JP4837666B2 - Catalyst system for production of cyclic olefin polymer having polar functional group, polymer production method using the same, olefin polymer produced by this method, and optical anisotropic film containing the polymer - Google Patents

Description

  The present invention relates to a catalyst for producing a polar cyclic olefin polymer and a method for producing the polymer. More specifically, the present invention relates to a catalyst system for producing a cyclic olefin polymer containing a polar functional group, and a polymer weight using the catalyst system. The present invention relates to a combined method, an olefin polymer produced by this method, and an optically anisotropic film containing the polymer.

  In a catalyst system used in polymer polymerization, a conventional Ziegler-Natta catalyst system, which is a general multi-active site catalyst, is a methylaluminum oxy-oxide catalyst as a co-catalyst for improving the reactivity of the catalyst. Although Sun (MAO) was used, it had to be used in an excessive amount in comparison with the catalyst precursor, and there were problems of economic efficiency and aftertreatment.

  Thereafter, with the emergence of single active site catalysts represented by the metallocene series, as a solution to this problem, a single cationic active species can be imparted to the catalyst precursor, and a charge as low as -1 or -2, A non-coordinating anion in the form of perfluoroarylborate, which is easy to delocalize, has emerged as a co-catalyst (Chem. Rev. 1988, Vol. 88, 1405-1421; Chem. Rev. 1993, Vol. .93, 927-942).

Such an anion is used in a salt form together with a trityl which performs an alkyd or hydride removal reaction or a dialkylammonium cation which performs a protonation reaction. Typical borate promoter compounds include [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] and [PhNme ₂ H] [B (C ₆ F ₅ ) ₄ ].

  During the polymerization reaction, the cation portion of the cocatalyst reacts with the leaving group of the metal precursor to impart cationicity to the metal precursor, and forms an ion pair with the anion portion of the cocatalyst. At this time, the anion is weakly coordinated with the metal and is easily exchanged with the olefin monomer, resulting in a polymerization reaction.

  However, while these ion pairs play the role of a substantially catalytically active species, they are in a thermally and chemically unstable state, so that they react sensitively with solvents and monomers to react with the catalyst. It is easy to lower. In particular, in the case of a nitrogen-containing cocatalyst compound, a neutral amine compound is produced during the catalytically active reaction process, and such an amine compound can have a strong interaction with the organometallic catalytic activity in the cationic form, which is a polymerization activity. Cause a decline. In order to prevent this, it is known that cation of carbenium, oxonium and sulfonium is used instead of ammonium cation (European Patent No. EP 0426,637).

  On the other hand, when polymerizing cyclic olefins using MAO or organoaluminum as a co-catalyst, it exhibits high polymerization activity for nonpolar norbornene polymerization such as norbornene, alkylnorbornene, and silylnorbornene, while it is similar to ester or acetylnorbornene. Remarkably low polymerization activity was shown for polar norbornene (US Pat. Nos. 5,468,819, 5,569,730, 5,912,313, 6,031,058, 6,455,650).

  The norbornene polymer is a polymer composed of a cyclic monomer such as norbornene, which is superior in transparency, heat resistance, chemical resistance, and birefringence and moisture absorption compared to existing olefin polymers. The rate is very low, such as CD, DVD, optical material such as POF (Plastic Optical Fiber), capacitor film, information electronic material such as low dielectric, low water absorption syringe, blister packaging, etc. It can be applied in various ways as a medical material. However, in order to be used for information electronic material applications, it has adhesion to metal surfaces such as silicon, silicon oxide, silicon nitride, alumina, copper, aluminum, gold, silver, platinum, titanium, nickel, tantalum and chromium. In order to adjust the metal adhesion and various electrical, optical, chemical and physical properties of the norbornene polymer, it is necessary to introduce polar functional groups into the norbornene monomer. there were. However, in such a case, the above-described problem of decreased reactivity occurred.

  That is, in the case of a cyclic olefin polymerization catalyst system having a polar functional group, the catalyst system was manufactured using various cocatalysts. Levels that are practically required as in the case of general olefins with polar functional groups, exposing the problems of being deactivated or having poor thermal stability and difficult to use in high temperature polymerization The polymerization yield, the molecular weight of the polymer obtained, and the amount of catalyst used were not obtained. Further, when an excessive amount of catalyst is used, the obtained polymer is colored or a problem occurs in transparency.

  Therefore, the structure of the co-catalyst and the structure of the pre-catalyst can be appropriately adjusted at the same time to provide thermal chemical stability against solvents, monomers, small amounts of moisture and oxygen, etc. It was necessary to develop a new catalyst system capable of commercial production of cyclic olefin polymers containing polar functional groups.

  The first technical problem to be solved by the present invention is to solve the above-mentioned problems of the prior art by having excellent thermal chemical stability and no deactivation of the catalyst by polar functional groups. Another object of the present invention is to provide a catalyst system capable of producing a cyclic olefin polymer having a polar functional group with a high molecular weight and a high yield.

  The second technical problem to be solved by the present invention is to provide a polymerization method capable of producing a cyclic olefin polymer having a polar functional group with a high molecular weight and a high yield using the catalyst system.

  The third technical problem to be solved by the present invention is to provide a cyclic olefin polymer having a polar functional group having a high glass transition temperature and excellent thermal stability, oxidation stability, chemical resistance and metal adhesion. It is to be.

  The fourth technical problem to be solved by the present invention is to provide an optically anisotropic film produced by containing the olefin polymer.

