JP2014025043A - Method for manufacturing pentadiene alone or copolymer, and pentadiene alone or copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel method for manufacturing pentadiene alone or copolymer, and to provide a polymer.SOLUTION: A method for manufacturing includes a polymerization process that polymerizes pentadiene by using a polymerization catalyst composition containing a metallocene complex comprising a central metal M which is scandium (Sc), a ligand Cpcomprising a substituted cyclopentadienyl derivative, a monoanionic ligands Qand Qand a neutral Lewis base L, and an ionic compound comprising a non-coordinating anion and cation as a catalyst.

Description

  The present invention relates to a method for producing pentadiene homo- or copolymer and pentadiene homo- or copolymer.

  Recently, research on precise structure-controlled polymerization (stereospecific / regioselective living polymerization) of 1-alkene and conjugated diene has been actively conducted. Then, precise structure-controlled polymerization has become possible under conditions of room temperature or higher, which has been considered difficult in the past (Non-Patent Documents 3 and 7).

  In addition, 1,3-butadiene (BD) and isoprene (IP) are low in cost and have high potential for application to the petrochemical industry. Therefore, using various catalysts, high cis-1, Studies have been made to obtain a polymer of 1,3-butadiene and isoprene having 4 selectivity (Non-patent Document 1).

  Also, regioselective and stereoselective control is very important in the polymerization of 1,3-butadiene and isoprene. In particular, polymers with high cis-1,4 selectivity are expected to be further processed to produce synthetic rubbers with excellent thermal and mechanical properties.

  On the other hand, with the development of the petrochemical industry, the production of C5-dienes such as 1,3-pentadiene (PD) is increasing. PD monomer is easily obtained as a byproduct when industrially producing isoprene (Non-patent Document 2).

Of the C5 fraction obtained by refining crude oil, about 20% of isoprene is effectively utilized through further refining processes. The remaining 80% is the surplus fraction, which is actually consumed and used as fuel. Moreover, if a part of the surplus C5 fraction can be converted into an IP alternative material or the like, energy applied to the purification process can be saved and CO ₂ emission can be suppressed.

  In the petrochemical industry, polybutadiene (PBD) or polyisoprene (PIP) used for tires or belt materials and the like has a remarkable improvement in thermophysical properties and mechanical properties when controlled to a cis-1,4 structure at a high level (non- Patent Document 9). Therefore, even in the polymerization of pentadiene, which is a compound similar to butadiene and isoprene, there is a possibility that it can be converted into a useful material if the structure can be controlled to a high degree.

  As described above, the diversion of pentadiene as a polymer material takes into consideration the low environmental load and is very interesting and important not only in the academic field but also in the industrial field.

By the way, living polymerization in which neither chain transfer reaction nor deactivation occurs can generate a polymer having a controlled molecular weight and a small molecular weight distribution ( _Mw / _Mn , MWD: molecular weight distributions). Living polymerization is useful in synthesizing end-functionalized polymers and block copolymers. Various catalysts have been reported to be used in living polymerization of olefins (such as 1,3-butadiene and isoprene) (Non-Patent Documents 3 to 5). However, regioselective and stereoselective PD living polymerization has not been achieved.

Several catalyst systems based on lanthanoids or transition metals such as Nd, Ti, Co, Ni in polymerizing (E) -PD or (Z) -PD have been reported (Non-Patent Documents 1 and 6). ). For example, in Non-Patent Document 1, with respect to polymerization using pentadiene, a complex catalyst system capable of controlling the cis-1,4 structure with a selectivity of 95% but generating a crystalline (isotactic structure-containing) polymer, although the polymerization activity is low. Has been reported. Further, in (a) of Non-Patent Document 6, (Z) -PD is polymerized at room temperature in a CrCl ₂ (dmpe) ₂ / MAO (methylaluminoxane) system, and high cis-1,4 selectivity (99 %) Is reported to be produced. In this case, the polymer does not show crystallinity, suggesting that the methyl group has an atactic arrangement. Further, the neodymium catalyst system, Nd (OCOC ₇ H ₁₅ ) ₃ / AlEt ₂ Cl / AlBu _{3, which} is another component, is a polymer of (E) -PD having both high isoselectivity and cis-1,4 selectivity. Although it showed moderate activity in the production of (crystalline polymer, cis-1,4 selectivity, 95%), it lacked living properties ((b) of Non-Patent Document 6).

The inventors have recently reported a living polymerization of BD or IP using a cationic half-sandwich scandium catalyst system (Non-Patent Document 7). This catalyst system is, for example, Cp′ScR ₂ (THF) _n (Cp ′ = C ₅ H ₅ , C ₅ Me ₄ SiMe ₃ ; R = CH ₂ SiMe ₃ , n = 1; R = CH ₂ C ₆ H _{4 NMe 2 -o, n = 0;} R = C 3 H 5, n = 0) the various active agents neutral half sandwich dialkyl precursors such as _{[PhNMe 2 H] [B (} C 6 F 5) 4] ([PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] or B (C ₆ F ₅ ) ₃ ). This allows unprecedented behavior in a wide range of olefin or polar monomer polymerization, copolymerization, terpolymerization (eg, cis-1,4 structure or isotactic-3, with almost 100% selectivity of the polymer structure). Control to 4 structures).

International Publication No. WO2006 / 004068 Pamphlet (January 12, 2006 International Publication)

Proto, A .; Capacchione, C. In Stereoselective Polymerization with Single-Site Catalysts; Baugh, L. S., Canich, J. A. M., Eds .; CRC Press: New York, US, 2007; p 447, and references including. Vautrin-Ul, C .; Pla, F .; Petit, A. Polymer 1996, 37, 4209 and references contains. (a) Domski, GJ; Rose, JM; Coates, GW; Bolig, AD; Brookhart, M. Prog.Polym.Sci. 2007, 32, 30. (b) Edson, JB; Domski, GJ; Rose, JM; Bolig, AD; Brookhart, M .; Coates, GW In Controlled and Living Polymerizations; Muller, AHE, Matyjaszewski, K., Eds .; Wiley-VCH, US, 2009; p 167 and references containing. (a) Miyazawa, A .; Kase, T .; Hashimoto, K .; Choi, J .; Sakakura, T .; Jizhu, J. Macromolecules 2004, 37, 8840. (b) Kaita. S .; Yamanaka, M .; Horiuchi, AC; Wakatsuki, Y. Macromolecules 2006, 39, 1359. (a) Zhang, L .; Suzuki, T .; Luo, Y .; Nishiura, M .; Hou, Z. Angew. Chem., Int. Ed. 2007, 46, 1909. (b) Wang, L .; Cui, D .; Hou, Z .; Li, W .; Li, Y. Organometallics 2011, 30, 760. (a) Ricci, G .; Battistella, M .; Porri, L. Macromolecules 2001, 34, 5766. (b) Purevsuren, B .; Allegra, G .; Meille, SV; Farina, A .; Porri, L. ; Ricci, G. Polymer J. 1998, 30, 431. Selected reviews in recent our studies: (a) Nishiura, M .; Hou, Z. Bull. Chem. Soc. Jpn. 2010, 83, 595. (b) Nishiura, M .; Hou, Z. Nature Chem. 2010, 2, 257. (a) Li, X .; Nishiura, M .; Mori, K .; Mashiko, T .; Hou, Z. Chem. Commun. 2007, 4137. (b) Yu, N .; Nishiura, M .; Li, X .; Xi, Z .; Hou, Z. Chem. Asian J. 2008, 3, 1406. (c) Li, X .; Nishiura, M .; Hu, Li .; Mori, K .; Hou, ZJ Am Chem. Soc. 2009, 131, 13870. S. Kaita et al., Macromolecules 2004, 37, 5860.

