JP2002538236A - How to use controlled polymerization initiators - Google Patents

Abstract

(57) Abstract The present invention uses a controlled polymerization initiator. The initiator comprises a unit of formula _{^{(R 7 3 SiO) (R}} 7 2 SiO 3/2) and / or (SiO _4/2), and having at least one group D-CR ⁸ ₂ X ', Wherein each R ⁷ is independently a suitably substituted hydrocarbon group, and D is a divalent linear or branched alkylene group containing an oxygen or nitrogen heteroatom and / or substituted by a carbonyl group. And each R ⁸ is independently an alkyl group or a hydrogen atom, and X ′ is a halogen atom. Preferably each R ⁷ is a methyl group, initiator comprises two terminal groups -D-CR ⁸ ₂ X, each R ⁸ here is a methyl group, X is bromine atom, D is group CO —NR ⁹ R ¹⁰ or a group CO— (OR ¹⁰ ), wherein R ⁹ is an alkyl group or a hydrogen atom, and each R ¹⁰ is independently a linear or branched alkylene group. Initiators are particularly useful for initiating controlled polymerization of vinyl-containing monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to the use of initiators for controlled polymerization reactions, and more particularly to the use of initiators for controlled polymerization reactions using vinyl-containing monomers to produce polymers or copolymers.

[0002]

[Prior art]

Controlled polymerization systems are of considerable importance in macromolecular chemistry because they allow for the controlled production of polymers with the desired specific morphological properties. For example,
By controlling the monomer to initiator concentration ratio, the molecular weight, molecular weight distribution, functionality, topology and / or dimensional structure of the resulting polymer can be controlled.

[0003] For many years, radical polymerization has been an industrially important method for producing high molecular weight polymers. A wide variety of monomers can be polymerized or copolymerized by radical polymerization under relatively simple conditions in bulk, solution, emulsion, suspension or dispersion polymerization. However, a disadvantage of conventional radical polymerization was that the morphology of the resulting polymer could not be controlled.

[0004] Controlled radical polymerization methods have been proposed. For example, WO 96/30421
Nos. WO 97/18247 and WO 98/01480 disclose atom transfer radical polymerization (ATRP), which results in controlled radical polymerization of styrene, methacrylates and / or acrylates, and other radically polymerizable monomers.
A system polymerization method is disclosed. The disclosed method comprises: (i) an initiator having a radically transferable atom or group, such as 1-phenylethyl halide, alkyl 2-halopropionate, p-halomethylstyrene or α, α′-dihaloxylene. An initiator system comprising: (ii) a transition metal compound such as Cu (I) Cl, Cu (I) Br
, Ni (O), FeCl ₂ , or RuCl ₂ , (iii) C-, N-, O-, S-, or P-containing ligands that can coordinate with a transition metal, such as bipyridine or (alkoxy) ₃ P Are disclosed. Chem. Commun. (1999
Haddleton et al., Pp. 99-100, describe solid-supported copper catalysts and 2-bromoisobutyrate ethyl as an initiator for those catalysts, which are said to be easily removable and reusable from so-called polymer products. Discloses the use of these catalysts in the atom transfer polymerization of methyl methacrylate using

[0005]

[Problems to be solved by the invention]

WO 98/01480 further discloses the preparation and use of polydimethylsiloxane (PDMS) based macroinitiators. For example, benzyl chloride is introduced as a terminal group into PDMS by a hydrosilylation reaction using a platinum catalyst between PDMS having a hydrogen atom bonded to a silicon atom and vinylbenzyl chloride. However, this route produces two isomers with different activities, an alpha isomer and a beta isomer. The β isomer, which accounts for 65% of the product, is completely inert to the initiation of the controlled polymerization of vinyl monomers, and the use of the α isomer is difficult to remove due to the slow start of the reaction, which is unacceptably high. Produces large amounts of unreacted siloxane-containing polymer or copolymer.

[0006]

[Means for Solving the Problems]

Therefore, the present inventors prepared another PDMS-based macroinitiator by a condensation reaction. This initiator is capable of initiating a controlled polymerization reaction of the vinyl monomer, producing a well-regulated polymer or copolymer, is more reactive than the above-described prior art PDMS-based macroinitiators, and includes in the reaction product Little or no residual unreacted siloxane remains.

As used herein, the term “comprises” refers to “includes”
, "Comprehends" and "consists of" are used in the broadest sense to refer to and include wrapping.

According to the present invention, there is provided a method of using an initiator for initiating a controlled polymerization reaction where the initiator has at least one group -D-CR ⁸ ₂ X ', formula _{^{(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, and each R ⁸ is independently an alkyl group or a hydrogen atom , X 'is a halogen atom, each R ⁷ is independently a group -D-CR ⁸ ₂ X' is a substituted or an optionally hydrocarbon group.