前記化学式１で、
Ｘは、それぞれＳ、Ｏ及びＮのうちから選択されたヘテロ原子であり、Ｒ_１は、−ＣＨ＝ＣＨＲ^２０、−ＯＲ^２０、−ＳＲ^２０、−Ｎ（Ｒ^２０）_２、−Ｎ＝ＮＲ^２０、−Ｐ（Ｒ^２０）_２、−Ｃ（Ｏ）Ｒ^２０、−Ｃ（Ｒ^２０）＝ＮＲ^２０、−Ｃ（Ｏ）ＯＲ^２０、−ＯＣ（Ｏ）ＯＲ^２０、−ＯＣ（Ｏ）Ｒ^２０、−Ｃ（Ｒ^２０）＝ＣＨＣ（Ｏ）Ｒ^２０、−Ｒ^２１Ｃ（Ｏ）Ｒ^２０、−Ｒ^２１Ｃ（Ｏ）ＯＲ^２０または−Ｒ^２１ＯＣ（Ｏ）Ｒ^２０であり、前記でＲ^２０は、水素、ハロゲン、線形または分枝型炭素数１ないし５のアルキル、線形または分枝型炭素数１ないし５のハロアルキル、炭素数５ないし１０のシクロアルキル、線形または分枝型炭素数２ないし５のアルケニル、線形または分枝型炭素数２ないし５のハロアルケニル、置換または非置換の炭素数７ないし２４のアラルキルであり、Ｒ^２１は、炭素数１ないし２０のヒドロカルビレンであり、Ｒ_２は、炭素数１ないし２０の線形または分枝型アルキル、アルケニルまたはビニル；炭化水素に置換または非置換の炭素数５ないし１２のシクロアルキル；炭化水素に置換または非置換の炭素数６ないし４０のアリール；炭化水素に置換または非置換の炭素数７ないし１５のアラルキル；または炭素数３ないし２０のアルキニルであり、Ｍは、１０族金属であり、ｐは、０ないし２である。
［（Ｒ_３）−Ｐ（Ｒ_４）_ａ（Ｒ_４’）_ｂ［Ｚ（Ｒ_５）_ｄ］_ｃ］［Ａｎｉ］ ＜化２＞
前記化学式２で、ａ、ｂ、ｃは、０ないし３の整数であり、ａ＋ｂ＋ｃ＝３であり、Ｚは、酸素、硫黄、シリコン、または窒素であり、ｄは、Ｚが酸素または硫黄である場合に１であり、Ｚが窒素である場合に２であり、Ｚがシリコンである場合に３であり、Ｒ_３は、水素またはアルキル、アリール基であり、Ｒ_４及びＲ_４’、Ｒ_５は、それぞれ独立して水素；炭素数１ないし２０の線形または分枝型アルキル、アルコキシ、アリル、アルケニル、またはビニル；炭化水素に置換または非置換の炭素数３ないし１２のシクロアルキル；炭化水素に置換または非置換の炭素数６ないし４０のアリール；炭化水素に置換または非置換の炭素数７ないし１５のアラルキル；炭素数３ないし２０のアルキニル；トリ（炭素数１ないし１０の線形または分枝型アルキル）シリル、トリ（炭素数１ないし１０の線形または分枝型アルコキシ）シリル；トリ（置換または非置換の炭素数３ないし１２のシクロアルキル）シリル；トリ（置換または非置換の炭素数６ないし４０のアリール）シリル；トリ（置換または非置換の炭素数６ないし４０のアリールオキシ）シリル；トリ（炭素数１ないし１０の線形または分枝型アルキル）シロキシ；トリ（置換または非置換の炭素数３ないし１２のシクロアルキル）シロキシ；トリ（置換または非置換の炭素数６ないし４０のアリール）シロキシであり、このとき、前記それぞれの置換基は、ハロゲンまたは炭素数１ないし２０のハロアルキルであり、［Ａｎｉ］は、前記化学式１の金属Ｍに弱く配位されうる陰イオンであり、ホウ酸塩、アルミン酸塩、[ＳｂＦ_６]−、[ＰＦ_６]−、[ＡｓＦ_６]−、パーフルオロ酢酸（[ＣＦ_３ＣＯ_２]−）、パーフルオロプロピオン酸塩（ [Ｃ_２Ｆ_５ＣＯ_２]−）、パーフルオロ酪酸塩（ [ＣＦ_３ＣＦ_２ＣＦ_２ＣＯ_２]−）、過塩素酸塩（ [ＣｌＯ_４]−）、ｐ−トルエンスルホン酸塩（ [ｐ−ＣＨ_３Ｃ_６Ｈ_４ＳＯ_３]−）、[ＳＯ_３ＣＦ_３]−、ボラタベンゼン、及びハロゲンに置換または非置換のカルボランからなる群から選択いずれか一つである。 In order to achieve the first technical problem, the present invention provides a heteroatom directly coordinated to a metal represented by the following chemical formula 1 in a catalyst system for producing a cyclic olefin polymer containing a polar functional group. A catalyst system for producing a cyclic olefin-based polymer comprising a polar functional group comprising a group 10 metal-containing pre-catalyst having a ligand containing and a promoter containing a phosphonium-containing salt compound represented by the following chemical formula 2 .

In Formula 1,
X is a heteroatom selected from S, O and N, respectively, and R ₁ is —CH═CHR ²⁰ , —OR ²⁰ , —SR ²⁰ , —N (R ²⁰ ) ₂ , —N═NR. ²⁰ , —P (R ²⁰ ) ₂ , —C (O) R ²⁰ , —C (R ²⁰ ) = NR ²⁰ , —C (O) OR ²⁰ , —OC (O) OR ²⁰ , —OC (O) R ²⁰ , —C (R ²⁰ ) ═CHC (O) R ²⁰ , —R ²¹ C (O) R ²⁰ , —R ²¹ C (O) OR ²⁰ or —R ²¹ OC (O) R ²⁰ , R ²⁰ is hydrogen, halogen, linear or branched alkyl having 1 to 5 carbon atoms, linear or branched haloalkyl having 1 to 5 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, linear or branched carbon number 2 to 5 alkenyl, linear or branched, 2 to 5 carbon atoms Roarukeniru, aralkyl, substituted or unsubstituted 24 having 7 to carbon atoms of, R ²¹ is hydrocarbylene of from 1 to 20 carbon atoms, R ₂ is a linear or branched alkyl of from 1 to 20 carbon atoms, Alkenyl or vinyl; hydrocarbon substituted or unsubstituted cycloalkyl having 5 to 12 carbon atoms; hydrocarbon substituted or unsubstituted aryl having 6 to 40 carbon atoms; hydrocarbon substituted or unsubstituted 7 to 15 carbon atoms Or alkynyl having 3 to 20 carbon atoms, M is a Group 10 metal, and p is 0 to 2.
[(R ₃ ) -P (R ₄ ) _a (R _{4 ′} ) _b [Z (R ₅ ) _d ] _c ] [Ani] <Chemical Formula 2>
In Formula 2, a, b, and c are integers of 0 to 3, a + b + c = 3, Z is oxygen, sulfur, silicon, or nitrogen, and d is Z is oxygen or sulfur. 1 when Z is 2 when Z is nitrogen, 3 when Z is silicon, R ₃ is hydrogen or an alkyl, aryl group, R ₄ and R _{4 ′} , R ₅ Each independently represents hydrogen; linear or branched alkyl having 1 to 20 carbon atoms, alkoxy, allyl, alkenyl, or vinyl; hydrocarbon substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; hydrocarbon substituted or unsubstituted aralkyl having 7 to 15 carbon atoms; alkynyl having 3 to 20 carbon atoms; tri (linear or linear having 1 to 10 carbon atoms) Branched alkyl) silyl, tri (linear or branched alkoxy having 1 to 10 carbon atoms) silyl; tri (substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms) silyl; tri (substituted or unsubstituted carbon) Tri (substituted or unsubstituted aryloxy having 6 to 40 carbon atoms) silyl; tri (linear or branched alkyl having 1 to 10 carbon atoms) siloxy; tri (substituted or unsubstituted) A cycloalkyl) having 3 to 12 carbon atoms) siloxy; tri (substituted or unsubstituted aryl having 6 to 40 carbon atoms) siloxy, wherein each of the substituents is halogen or a haloalkyl having 1 to 20 carbon atoms. And [Ani] is an anion that can be weakly coordinated to the metal M of Formula 1; borate, aluminate _{[SbF 6] -, [PF} 6] -, [AsF 6] -, perfluoro acid _{([CF 3 CO 2] -} ), perfluoro propionate _{([C 2 F 5 CO 2} ] -), perfluoro butyrate _{([CF 3 CF 2 CF 2} CO 2] -), perchlorate _{([ClO 4] -),} p- toluenesulfonate _{([p-CH 3 C 6} H 4 SO 3] -), It is any one selected from the group consisting of [SO ₃ CF ₃ ]-, boratabenzene, and halogen substituted or unsubstituted carborane.

According to an embodiment of the present invention, in the catalyst system for producing a cyclic olefin polymer containing a polar functional group, the borate or aluminate of the chemical formula 2 is represented by the following chemical formula 2a or 2b. It is desirable to consist of ions.
[M ′ (R ₆ ) ₄ ] <Chemical 2a>
[M ′ (OR ₆ ) ₄ ] <Chemical 2b>
In Formulas 2a and 2b, M ′ is boron or aluminum, and R ₆ is independently halogen; halogen-substituted or unsubstituted C 1-20 linear or branched alkyl, alkenyl; C3-C12 cycloalkyl substituted or unsubstituted with halogen; C6-C40 aryl substituted or unsubstituted with hydrocarbon; C3-C20 linear or branched trialkylsiloxy or C18 Aryl having 6 to 40 carbon atoms substituted by linear or branched triarylsiloxy having from 48 to 48; aralkyl having 7 to 15 carbon atoms substituted or unsubstituted by halogen.