  However, there have been few reports on complex catalyst systems that polymerize PD to produce polypentadiene (PPD), and new block copolymers based on PPD have been reported so far. Absent.

  Therefore, an object of the present invention is to provide a novel method for producing a pentadiene homopolymer or copolymer, and a pentadiene homopolymer or copolymer.

In order to solve the above problems, the method for producing a pentadiene homo- or copolymer according to the present invention includes (1) a central metal M which is scandium (Sc), and a substituted cyclopentadienyl derivative bonded to the central metal. A metallocene represented by the general formula (I), including a ligand Cp ^* containing monoanionic ligands Q ¹ and Q ² , and W (W is an integer of 0 to 3) neutral Lewis bases L A polymerization step of polymerizing pentadiene is carried out using a complex and (2) a polymerization catalyst composition containing an ionic compound comprising a non-coordinating anion and a cation as a catalyst.

(The ligand Cp ^* in the general formula (I) has a cyclopentadienyl ring having a substituent, a substituted or unsubstituted fluorenyl ring, a substituted or unsubstituted octahydrofluorenyl ring, and a substituent. Any one selected from the group consisting of indenyl rings,
When Cp ^* is a cyclopentadienyl ring having a substituent, it is represented by the following general formula (II):

In general formula (II), Rx is a hydrocarbyl group having 1 to 20 carbon atoms or a metalloid group substituted with a hydrocarbyl group having 1 to 20 carbon atoms, which is bonded to the carbon atom constituting the skeleton of the cyclopentadienyl ring. * Represents a bond with M, and n is an integer of 3 to 5. In addition, one of the carbon atoms constituting the skeleton of the cyclopentadienyl ring shown in the general formula (II) is substituted with a group 14 atom (excluding carbon atoms and lead atoms) or a group 15 atom. It may be.
When Cp ^* is an indenyl ring having a substituent, it is represented by the following general formula (III).

In general formula (III), Rx1 is a metalloid substituted with a hydrocarbyl group having 1 to 20 carbon atoms or a hydrocarbyl group having 1 to 20 carbon atoms bonded to a carbon atom constituting a 5-membered skeleton of an indenyl ring. Refers to a group, * represents a bond with M, and n1 is an integer of 1 to 3. )
Furthermore, in the production method according to the present invention, the ligand Cp ^* is a cyclopentadienyl ring having a substituent represented by the general formula (II), and in the general formula (II), Rx is: The term refers to a hydrocarbyl group having 1 to 3 carbon atoms or a silyl group substituted with a hydrocarbyl group having 1 to 3 carbon atoms, which is bonded to the carbon atom constituting the skeleton of the cyclopentadienyl ring, and n is more preferably 5. preferable.

Furthermore, in the production method according to the present invention, the ligand Cp ^* is more preferably a tetramethyl (trimethylsilyl) cyclopentadienyl ring.

  Furthermore, in the production method according to the present invention, the polymerization step is more preferably performed in a temperature range of −60 ° C. or more and 0 ° C. or less.

  Furthermore, in the production method according to the present invention, copolymerization is performed by adding a conjugated diene other than pentadiene or 1-alkene to the reaction product containing the pentadiene homopolymer or copolymer obtained in the above polymerization step. preferable.

Furthermore, in the production method according to the present invention, the monoanion ligands Q ¹ and Q ² are a trimethylsilylmethyl group, η ³ -allyl group (η ³ indicates that the hapto number is 3) or ortho-. A dimethylaminobenzyl group is more preferable.

  Furthermore, in the production method according to the present invention, the neutral Lewis base L is more preferably tetrahydrofuran.

  Moreover, the pentadiene homo- or copolymer according to the present invention contains 85% or more of pentadiene units having a cis-1,4 structure with respect to the whole pentadiene units, and exhibits 90% or more isotacticity in pentad display. It is characterized by that.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a pentadiene single or a copolymer can be provided by using a predetermined scandium complex catalyst for the polymerization reaction of pentadiene.

In Example 1 and 2, it is a figure which shows the graph of GPC of each run shown in Tables 1-4. In Example 2, it is a figure which shows the graph of GPC of run 5-8 shown to Table 3 and 4. FIG. In Example 2, it is a figure which shows the graph of GPC of run9 and 10 shown in Table 3 and 4. FIG. In Example 1, a diagram illustrating the ¹ H NMR spectrum of the polymer poly cyclopentadiene obtained in (25 ℃) (run1~4) using complex 1-4. In Example 1, it is a figure which shows the ¹³ C NMR spectrum of the polypentadiene (run1-4) obtained by superposition | polymerization (25 degreeC) using the complexes 1-4. In Example 1, a diagram illustrating the ¹ H NMR spectrum of the polymer poly cyclopentadiene obtained in (25 ℃ ~-60 ℃) (run4 and Run15～18) using complex 4. In Example 1, it is a figure which shows the ¹³ C NMR spectrum of the polypentadiene (run4 and run15-18) obtained by superposition | polymerization (25 degreeC--60 degreeC) using the complex 4. FIG. In Example 1, it is a figure which shows the ¹³ C NMR spectrum of the polypentadiene (run4 and run15-18) obtained by superposition | polymerization (25 degreeC--60 degreeC) using the complex 4. FIG. In Example 1, it is a figure which shows the ¹³ C NMR spectrum of the polypentadiene in each run. In Example 1, a diagram illustrating the ¹ H- ¹³ C HMQC spectra of poly pentadiene in Run7. In Example 1, it is a figure which shows the DSC curve of the polypentadiene (run4 and run15-18) obtained by superposition | polymerization (25 degreeC--60 degreeC) using the complex 4. In FIG. In Example 3, it is a figure which shows the GPC curve of a pentadiene butadiene diblock copolymer. In Example 3, pentadiene - a diagram showing the ^{1 H} NMR spectrum of butadiene diblock copolymers. In Example 3, it is a figure which shows the ¹³ C NMR spectrum of a pentadiene-butadiene diblock copolymer. In Example 3, it is a figure which shows the DSC curve of a pentadiene-butadiene diblock copolymer. In Example 1, it is a figure which shows the relationship of the molecular weight ( _Mn ) with respect to a polymer yield, and molecular weight distribution ( _Mw / _Mn ). (A) is a reaction diagram showing polymerization of pentadiene and copolymerization of butadiene with pentadiene, and (b) is polymerization of (E) -1,3-pentadiene when complex 4 is used as a catalyst. It is a reaction diagram which shows the powerful reaction mechanism of. FIG. 2 is a reaction diagram showing polymerization of pentadiene and copolymerization of pentadiene with butadiene. It is a figure which shows the structure of the complexes 1-7 used in each Example and the comparative example.