[0009] The initiator can be a linear siloxane, a branched siloxane, a cyclic siloxane, or a resinous siloxane.

R ⁷ is an alkyl group (eg, a methyl group, an ethyl group, a propyl group or a butyl group, a pentyl group or a hexyl group), a substituted alkyl group (eg, a fluoropropyl group), an alkenyl group (eg, a vinyl group or a hexenyl group) , Aryl group (
It can be, for example, a phenyl group), an aralkyl group (eg, a benzyl group) or an alkaryl group (eg, a tolyl group), preferably a C ₁ -C ₆ alkyl group.

[0011] Preferably, in 'at least one of R ⁸ groups are alkyl groups, i.e. X in the group' group is preferably a secondary or tertiary halogen atom each -D-CR ⁸ ₂ X, more preferably each -D-CR ⁸ ₂ X _'2 two R ⁸ groups are both alkyl groups at the base, i.e. X' groups and more preferably a tertiary halogen atom. In a particularly preferred embodiment, each R ⁸ group is a methyl group. X is preferably a bromine atom.

Suitable examples of the divalent radical D include compounds of the formula:

[0013]

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In the above formula, R ⁹ is an alkyl group such as a methyl group or a hydrogen atom, and each R ¹⁰ is independently a linear alkylene group or a branched alkylene group, and r is an integer of 1 to 4.

[0015] Suitable initiators for use in the present invention is represented by the formula ^{_{R 7 3 SiO (SiR 7 2}} O) q SiR 7 3, wherein R ⁷ has the same significance as described above, q is Zero or a positive integer, for example, an integer from 10 to 100.

Particularly suitable initiators have the following general formula (VIII):

[0017]

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In the above formula, R ⁷ , R ⁸ , D, X ′ and q have the same meaning as described above.

Examples of initiators of the formula (VIII) include:

[0020]

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In the above formula, s is zero or a positive integer, for example, an integer of 1 to 100, and t is a positive integer, for example, an integer of 1 to 10.

The initiator used in the present invention, (i) at least one having and wherein the group ^{_{R 11 (R 11 3 SiO 1/2}} ), (R 11 2 SiO 2/2), (R 11 SiO a siloxane containing units of _3/2) and / or (SiO _4/2), can be prepared by a process comprising the condensation reaction between (ii) compound X'CR ⁸ ₂ -E. In the above formula (i), at least one group R ¹¹ is an amino group, a hydroxy group or an alkoxy group or an amino group, a hydroxy group or an alkoxy group-substituted alkyl group, and the remaining groups R ¹¹ are each independently to a group R ⁷ as defined above, in the above (ii), the amino group of E is the (i), hydroxy or alkoxy group or an amino group, hydroxy group or alkoxy group - a condensation reaction with a substituted alkyl group A group capable of forming a divalent linear or branched alkylene group containing an oxygen or nitrogen heteroatom and / or substituted by a carbonyl group, wherein R ⁸ and X ′ are as defined above. It has the same significance as it did.

The individual reactants (i) and (ii) used in the process for producing an initiator according to the present invention.
) Will vary depending on the particular initiator to be produced. For example, if the divalent group D defined above contains a peptide bond, the condensation reaction can be performed between an aminoalkyl-substituted siloxane and an acyl halide according to the following formula:

[0024]

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As another illustrative example, if the divalent group D should contain a carboxy bond, then the condensation reaction can be carried out between the hydroxyalkyl-substituted siloxane and the acyl halide according to the following formula: it can:

[0026]

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

According to the invention, the initiator is a controlled polymerization reaction, in particular a controlled polymerization reaction of vinyl-containing monomers, for example WO 96/30421, WO 97/18247.
, The controlled polymerization reaction described in WO 98/01480 and Che
m. Commun. (1999) used to initiate a controlled polymerization reaction according to pages 99-100 (Handleton et al.). The initiators of the present invention can initiate controlled polymerization reactions of vinyl monomers to produce well-defined polymers or copolymers. The initiators of the present invention are more reactive than prior art PDMS-based macroinitiators and leave little or no unreacted siloxane remaining in the reaction product.

The present inventors have determined that the initiator is solid at room temperature and has an average of one or more ligands coordinated to the transition metal or transition metal compound [each of these ligands is a divalent group R ( C ₁ -C ₂₀ straight chain R is which is optionally substituted, branched or cyclic alkylene group, an arylene group, a transition metal having a 'is supported by a support via a is) alkarylene group or Ararukiren group Alternatively, it has been found that when a catalyst compound containing a transition metal compound is used together, it is particularly effective for a controlled polymerization reaction of a vinyl monomer.

Transition metals include, for example, copper, iron, ruthenium, chromium, molybdenum, tungsten, rhodium, cobalt, rhenium, nickel, manganese, vanadium, zinc,
You can choose from gold and silver. Suitable transition metal compounds are those having the formula MY, where M is a transition metal cation and Y is a counter ion, where M is preferably 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 (t
riflate) (CF ₃ SO ₃ ), most preferably Cl or Br.