前記化学式３で、Ｘ’及びＹ’は、それぞれＳ及びＯのうちから選択されたヘテロ原子であり、Ｒ_１’、Ｒ_２’、Ｒ_２’’及びＲ_２’’’は、それぞれ独立して炭素数１ないし２０の線形または分枝型アルキル、アルケニルまたはビニル；炭化水素に置換または非置換の炭素数５ないし１２のシクロアルキル；炭化水素に置換または非置換の炭素数６ないし４０のアリール；炭化水素に置換または非置換の炭素数７ないし１５のアラルキル；または炭素数３ないし２０のアルキニルであり、Ｍは、１０族金属であり、ｒ及びｓは、０ないし２であり、ｒ＋ｓは２である。
[Ｈ−Ｐ（Ｒ_４）_３]［Ａｎｉ］ ＜化４＞
前記化学式４で、Ｒ_４は、それぞれ独立して水素；炭素数１ないし２０の線形または分枝型アルキル、アルコキシ、アリル、アルケニル、またはビニル；置換または非置換の炭素数３ないし１２のシクロアルキル；置換または非置換の炭素数６ないし４０のアリール；置換または非置換の炭素数７ないし１５のアラルキル；炭素数３ないし２０のアルキニルであり、このとき、前記それぞれの置換基は、ハロゲンまたは炭素数１ないし２０のハロアルキルであり、［Ａｎｉ］は、前記化学式１の金属Ｍに弱く配位されうる陰イオンであり、ホウ酸塩、アルミン酸塩、[ＳｂＦ_６]−、[ＰＦ_６]−、[ＡｓＦ_６]−、パーフルオロ酢酸（[ＣＦ_３ＣＯ_２]−）、パーフルオロプロピオン酸（[Ｃ_２Ｆ_５ＣＯ_２]−）、パーフルオロ酪酸塩（[ＣＦ_３ＣＦ_２ＣＦ_２ＣＯ_２]−）、過塩素酸塩（[ＣｌＯ_４]−）、ｐ−トルエンスルホン酸塩（[ｐ−ＣＨ_３Ｃ_６Ｈ_４ＳＯ_３]−）、[ＳＯ_３ＣＦ_３]−、ボラタベンゼン、及びハロゲンに置換または非置換のカルボランからなる群から選択いずれか一つである。 According to another embodiment of the present invention, in the catalyst system for producing a cyclic olefin polymer containing a polar functional group, the pre-catalyst represented by the chemical formula 1 and the co-catalyst represented by the chemical formula 2 are respectively It is desirable to be a group 10 metal-containing pre-catalyst represented by the following chemical formula 3 and a co-catalyst represented by the following chemical formula 4.

In Formula 3, X ′ and Y ′ are heteroatoms selected from S and O, respectively, and R ₁ ′, R ₂ ′, R ₂ ″ and R ₂ ′ ″ are each independently Linear or branched alkyl, alkenyl or vinyl having 1 to 20 carbon atoms; cycloalkyl having 5 to 12 carbon atoms substituted or unsubstituted with hydrocarbon; aryl having 6 to 40 carbon atoms substituted or unsubstituted with hydrocarbon Hydrocarbon substituted or unsubstituted aralkyl having 7 to 15 carbon atoms; or alkynyl having 3 to 20 carbon atoms, M is a Group 10 metal, r and s are 0 to 2, and r + s is 2.
[HP (R ₄ ) ₃ ] [Ani] <Formula 4>
In Formula 4, each R ₄ is independently hydrogen; linear or branched alkyl having 1 to 20 carbon atoms, alkoxy, allyl, alkenyl, or vinyl; substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms. Substituted or unsubstituted aryl having 6 to 40 carbon atoms; substituted or unsubstituted aralkyl having 7 to 15 carbon atoms; alkynyl having 3 to 20 carbon atoms, wherein each of the substituents is halogen or carbon [Ani] is an anion that can be weakly coordinated to the metal M of Formula 1; borate, aluminate, [SbF ₆ ] −, [PF ₆ ] — , [AsF ₆ ] −, perfluoroacetic acid ([CF ₃ CO ₂ ] −), perfluoropropionic acid ([C ₂ F ₅ CO ₂ ] −), perfluorobutyrate ([CF _{3 CF 2 CF 2 CO 2]} -), perchlorate _{([ClO 4] -),} p- toluenesulfonate _{([p-CH 3 C 6} H 4 SO 3] -), [SO 3 CF 3 ]-, Boratabenzene, and halogen-substituted or unsubstituted carborane.

前記化学式３ａで、Ｒ_１’、Ｒ_２’、Ｒ_２’’及びＲ_２’’’は、それぞれ独立して炭素数１ないし２０の線形または分枝型アルキル、アルケニルまたはビニル；炭化水素に置換または非置換の炭素数５ないし１２のシクロアルキル；炭化水素に置換または非置換の炭素数６ないし４０のアリール；炭化水素に置換または非置換の炭素数７ないし１５のアラルキル；または炭素数３ないし２０のアルキニルであり、ｒ及びｓは０ないし２であり、ｒ＋ｓは２である。
[Ｈ−Ｐ（Ｒ_４）_３]［Ａｎｉ］ ＜化４＞
前記化学式４で、Ｒ４及び［Ａｎｉ］は、前記と同様である。 According to another embodiment of the present invention, in the catalyst system for producing a cyclic olefin polymer containing a polar functional group, the pre-catalyst represented by the chemical formula 1 and the co-catalyst represented by the chemical formula 2 are respectively A Pd metal-containing pre-catalyst represented by the following chemical formula 3a and a co-catalyst represented by the following chemical formula 4 are desirable.

In Formula 3a, R ₁ ′, R ₂ ′, R ₂ ″, and R ₂ ″ are each independently a linear or branched alkyl, alkenyl, or vinyl having 1 to 20 carbon atoms; substituted with a hydrocarbon Or an unsubstituted cycloalkyl having 5 to 12 carbon atoms; a hydrocarbon substituted or unsubstituted aryl having 6 to 40 carbon atoms; a hydrocarbon substituted or unsubstituted aralkyl having 7 to 15 carbon atoms; or 3 to 3 carbon atoms 20 alkynyls, r and s are 0 to 2 and r + s is 2.
[HP (R ₄ ) ₃ ] [Ani] <Formula 4>
In Formula 4, R4 and [Ani] are the same as described above.

According to another embodiment of the present invention, in the catalyst system for producing a cyclic olefin polymer containing a polar functional group, the pre-catalyst represented by Formula 1 is Pd, and p = 2. The ligand containing a hetero atom directly coordinated to a metal is acetylacetonate or acetate, and b = 0, c = 0, and R ₃ is H as a co-catalyst of a phosphonium-containing salt compound represented by Formula 2. And R ₄ is preferably cyclohexyl, isopropyl, t-butyl, n-butyl or ethyl.

  According to another embodiment of the present invention, in the catalyst system for producing a cyclic olefin polymer containing a polar functional group, the ratio of the promoter to the precatalyst containing the Group 10 transition metal is 1 mol of the precatalyst. It is desirable that it is 0.5 to 10 moles.

  According to another embodiment of the present invention, in the catalyst system for producing a cyclic olefin polymer containing a polar functional group, it is preferable that the catalyst mixture comprising the pre-catalyst and the co-catalyst is supported on a fine particle support. .

  According to another embodiment of the present invention, in the catalyst system for producing a cyclic olefin polymer containing a polar functional group, the fine particle support is silica, titania, silica / chromia, silica / chromia / titania, silica / Desirable is alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite.

  According to another embodiment of the present invention, in a catalyst system for producing a cyclic olefin polymer containing a polar functional group, the catalyst mixture comprising the pre-catalyst and the co-catalyst is composed of dichloromethane, dichloroethane, toluene, chlorobenzene and a mixture thereof. It is desirable to use it dissolved in an organic solvent selected from the group consisting of:

  According to another embodiment of the present invention, in the catalyst system for producing a cyclic olefin polymer containing a polar functional group, the catalyst mixture comprising the pre-catalyst and the co-catalyst is a metal comprising the pre-catalyst and the co-catalyst. It is desirable to include a catalyst complex compound.

  In order to achieve the second technical problem, the present invention provides a method for producing a cyclic olefin polymer containing a polar functional group, the step of producing a catalyst system mixture according to the above, and in the presence of the catalyst system mixture, And a step of subjecting a monomer solution containing a cyclic olefin monomer containing a polar functional group to addition polymerization at a temperature of 80 ° C. to 150 ° C., and a method for producing a cyclic olefin polymer containing a polar functional group containing To do.