  Hereinafter, embodiments of the present invention will be described in detail. A method for producing a pentadiene homo- or copolymer according to the present invention comprises 1) a metallocene complex represented by the following general formula (I), and 2) a polymerization catalyst comprising an ionic compound comprising a non-oriented anion and a cation. A polymerization step of polymerizing pentadiene using the composition as a catalyst is included.

The metallocene complex represented by the general formula (I) includes a central metal M which is scandium (Sc), a ligand Cp ^* containing a substituted cyclopentadienyl derivative bonded to the central metal, a monoanionic ligand Q ¹ and Q ² , and W (W is an integer of 0 to 3) neutral Lewis bases L are included.

The ligand Cp ^* in the general formula (I) is a cyclopentadienyl ring having a substituent, a substituted or unsubstituted fluorenyl ring, a substituted or unsubstituted octahydrofluorenyl ring, and a substituent. Any one selected from the group consisting of indenyl rings having

When Cp ^* is a cyclopentadienyl ring having a substituent, it is represented by the following general formula (II).

  In the above general formula (II), Rx is a hydrocarbyl group having 1 to 20 carbon atoms or a metalloid substituted with a hydrocarbyl group having 1 to 20 carbon atoms, which is bonded to the carbon atom constituting the skeleton of the cyclopentadienyl ring. Refers to a group, * represents a bond with M, and n is an integer of 3-5. In addition, one of the carbon atoms constituting the skeleton of the cyclopentadienyl ring shown in the general formula (II) is substituted with a group 14 atom (excluding carbon atoms and lead atoms) or a group 15 atom. It may be. Preferable examples of the group 15 atom include a nitrogen atom or a phosphorus atom.

  The hydrocarbyl group is preferably a hydrocarbyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), phenyl Group or an allyl group such as a naphthyl group, a benzyl group, and the like, and most preferably a methyl group.

  The hydrocarbyl group may have a substituent (referred to as a substituted hydrocarbyl group). The hydrocarbyl group in the substituted hydrocarbyl group is the same as the hydrocarbyl group described above. The substituted hydrocarbyl group is a hydrocarbyl group in which at least one hydrogen atom of the hydrocarbyl group is substituted with a halogen atom, an amide group, a phosphide group, an alkoxy group, an aryloxy group, or the like.

  Examples of the metalloid in the metalloid group substituted with the hydrocarbyl group include germyl (Ge), stannyl (Sn), and silyl (Si). The hydrocarbyl group substituted with a metalloid group is the same as the hydrocarbyl group described above, and the number of substitutions is determined by the type of metalloid (for example, in the case of a silyl group, the number of substitutions of the hydrocarbyl group is 3).

  Preferably, at least one Rx of the cyclopentadienyl ring is a metalloid group (preferably a silyl group) substituted with a hydrocarbyl group, more preferably a trimethylsilyl group.

  From the viewpoint of further improving the syndiotacticity of the pentadiene monomer, in the general formula (II), n is preferably 4 or 5, and more preferably 5. More specifically, the cyclopentadienyl ring represented by the general formula (II) is more preferably tetramethyl (trimethylsilyl) cyclopentadienyl, pentamethylcyclopentadienyl, or tetramethylcyclopentadienyl. Tetramethyl (trimethylsilyl) cyclopentadienyl or pentamethylcyclopentadienyl is more preferable.

  One of the carbon atoms constituting the skeleton of the cyclopentadienyl ring shown in the general formula (II) is a group 14 atom (excluding the carbon atom and lead atom) or a group 15 atom (heteroatom). Rx may be bonded to this hetero atom.

Further, as an example, the ligand Cp ^* is a cyclopentadienyl ring having a substituent represented by the general formula (II). In the general formula (II), Rx is a cyclopentadienyl ring. 1 to 3 or a silyl group substituted with a hydrocarbyl group having 1 to 3 carbon atoms bonded to the carbon atom constituting the skeleton of n.

When the substituted or unsubstituted cyclopentadienyl derivative contained in Cp ^* is an indenyl ring having a substituent, it is represented by the following general formula (III).

  In the general formula (III), Rx1 is substituted with a hydrocarbyl group having 1 to 20 carbon atoms or a hydrocarbyl group having 1 to 20 carbon atoms bonded to a carbon atom constituting the skeleton of the 5-membered ring of the indenyl ring. It refers to a metalloid group, * represents a bond with M, and n1 is an integer of 1 to 3. In addition, the definition of the hydrocarbyl group and metalloid group in general formula (III) is the same as Rx in general formula (II).

  Preferably, at least one of Rx1 of the indenyl ring is a metalloid group (preferably a silyl group) substituted with a hydrocarbyl group, more preferably a trimethylsilyl group.

  From the viewpoint of further improving the syndiotacticity of the pentadiene monomer, in the general formula (III), n is preferably 2 or 3, and more preferably 3. More specifically, in the indenyl ring represented by the general formula (III), n is 3, and all three Rx1 are methyl groups, or two Rx1 are methyl groups and one Rx1 is a trimethylsilyl group. is there.

The substituted or unsubstituted cyclopentadienyl derivative contained in Cp ^* is a substituted or unsubstituted fluorenyl ring (composition formula: C ₁₃ H _9-x R _x ), or a substituted or unsubstituted octahydrofluorenyl. It may be a ring (composition formula: C ₁₃ H _17-x R _x ). Here, R is the same as Rx shown in the general formula (II) in the above-described cyclopentadienyl ring, and X is an integer of 0 to 9 or 0 to 17.

In the complex represented by the general formula (I) used in the present invention, Q ¹ and Q ² are the same or different monoanionic ligands (monoanionic ligands). As monoanionic ligands, 1) hydride, 2) halide, 3) substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, 4) alkoxy group or aryloxy group, 5) amide group, or 6) Examples include, but are not limited to, phosphino groups. Further, the category of ^{Q 1} and _{^{Q 2, CH 2 C 6 H}} 4 N (CH 3) 2 -o like are also included.

Q ¹ and Q ² may be bonded to each other or may be combined to form a so-called dianionic ligand. Examples of dianionic ligands include alkylidene, dienes, cyclometallated hydrocarbyl groups, and bidentate chelate ligands.

  The halide may be any of chloride, bromide, fluoride, and iodide.

The C1-C20 hydrocarbyl group is preferably a methyl group, ethyl group, propyl group, butyl group, amyl group, isoamyl group, hexyl group, isobutyl group, heptyl group, octyl group, nonyl group, decyl group, cetyl group. Group, alkyl group such as 2-ethylhexyl group, allyl group such as phenyl group or naphthyl group, unsubstituted hydrocarbyl group such as benzyl group, substituted benzyl group, trialkylsilylmethyl group, bis (trialkylsilyl) methyl group Substituted hydrocarbyl groups such as Examples of preferred hydrocarbyl groups include substituted or unsubstituted benzyl groups and trialkylsilylmethyl groups, and more preferred examples include trimethylsilylmethyl groups and η ³ -allyl groups (η ³ has a hapto number of 3). And an ortho-dimethylaminobenzyl group is included.

  The alkoxy group or aryloxy group is preferably a methoxy group, a substituted or unsubstituted phenoxy group, and the like.

