyde) and 10.7 g (74.6 mmol) of CuBr were mixed in 62 ml of tetrahydrofuran in a 100 ml flask equipped with a magnetic stirrer and condenser. The insoluble material was dissolved by the addition of 33.5 g (186.8 mmol) of 3-aminopropyltrimethoxysilane. The reaction was exothermic and resulted in a dark red solution, which was cooled to room temperature and then 0.07 g (1.9 mmol) of NH ₄ F diluted in 1.7 ml of water was added. The solution is then brought to 60 ° C for 2 hours.
Heat with stirring for 4 hours. The volatiles were evaporated in vacuo and the solid obtained was triturated, washed with ether and dried in vacuo at 80 ° C. to give 45.5 g of a brown-red powder (Cu (% m / m) = 8 .92%, insoluble in toluene, xylene and acetone).

Reference Example 1 Preparation of 1-Bromoisobutyrylamide-Endcap-Polydimethylsiloxane (PDMS) Macroinitiator In a 250 ml flask equipped with a magnetic stirrer, condenser and addition funnel in 40 ml of toluene under N ₂ To a solution of 9.0 g (62.9 mmol) of tetramethylazasilacyclopentane was added dropwise at room temperature 100.0 g of hydroxy-terminated PDMS (degree of polymerization (Dp) = 45) in 40 ml of toluene. After heating at 50 ° C. for 2 hours, the volatiles were removed in vacuo to give 93.0 g of a colorless liquid. Analysis by ¹³ C, ²⁹ Si NMR and FTIR revealed that the liquid was amine-endcapped PDM.
S (Dp = 45).

Next, 30 g of amine end-capped PDMS in 50 ml of triethylamine in a 100 ml flask equipped with a magnetic stirrer, condenser and addition funnel were charged at room temperature with 4.25 g (18.5 mmol) of bromoisopropane in 20 ml of toluene. the butyryl bromide was added dropwise under N _2. After holding the mixture at 90 ° C. for 1 hour with stirring, the salts were filtered and the solvent was evaporated in vacuo. The polymer was washed with toluene and water. 26. Dry the organic phase over magnesium sulfate, filter to remove volatiles, 27.
8 g (86% yield) of a pale yellow liquid was obtained. Liquid ¹ H, ¹³ C and ²⁹ Si NM
R characterization is, N- bromo isobutyryl, N- methylamino, 2-methylpropyl end blocks _{PDMS (Br (CH 3) 2} CCON (CH 3) CH 2 CH (CH 3)
CH ₂₎ - the generation of) were confirmed.

Example 2 Polymerization of Methyl Methacrylate 5.39 g (53.9 mmol) of methyl methacrylate (MMA) in 11.5 ml of anhydrous p-xylene was prepared from the catalyst prepared in Example 1 above in a Schlenk tube 0.66 g. At room temperature, the mixture was deoxygenated by one freeze-pump-thaw cycle before adding 1.0 g of the macroinitiator prepared in Reference Example 1 above. The solution was heated at 90 ° C. under N ₂ for 6 hours and sampled against time for ¹ H NMR analysis. The final polymer and copolymer were separated by simple filtration on filter paper. The polymer was dried in vacuo to give 3.9 g of a pale yellow solid. ¹ H
The conversion of the monomer observed by NMR was 59%. The catalyst is washed with toluene and ether, dried in vacuo and re-used for further polymerization.
1 g of active copper catalyst was obtained. The results are shown in Table 1 below, which shows a very good correlation between theoretical and experimental molecular weights and thus a controlled polymerization.

[0056]

[Table 1] Mn = number average molecular weight Mn _th = theoretical number average molecular weight

Example 3 Polymerization of MMA Using Recycle Catalyst 4.01 g (40.1 mmol) of MMA in 8.6 ml of anhydrous p-xylene
Was added to 0.49 g of the copper catalyst recycled from Example 2 above in a Schlenk tube. The mixture was deoxygenated by one freeze-pump-thaw cycle before adding 0.744 g of the macroinitiator prepared in Reference Example 1 above. The solution was heated at 90 ° C. under N ₂ for 24 hours and sampled against time for ¹ H NMR analysis. The results are shown in Table 2 below, which shows a good correlation between theoretical and experimental molecular weights, and thus a controlled polymerization.