The catalyst composition comprises an average of one or more ligands coordinated with the transition metal or transition metal compound, preferably at least two coordinated ligands. Suitable ligands include C-, N-, O-, P- and S- which coordinate with the transition metal or transition metal compound.
-Containing ligands. WO 97/47661, WO 96/30421
Nos. WO 97/18247 and WO 98/01480 disclose a number of examples of suitable ligands. Suitable ligands are ligands containing organic diimine groups, especially 1,4-diaza-1,3-butadiene of the formula (I):

[0032]

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2,2′-bipyridine represented by the following formula (II):

[0034]

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A pyridine-2-carboxaldehyde represented by the following formula (III):

[0036]

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Oxazolidone represented by the following formula (IV):

[0038]

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Alternatively, a quinoline carbaldehyde represented by the following formula (V):

[0040]

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Is as follows. In the above formula, R ¹ is independently a hydrogen atom, an optionally substituted C ₁ -C ₂₀ linear, branched or cyclic alkyl group, aryl group, alkaryl group, aralkyl group, or halogen atom. Preferably, R ¹ is a hydrogen atom or an 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 a carbonyl group.

One or more adjacent R ¹ and R ² groups and R ² and R ² groups are C ₅ -C ₈ cycloalkyl groups, cycloalkenyl groups, polycycloalkyl groups, polycycloalkenyl groups Alternatively, it may form a cyclic aryl group, for example a cyclohexyl, cyclohexenyl or norbornyl group. The 2-pyridine carbaldehyde imine of the formula (III) may form a fused ring on the pyridine group.

Suitable organic diimine-containing groups are compounds of the formula (III) in which each R ² consists of a hydrogen atom.

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

The support can be an inorganic or organic network or a polymer. Suitable
Severe inorganic networks or polymers are oxides or oxides of Si, Zr, Al or Ti.
And mixed oxides thereof, for example, zeolite. Suitable inorganic support
The body has the formula (R^Three _ThreeSiO_1/2)_a(R^Three _TwoSiO_2/2)_b(R^ThreeSiO_3/2)_c(SiO_4/2)_dso
A siloxane polymer or network having the units represented by ^Three Is independently an alkyl group, preferably a methyl group, a hydroxyl group or an alkoxy group
Wherein a, b, c and d are independently zero or a positive integer, and a + b + c + d is a small number.
It is an integer of at least 10. The siloxane polymer and the network are silicon-containing
The polymerization or cross-linking of the nominal or oligomer allows, for example, organofunctional sila
, Silica, and the formula (R^Four _TwoSiO)_ePolymerization of organocyclosiloxanes with
Or it can be made by cross-linking. In the above formula, R^FourIs an alkyl group such as C₁ ~ C₆An alkyl group, most preferably a methyl group.

A suitable organic network or polymer support can be any organic material that renders the catalyst composition solid at room temperature and does not interfere with the polymerization reaction in which the catalyst composition exhibits catalysis. Examples of suitable organic networks or polymers include polyolefins, halogenated polyolefins, polyolefin oxides, polyolefin glycols, polymethacrylates, polyarylenes and polyesters.

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

Particularly preferred catalyst compositions for contacting the controlled polymerization reaction initiated according to the invention are compounds of the formulas (VI) and (VII):

[0049]

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[0050] In the above formula, the siloxane polymer or network structure 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 ) The unit represented by _d (R ³ , a, b, c
And d have the same meaning as defined above, and n is a positive integer.

[0051] The catalyst composition can be made by conventional methods known to those skilled in the art. The molar ratio of the reactants used to make the catalyst composition depends on the average of one or more ligands in which the transition metal or transition metal compound is coordinated to the transition metal or transition metal compound in the catalyst composition. Must have a molar ratio of

As an illustrative example, an organodiimine-containing group that is diazabutadiene includes:

[0053]

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Wherein g is a leaving group such as a hydroxy or alkoxy group or a halogen atom, where glyoxal is reacted with an aniline derivative and the resulting diazabutadiene is then reacted with a suitable support The catalyst composition reacts with the substance and the transition metal compound, for example, the following catalyst composition:

[0055]

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(N has the same meaning as described above).

As yet another illustrative example, an organodiimine-containing group which is pyridine-2-carboxaldehyde imide represented by the above formula (III) is composed of ethanolamine and pyridine
It can be made by reacting with 2-carboxaldehyde:

[0058]

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Next, the pyridine-2-carboxaldehyde imine can be made by reacting with a suitable support material Z and a transition metal compound to produce the catalyst composition described above.