  The amide group is preferably a dimethylamide group, a diethylamide group, a methylethylamide group, a di-t-butylamide group, a diisopropylamide group, an unsubstituted or substituted diphenylamide group, and the like.

  The phosphino group is preferably a diphenylphosphino group, a dicyclohexylphosphino group, a diethylphosphino group, a dimethylphosphino group, or the like.

  The alkylidene is preferably methylidene, ethylidene, propylidene or the like.

  The cyclometallated hydrocarbyl group is preferably propylene, butylene, pentylene, hexylene, octylene or the like.

  The diene is preferably 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,4-dimethyl-1, 3-pentadiene, 2-methyl-1,3-hexadiene, 2,4-hexadiene, and the like.

  In the complex represented by the general formula (I) used in the present invention, L is a neutral Lewis base. Neutral Lewis bases include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride and the like.

L may be bonded to Q ¹ and / or Q ² to form a so-called multidentate ligand.

W of _{L W} in the general formula (I) represents the number of neutral Lewis bases L. w is an integer of 0 to 3, preferably 0 to 1.

  The metallocene complex is prepared by the method described above, for example, (1) Reference: Tardif, O .; Nishiura, M .; Hou, ZM Organometallics 22, 1171, (2003). (2) Reference: Hultzsch, KC; Spaniol, TP; Okuda, J. Angew. Chem. Int. Ed, 38, 227, (1999)., (3) Reference: International Publication WO 2006/004068 Pamphlet, (4) Reference: Japanese Patent Publication No. 2008-222780, (5) Reference: Can be synthesized according to the method described in Japanese Patent Application Laid-Open No. 2008-095008.

(Ionic compounds consisting of non-coordinating anions and cations)
As described above, the polymerization catalyst composition includes an ionic compound. Here, the ionic compound includes an ionic compound composed of a non-coordinating anion and a cation. When the ionic compound is combined with the metallocene complex, the metallocene complex exhibits activity as a polymerization catalyst. As the mechanism, it can be considered that the ionic compound reacts with the metallocene complex to generate a cationic complex (active species).

  As the non-coordinating anion which is a constituent component of the ionic compound, for example, a tetravalent boron anion is preferable, and tetra (phenyl) borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (tri Fluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) Examples thereof include borate, [tris (pentafluorophenyl), phenyl] borate, and tridecahydride-7,8-dicarbaoundecaborate.

  Of these non-coordinating anions, tetrakis (pentafluorophenyl) borate is preferred.

  Examples of the cation that is a constituent component of the ionic compound include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.

  Specific examples of the carbonium cation include a tri-substituted carbonium cation such as a triphenylcarbonium cation and a tri-substituted phenylcarbonium cation. Specific examples of the tri-substituted phenyl carbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation.

  Specific examples of ammonium cations include trialkylammonium cations, triethylammonium cations, tripropylammonium cations, tributylammonium cations, tri (n-butyl) ammonium cations, and the like, N, N-dimethylanilinium cations, N Dialkyl ammonium cations such as N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, di (isopropyl) ammonium cation, dicyclohexylammonium cation, etc. included.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as a triphenylphosphonium cation, a tri (methylphenyl) phosphonium cation, and a tri (dimethylphenyl) phosphonium cation.

  Among these cations, an anilinium cation or a carbonium cation is preferable, and a triphenylcarbonium cation is more preferable.

  That is, the ionic compound contained in the polymerization catalyst composition of the present invention may be a combination of those selected from the above-mentioned non-coordinating anions and cations.

  Preferably, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocete Examples thereof include nium tetrakis (pentafluorophenyl) borate. One ionic compound may be used, or two or more ionic compounds may be used in combination.

  Among these ionic compounds, particularly preferred are triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like.

In addition, B (C ₆ F ₅ ) ₃ , Al (C ₆ F ₅ ) _3, etc., which are Lewis acids that can react with transition metal compounds to form cationic transition metal compounds, are used as ionic compounds. These may be used in combination with the ionic compound.

  Furthermore, an alkylaluminum compound (aluminoxane, preferably MAO or MMAO), or a combination of an alkylaluminum compound and a borate compound can also be used as the ionic compound, or may be used in combination with other ionic compounds. . In particular, when the monoanionic ligand Q of the complex (general formula (I)) is other than alkyl or hydride (for example, when it is halogen), it is an alkylaluminum compound, or a combination of an alkylaluminum compound and a borate compound. It is considered preferable to use

(Other optional components contained in the polymerization catalyst composition)
The polymerization catalyst composition of the present invention can contain an optional component in addition to the metallocene complex and the ionic compound. Examples of the optional component include alkyl aluminum compounds, silane compounds, hydrogen and the like.

The alkylaluminum compound usually includes an organoaluminum compound called aluminoxane (alumoxane) used in a metallocene polymerization catalyst. For example, methylaluminoxane (MAO) etc. are mentioned. Other alkylaluminum compounds include AlR ₃ (R = Et, Bu), and these may be added to the reaction system to polymerize pentadiene.

  Examples of the silane compound include phenylsilane.

(Composition ratio etc. in the polymerization catalyst composition)
As described above, the polymerization catalyst composition includes the metallocene complex and an ionic compound. In the polymerization catalyst composition, the molar ratio of the ionic compound to the metallocene complex varies depending on the type of the complex and the ionic compound.

The molar ratio is, for example, 0.5 to 1 when the ionic compound is composed of a carbonium cation and a boron anion (for example, [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]). In the case of MAO or the like, it is preferably about 300 to 4000. If the molar ratio of the ionic compound and the complex is within the above range, the metallocene complex can be sufficiently activated, and the ionic compound and the monomer to be polymerized react undesirably. It is possible to reduce the fear more reliably.

  For example, 1) providing a composition containing each component (such as a metallocene complex and an ionic compound) in the polymerization reaction system, or 2) providing each component separately in the polymerization reaction system, By constituting the composition, it can be used as a polymerization catalyst composition. In the above 1), “providing as a composition” includes providing a metallocene complex (active species) activated by reaction with an ionic compound.

(Polymerization process)
In one embodiment, the polymerization step is performed in the presence of the polymerization catalyst composition (metallocene complex and ionic compound) and pentadiene in the same reaction system. There are no particular restrictions on the order, method, and the like of supplying these components into the reaction system. In addition, a monomer other than pentadiene may be added to the reaction system to carry out copolymerization with pentadiene. Examples of monomers other than pentadiene include ethylene and styrene. By these, pentadiene homo- or copolymer can be produced.

  The polymerization method may be any method such as a gas phase polymerization method, a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, or a solid phase polymerization method. In the case of the solution polymerization method, the solvent to be used is not particularly limited as long as it is inactive in the polymerization reaction and can dissolve the polymer material and the catalyst. For example, saturated aliphatic hydrocarbons such as butane, pentane, hexane and heptane; saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; methylene chloride, chloroform, carbon tetrachloride and trichloro Halogenated hydrocarbons such as ethylene, perchlorethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorotoluene and the like can be mentioned.

  A solvent having low toxicity to the living body is preferable. Specifically, an aromatic hydrocarbon, particularly toluene is preferable. The solvent may be used alone or in combination of two or more.