前記化学式５で、ｍは、０ないし４の整数であり、Ｒ_７、Ｒ_７’、Ｒ_７’’及びＲ_７’’’のうち少なくとも一つは、極性官能基を表し、残りは非極性官能基であり、Ｒ_７、Ｒ_７’、Ｒ_７’’及びＲ_７’’’は、互いに連結されて炭素数４ないし１２の飽和または不飽和環基、または炭素数６ないし２４の芳香族環を形成でき、前記非極性官能基は、水素；ハロゲン；炭素数１ないし２０の線形または分枝型アルキル、ハロアルキル、アルケニル、ハロアルケニル；炭素数３ないし２０の線形または分枝型アルキニル、ハロアルキニル；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数３ないし１２のシクロアルキル；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数６ないし４０のアリール；またはアルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数７ないし１５のアラルキルであり、
前記極性官能基は、少なくとも一つ以上の酸素、窒素、リン、硫黄、シリコン、またはホウ素を含む非炭化水素極性基であって、−Ｒ^８ＯＲ^９、−ＯＲ^９、−ＯＣ（Ｏ）ＯＲ^９、−Ｒ^８ＯＣ（Ｏ）ＯＲ^９、−Ｃ（Ｏ）Ｒ^９、−Ｒ^８Ｃ（Ｏ）ＯＲ^９、−Ｃ（Ｏ）ＯＲ^９、−Ｒ^８Ｃ（Ｏ）Ｒ^９、−ＯＣ（Ｏ）Ｒ^９、−Ｒ^８ＯＣ（Ｏ）Ｒ^９、−（Ｒ^８Ｏ）_ｋ−ＯＲ^９、−（ＯＲ^８）_ｋ−ＯＲ^９、−Ｃ（Ｏ）−Ｏ−Ｃ（Ｏ）Ｒ^９、−Ｒ^８Ｃ（Ｏ）−Ｏ−Ｃ（Ｏ）Ｒ^９、−ＳＲ^９、−Ｒ^８ＳＲ^９、−ＳＳＲ^８、−Ｒ^８ＳＳＲ^９、−Ｓ（＝Ｏ）Ｒ^９、−Ｒ^８Ｓ（＝Ｏ）Ｒ^９、−Ｒ^８Ｃ（＝Ｓ）Ｒ^９、−Ｒ^８Ｃ（＝Ｓ）ＳＲ^９、−Ｒ^８ＳＯ_３Ｒ^９、−ＳＯ_３Ｒ^９、−Ｒ^８Ｎ＝Ｃ＝Ｓ、−ＮＣＯ、Ｒ^８−ＮＣＯ、−ＣＮ、−Ｒ^８ＣＮ、−ＮＮＣ（＝Ｓ）Ｒ^９、−Ｒ^８ＮＮＣ（＝Ｓ）Ｒ^９、−ＮＯ_２、−Ｒ^８ＮＯ_２、

であり、
前記極性官能基で、それぞれのＲ^８及びＲ^１１は、炭素数１ないし２０の線形または分枝型アルキレン、ハロアルキレン、アルケニレン、ハロアルケニレン；炭素数３ないし２０の線形または分枝型アルキニレン、ハロアルキニレン；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、ハロアルキニルに置換または非置換の炭素数３ないし１２のシクロアルキレン；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、ハロアルキニルに置換または非置換の炭素数６ないし４０のアリーレン；またはアルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、ハロアルキニルに置換または非置換の炭素数７ないし１５のアラルキレンであり、それぞれのＲ^９、Ｒ^１０、Ｒ^１２及びＲ^１３は、水素；ハロゲン；炭素数１ないし２０の線形または分枝型アルキル、ハロアルキル、アルケニル、ハロアルケニル；炭素数３ないし２０の線形または分枝型アルキニル、ハロアルキニル；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数３ないし１２のシクロアルキル；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数６ないし４０のアリール；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数７ないし１５のアラルキル；またはアルコキシ、ハロアルコキシ、カルボニルオキシ、ハロカルボニルオキシであり、ｋは、１ないし１０の整数である。 According to an embodiment of the present invention, in the method for producing a cyclic olefin polymer containing a polar functional group, the cyclic olefin monomer containing the polar functional group is preferably a compound represented by the following chemical formula 5. .

In Formula 5, m is an integer of 0 to 4, and at least one of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ represents a polar functional group, and the rest is nonpolar. R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are functional groups connected to each other to form a saturated or unsaturated ring group having 4 to 12 carbon atoms, or an aromatic group having 6 to 24 carbon atoms. The non-polar functional group can form a ring; hydrogen; halogen; linear or branched alkyl having 1 to 20 carbon atoms, haloalkyl, alkenyl, haloalkenyl; linear or branched alkynyl having 3 to 20 carbon atoms, halo Alkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; alkyl, alkenyl, alkynyl, halogen Substituted or unsubstituted aryl having 6 to 40 carbon atoms substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl with 7 carbon atoms substituted or unsubstituted Or 15 aralkyls,
The polar functional group is a non-hydrocarbon polar group containing at least one oxygen, nitrogen, phosphorus, sulfur, silicon, or boron, and is —R ⁸ OR ⁹ , —OR ⁹ , —OC (O) OR. ⁹ , —R ⁸ OC (O) OR ⁹ , —C (O) R ⁹ , —R ⁸ C (O) OR ⁹ , —C (O) OR ⁹ , —R ⁸ C (O) R ⁹ , —OC (O) R ⁹ , —R ⁸ OC (O) R ⁹ , — (R ⁸ O) _k —OR ⁹ , — (OR ⁸ ) _k —OR ⁹ , —C (O) —O—C (O) R ^{9, -R 8 C (O)} -O-C (O) R 9, -SR 9, -R 8 SR 9, -SSR 8, -R 8 SSR 9, -S (= O) R 9, -R ⁸ S (= O) R ⁹ , -R ⁸ C (= S) R ⁹ , -R ⁸ C (= S) SR ⁹ , -R ⁸ SO ₃ R ⁹ , -SO ₃ R ⁹ , -R ⁸ N = C = S, -NCO ^{R 8 -NCO, -CN, -R 8} CN, -NNC (= S) R 9, -R 8 NNC (= S) R 9, -NO 2, -R 8 NO 2,

And
In the polar functional group, each R ⁸ and R ¹¹ is linear or branched alkylene having 1 to 20 carbon atoms, haloalkylene, alkenylene, haloalkenylene; linear or branched alkynylene having 3 to 20 carbon atoms, or haloalkynylene. Alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or non-substituted Substituted or unsubstituted arylene having 6 to 40 carbon atoms; or an alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or unsubstituted aralkylene having 7 to 15 carbon atoms, and each R ⁹ R ¹⁰ , R ¹² and R ¹³ are hydrogen; halogen; linear or branched alkyl having 1 to 20 carbon atoms, haloalkyl, alkenyl, haloalkenyl; linear or branched alkynyl having 3 to 20 carbon atoms, haloalkynyl. Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl Or unsubstituted aryl having 6 to 40 carbon atoms; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted aralkyl having 7 to 15 carbon atoms; or alkoxy, haloalkyl Koxy, carbonyloxy, halocarbonyloxy, and k is an integer of 1 to 10.

  According to another embodiment of the present invention, in the method for producing a cyclic olefin polymer containing a polar functional group, the total amount of the organic solvent in the reaction system is 50 to 50% relative to the total monomer weight in the monomer solution. 800% is desirable.

  According to another embodiment of the present invention, in the method for producing a cyclic olefin polymer containing a polar functional group, it is preferable that the catalyst mixture is charged into the monomer solution in a solid phase.