[0058]

[Table 2]

Example 4 Preparation of Secondary Solid Support Copper Catalyst 100.4 g (560.0 mmol) of 3-aminopropyltrimethoxysilane and 63.0 g (558.2 mmol) of 2-pyridinecarboxaldehyde were magnetically treated. Mix in a 1 liter flask equipped with stirrer and condenser. 1
After stirring for 0 minutes, 26.8 g (186.8 mmol) of CuBr, 170.4 g (
1119.4 mmol) of tetramethoxysilane, 45.2 g (2511.1 m
The NH ₄ F water and 0.6 g (16.2 mmol) of mol) were sequentially added to the flask. A strong exotherm was observed, yielding a homogeneous dark solution at room temperature. After 48 hours, the solution gelled into a soft gel. After aging the solid for one week, the volatiles were removed by vacuum evaporation. The obtained solid was pulverized, washed with ether, and vacuum-dried at 80 ° C. for 8 hours to obtain 202.5 g of a brown-red powder.

Reference Example 2-Preparation of Bromoisobutyrate-Endcap-PDMS Macroinitiator In a 100 ml flask equipped with a magnetic stirrer, condenser and addition funnel containing 20 ml of toluene, was added -Si (CH ₃ ) _2- (CH ₂ ) ₂ -o- (CH ₂ ) ₃ C
51 g of PDMS with H ₂ OH terminal units and a number average molecular weight of 2084 (0.049 mol OH) and 5.43 g (0.053 mol) of triethylamide were charged. 12.37 g (0.053 mol) of bromobutyrate bromide were added dropwise at room temperature and the reaction was allowed to react overnight at room temperature before filtering the salts and evaporating the solvent. The polymer was washed with toluene and water. The organic phase was dried over magnesium sulfate and filtered under reduced pressure to remove volatiles. ^{The 1} H NMR spectrum shows a total loss of carbinol function (δ = 3.56 ppm) and a − at 4.19 ppm.
Si (CH _{3) 2} - and _{(CH 2) 2 -o- (CH} 2) 3 CH 2 OCOC (CH 3) confirmed the occurrence of the ₂ Br.

Example 5 Polymerization of MMA 190 g (1.9 mol) of MMA in 300 ml of anhydrous p-xylene was added to 5
Added to 10 g of the catalyst prepared in Example 5 above in a 00 ml Schlenk tube (pre-extracted with p-xylene for 6 hours in a Soxhlet extractor). The mixture was deoxygenated by one freeze-pump-thaw cycle and heated at 90 ° C. before adding 10 g of the macroinitiator prepared in Example 6 above. The reaction was continued at 90 ° C. for 30 minutes. Samples were taken over time for ¹ H NMR analysis. During polymerization,
The solution became highly viscous, but remained clear, and the catalyst was still visible in the polymer solution. After the polymerization, the solid catalyst was filtered off. ^The degree of conversion of the monomer observed by ¹ H NMR was 44%, and the Mn as measured by ¹ H NMR was 20,900. The catalyst available for further polymerization was extracted with p-xylene in a Soxhlet extractor for 6 hours. GPC analysis of the polymer showed a narrower molecular weight distribution (Mn _th /Mn=1.29) compared to the starting polysiloxane macroinitiator (Mn _th /Mn=1.5).