The catalyst composition described in detail above has the following advantages over the controlled polymerization process according to the prior art described above: The catalyst composition used in the present invention has a room temperature And is solid, thus recoverable and reusable from the polymer product, and allows a high degree of control over the polymerization reaction. Particularly advantageous catalyst compositions are those which are solid at room temperature and have a melting point below the temperature at which the polymerization reaction takes place. In this way, a particularly effective polymerization reaction can be carried out when the catalyst composition is fluid in the reaction mixture at the reaction temperature, so that the transition metal compound is more easily incorporated into the reaction mixture. To provide a catalytic effect on the reaction. After the reaction has occurred, when the temperature of the product is cooled below the melting point of the catalyst composition, the catalyst solidifies and can be recovered from the reaction mixture.

The vinyl-containing monomer to be polymerized is methacrylate, acrylate, styrene
, Methacrylonitrile or diene. Of vinyl-containing monomers
Examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate
, Butyl methacrylate and other alkyl methacrylates; and corresponding
Acrylates; glycidyl methacrylate, trimethoxysilylpropyl methacrylate
Tacrylate, allyl methacrylate, hydroxyethyl methacrylate, hydrate
Roxypropyl methacrylate, dialkylaminoalkyl methacrylate and
Organofunctional methacrylates, including fluoroalkyl (meth) acrylates
And acrylates. To other suitable vinyl-containing monomers
Is methacrylic acid, acrylic acid, fumaric acid and its esters, itaconic acid (
And its esters), maleic anhydride, styrene, α-methylstyrene,
Vinylogenates such as vinyl chloride and vinyl fluoride, acrylonitrile,
Tacrylonitrile, formula CH_Two= C (halogen)_TwoHalogenated vinylide represented by
(Where halogen is Cl, F, optionally substituted formula CH_Two= CR^Five-CR^Five= CH _Two Butadiene represented by the formula:^FiveAre independently H and C₁~ C_TenAlkyl group, C
l, F, acrylamide or formula CH_Two= CHCONR⁶ _TwoAcrylamide with
Of the formula (wherein R⁶Is H, C₁~ C_TenAn alkyl group or Cl), and meta
Acrylamide or formula CH_Two= C (CH_Three) CONR⁶ _TwoOf methacrylamide with
Derivative (R⁶Has the same meaning as described above)]. varied
Mixtures of the following monomers can also be used.

The polymerization takes place in an inert atmosphere, for example under an argon or nitrogen atmosphere.

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

Various polymers or copolymers can be made by controlled polymerization reactions initiated according to the present invention. By polymerizing a wide variety of monomers, homopolymers, random or gradient copolymers, periodic copolymers, block copolymers, functionalized polymers, branched or hyperbranched polymers, grafts or combs ( comb) polymers and polysiloxane-organic copolymers can be produced. 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 can be used for antifoaming agents and dye transfer inhibitors, short-chain aminoacrylate blocks. Polysiloxane-amino acrylate copolymers having the following formulas can be used as textile treatment agents, and polyalkoxysilylalkyl acrylate-polysiloxane copolymers and polyepoxyglycidyl acrylate-polysiloxane copolymers can be used as additives for epoxy resins, curable powder coating agents and sealants. Long chain alkyl methacrylate- or acrylate-polysiloxane copolymers can be used as surface modifiers or as polyolefins or polyolefins. ABA methacrylate or acrylate polysiloxane block copolymers can be used as plasma crosslinkable oxygen barrier coatings, and phosphobetaine- or sulfobetaine-polysiloxane ionomers can be used, for example, as shampoos and other It is biocompatible when used in hair treatment agents.

[0065]

【Example】

 Hereinafter, the present invention will be described by way of examples for illustrative purposes.

Reference Example 1 Preparation of bromoisobutyrylamide end-capped polydimethylsiloxane (P DMS) macroinitiator N _{2 in} a 250 ml flask equipped with a magnetic stirrer, condenser and addition funnel
9.0 g of tetramethylazasilacyclopentane in 40 ml of toluene under an atmosphere (
62.9 mmol) in a solution of PD with hydroxy end groups in 40 ml of toluene.
A solution of 100.0 g of MS [degree of polymerization (Dp) = 45] was added dropwise at room temperature. After heating at 50 ° C. for 2 hours, volatile substances were removed under reduced pressure to obtain 93.0 g of a colorless liquid. NMR and FTIR analysis of ¹³ C and ²⁹ Si confirmed that the resulting liquid was amine-terminated PDMS (Dp = 45).