  Although the quantity of the solvent used is arbitrary, it is preferable that it is the quantity which makes the density | concentration of the metallocene complex contained in the polymerization catalyst composition based on this invention 0.1-0.0001 mol / l, respectively.

  Although the temperature (polymerization temperature) which performs a polymerization reaction should just be arbitrary temperature which a polymerization reaction advances, it can carry out within the range of -90 degreeC or more and 100 degrees C or less, for example. The polymerization temperature can be performed, for example, around room temperature, that is, about 25 ° C.

  Moreover, it is preferable to perform a polymerization reaction in the range whose polymerization temperature is -60 degreeC or more and 0 degreeC or less. By performing polymerization of pentadiene within this range, polypentadiene having high cis-1,4 selectivity can be produced.

  The polymerization time is, for example, about several seconds to several days, and more preferably 5 minutes to 24 hours. The polymerization time may be, for example, 1 hour or less, and in some cases, 30 minutes or less. Moreover, it is preferable to lengthen polymerization time, so that reaction temperature becomes low.

  Moreover, the amount of the monomer to be subjected to the polymerization reaction can be appropriately set according to the intended pentadiene polymer to be produced. For example, pentadiene is preferably 50 times or more and 2500 times or less, and more preferably 100 times or more and 1000 times or less in molar ratio to the metallocene complex constituting the polymerization catalyst composition.

  As a result of the polymerization reaction, a pentadiene homo- or copolymer having a predetermined stereoselectivity and regioselectivity (cis-1,4 selectivity) is obtained. Further, for example, by lowering the polymerization temperature, pentadiene alone containing 85% or more of pentadiene units having a cis-1,4 structure with respect to the whole pentadiene units and showing 90% or more of isotacticity in pentad display Or a copolymer is obtained. By lowering the polymerization temperature, a pentadiene homo- or copolymer containing 90% or more, more preferably 95% or more of pentadiene units having a cis-1,4 structure with respect to the entire pentadiene units can be obtained. Further, by lowering the polymerization temperature, a pentadiene homo- or copolymer having an isotactic property of 95% or more, more preferably 98% or more, more preferably 99% or more in pentad display can be obtained.

Further, pentadiene homopolymer obtained as a result of the thermal property measurement, having a polyisoprene comparable glass transition temperature (T _g) having a number of cis-l, 4 structure.

  Copolymerization may be carried out by adding a conjugated diene or 1-alkene other than pentadiene to the reaction product containing the pentadiene homopolymer or copolymer obtained in the polymerization step. When carrying out the copolymerization, the conjugated diene or 1-alkene may be added to the reaction system containing the reaction product and polymerized. Thereby, the block copolymer containing a pentadiene block can be polymerized. It is preferable to add the conjugated diene or 1-alkene to the reaction system after the pentadiene is completely consumed.

  Moreover, you may add a pentadiene to the polymer obtained by superposing | polymerizing conjugated dienes other than pentadiene, or 1-alkene, and may copolymerize. Thereby, the block copolymer containing a pentadiene block can be polymerized. For polymerization of the conjugated diene or 1-alkene, for example, a method similar to the polymerization of pentadiene using the polymerization catalyst composition described in this specification can be applied.

  Here, examples of conjugated dienes other than pentadiene include 1,3-butadiene, isoprene, 4-methyl-1,3-pentadiene, and examples of 1-alkene include ethylene, propylene, 1-butene, and 1-hexene. , 1-octene and the like.

  The reaction temperature for carrying out the copolymerization may be any temperature at which the polymerization reaction proceeds, and can be appropriately determined according to the conjugated diene or 1-alkene. The polymerization time may be any time for completing the polymerization reaction, and can be appropriately determined according to the conjugated diene or 1-alkene. As an example, the reaction temperature and polymerization time for copolymerization may be the same as the reaction temperature and polymerization time for pentadiene polymerization.

  Further, the amount of the conjugated diene or 1-alkene to be subjected to the copolymerization reaction can be appropriately set according to the block copolymer to be produced. For example, the conjugated diene or 1-alkene is preferably 50 times or more and 2500 times or less in molar ratio to the metallocene complex constituting the polymerization catalyst composition, more preferably 100 times or more and 1000 times or less. preferable.

  In the above polymerization of pentadiene and block copolymerization of pentadiene and other monomers, stereoselective and regioselective living polymerization proceeds in the range from low temperature to room temperature. Therefore, in the present invention, a chain transfer reaction and deactivation do not occur, and a polymer with a controlled molecular weight and a small molecular weight distribution can be produced.

  Examples will be shown below, and the embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail. Further, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and the present invention is also applied to the embodiments obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention. Moreover, all the literatures described in this specification are used as reference.

〔basic operation〕
All operations were performed using the Schlenk technique in a high purity nitrogen glove box (Mbraun) with strict removal of air and moisture. Nitrogen was passed through a clean column (4A molecular sieve, manufactured by Nikka Seiko Co., Ltd.) and a Gasclean CC-XR column (manufactured by Nikka Seiko Co., Ltd.) for purification. Moreover, the solvent was refine | purified using Mbraun SPS-800 Solvent Purification System in the glove box, and it dried through Na Chips.

[Complex and raw materials]
Complexes 1 to 7 shown in FIG. 19 were prepared. Complexes 1 to 4 were prepared as described in Non-Patent Document 8. For complexes 5-7, a: Nishiura, M .; Hou, Z. Nature Chem. 2010, 2, 257. b: Pan, L .; Zhang, K .; Nishiura, M .; Hou, Z. Angew. Prepared as described in Chem., Int. Ed. 2011, 50, 12012.

As ionic compounds, [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ], [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] and B (C ₆ F ₅ ) ₃ was used without purification.

Further, AlR ₃ (R = Me, Et, Bu) manufactured by Kanto Chemical Co. and Tosoh Finecom Co., Ltd. was used as a co-catalyst without purification.

As monomers used in the polymerization, (E) -1,3-pentadiene manufactured by Aldrich, (Z) -1,3-pentadiene manufactured by TCl, and 1,3-butadiene manufactured by Aldrich were used. . (E) -1,3-pentadiene and 1,3-butadiene were stirred for 24 hours using MS-4A (Aldrich) and dried. In addition, (Z) -1,3-pentadiene was dried with CaH ₂ before polymerization, vacuum transported, and freeze-deaerated twice.

[ ¹ H NMR and ¹³ C NMR]
The deuterated solvent is ISOTEC. Obtained from. Also, ¹ H and ¹³ C NMR and ¹ H- ¹³ C HMQC spectra are recorded on a JEOL EX270 (270 MHz for ¹ H, 67 MHz for ¹³ C) spectrometer and JEOL ECA 400WB (400 MHz for ¹ H, 100 MHz for ¹³ C). It was. The deuterated NMR solvent was all adsorbed on the molecular sieves under a nitrogen atmosphere.