Example 6 Polymerization of MMA Using Recycle Catalyst 30 g (0.3 mol) of MMA in 30 ml of anhydrous p-xylene was converted to 100
Added to 2.3 g of the catalyst collected from Example 7 above (pre-extracted with p-xylene in a Soxhlet extractor for 6 hours) in a ml Schlenk tube. The mixture was deoxygenated and heated at 90 ° C. by one freeze-pump-thaw cycle before adding 3 g of the macroinitiator prepared in Example 6 above. The reaction was continued at 90 ° C. for 44 hours. Samples were taken over time for ¹ H NMR analysis. During polymerization,
The solution became highly viscous, but remained clear, and the catalyst was still visible in the polymer solution. After the polymerization, the solid catalyst was filtered off. The results are shown in Table 3 below, which shows a good correlation between theoretical and experimental molecular weights, and thus a controlled polymerization.

[0063]

[Table 3]

Example 7 Preparation of Tertiary Solid Supported Copper Catalyst 5 g (0.01 mol NH ₂ ) of aminomethyl polystyrene and 1.2 g
(0.012 mol) of pyridinecarboxaldehyde was added at room temperature to a 100 ml flask containing 50 ml of diethyl ether and reacted overnight under nitrogen. After the reaction, a yellow powder was collected, washed with dichloromethane and toluene,
Dry at 5 ° C. for 2 hours. 4.5 g of the powder are mixed with 1.02 g in 50 ml of acetone.
And stirred until all of the powder turned black. The reaction was continued for 3 hours under acetone reflux. After the reaction, the powder was washed with water and extracted with methanol for 7 hours in a Soxhlet extractor. Solid state ¹³ C NMR confirmed the presence of imine groups and the absence of amine groups.

Example 8-Polymerization of MMA 20 ml of anhydrous p-xylene and 10 g (1.9 mol) of MMA were added to a 100 ml Schlenk tube containing 5.3 g of the copper catalyst prepared according to Example 9 above. . The mixture was deoxygenated by one freeze-pump-thaw cycle prior to addition of 1.01 g of the PDMS macroinitiator prepared in Example 6 above, and then 90 ° C.
And heated. The reaction was continued at 90 ° C. for 5 hours and sampled over time. During the polymerization, the solution became highly viscous, but remained clear. The catalyst particles are visible in the polymer solution. After 5 hours of polymerization, the ¹ H NMR test measured 33% monomer conversion and Mn = 7100.

Example 9 Polymerization of MMA 47.4 g (0.47 mol) of MMA in 50 ml of anhydrous p-xylene was
Added to 19.4 g of the copper catalyst prepared according to Example 5 above in a 250 ml Schlenk tube. Before adding 5.0 g of the macroinitiator prepared according to Example 6 above, 1
The mixture was deoxygenated by multiple freeze-pump-thaw cycles and heated at 90 ° C. The reaction was continued at 90 ° C. under N ₂ for 4 hours. Samples were taken over time for ¹ H NMR analysis. During the polymerization, the solution became highly viscous, but the catalyst is still visible in the polymer solution. The results are shown in Table 4 below, which shows a good correlation between theoretical and experimental molecular weights, and thus a controlled polymerization.

[0067]

[Table 4]

Reference Example 3-Preparation of PDMS macroinitiator with pendant bromoisobutyrate groups.
With a degree of polymerization of 100 and 0.018 mol of NH_TwoAnd 100 ml of p-xylene
80.5 g of dimethylethoxy endblocked dimethylmethyl containing amine
Nopropyl) siloxane was charged. After homogenization, 3.35 ml (0.024 mo
l) triethylamine was added, and 5.53 g (0.024 mol) of bromide was added.
Sobutyryl bromide was slowly injected at room temperature. 3 hours at 50 ° C with stirring
The response progressed. After the reaction, p-xylene was evaporated, and 300 ml of n-hexene was removed.
Sun was added to precipitate the triethylammonium salt. After this step, filtration
And the hexane was evaporated. The product was a clear yellow, highly viscous polymer.¹
1 H NMR spectroscopy confirmed the disappearance of the amine function. CH_TwoCH _Two NH _Two Shifts from 3.99 ppm to 3.30 ppm,H-COC (
CH_Three)_TwoA new signal corresponding to Br appears at 6.99 ppm. Bromination yield
% = 100%, but some terminal ethoxy groups are hydrolyzed.