Then, under nitrogen atmosphere, under nitrogen atmosphere, 4.25 g of bromoisobutyryl bromide (1.25 g) in 20 ml of toluene at room temperature under N ₂ atmosphere in a 100 ml flask equipped with a magnetic stirrer, condenser and addition funnel.
8.5 mmol) was added dropwise. After the resulting mixture was kept under stirring at 90 ° C. for 1 hour, the salt formed was filtered and the solvent was evaporated off under reduced pressure. The polymer was washed with toluene and water, the organic phase was dried over magnesium sulfate, filtered and stripped of volatiles to give 27.8 g (86% yield) of a pale yellow liquid. NMR characterization of ¹ H, ¹³ C and ²⁹ Si of the resulting liquid revealed N-bromoisobutyryl, N-methylamino, 2-methylpropyl end-capped PDMS [Br (CH ₃ ) ₂ CCO
The formation of N (CH ₃ ) CH ₂ CH (CH ₃ ) CH _2- ] was confirmed.

REFERENCE EXAMPLE 2 Preparation of First Solid Supported Copper Catalyst In a 100 ml flask equipped with a magnetic stirrer and a condenser, 20.0 g (186.7 mmol) of 2-pyridinecarboxaldehyde and 10.7 g (74.7 g) of CuBr were used.
6 mmol) was mixed with 62 ml of tetrahydrofuran. The insoluble material was dissolved by adding 33.5 g (186.8 mmol) of 3-aminopropyltrimethoxysilane. A deep red solution was formed due to the exothermic reaction. The solution was allowed to cool to room temperature, and then 0.07 g (1.9 mmol) of NH ₄ F diluted with 1.7 ml of water was added. Then, the mixture was heated under stirring at 60 ° C. for 24 hours. The volatiles are evaporated off under reduced pressure and the solid obtained is triturated, washed with ether and dried at 80 ° C. under reduced pressure to give a reddish-brown powder 45 insoluble in toluene, xylene and acetone.
0.5 g [Cu (m / m%) = 8.92%] were obtained.

Example 1 Polymerization of methyl methacrylate 5.39 g of methyl methacrylate (MMA) in 11.5 ml of anhydrous p-xylene
53.9 mmol) was added to 0.66 g of the catalyst prepared in Reference Example 2 above in a Schlenk tube, and the resulting mixture was subjected to deoxygenation by one freeze-pump-thaw cycle. 1.0 g of the macroinitiator prepared in Reference Example 1 was added at room temperature. The obtained solution was heated at 90 ° C. for 6 hours under a N ₂ atmosphere, a sample was taken at a predetermined time, and ¹ H NMR was performed. The final polymer and catalyst were separated by simple filtration on filter paper and the polymer was dried under reduced pressure to give 3.9 g of a pale yellow solid. The conversion of methyl methacrylate monomer observed by ¹ H NMR was 59%. The catalyst is washed with toluene and ether and dried under reduced pressure to recover 0.51 g of active copper catalyst, which can be reused in the polymerization reaction. The results are shown in Table 1 below. The results obtained indicated a very good correspondence between the theoretical and experimental molecular weights, and thus that a controlled polymerization was carried out.

[0070]

[Table 1]

Example 2 Polymerization of MMA Using a 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 1 above in a Schlenk tube.
be), and the resulting mixture was deoxygenated by one freeze-pump-thaw cycle. Then, 0.744 g of the macroinitiator prepared in Reference Example 1 was added. The resulting solution was heated at 90 ° C. for 24 hours under a N ₂ atmosphere, and a sample was taken at a predetermined time to obtain ¹ H
NMR was performed. The results are shown in Table 2 below. The results obtained indicated a good correspondence between the theoretical and experimental molecular weights, thus indicating that a controlled polymerization was carried out.

[0072]

[Table 2]

Reference Example 3 Preparation of PDMS macroinitiator having bromoisobutyrate terminal-capped -Si (CH ₃ ) _2- (CH ₂ ) ₂ -O- (CH ₂ ) ₃ CH ₂ OH Is 2084 (OH: 0.049 mol), 51 g of PDMS and triethylamine 5
0.43 g (0.053 mol) are placed in a 100 ml flask equipped with a magnetic stirrer, a condenser and an addition funnel containing 20 ml of toluene, and 12.37 g (0.053 mol) of bromobutyrate bromide are added dropwise at room temperature. Was added and the reaction continued at room temperature overnight, after which the salts were filtered and the solvent was evaporated. The obtained polymer was washed with toluene and water. The organic phase was dried over magnesium sulfate, filtered, and volatiles were removed under reduced pressure. Carbinol functionality (δ = 3.56 ppm) by ¹ H NMR spectrum
Completely disappears, and -Si (CH ₃ ) _2- (CH ₂ ) ₂ -O- (CH ₂ ) ₃ CH ₂ OCOC (CH ₃ ) ₂
Br appeared at 4.19 ppm.