  According to another embodiment of the present invention, in the method for producing a cyclic olefin-based polymer containing a polar functional group, the catalyst mixture is based on the precatalyst component basis, and the total monomer moles in the monomer solution. It is desirable that the reaction system is charged in an amount of 1 / 2,500 to 1 / 200,000 with respect to the amount.

  According to another embodiment of the present invention, in the method for producing a cyclic olefin polymer containing a polar functional group, the monomer solution preferably further contains a cyclic olefin compound containing no polar functional group.

  According to another embodiment of the present invention, in the method for producing a cyclic olefin polymer containing a polar functional group, the monomer solution preferably further contains a linear or branched olefin having 1 to 20 carbon atoms. .

前記化学式５で、
ｍ、Ｒ_７、Ｒ_７’、Ｒ_７’’及びＲ_７’’’は、前記と同様である。 In order to achieve the third technical problem, the present invention provides a polymer produced by the method described above, wherein a cyclic olefin monomer containing a polar functional group represented by the following chemical formula 5 is attached. Provided is a cyclic olefin polymer which is a polymer and has a polar functional group having a weight average molecular weight _Mw of 10,000 to 1,000,000.

In Formula 5,
m, R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are the same as described above.

  According to one embodiment of the present invention, the cyclic olefin polymer containing a polar functional group is a cyclic olefin homopolymer containing a polar functional group, and a copolymer of cyclic olefin monomers containing different polar functional groups. It is desirable to include a copolymer or a copolymer of a cyclic olefin monomer containing a polar functional group and a cyclic olefin monomer not containing a polar functional group.

  In order to achieve the fourth technical problem, the present invention provides an optically anisotropic film comprising a cyclic olefin polymer containing a polar functional group according to the above.

前記数式１で、ｎ_ｙは、波長５５０ｎｍで測定される面内の高速軸の屈折率であり、
ｎ_ｚは、波長５５０ｎｍで測定される厚さ方向の屈折率であり、ｄは、フィルムの厚さである。 According to an embodiment of the present invention, the optically anisotropic film, it is desirable that the 1000nm to by 70 retardation value R _th represented by Equation 1 below.

In Equation 1, n _y is the refractive index of the fast axis in the plane, measured at a wavelength of 550 nm,
_nz is the refractive index in the thickness direction measured at a wavelength of 550 nm, and d is the thickness of the film.

（ｎ_Ｘは、面内の低速軸の屈折率である）
で表される関係を満足する液晶ディスプレイ用のネガティブＣプレート型光学補償フィルムであることが望ましい。 According to another embodiment of the present invention, the refractive index of the optically anisotropic film is expressed by the following formula:

(N _X is the in-plane slow axis refractive index)
It is desirable that the film be a negative C plate type optical compensation film for a liquid crystal display that satisfies the relationship expressed by:

  According to the catalyst for olefin polymerization and the polymer production method using the same according to the present invention, it is possible to suppress the deactivation of the catalyst due to the polar functional group of the monomer by the catalyst system having excellent thermal chemical stability. Therefore, the polyolefin can be produced with a high molecular weight and a high polymerization yield at the time of polyolefin polymerization, and the activity of the catalyst is excellent, so that the amount of catalyst to monomer used can be used in a range of less than 1/5000, and the catalyst residue can be used. There is no need for a removal step.

  Hereinafter, the present invention will be described in detail.

  According to the catalyst for olefin polymerization and the polymer production method using the same according to the present invention, it is possible to suppress the deactivation of the catalyst due to the polar functional group of the monomer by the catalyst system having excellent thermal chemical stability. Therefore, a polymer with a high molecular weight can be produced in a high yield, the amount of the monomer-corresponding catalyst used can be reduced, and a separate step for removing the catalyst residue is not necessary.

  The catalyst system used in the present invention includes: i) a group 10 metal-containing pre-catalyst having a ligand containing a hetero atom directly coordinated to the metal represented by Formula 1, and ii) a phosphonium represented by Formula 2. Wherein the precatalyst is highly stable with respect to a monomer having a polar functional group, and the promoter is an ammonium borate. Thus, the amine which reduces catalyst reactivity is not generated. Instead, the phosphonium cocatalyst reacts with the Group 10 metal pre-catalyst to activate the pre-catalyst to a cationic form of the catalyst, while simultaneously generating phosphine to stabilize the cationic form of the catalyst, It plays a role of suppressing the deactivation of the catalyst by the polar group.

The borate or aluminate of Formula 2 may be an anion represented by the following Formula 2a or 2b.
[M ′ (R ₆ ) ₄ ] <Chemical 2a>
[M ′ (OR ₆ ) ₄ ] <Chemical 2b>
In Formulas 2a and 2b, M ′ is boron or aluminum, and R ₆ is independently halogen; halogen-substituted or unsubstituted C 1-20 linear or branched alkyl, alkenyl; C3-C12 cycloalkyl substituted or unsubstituted with halogen; C6-C40 aryl substituted or unsubstituted with hydrocarbon; C3-C20 linear or branched trialkylsiloxy or C18 Aryl having 6 to 40 carbon atoms substituted by linear or branched triarylsiloxy having from 48 to 48; aralkyl having 7 to 15 carbon atoms substituted or unsubstituted by halogen.

前記化学式３で、Ｘ’及びＹ’は、それぞれＳ及びＯのうちから選択されたヘテロ原子であり、Ｒ_１’、Ｒ_２’、Ｒ_２’’及びＲ_２’’’は、それぞれ独立して炭素数１ないし２０の線形または分枝型アルキル、アルケニルまたはビニル；炭化水素に置換または非置換の炭素数５ないし１２のシクロアルキル；炭化水素に置換または非置換の炭素数６ないし４０のアリール；炭化水素に置換または非置換の炭素数７ないし１５のアラルキル；または炭素数３ないし２０のアルキニルであり、Ｍは、１０族金属であり、ｒ及びｓは、０ないし２であり、ｒ＋ｓは２である。
[Ｈ−Ｐ（Ｒ_４）_３]［Ａｎｉ］ ＜化４＞
前記化学式４で、Ｒ_４は、それぞれ独立して水素；炭素数１ないし２０の線形または分枝型アルキル、アルコキシ、アリル、アルケニル、またはビニル；置換または非置換の炭素数３ないし１２のシクロアルキル；置換または非置換の炭素数６ないし４０のアリール；置換または非置換の炭素数７ないし１５のアラルキル；炭素数３ないし２０のアルキニルであり、このとき、前記それぞれの置換基は、ハロゲンまたは炭素数１ないし２０のハロアルキルであり、［Ａｎｉ］は、前記化学式１の金属Ｍに弱く配位されうる陰イオンであり、ホウ酸塩、アルミン酸塩、[ＳｂＦ_６]−、[ＰＦ_６]−、[ＡｓＦ_６]−、パーフルオロ酢酸（[ＣＦ_３ＣＯ_２]−）、パーフルオロプロピオン酸（[Ｃ_２Ｆ_５ＣＯ_２]−）、パーフルオロ酪酸塩（[ＣＦ_３ＣＦ_２ＣＦ_２ＣＯ_２]−）、過塩素酸塩（[ＣｌＯ_４]−）、ｐ−トルエンスルホン酸塩（[ｐ−ＣＨ_３Ｃ_６Ｈ_４ＳＯ_３]−）、[ＳＯ_３ＣＦ_３]−、ボラタベンゼン、及びハロゲンに置換または非置換のカルボランからなる群から選択いずれか一つである。 In the catalyst system for producing the cyclic olefin polymer containing the polar functional group, the precatalyst represented by the chemical formula 1 and the promoter represented by the chemical formula 2 are each a group 10 metal represented by the following chemical formula 3. A pre-contained catalyst and a co-catalyst represented by the following chemical formula 3 are desirable.