Example 10-Preparation of quaternary solid supported copper catalyst In a 2000 ml three-neck reaction flask equipped with a dropping funnel, thermometer and reflux condenser, 246 g (1.37 mol) of aminopropyltrimethoxysilane and 3
00 ml of p-xylene was charged. Next, while evaporating methanol, 75
g (4.16 mol) of water was added over 60 minutes. After removing the methanol, p-xylene was stripped under reduced pressure to produce a white brittle solid. 84 g of solid and 300 ml of p-xylene were then charged to a 1000 ml reaction flask and 70 g
g (1.0 mol) of 2-pyridinecarboxaldehyde was added slowly with cooling. After the addition of 2-pyridinecarboxaldehyde, the temperature was kept below 30 ° C. and 57 g of CuBr were added with vigorous stirring. Stirring was maintained until the green features of free Cu (I) had disappeared entirely. After the reaction, the solid was separated from the solvent, washed with toluene and used without further extraction. Theoretical CuBr (w / w%
) = 29.

Example 11 Polymerization of MMA The catalyst prepared in Example 10 above in a 250 ml Schlenk reaction flask.
65 g (0.76 mol) and 4.8 of the macroinitiator prepared in Reference Example 3 above.
5 g (1.2 mmol) were charged. The contents of the flask were vacuum dried at 80 ° C. to remove oxygen and then covered with a nitrogen blanket. Then 28 g of MMA were added under nitrogen. The mixture was deoxygenated by three freeze-thaw pump cycles in liquid nitrogen. Next, the flask was rapidly heated in an oil bath to bring the reaction temperature to 90 ° C. During the polymerization reaction, the viscosity increases and the solid particles of the catalyst remain in the polymer solution as a suspension. After the polymerization, the polymer solution was filtered, evaporated residual monomers, ¹
The polymers were analyzed by 1 H NMR and / or by SEC to determine the average number molecular weight and polydispersity. Based on 100% monomer conversion and total macroinitiator conversion, the theoretical degree of polymerization is 233. ^{From the 1} H NMR calculation, the experimental degree of polymerization is 113 after 4 hours.

Reference Example 4-Preparation of a Bromoisobutyrylamide Functional MT Resin Macroinitiator 3.6% by weight in 200 ml of toluene under N ₂ in a 500 ml flask equipped with a magnetic stirrer, condenser and addition funnel 100.0 g containing OH functional groups (
To a solution of 1.45 mol) of MeSiO _3/2 resin was added dropwise at room temperature 32.2 g (225.2 mmol, excess) of tetramethylazasilacyclopentane in 50 ml of toluene. After heating at 60 ° C. for 1 hour, the volatiles were removed in vacuo.
0 g of a colorless liquid was obtained. Analysis by ¹³ C, ²⁹ Si NMR and FTIR confirmed that the liquid was an amine functional MT resin containing 4.75 wt% -NMeH functionality.

Next, 112.7 g of amine functional MT resin in 200 ml of triethylamine in a 500 ml flask equipped with a magnetic stirrer, condenser and addition funnel were added at room temperature to 50.0 g (217.5 mmol, 217.5 mmol, bromo isobutyryl bromide in an excess) was added dropwise under N _2. After holding the mixture at 60 ° C. with stirring for 2 hours, the salts were filtered and the solvent was evaporated in vacuo. The functional MT resin was washed with toluene and water. The organic phase was dried over magnesium sulfate and filtered to remove volatiles, yielding 108.2 g of a yellow viscous liquid. Liquid ¹ H, ¹³ C and ²⁹ S
i NMR characterization is, N- bromo isobutyryl, N- methylamino, 2-methylpropyl functional MT resin _{(Br (CH 3) 2 CCON} (CH 3) CH 2 CH (CH 3
) CH ₂₎ -) (confirmed the formation of containing) a 9.89% by weight of Br.