Reference Example 4 Preparation of second solid supported copper catalyst In a 1 l flask equipped with a magnetic stirrer and a condenser, 100.4 g (560.0 mmol) of 3-aminopropyltrimethoxysilane and 2-pyridinecarboxa were added. 63.0 g (558.2 mmol) of aldehyde and stirred for 10 minutes.
26.8 g (186.8 mmol) of uBr and 170.4 g of tetramethoxysilane (
1119.4 mmol), 45.2 g (2511.1 mmol) of water, NH ₄ F
0.6 g (16.2 mmol) were added sequentially to the flask. A strong exotherm was observed and a dark, homogeneous solution was obtained at room temperature. After 48 hours, the solution gelled to form a soft gel. After aging the solid for one week, the volatiles were evaporated off under reduced pressure. The resulting solid was triturated, washed with ether, and dried at 80 ° C. under reduced pressure for 8 hours to obtain 202.5 g of a reddish brown powder.

Example 3 Polymerization of MMA 190 g (1.9 mol) of MMA in 300 ml of anhydrous p-xylene was prepared in the same manner as in Reference Example 4 described above.
Was added in a 500 ml Schlenk tube and the resulting mixture was deoxygenated in one freeze-pump-thaw cycle. After heating at 90 ° C., 10 g of the macroinitiator produced in Reference Example 3 was added. The reaction was continued at 90 ° C. for 30 hours, and a sample was taken at a predetermined time and analyzed by ¹ H NMR. The reaction solution became very viscous during the polymerization, but maintained transparency and the catalyst remained visible in the polymer solution. After the polymerization, the solid catalyst was separated by filtration. The conversion of the MMA monomer observed by ¹ H NMR analysis was 44%, and the number average molecular weight (Mn) measured by ¹ H NMR was 20,900. If the catalyst was extracted with p-xylene in a Soxhlet extractor for 6 hours, the catalyst could be used for further polymerization. GPC of polymer
The analysis was based on the molecular weight distribution (Mn _th /Mn=1.5) of the starting polysiloxane macroinitiator.
) Showed a narrower molecular weight distribution (Mn _th /Mn=1.29).

Example 4 Polymerization of MMA Using a Recycle Catalyst 2.3 g of catalyst collected from Example 3 above with 30 g (0.3 mol) of MMA in 30 ml of anhydrous p-xylene (using p-xylene in a Soxhlet extractor) The mixture was deoxygenated by one freeze-pump-thaw cycle, heated to 90 ° C., and then purified by the macromolecule prepared in Reference Example 3 above. 3 g of initiator were added. The reaction was continued at 90 ° C. for 44 hours, and a sample was taken at a predetermined time and subjected to ¹ H NMR analysis. During the polymerization, the solution became very viscous, but maintained transparency and the catalyst remained visible in the polymer solution. After the polymerization, the solid catalyst was separated by filtration. Table 3 shows the results. The results obtained showed a very good correspondence between the theoretical and the experimental molecular weights, thus indicating that a controlled polymerization was carried out.

[0077]

[Table 3]

REFERENCE EXAMPLE 5 Preparation of third solid supported copper catalyst 100 g of 5 g of aminomethylpolystyrene (0.01 mol of -NH ₂ ) and 1.2 g (0.012 mol) of pyridinecarboxaldehyde containing 50 ml of diethyl ether
The reaction mixture was added to a flask at room temperature and reacted overnight under a nitrogen atmosphere. After the reaction, a yellow powder was collected, washed with dichloromethane and toluene, and dried at 65 ° C for 2 hours.
4.5 g of the obtained powder were mixed with 1.02 g of CuBr in 50 ml of acetone, stirred until all the powder turned black, and the reaction was continued under acetone reflux for 3 hours. After the reaction, the powder was washed with water and extracted with methanol in a Soxhlet extractor for 7 hours.
The presence of imine groups and disappearance of amino groups were confirmed by ¹³ C NMR of the solid substance.

Example 5 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 a copper catalyst produced according to the above Reference Example 5, and the resulting mixture was added to 1 ml of a tube. After deoxygenation with freeze-pump-thaw cycles, and heating to 90 ° C., 1.01 g of the PDMS macroinitiator prepared in Reference Example 3 above was added. The reaction was continued at 90 ° C. for 5 hours, and a sample was taken at a predetermined time. The solution became very viscous during the polymerization, but remained clear. The catalyst particles were visible in the polymer solution. After polymerization for 5 hours, the monomer conversion measured by ¹ H NMR analysis was 33%, and Mn was 7,100.

Example 6 Polymerization of MMA 47.4 g (0.47 mol) of MMA in 50 ml of anhydrous p-xylene were added to 19.4 g of the copper catalyst prepared according to the above Reference Example 4 in a 250 ml Schlenk tube, and the resulting mixture was obtained. Is deoxygenated in one freeze-pump-thaw cycle and then 90
After heating to ℃, 5.0 g of the macroinitiator prepared in Reference Example 3 above was added. The reaction was continued at 4 hours N ₂ atmosphere at 90 ° C. and samples were taken at predetermined time, ¹ H N
MR analysis was performed. The solution became very viscous during the polymerization, but the catalyst remained visible in the polymer solution. The results are shown in Table 4 below. The results showed a very good correspondence between the theoretical and experimental molecular weights, and thus showed that a very good controlled polymerization took place.