The microstructure of polypentadiene (PPD) and polybutadiene (PBD) was determined by ¹ H and ¹³ C NMR spectroscopy with CDCl ₃ (and C ₆ D ₆ ) at 25 ° C. ¹ H NMR (PPD) δ = 0.85-0.94 (1,4-PPD —CH ₃ ), 1.10-1.32 (1,2-PPD —CH ₂ —), 1.61-1.70 (1,2-PPD— CH ₃ ), 1.89-2.18 (-CH- of 1,2-PPD and -CH ₂ -of 1,4-PPD), 2.42-2.55 (-CH- of 1,4-PPD), 5.11-5.35 ppm ( -CH = for 1,2-PPD and -CH = for 1,4-PPD). ¹³ C NMR (PPD): δ = 17.96 (syndiotactic-trans-1,2-PPD unit), 20.91 (isotactic-cis-1,4-PPD unit), 32.29 (isotactic-cis-1,4-PPD unit) , 35.15 (isotactic-cis-1,4-PPD unit), 40.44 (isotactic-trans-1,4-PPD unit), 123.90-127.91 and 135.52-137.35 ppm (1,2-PPD unit and 1,4-PPD unit). ¹ H NMR (PBD): δ = 4.80-5.10 (1,2-PBD = CH ₂ ), 5.33-5.70 ppm (1,2-PBD—CH═ and 1,4-PBD—CH═). ¹³ C NMR (PBD): δ = 27.41 (cis-1,4-PBD unit), 32.76 (trans-1,4-PBD unit), 128.02-130.07 (1,4-PBD unit), 114.43 and 142.56 ppm ( 1,2-PBD unit).

The amount of polypentadiene product isomers was calculated from ¹ H and ¹³ C NMR spectra using the following formula:

(Formula 1)
Mol 1,4-PD% = {I _H5 / (I _H5 + I _H5v )} × 100 (1)
(Formula 2)
Mol 1,2-PD% = {I _H5 / (I _H5 + I _H5v )} × 100 (2)
(I _H5 is an integral value at 0.85 to 0.94 ppm in ¹ H NMR, and I _H5v is an integral value at 1.61 to 1.70 ppm in ¹ H NMR (see FIGS. 4 to 6). reference).)
The amount of isomer was calculated from ¹ H and ¹³ C NMR spectra.

(Formula 3)
Mol cis-1,4-PD% = {I _C1 / (I _C1 + I _C1t )} × 100 (3)
(Formula 4)
Mol trans-1,4-PD% = {I _C1t / (I _C1 + I _C1t )} × 100 (4)
_{(I Cl} ^is the integral value of 35.15ppm assigned to the methylene carbon of the cis-1,4-PD by 13 C _{NMR, I Clt} ^is a trans-1,4-PD by 13 C NMR Integral value at 40.44 ppm assigned to methylene carbon (see FIGS. 5 and 7).
[Molecular weight and molecular weight distribution of polymer]
The molecular weight and molecular weight distribution of the obtained polymer were analyzed by gel permeation chromatography (GPC, Tosoh HLC) using THF as an eluent at 40 ° C. (45 ° C. in Examples 2 and 3) at a flow rate of 0.35 mL / min. -8220 GPC, Column Super HZM-H HT × 3). Molecular weights were calculated using standard methods based on calibration with standard polystyrene. Further, DSC measurement was performed at 20 ° C./min with DSC 6220 (SII Co.). FIG. 1 shows a GPC graph of each run shown in Tables 1 to 4 in Examples 1 and 2.

The glass transition temperature (T _g ) was measured by DSC.

[Comparative Example 1]
In Comparative Example 1, only (E) -1,3-pentadiene was polymerized to produce a pentadiene homopolymer.

First, in a glove box, a predetermined amount of (E) -1,3-pentadiene and a 40 μmol [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] toluene solution were placed in a 30 mL round bottom flask containing a stir bar. Were added sequentially at room temperature.

  After a few minutes, 40 μmol of Complex 1 in toluene solution was added to the flask to initiate the polymerization. After carrying out the polymerization for a predetermined time, 2 mL of methanol was added to terminate the reaction. The resulting mixture was poured into methanol (100 mL) to precipitate the polymer. The polymer was collected by filtration and dried under reduced pressure at 60 ° C. until constant weight. The results are shown in Tables 1 and 2. The structural formula of Complex 1 is as shown in FIG.

As shown in run1, Complex 1 with C ₅ H ₅ ligand produced poly (E) -PD (PPD: polypentadiene) with low activity and low selectivity.

[Example 1]
In Example 1, only (E) -1,3-pentadiene or (Z) -1,3-pentadiene was polymerized to produce a pentadiene homopolymer.

First, in a glove box, a predetermined amount of (E) -1,3-pentadiene and 40 μmol [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] ([PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] or B (C ₆ F ₅ ) ₃ ) in toluene was sequentially added to a 30 mL round bottom flask containing a stirring bar at room temperature.

  Several minutes later, 40 μmol of complex 2-4 in 10 ml toluene solution was added to the flask to initiate the polymerization. After carrying out the polymerization for a predetermined time, 2 mL of methanol was added to terminate the reaction. The resulting mixture was poured into methanol (100 mL) to precipitate the polymer. The polymer was collected by filtration and dried under reduced pressure at 60 ° C. until constant weight. The results are shown in Tables 1 and 2. The structures of complexes 2 to 4 are as shown in FIG.

FIG. 4 shows the ¹ H NMR spectrum of polypentadiene (run 1 to 4) obtained by polymerization (25 ° C.) using complexes 1 to 4. FIG. 5 shows a ¹³ C NMR spectrum of polypentadiene (run 1 to 4) obtained by polymerization (25 ° C.) using complexes 1 to 4.

On the other hand, as shown in run 2 to 4, complexes 2 to ₄ having a C ₅ Me ₄ SiMe ₃ ligand showed high catalytic activity and higher cis-1,4 selectivity than complex 1. The pentadiene homopolymer obtained by the polymerization of (E) -pentadiene using Complex 4 and [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] is shown below. The pentadiene homopolymer has a 1,2-structure, a trans-1,4-structure and a cis-1,4-structure as pentadiene units.

As shown in run 4, when Complex 4 was used, PPD (M _w / M _n = 1.27) having the smallest molecular weight distribution was generated.

  From the above, it has been clearly shown that the change of the ligand in the central metal of the complex has a great influence on the polymerization activity and cis-1,4 selectivity of PPD.

  Next, PD was polymerized using Complex 4 under various conditions (runs 5 to 18 in Tables 1 and 2).

First, in run ₅ , complex 4 was activated using [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] as an ionic compound. At this time, as shown in Tables 1 and 2, the polymerization activity was the same as that of run4. However, it showed lower cis-1,4 selectivity and larger molecular weight distribution compared to run4.

Next, in run 6, (Z) -PD was polymerized instead of (E) -PD. At this time, the polymerization activity was lower than that of run4. It also showed lower cis-1,4 selectivity and larger molecular weight distribution compared to run4. The polymer obtained with run 6 had an atactic structure in the ¹³ C NMR spectrum.

  It is known that the difference between the E and Z stereoisomers of PD affects the polymerization behavior. For example, the reactivity of (E) -PD is much higher than that of (Z) -PD and has been reported previously in bis (phenoxyimino) Ti (IV) catalyst systems (see Non-Patent Document 1). reference). This experiment also showed that the reactivity of (E) -PD is higher than that of (Z) -PD.