Reference Example 12 Preparation of Fifth Solid Supported Copper Catalyst In a 500 ml three-necked reaction flask equipped with a dropping funnel, thermometer and reflux condenser, 50 g (279.3 mmol) of aminopropyltrimethoxysilane and 2
00 ml of p-xylene was charged. While evaporating the methanol, 18 g (1
. 25 mol) of water was added over 60 minutes. After removing methanol, p-xylene was removed under reduced pressure to obtain a white solid. Next, 200 ml of toluene was added to the solid and the flask was equipped with a Dean-Stark apparatus. Water was azeotropically distilled from the reaction by heating at 120 ° C. for 4 hours. The toluene was removed under reduced pressure to give a white brittle solid, which was extracted in a Soxhlet extractor with p-xylene for 4 hours and then dried in a vacuum oven at 120 ° C. for 4 hours.

10 g of a white solid and 50 ml of p-xylene were charged into a 250 ml reaction flask, and 8.6 g (69.9 mmol) of 2-pyridinecarboxaldehyde was gradually added thereto, and left to react overnight. An orange solid was collected by filtration and washed with p-xylene.

8.6 g of orange solid, 3.5 g of CuBr (24.5 mmol) and 30 m
One liter of p-xylene was added to a 100 ml flask and heated at 80 ° C. for 4 hours. After cooling, the solvent was colorless and no green features of free CuBr were observed. The reaction product was filtered to produce a black solid which was extracted with p-xylene in a Soxhlet extractor for 4 hours and dried in a vacuum oven at 50 ° C. for 6 hours (theoretical CuBr% (w
/ W) = 35).

Example 13 Polymerization of MMA 2.7 g (1.17 mmol) of the macroinitiator prepared in Reference Example 4 and 3.55 g of the catalyst prepared in Example 12 are weighed into a Schlenk container and evacuated for 30 minutes. It was deoxygenated by exposure. 23.6 g (0.236 mol) of distilled methyl methacrylate were added under nitrogen and degassed by three freeze-pump-thaw cycles. The solution was heated at 90 ° C. for 195 minutes and a sample was removed. During the polymerization, the solution became highly viscous, which prevented sample removal. After 195 minutes polymerization, ¹
77% monomer conversion was measured by 1 H NMR.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 36/02 C08F 36/02 C08G 77/26 C08G 77/26 77/385 77/385 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN , CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG , SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Tapper, Tristan UK, Cardiff CF24.4 JW, Cathays, Pentark Street 17F Term (Reference) 4J015 CA00 4J035 BA06 CA08U CA15M CA15N CA151 CA18N CA18U CA181 CA19U CA22M CA22N CA221 CA29M CA29N CA291 EB01 EB10 FB01 FB02 FB10 4P02P02P02P02P02P02P02P03 P AL09P AL10P AM02P AM15P AM19P AS02P BA31P BB17P CA01 CA04 FA03 FA04 FA10 FA19 JA00

Claims (20)