[0081]

[Table 4]

Reference Example 6 Preparation of PDMS Macroinitiator Having a Suspended Bromoisobutyrate Group A 500 ml three-necked reaction flask equipped with a dropping funnel, a thermometer, and a magnetic stirrer was prepared by adding an NH ₂ group with a degree of polymerization of 100. 80.5 g of dimethylethoxy-capped dimethylmethyl (aminopropyl) siloxane containing 0.018 mol and 100 ml of p-xylene were charged. After homogenization, 3.35 ml (0.024 mol) of triethylamine was added at room temperature.
Was added, and 5.53 g (0.024 mol) of bromoisobutyryl bromide was gradually added. The reaction was continued at 50 ° C. for 3 hours with stirring. After the reaction, p-xylene was removed by evaporation, and 300 ml of n-hexane was added to precipitate a triethylammonium salt. After this step, the reaction mixture was filtered and the hexane was evaporated to give the product as a clear yellow, very viscous polymer. ¹ loss of amine function
1 H NMR spectrum analysis confirms -CH ₂ CH ₂ NH ₂ peak at 3.99
It shifted from ppm to 3.30 ppm, a new peak corresponding to the _{-NH-COC (CH 3) 2} Br is expressed in 6.99Ppm. Although the bromination yield was 100%, some terminal ethoxy groups were hydrolyzed.

Reference Example 7 Preparation of fourth solid supported copper catalyst In a 2000 ml three-necked reaction flask equipped with a dropping funnel, a thermometer and a reflux condenser, 246 g (1.37 mol) of aminopropyltrimethoxysilane and p-xylene were added. 300 ml were charged. Then, 75 g (4.16 mol) of water were added over a period of 60 minutes, and at the same time methanol was distilled off. After removal of the methanol, p-xylene was stripped under reduced pressure to give a white brittle solid. 84 g of this solid substance and 300 ml of p-xylene were charged into a 1000 ml reaction flask,
To this, 70 g (1.0 mol) of 2-pyridinecarboxaldehyde was gradually added while cooling. After the addition of 2-pyridinecarboxaldehyde, 57 g of CuBr was added under vigorous stirring while maintaining the temperature at 30 ° C. or lower. The stirring of the reaction mixture was maintained until the green color characteristic of free Cu (I) had completely disappeared. After completion of the reaction, the solid substance is separated from the solvent, washed with toluene, and used without further extracting the solid substance. Theoretical CuBr w / w% was 29%.

Example 7 Polymerization of MMA The catalyst 2.65 prepared in Reference Example 7 was placed in a 250 ml Schlenk reaction flask.
g (0.76 mol) and 4.85 g (1.2%) of the macroinitiator prepared in Reference Example 6 above.
Mmol). The contents of the flask were dried at 80 ° C. under reduced pressure to remove oxygen and then covered with a nitrogen gas atmosphere. Then, 28 g of MMA was added under a nitrogen atmosphere and the resulting mixture was deoxygenated by three freeze-thaw pump cycles in liquid nitrogen. The flask was then rapidly heated in an oil bath to a reaction temperature of 90 ° C. Although the viscosity of the reaction solution increased during the polymerization reaction, the solid particles of the catalyst remained as a suspension in the polymer solution. After polymerization, the polymer solution was filtered, the residual monomer was evaporated off, and the polymer was analyzed by ¹ H NMR and / or SEC to determine the average number molecular weight and polydispersity (molecular weight distribution). The theoretical degree of polymerization is 233, based on 100% monomer conversion and total macroinitiator. ^{From 1} H NMR calculation, the experimental polymerization degree was 4
After an hour it was 113.

Reference Example 8 Preparation of bromoisobutyrylamide-functional MT resin macroinitiator 3.6% by weight in 200 ml of toluene under a N ₂ atmosphere in a 500 ml flask equipped with a magnetic stirrer, condenser and addition funnel. Me containing OH functional groups
To a solution of 100.0 g (1.45 mol) of the SiO _3/2 resin, 32.2 g (225.2 mmol, excess) of tetramethylazasilacyclopentane in 50 ml of toluene were added dropwise at room temperature. After heating at 60 ° C. for 1 hour, volatile substances were removed under reduced pressure to obtain 114.0 g of a colorless liquid. ¹³ C and ²⁹ Si NMR analysis and FTIR
Analysis confirmed that the resulting liquid was an amine-functional MT resin containing 4.75% by weight of -NMeH functionality.