In Formula 3, X ′ and Y ′ are heteroatoms selected from S and O, respectively, and R ₁ ′, R ₂ ′, R ₂ ″ and R ₂ ′ ″ are each independently Linear or branched alkyl, alkenyl or vinyl having 1 to 20 carbon atoms; cycloalkyl having 5 to 12 carbon atoms substituted or unsubstituted with hydrocarbon; aryl having 6 to 40 carbon atoms substituted or unsubstituted with hydrocarbon Hydrocarbon substituted or unsubstituted aralkyl having 7 to 15 carbon atoms; or alkynyl having 3 to 20 carbon atoms, M is a Group 10 metal, r and s are 0 to 2, and r + s is 2.
[HP (R ₄ ) ₃ ] [Ani] <Formula 4>
In Formula 4, each R ₄ is independently hydrogen; linear or branched alkyl having 1 to 20 carbon atoms, alkoxy, allyl, alkenyl, or vinyl; substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms. Substituted or unsubstituted aryl having 6 to 40 carbon atoms; substituted or unsubstituted aralkyl having 7 to 15 carbon atoms; alkynyl having 3 to 20 carbon atoms, wherein each of the substituents is halogen or carbon [Ani] is an anion that can be weakly coordinated to the metal M of Formula 1; borate, aluminate, [SbF ₆ ] −, [PF ₆ ] — , [AsF ₆ ] −, perfluoroacetic acid ([CF ₃ CO ₂ ] −), perfluoropropionic acid ([C ₂ F ₅ CO ₂ ] −), perfluorobutyrate ([CF _{3 CF 2 CF 2 CO 2]} -), perchlorate _{([ClO 4] -),} p- toluenesulfonate _{([p-CH 3 C 6} H 4 SO 3] -), [SO 3 CF 3 ]-, Boratabenzene, and halogen-substituted or unsubstituted carborane.

前記化学式３ａで、Ｒ_１’、Ｒ_２’、Ｒ_２’’及びＲ_２’’’は、それぞれ独立して炭素数１ないし２０の線形または分枝型アルキル、アルケニルまたはビニル；炭化水素に置換または非置換の炭素数５ないし１２のシクロアルキル；炭化水素に置換または非置換の炭素数６ないし４０のアリール；炭化水素に置換または非置換の炭素数７ないし１５のアラルキル；または炭素数３ないし２０のアルキニルであり、ｒ及びｓは０ないし２であり、ｒ＋ｓは２である。
[Ｈ−Ｐ（Ｒ_４）_{３]［Ａｎｉ］ ＜化４＞
前記化学式４で、Ｒ４及び［Ａｎｉ］は、前記と同様である。} In the catalyst system for producing the cyclic olefin polymer containing the polar functional group, the pre-catalyst represented by the chemical formula 1 and the co-catalyst represented by the chemical formula 2 are each Pd represented by the following chemical formula 3a. It is more desirable to use a metal-containing pre-catalyst and a co-catalyst represented by the following chemical formula 4.

In Formula 3a, R ₁ ′, R ₂ ′, R ₂ ″, and R ₂ ″ are each independently a linear or branched alkyl, alkenyl, or vinyl having 1 to 20 carbon atoms; substituted with a hydrocarbon Or an unsubstituted cycloalkyl having 5 to 12 carbon atoms; a hydrocarbon substituted or unsubstituted aryl having 6 to 40 carbon atoms; a hydrocarbon substituted or unsubstituted aralkyl having 7 to 15 carbon atoms; or 3 to 3 carbon atoms 20 alkynyls, r and s are 0 to 2 and r + s is 2.
[ _HP (R ₄ ) _{3] [Ani] <Chemical formula 4>
In Formula 4, R4 and [Ani] are the same as described above.}

_{Finally, in the catalyst system for producing the cyclic olefin polymer containing the polar functional group, the metal is Pd in the pre-catalyst represented by the chemical formula 1, and p = 2, and is directly coordinated to the metal. ligand containing a hetero atom is acetylacetonate or acetate, wherein b = 0 in the cocatalyst salt compound having phosphonium represented by formula 2, c = 0, R3} is H, cyclohexyl R ₄ is cyclohexylene Most preferably, isopropyl, t-butyl, n-butyl or ethyl.

  The catalyst mixture constituting the catalyst system according to the present invention comprises i) a co-catalyst containing a Group 10 metal-containing pre-catalyst represented by Formula 1 and ii) a phosphonium-containing salt compound represented by Formula 2. It is not thermally decomposed at a polymerization temperature of 80 to 150 ° C. and exhibits high activity.

  The phosphonium-containing compound used as a co-catalyst in the present invention has an electronic stabilizing ability and plays a role of thermally and chemically activating the transition metal compound. The ratio of the cocatalyst to the precatalyst containing the Group 10 transition metal is 0.5 to 10 moles per mole of the precatalyst, but the number of moles of the cocatalyst is less than 0.5 mole The activation effect of the pre-catalyst is small, and when it exceeds 10 mol, an excessive amount of phosphonium is coordinated to the metal, sterically suppressing the norbornene monomer coordination, and electronically in the cation form. The catalytically active species are excessively stabilized and the double bond and interaction of the norbornene monomer are weakened. As a result, both the polymerization yield and the molecular weight are reduced, which is not desirable.

  The catalyst mixture comprising the precatalyst and the cocatalyst according to the present invention can be used by being supported on a fine particle support, and the fine particle support is composed of silica, titania, silica / chromia, silica / chromia / titania. Silica / alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite. As described above, when used while being supported on the fine particle support, there is an advantage that the molecular weight distribution can be adjusted according to the application, and the apparent density of the resulting polymer can be improved.

  The catalyst mixture comprising the pre-catalyst and the co-catalyst according to the present invention can be directly charged in the solid phase without using a solvent, but is charged after the catalyst solution is activated by mixing them on the solvent. The pre-catalyst and the co-catalyst may be dissolved in separate solutions and added during polymerization. Examples of the solvent that can be used when the catalyst mixture is dissolved in a solvent include dichloromethane, dichloroethane, toluene, chlorobenzene, and mixtures thereof.

  The catalyst mixture according to the present invention may be a metal catalyst complex compound composed of the precatalyst and a cocatalyst.

  The present invention also includes i) a Group 10 metal-containing pre-catalyst having a ligand containing a heteroatom directly coordinated to the metal represented by Chemical Formula 1, and ii) a phosphonium represented by Chemical Formula 2. After preparing a catalyst mixture comprising a co-catalyst containing a salt compound, a polar functional group for subjecting a cyclic monomer containing a polar functional group to addition polymerization at a temperature of 80 ° C. to 150 ° C. in the presence of the catalyst mixture. A method for producing a cyclic olefin polymer is provided.

  More specifically, in connection with the temperature limitation of the present invention, if the polymerization temperature is increased in the case of a general organometallic polymerization catalyst, the polymerization yield increases while the molecular weight of the polymer decreases, The catalyst tends to be pyrolyzed and does not exhibit polymerization activity (Kaminsky et al. Angew. Chem. Int. Ed., 1985, vol 24,507; Brookhart et al. Chem. Rev. 2000, vol 100, 1169; Resconi et al., Chem. Rev. 2000, vol 100, 1253). The molecular weight decreases as the polymerization temperature rises in this way because the polymer chain is separated from the catalyst by the movement of hydrogen placed at the β-position of the polymer bound to the catalyst to the catalyst. It is.

  In contrast, the polar functional group of the norbornene monomer interacts with the cation-type catalyst at room temperature to prevent the catalytic active site where the double bond of norbornene is inserted, thereby lowering the polymerization yield and molecular weight. When the polymerization temperature is increased, hydrogen placed at the β-position of the norbornene polymer bound to the catalyst forms a three-dimensional environment that can interact with the catalyst due to the unique properties of the norbornene monomer. However, since β-hydrogen is difficult to move to the catalyst, the molecular weight increases (Kaminsky et al. Macromol. Symp. 1995, vol 97, 225). Therefore, it is necessary to raise the polymerization temperature. However, the catalyst used when producing a norbornene polymer containing a known polar functional group is almost thermally decomposed and has low activity if the polymerization temperature is raised to 80 ° C. or higher. A high molecular weight polymer could not be obtained.