Next, in run 7-9, an excess amount of AlR ₃ (R = Me, Et, Bu) was added at 25 ° C., and PD was polymerized. At this time, in any of the run 7 to 9, the polymerization of PD was performed in a good yield. On the other hand, the selectivity for cis-1,4 is influenced by the bulk height of the alkylaluminum, so AlBu ₃ (run 9 (68%))> AlEt ₃ (run 8 (62%))> AlMe ₃ (run 7 (43% )). In addition, the influence on the cis-1,4 selectivity by the bulkiness of the alkyl group is as described in (b) of Non-Patent Document 4. FIG. 10 shows the ¹ H- ^13C HMQC spectrum of polypentadiene in run7.

Next, in run 4 and run 10-14, the monomer / catalyst ratio is changed to confirm the performance of the catalyst system of complex 4 and [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] in living polymerization. (E) -PD polymerization was performed at 25 degreeC by this.

FIG. 16 shows the relationship between the molecular weight (M _n ) and the molecular weight distribution (M _w / M _n ) with respect to the polymer yield in Example 1. As shown in FIG. 16, run 4 and run 10 to 14 had a living property of cis-1,4 polymerization of (E) -PD having stereoselectivity (isoselectivity). When the monomer / catalyst ratio was doubled (see, eg, run 10 and 12 and run 11 and 13), the molecular weight (Mn) of the resulting polymer increased nearly double. On the other hand, even when the monomer / catalyst ratio was increased, the molecular weight distribution remained small (M _w / M _n = 1.2-1.27).

Next, in run 4 and 15-18, the influence of the reaction temperature (0-60 ° C.) on PD polymerization was examined. The cis-1,4 selectivity and glass transition temperature (T _g ) increased as the reaction temperature decreased. On the other hand, the molecular weight distribution was almost constant regardless of the temperature. FIG. 6 shows a ¹ H NMR spectrum of polypentadiene obtained by polymerization using complex 4 (25 ° C. to −60 ° C.). 7 and 8 show ¹³ C NMR spectra of polypentadiene obtained by polymerization using complex 4 (25 ° C. to −60 ° C.). FIG. 9 shows the ¹³ C NMR spectrum of polypentadiene in each run. FIG. 11 shows a DSC curve of polypentadiene obtained by polymerization using Complex 4 (25 ° C. to −60 ° C.).

At low reaction temperatures such as run 18, the isotacticity and cis-1,4 selectivity increased, but the catalytic activity decreased greatly. Moreover, run18 showed the highest regioselectivity and stereoselectivity (isotactic-1,4-PPD, 1,4-cis, 99%, mm (pentad display)> 99%, see FIG. 18). Moreover, the grounds showing other structures were not observed in ¹ H, ¹³ C NMR and ¹ H- ¹³ C HMQC spectra (see FIG. 10). As shown in FIG. 6, in the ¹ H NMR spectrum, vinyl and methine protons are assigned to the region of 5.4 to 5.1 and 2.6 to 2.4 ppm, and methylene and methyl protons are 2.1 to Assigned to the 1.9 and 1.0-0.9 ppm regions. From the assignment of the proton signal and the interphase data between the carbon signals obtained in the ¹ H- ¹³ C HMQC spectrum, the carbon signal was assigned constant. Furthermore, isotactic-cis-1,4-PPD was crystalline and had a melting point greater than 43 ° C. (T _m = 43.4 ° C.).

[Example 2]
In Example 2, only (E) -1,3-pentadiene was polymerized to produce a pentadiene homopolymer.

That is, in run 1 to 10, in order to investigate the influence of the ligand on the catalytic activity and regioselectivity when the temperature is changed (25 ° C. to −60 ° C.), 1 equivalent of [PhNMe _{2 in} 10 ml of toluene. (E) -PD was polymerized using complex 4 activated with H] [B (C ₆ F ₅ ) ₄ ]. The results are shown in Tables 3 and 4. Note that run1 in Tables 3 and 4 is the same as run4 in Tables 1 and 2.

  As shown in run 2 to 8, these polymerization reactions showed high catalytic activity and higher cis-1,4 selectivity than run1. Moreover, higher cis-1,4 selectivity was shown as reaction temperature became low.

  In run 6, after 10 minutes had passed since the reaction under the conditions of run 5, the same amount of PD as that added first was further added, and the mixture was allowed to react with stirring for 10 minutes. Even in this case, the catalyst activity and regioselectivity similar to run5 were shown.

  In run 8, 50 minutes after the reaction under the condition of run 7, PD was added in the same amount as the amount added first, and the reaction was allowed to proceed for 50 minutes with stirring. Even in this case, the catalyst activity and regioselectivity similar to run7 were shown.

  FIG. 2 shows a GPC graph of run 5 to 8 shown in Tables 3 and 4. As shown in FIG. 2, when (E) -PD is added again and the PPD chain grows again, a GPC curve having a sharper peak is observed as compared with the case where (E) -PD is added only once. It was.

  At low reaction temperatures such as run 9 and 10, isotacticity and cis-1,4 selectivity increased. In run 9, the melting point was 45.2 ° C, and in run 10, the melting point was 43.4 ° C. Further, FIG. 3 shows a GPC graph of run 9 and 10 shown in Tables 3 and 4.

Example 3
In Example 3, (E) -1,3-pentadiene and 1,3-butadiene were block copolymerized to produce a pentadiene copolymer.

First, in a glove box, a toluene solution of a predetermined amount of 1,3-butadiene (BD) and 40 μmol [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ was placed in a 30 mL round bottom flask containing a stir bar. Sequentially added at room temperature. After a few minutes, 40 μmol (12.8 mg) of Complex 4 in toluene solution was added to the flask. After 1,3-butadiene was polymerized and completely consumed, (E) -1,3-pentadiene (PD) was added to the reaction mixture. After carrying out the polymerization for a predetermined time, 2 mL of methanol was added to terminate the reaction.

  The resulting mixture was poured into methanol (100 mL) to precipitate the PD and BD copolymer. The copolymer was collected by filtration and dried under reduced pressure at 60 ° C. until constant weight.

First, in run 1 and 2, in order to investigate the influence of the ligand on the catalytic activity and regioselectivity when the temperature is changed (25 ° C. to −60 ° C.), 1 equivalent of [PhNMe _{2 in} 10 ml of toluene. (E) -PD was polymerized using complex 4 activated with H] [B (C ₆ F ₅ ) ₄ ]. FIG. 12 shows a GPC curve of a pentadiene-butadiene diblock copolymer. FIG. 13 shows a ¹ H NMR spectrum of the pentadiene-butadiene diblock copolymer. FIG. 14 shows a ¹³ C NMR spectrum of a pentadiene-butadiene diblock copolymer. FIG. 15 shows a GPC curve of a pentadiene-butadiene diblock copolymer.

Polymerization of 1,3-butadiene and of 1,3-butadiene and (E) -1,3-pentadiene using complex 4 / [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] at −40 ° C. Block copolymerization was performed. The results are shown in Tables 5 and 6. The BD content was calculated from the yield.

  In run 2, after 120 minutes from the reaction under the conditions of run 1, the same amount of PD ([PD] / [Sc] = 150) as the amount of BD added first ([BD] / [Sc] = 150) Furthermore, it was made to react for 120 minutes, stirring. The block copolymer in run 2 also showed high catalytic activity and regioselectivity, like the polybutadiene in run 1. Although not shown in the table, the microstructure of the PD block portion in run 2 was cis-1,4 / trans-1,4 / 1,2 = 96.5 / 1.5 / 2.0.