[0086] Next, a magnetic stirrer, condenser and triethylamine 200ml of amine functional MT resin 112.7g of N ₂ atmosphere with toluene 150ml in bromoisobutyryl bromide 50.0g additives in 500ml flask equipped with a funnel (217.
(5 mmol, excess) at room temperature. 60 ° C. while stirring the resulting mixture
After 2 hours, the salts were filtered off and the solvent was evaporated off under reduced pressure. The functionalized MT resin was washed with toluene and water, the organic phase was dried over magnesium sulfate, filtered and stripped to give 108.2 g of a yellow viscous liquid. N-bromoisobutyryl, N-methylamino, 2-methylpropyl [Br (CH ₃ ) ₂ CCO containing 9.89% by weight of Br by ¹ H, ¹³ C and ²⁹ Si NMR characterization analysis of this liquid
_{N (CH 3) CH 2 CH} (CH 3) CH 2 -] was confirmed to be functional MT resin.

Reference Example 9 Preparation of Fifth Solid Supported Copper Catalyst 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 aminopropyltrimethoxysilane and p-
200 ml of xylene were charged. To this, 18 g (1.25 mol) of water was added over 60 minutes while distilling off methanol. After removing methanol, p-xylene was removed under reduced pressure to obtain a white solid. 200 ml of toluene was added to this solid in a flask equipped with a Dean-Stark trap and added at 120 ° C. for 4 hours.
Azeotropic distillation of water produced by the reaction. Removal of the toluene under reduced pressure gave a white brittle solid which was extracted with p-xylene in a Soxhlet extractor for 4 hours and then dried in a vacuum oven at 120 ° C. for 4 hours.

A 250 ml reaction flask was charged with 10 g of a white solid and 50 ml of p-xylene, and 8.6 g (69.9 mmol) of 2-pyridinecarboxaldehyde was gradually added, followed by a reaction overnight. The reaction solution was filtered to collect an orange solid, which was washed with p-xylene.

8.6 g of an orange solid, 3.5 g (24.5 mmol) of CuBr, and 30 ml of p-xylene were added to a 100 ml flask and heated at 80 ° C. for 4 hours. After cooling, the solvent was colorless and no green color, characteristic of free CuBr, was seen. The reaction product was filtered to give 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 8 Polymerization of MMA 2.7 g (1.17 mmol) of the macroinitiator prepared in Reference Example 8 and 3.55 g of the catalyst prepared in Reference Example 9 were weighed in a Schlenk container, and the pressure was reduced for 30 minutes. Deoxygenated by exposing underneath. 23.6 g (0.236 mol) of distilled methyl methacrylate are added under a nitrogen atmosphere and deoxygenated by three freeze-pump-thaw cycles.
Gas). The resulting solution was heated at 90 ° C. for 195 minutes and a sample was taken.
During the polymerization, the solution became extremely viscous, making it difficult to collect a sample. A 77% monomer conversion was determined by ¹ H NMR analysis after 195 minutes of polymerization.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country 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 Cardiff C.F.24.4 J.D.B., Cathays, Pentak Street 17 F-term (reference) CA19U CA30M CA301 FB01 LB20

Claims (8)

[Claims] 1. An initiator for initiating a controlled polymerization reaction comprising at least one
It has a number of groups -D-CR ⁸ ₂ X ', and the formula _{^{(R 7 3 SiO 1/2),}} (R 7 2 SiO 2/2)
, (R ⁷ SiO _3/2 ) and / or (SiO _4/2 ) wherein D contains an oxygen or nitrogen heteroatom and / or is substituted by a carbonyl group. A branched alkylene group, each R ⁸ is independently an alkyl group or a hydrogen atom, X ′ is a halogen atom, and each R ⁷ is independently -D-CR ⁸ ₂ X ′ or an appropriately substituted hydrocarbon The use of an initiator, wherein the initiator comprises a unit of the formula: Wherein at least one radical R ⁸ is an alkyl group in each -D-CR ⁸ ₂ X 'group, The method of claim 1, wherein. 3. is a 2 radicals R ⁸ is an alkyl group in each -D-CR ⁸ ₂ X 'group, The method of claim 2 wherein. 4. The method according to claim 1, wherein the initiator is of the formula R⁷ _ThreeSiO (SiR⁷ _TwoO)_qSiR⁷ _Three(Where R ⁷ Has the same meaning as defined above, and q is zero or a positive integer.)
A method according to any one of claims 1 to 3. 5. The method according to claim 1, wherein the initiator is represented by the following formula (VIII): (Wherein R ⁷ , R ⁸ , X ′, D and q have the same meanings as defined above). 6. Each R ⁷ is a C ₁ -C ₆ alkyl group and D is the following group: (Wherein R ⁹ is an alkyl group or a hydrogen atom, each R ¹⁰ is independently a linear or branched alkylene group, and r is an integer of 1 to 4). 6. The method according to claim 5. 7. The method according to claim 1, wherein the initiator is: The method of claim 6, wherein s is 40-45 and t is 4. 8. Use of the initiator in the controlled polymerization of a vinyl-containing monomer,
The method according to any one of claims 1 to 7.