  However, in the case of the catalyst used in the present invention, it is thermally stable to the extent that it is not decomposed at a temperature of 80 ° C. or higher, and disturbs the interaction between the polar functional group of the norbornene monomer and the cationic catalyst at a high temperature. As a result, the catalytically active sites can be formed or recovered, so that a cyclic olefin polymer containing a high molecular weight polar functional group can be produced in a high yield. On the other hand, when the polymerization temperature exceeds 150 ° C., the catalyst component is thermally decomposed and becomes less active, making it difficult to produce a cyclic olefin polymer containing a high molecular weight polar functional group.

前記化学式５で、ｍは、０ないし４の整数であり、Ｒ_７、Ｒ_７’、Ｒ_７’’及びＲ_７’’’のうち少なくとも一つは、極性官能基を表し、残りは非極性官能基であり、Ｒ_７、Ｒ_７’、Ｒ_７’’及びＲ_７’’’は、互いに連結されて炭素数４ないし１２の飽和または不飽和環基、または炭素数６ないし２４の芳香族環を形成でき、前記非極性官能基は、水素；ハロゲン；炭素数１ないし２０の線形または分枝型アルキル、ハロアルキル、アルケニル、ハロアルケニル；炭素数３ないし２０の線形または分枝型アルキニル、ハロアルキニル；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数３ないし１２のシクロアルキル；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数６ないし４０のアリール；またはアルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数７ないし１５のアラルキルであり、前記極性官能基は、少なくとも一つ以上の酸素、窒素、リン、硫黄、シリコン、またはホウ素を含む非炭化水素極性基であって、−Ｒ^８ＯＲ^９、−ＯＲ^９、−ＯＣ（Ｏ）ＯＲ^９、−Ｒ^８ＯＣ（Ｏ）ＯＲ^９、−Ｃ（Ｏ）Ｒ^９、−Ｒ^８Ｃ（Ｏ）ＯＲ^９、−Ｃ（Ｏ）ＯＲ^９、−Ｒ^８Ｃ（Ｏ）Ｒ^９、−ＯＣ（Ｏ）Ｒ^９、−Ｒ^８ＯＣ（Ｏ）Ｒ^９、−（Ｒ^８Ｏ）_ｋ−ＯＲ^９、−（ＯＲ^８）_ｋ−ＯＲ^９、−Ｃ（Ｏ）−Ｏ−Ｃ（Ｏ）Ｒ^９、−Ｒ^８Ｃ（Ｏ）−Ｏ−Ｃ（Ｏ）Ｒ^９、−ＳＲ^９、−Ｒ^８ＳＲ^９、−ＳＳＲ^８、−Ｒ^８ＳＳＲ^９、−Ｓ（＝Ｏ）Ｒ^９、−Ｒ^８Ｓ（＝Ｏ）Ｒ^９、−Ｒ^８Ｃ（＝Ｓ）Ｒ^９、−Ｒ^８Ｃ（＝Ｓ）ＳＲ^９、−Ｒ^８ＳＯ_３Ｒ^９、−ＳＯ_３Ｒ^９、−Ｒ^８Ｎ＝Ｃ＝Ｓ、−ＮＣＯ、Ｒ^８−ＮＣＯ、−ＣＮ、−Ｒ^８ＣＮ、−ＮＮＣ（＝Ｓ）Ｒ^９、−Ｒ^８ＮＮＣ（＝Ｓ）Ｒ^９、−ＮＯ_２、−Ｒ^８ＮＯ_２、

であり、
前記極性官能基で、それぞれのＲ^８及びＲ^１１は、炭素数１ないし２０の線形または分枝型アルキレン、ハロアルキレン、アルケニレン、ハロアルケニレン；炭素数３ないし２０の線形または分枝型アルキニレン、ハロアルキニレン；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、ハロアルキニルに置換または非置換の炭素数３ないし１２のシクロアルキレン；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、ハロアルキニルに置換または非置換の炭素数６ないし４０のアリーレン；またはアルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、ハロアルキニルに置換または非置換の炭素数７ないし１５のアラルキレンであり、それぞれのＲ^９、Ｒ^１０、Ｒ^１２及びＲ^１３は、水素；ハロゲン；炭素数１ないし２０の線形または分枝型アルキル、ハロアルキル、アルケニル、ハロアルケニル；炭素数３ないし２０の線形または分枝型アルキニル、ハロアルキニル；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数３ないし１２のシクロアルキル；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数６ないし４０のアリール；アルキル、アルケニル、アルキニル、ハロゲン、ハロアルキル、ハロアルケニル、またはハロアルキニルに置換または非置換の炭素数７ないし１５のアラルキル；またはアルコキシ、ハロアルコキシ、カルボニルオキシ、ハロカルボニルオキシであり、ｋは、１ないし１０の整数である。 The monomer used when producing the cyclic olefin addition polymer containing a polar functional group in the present invention is a norbornene monomer containing a polar functional group. The cyclic norbornene monomer or norbornene derivative means a monomer containing at least one norbornene (bicyclo [2,2,1] hept-2-ene) unit. Such a norbornene-based monomer having a polar functional group is desirably a compound represented by the following chemical formula 5.

In Formula 5, m is an integer of 0 to 4, and at least one of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ represents a polar functional group, and the rest is nonpolar. R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are functional groups connected to each other to form a saturated or unsaturated ring group having 4 to 12 carbon atoms, or an aromatic group having 6 to 24 carbon atoms. The non-polar functional group can form a ring; hydrogen; halogen; linear or branched alkyl having 1 to 20 carbon atoms, haloalkyl, alkenyl, haloalkenyl; linear or branched alkynyl having 3 to 20 carbon atoms, halo Alkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; alkyl, alkenyl, alkynyl, halogen Substituted or unsubstituted aryl having 6 to 40 carbon atoms substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl with 7 carbon atoms substituted or unsubstituted 15 to 15 aralkyl, and the polar functional group is a non-hydrocarbon polar group containing at least one of oxygen, nitrogen, phosphorus, sulfur, silicon, or boron, and is —R ⁸ OR ⁹ , —OR ^{9. , -OC (O) OR 9,} -R 8 OC (O) OR 9, -C (O) R 9, -R 8 C (O) OR 9, -C (O) OR 9, -R 8 C ( O) R ⁹ , —OC (O) R ⁹ , —R ⁸ OC (O) R ⁹ , — (R ⁸ O) _k —OR ⁹ , — (OR ⁸ ) _k —OR ⁹ , —C (O) — OC (O) R ^{9 , -R 8 C (O) -O} -C (O) R 9, -SR 9, -R 8 SR 9, -SSR 8, -R 8 SSR 9, -S (= O) R 9, -R 8 S (= O) R ⁹ , -R ⁸ C (= S) R ⁹ , -R ⁸ C (= S) SR ⁹ , -R ⁸ SO ₃ R ⁹ , -SO ₃ R ⁹ , -R ⁸ N = C ^{= S, -NCO, R 8 -NCO} , -CN, -R 8 CN, -NNC (= S) R 9, -R 8 NNC (= S) R 9, -NO 2, -R 8 NO 2,

And
In the polar functional group, each R ⁸ and R ¹¹ is linear or branched alkylene having 1 to 20 carbon atoms, haloalkylene, alkenylene, haloalkenylene; linear or branched alkynylene having 3 to 20 carbon atoms, or haloalkynylene. Alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or non-substituted Substituted or unsubstituted arylene having 6 to 40 carbon atoms; or an alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or unsubstituted aralkylene having 7 to 15 carbon atoms, and each R ⁹ R ¹⁰ , R ¹² and R ¹³ are hydrogen; halogen; linear or branched alkyl having 1 to 20 carbon atoms, haloalkyl, alkenyl, haloalkenyl; linear or branched alkynyl having 3 to 20 carbon atoms, haloalkynyl. Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl Or unsubstituted aryl having 6 to 40 carbon atoms; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted aralkyl having 7 to 15 carbon atoms; or alkoxy, haloalkyl Koxy, carbonyloxy, halocarbonyloxy, and k is an integer of 1 to 10.