  (A) of FIG. 17 is a reaction diagram showing polymerization of pentadiene and copolymerization of butadiene with pentadiene, and (b) shows (E) -1,3- when the complex 4 is used as a catalyst. FIG. 3 is a reaction diagram showing an effective reaction mechanism of pentadiene polymerization. This catalyst system is also active for block copolymerization of BD and (E) -PD, has a small molecular weight distribution, as shown in FIG. A block copolymer containing a large amount of pentadiene units having a high gain was obtained.

The ¹³ C NMR spectrum of PPD polymerized by reacting PD for 120 minutes under the conditions of run 1 showed a typical signal of isotactic-cis-1,4-PPD (δ = 20.91 ppm, cis-1,4 Selectivity = 97%). Moreover, the ¹³ C NMR spectrum of the block copolymer produced in run 2 described in Table 5 and Table 6 showed a typical signal of isotactic-cis-1,4-PBD (δ = 27.41 ppm). , Cis-1,4 selectivity = 86%).

In run2, the copolymer showed a value a _{T g} based on the respective PBD block and PPD block (-104 ° C. and -70 ° C.). This result indicates that the polymer obtained is not a single polymer mixture but a diblock copolymer. This is a novel block copolymer with isotactic-cis-1,4-PPD.

Next, FIG. 17B shows an experimental and theoretical reaction mechanism based on (c) of Non-Patent Document 8. Incorporation of s-trans-η ² coordination and 1,2- (E) -PD into a Sc-alkyl bond can form an η ³ -σ-allyl intermediate (c) as a secondary growth chain. The coordination step in the polymerization of (E) -PD can be slow at low temperatures (−20 ° C., −40 ° C. and −60 ° C.). Therefore, there is no steric hindrance near the metal center due to the delay of the coordination monomer, and the σ-allyl intermediate (c) is passed through the rotation of the C3-C2 single bond of the η ¹ -σ-allyl intermediate (d and e). To η ³ -π-allyl intermediate (f).

These steps power the σ-π isomerization in these allyl intermediates. As described above, it is possible to shift the equilibrium to the η ³ -π-allyl intermediate (f), thereby making the main component a pentadiene unit having a cis-1,4 structure. Steric repulsion between the Cp ligand and the methyl group of the (E) -PD monomer will orient the methyl group of the (E) -PD monomer so as to provide high isoselectivity (up to 99% mm). Can be regulated (g and j). This summary is consistent with the results from this experiment (eg, run 16-18 in Example 1).
[Comparative Example 2]
In addition to Complexes 1 to 4, PD polymerization was investigated using three new types of Complexes 5 to 7. The structures of complexes 5 to 7 are shown in FIG. These complexes are known to be effective for regioselective and stereoselective polymerization of BD and IP (a: Nishiura, M .; Hou, Z. Nature Chem. 2010, 2, 257. b: Pan, L .; Zhang, K .; Nishiura, M .; Hou, Z. Angew. Chem., Int. Ed. 2011, 50, 12012.). However, experiments were conducted under the same conditions as in Examples 1 to 3, but no polymer could be obtained under these conditions. The results are shown in Table 7.

  From the results of the above examples, it is clear that the complexes 2 to 4 containing Sc metal, particularly the complex 4 when used for the polymerization of PD, show regioselective and stereoselective superiority and a small molecular weight distribution. It was. Moreover, it turned out that the polymerization reaction of the pentadiene using the complexes 2-4 containing Sc metal is regioselective and stereoselective living polymerization.

  The present invention leads to resource saving in material synthesis and effective use of surplus C5 fraction. Further, it can be an industrially important substitute material for polyisoprene. Further, the surplus C5 fraction can be used as a monomer, and the cost of the produced polymer is reduced and the load on the environment is low.

Claims (8)

(1) A central metal M which is scandium (Sc), a ligand Cp ^* containing a substituted cyclopentadienyl derivative bonded to the central metal, monoanionic ligands Q ¹ and Q ² , and W (W Is an integer of 0 to 3) containing a neutral Lewis base L, a metallocene complex represented by the general formula (I), and (2) an ionic compound comprising a non-coordinating anion and a cation. As a catalyst,
A method for producing a pentadiene homo- or copolymer comprising a polymerization step of polymerizing pentadiene.

(The ligand Cp ^* in the general formula (I) has a cyclopentadienyl ring having a substituent, a substituted or unsubstituted fluorenyl ring, a substituted or unsubstituted octahydrofluorenyl ring, and a substituent. Any one selected from the group consisting of indenyl rings,
When Cp ^* is a cyclopentadienyl ring having a substituent, it is represented by the following general formula (II):

In general formula (II), Rx is a hydrocarbyl group having 1 to 20 carbon atoms or a metalloid group substituted with a hydrocarbyl group having 1 to 20 carbon atoms, which is bonded to the carbon atom constituting the skeleton of the cyclopentadienyl ring. * Represents a bond with M, and n is an integer of 3 to 5. In addition, one of the carbon atoms constituting the skeleton of the cyclopentadienyl ring shown in the general formula (II) is substituted with a group 14 atom (excluding carbon atoms and lead atoms) or a group 15 atom. It may be.
When Cp ^* is an indenyl ring having a substituent, it is represented by the following general formula (III).

In general formula (III), Rx1 is a metalloid substituted with a hydrocarbyl group having 1 to 20 carbon atoms or a hydrocarbyl group having 1 to 20 carbon atoms bonded to a carbon atom constituting a 5-membered skeleton of an indenyl ring. Refers to a group, * represents a bond with M, and n1 is an integer of 1 to 3. ) The ligand Cp ^* is a cyclopentadienyl ring having a substituent represented by the general formula (II),
In general formula (II), Rx is a hydrocarbyl group having 1 to 3 carbon atoms or a silyl group substituted with a hydrocarbyl group having 1 to 3 carbon atoms, which is bonded to a carbon atom constituting the skeleton of the cyclopentadienyl ring. The manufacturing method according to claim 1, wherein n is 5. The production method according to claim 2, wherein the ligand Cp ^* is a tetramethyl (trimethylsilyl) cyclopentadienyl ring.   The said polymerization process is performed in the temperature range of -60 degreeC or more and 0 degrees C or less, The manufacturing method as described in any one of Claims 1-3 characterized by the above-mentioned. In the reaction product containing pentadiene homo- or copolymer obtained in the polymerization step,
Copolymerization is performed by adding a conjugated diene or 1-alkene other than pentadiene, and the production method according to any one of claims 1 to 4. The monoanionic ligands Q ¹ and Q ² are a trimethylsilylmethyl group, η ³ -allyl group (η ³ indicates that the hapto number is 3), or ortho-dimethylaminobenzyl group, The manufacturing method according to any one of claims 1 to 5.   The said neutral Lewis base L is tetrahydrofuran, The manufacturing method as described in any one of Claims 1-6 characterized by the above-mentioned.   A pentadiene homo- or copolymer containing 85% or more of a pentadiene unit having a cis-1,4 structure with respect to the whole pentadiene unit and having an isotactic property of 90% or more in pentad display.

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