[Claims] 1. A composition comprising a transition metal or a transition metal compound having an average of more than one ligand coordinated thereto, wherein each ligand is a solid at room temperature, wherein each ligand is a divalent radical R (wherein R is an optionally substituted C ₁ -C ₂₀ linear, branched or cyclic alkylene group, arylene, alkarylene or aralkylene group). 2. The method of claim 1, wherein the transition metal compound is of the formula MY wherein M is Cu (I),
A transition metal cation selected from Fe (II), Co (II), Ru (II) and Ni (II), wherein Y is Cl, Br, F, I, NO ₃ , PF ₆ , BF ₄ ,
The catalyst composition according to claim 1, wherein the catalyst composition has a counter anion selected from SO ₄ , CN, SPh, SCN, SePh, and (CF ₃ SO ₃ ). 3. The catalyst composition according to claim 2, wherein said M is Cu (I) and said Y is Cl or Br. 4. The catalyst composition according to claim 1, wherein the transition metal or transition metal compound has at least two ligands coordinated thereto. 5. The method according to claim 1, wherein each of the ligands contains an organic diimine group.
The catalyst composition according to any one of the above. 6. Each of the organic diimine groups is independently of the formula (I): 1,4-diaza-1,3-butadiene of the formula (II): 2,2′-bipyridine of the formula (III): Pyridine-2-carboxaldehyde imine of the formula (IV): And an oxazolidone of formula (V): Wherein R ¹ is independently a hydrogen atom, an optionally substituted C ₁ -C ₂₀ linear, branched or cyclic alkyl group, aryl, alkaryl, aralkyl group or halogen atom , R ² are each independently, R ¹ group, alkoxy group of _{C 1 ~C 20, NO 2 -} , CN-
Or a carbonyl group). 7. Each of the organic diimine groups has the formula (III): Wherein the R ² groups are each a hydrogen atom, wherein the pyridine-2-carboxaldehyde imine is a pyridine-2-carboxaldehyde imine. 8. The catalyst composition according to claim 1, wherein said R is a C ₁ -C ₆ unsubstituted linear or branched alkylene group, an aralkylene or an alkalylene group. Wherein said support has 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, a hydroxyl group or an alkoxy group, and a, b, c and d are each independently 0 Or a positive integer, wherein a + b + c + d is an integer of at least 10.) The catalyst composition according to any one of claims 1 to 8, which is a siloxane polymer or a network having units of: 10. The support according to claim 1, wherein the support is an organic network or polymer including polyolefin, polyolefin halide, oxide or glycol, polymethacrylate, polyarylene or polyester.
The catalyst composition according to any one of the above. 11. The method according to claim 1, wherein the compound of formula (V)
I) or according to any one of claims 1 to 8 and 10 and of formula (VII): (Wherein the siloxane polymer or network structure, 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 , a, b, c and d are the same as described above, and n is a positive number) A) a catalyst composition having units of 12. A process for producing a polymer or copolymer by controlled polymerization, comprising polymerizing a vinyl-containing monomer in the presence of an initiator and a catalyst composition according to any one of claims 1 to 11. how to. 13. The method according to claim 12, wherein said vinyl-containing monomer is methacrylate, acrylate, styrene, methacrylonitrile or diene. 14. The method of claim 13, wherein the initiator has at least one group -D-CR ⁸ ₂ X ', wherein ^{_{(R 7 3 SiO 1/2),}} (R 7 2 SiO 2/2), (R 7 SiO _3/2 ) and / or (SiO _4/2 ), wherein D is a divalent linear or branched alkylene group containing an oxygen or nitrogen heteroatom and / or substituted by a carbonyl group. There, R ⁸ are each independently an alkyl group or a hydrogen atom, X 'is halogen atom, R ⁷ are each independently a group -D-CR ⁸ ₂ X' is or optionally substituted hydrocarbon group 14. A method according to claim 12 or claim 13 comprising units of). 15. at least one group R ⁸ The method of claim 14 wherein the alkyl group in each group -D-CR ⁸ ₂ X '. 16. The method of claim 15 wherein the group R ⁸ Any alkyl group in the group -D-CR ⁸ ₂ X '. 17. The initiator has the formula ^{_{R 7 3 SiO (SiR 7 2}} O) q SiR 7 3, wherein, R ⁷ is as defined above, wherein q is 0 or a positive integer Item 17. The method according to any one of Items 12 to 16. 18. The method of claim 18, wherein the initiator is of the formula (VIII): ^{(Wherein, R 7, R 8, X} ', D and q are as defined above) The method of claim 17 further comprising a. 19. The above-mentioned R ⁷ is a C ₁ -C ₆ alkyl group, and the above-mentioned D is a group represented by the following formula: Wherein 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. 19. The method according to any one of claims 18 to 18. 20. The initiator as follows: 20. The method of claim 19, wherein s is 40-45 and t is 4.