  In the production method according to the present invention, the total amount of the organic solvent in the reaction system is 50% to 800%, preferably 50% to 400%, based on the total monomer weight in the monomer solution. However, if it is less than 50%, the solution viscosity is too high during the polymerization reaction, making it difficult to stir, unreacted monomers remain, the polymerization yield decreases, the viscosity is too high and an excessive amount of solvent is added. Since it is necessary to make the solution thin, there is a problem in commercialization, and when it exceeds 800%, the polymerization reaction rate tends to be slow and the polymerization yield and the molecular weight tend to decrease.

  In the production method according to the present invention, the amount of the catalyst mixture used is in the range of 1 / 2,500 to 1 / 200,000 compared with the total monomer molar amount in the monomer solution based on the pre-catalyst component. Can be within. That is, the norbornene-based monomer having a polar functional group can be polymerized in a high yield while using a much smaller amount of catalyst than the conventional catalyst system. The amount used is more preferably 1/5000 to 1/20000.

  In the production method according to the present invention, it is desirable that the monomer solution further contains a cyclic olefin compound containing no polar functional group.

The addition polymerization of the present invention is carried out by dissolving and mixing a norbornene monomer and a catalyst in a solvent as in a general method for producing a norbornene polymer. In the production method of the present invention, if a cyclic olefin-based addition polymer containing a polar functional group is produced, it can be produced at a high yield of at least 40%, and the produced addition polymer has a molecular weight _Mw of at least 10, It can have a high molecular weight of 000 to 1,000,000. In addition, if an addition film is used to produce an optical film, the molecular weight is preferably adjusted to 100,000 to 1,000,000. In order to control the molecular weight, a linear or branched, cyclic olefin having 1 to 20 carbon atoms may be further included. Specifically, examples of the olefin include 1-hexene, 1-octene, cyclopentene, and ethylene. A polymer chain having a desired molecular weight is formed by a reaction in which such an olefin is inserted into the terminal of the growing polymer chain and the hydrogen at the β-position of the inserted olefin is easily removed.

  Therefore, in the past, it was possible to produce a cyclic olefin-based addition polymer containing a polar functional group with a very low yield and only with a low molecular weight. However, the production method of the present invention has a high molecular weight with a high yield. It is possible to produce a cyclic olefin addition polymer in which the polar functional group is introduced.

  The present invention is a polymer produced by the above production method, which is an addition polymer of a cyclic olefin monomer containing a polar functional group represented by the chemical formula 5, and has a weight average molecular weight of 10,000 to Provided is a cyclic olefin polymer containing a polar functional group of 1,000,000.

  The norbornene addition polymer containing a polar functional group contains at least 0.1 to 99.9 mol% of a norbornene monomer containing a polar functional group. At this time, the norbornene containing a polar group is an endo, exo isomer. It consists of a mixture of bodies, and the composition ratio of the mixture is irrelevant.

  Whether the cyclic olefin-based addition polymer having a polar functional group is a homopolymer obtained by addition-polymerizing a norbornene-based monomer having at least one polar functional group in the presence of the above-described catalyst system. , By addition polymerization of norbornene monomers containing different polar functional groups to produce a binary or ternary copolymer comprising norbornene monomers containing polar functional groups, or A binary or ternary copolymer can be produced by addition polymerization of a norbornene-based monomer containing norbornene containing no polar functional group.

  The norbornene-based polymer having a polar functional group produced by the production method of the present invention is excellent in adhesion to a transparent polymer having a metal or other polar functional group, and can be used as an insulating electronic material. Is a cyclic olefin polymer having low thermal stability and strength. In addition, this polymer can adhere to an electronic material substrate without a coupling agent, adheres well to a metal substrate such as copper, silver, or gold, and has an optical property that can be used as a protective film for a polarizing plate. Excellent and can be used for electronic materials such as integrated circuits, circuit printed boards or multi-chip modules.

  The present invention can be manufactured by using an optically anisotropic film capable of adjusting the birefringence index that could not be conventionally manufactured using the polymer.

  Since a general cyclic olefin morphological unit has one or two stable rotational states, it can be extended like a polyimide having a hard phenyl ring as a main chain. If a polar group is introduced into a norbornene-based polymer having such an extended form, the introduction of the polar group increases the interaction between molecules compared to the case of a polymer having a simple form. The filling has a directional order and can be optically and electrically anisotropic.

  The birefringence can be adjusted according to the type and content of the polar functional group introduced into the cyclic olefin-based addition polymer, and in particular, the refractive index in the thickness direction to be produced can be easily adjusted in various modes. It can be produced as an optical compensation film for LCD (Liquid crystal display).

  The optically anisotropic film can be produced by dissolving the cyclic olefin-based addition polymer containing the polar functional group according to the present invention in a solvent and using a solvent casting method to form a film or a sheet. Films can also be made from blends of coalescence.

  A method for producing a film by dissolving a cyclic olefin-based addition polymer in a solvent by a solvent casting method is a method in which the cyclic olefin-based addition polymer has a polymer content of 5 to 95% by weight, more preferably 10 to 60% by weight. It is desirable to manufacture the mixture by stirring it at room temperature. At this time, the viscosity of the prepared solution is preferably 100 to 10000 cps for solvent casting, and more preferably 300 to 8000 cps. In addition, during film production, additives such as plasticizers, deterioration inhibitors, UV stabilizers, or antistatic agents are added to improve the mechanical strength, heat resistance, light resistance, and handleability of the film. it can.

前記数式１で、ｎ_ｙは、波長５５０ｎｍで測定される面内の高速軸の屈折率であり、ｎ_ｚは、波長５５０ｎｍで測定される厚さ方向の屈折率であり、ｄは、フィルムの厚さである。 The manufactured film as has an optically anisotropic film properties are 1000nm to by 70 retardation value R _th represented by Equation 1 below.

In Equation 1, n _y is the refractive index of the fast axis in the plane, measured at a wavelength of 550 nm, n _z is the refractive index in the thickness direction measured at a wavelength of 550 nm, d is the film Is the thickness.

（ｎ_Ｘは、面内の低速軸の屈折率である）
で表される関係を満足する液晶ディスプレイ用のネガティブＣプレート型光学補償フィルムとして使用できる。 A film having such an optical anisotropy characteristic has a refractive index of the following formula:

(N _X is the in-plane slow axis refractive index)
It can be used as a negative C plate type optical compensation film for a liquid crystal display that satisfies the relationship represented by:

Hereinafter, the present invention will be described in more detail with reference to preferred examples, but the present invention is not limited thereto.
In the following preparation examples and examples, all work dealing with air and water sensitive compounds was performed using standard Schlenk technology or dry box technology. Nuclear magnetic resonance spectra were obtained using a Bruker 300 spectrometer, ¹ H NMR was measured at 300 MHz, and ¹³ C NMR was measured at 75 MHz. The molecular weight and molecular weight distribution of the polymer were measured using GPC (Gel Permeation Chromatography), and at this time, a polystyrene sample was used as a standard. Thermal analysis such as TGA and DSC was performed using TA Instrument (TGA2050; heating rate 10K / min). Toluene was purified by distillation with potassium / benzophenone, and dichloromethane and chlorobenzene were purified by distillation with CaH ₂ .

Production Example 1 of Monomer Containing Polar Functional Group Production of 5-Norbornene-2-carboxylic acid methyl ester Dicyclopentadiene (DCPD, manufactured by Aldrich, 256.5 mL, 1.9 mol) was prepared in a 2 L high-pressure reactor. , Methyl acrylate (manufactured by Aldrich, 405 mL, 4.5 mol) and hydroquinone (3.2 g, 0.03 mol) were added, and the temperature was raised to 220 ° C. This was reacted for 5 hours while stirring at 300 rpm, and when completed, the reaction product was cooled and transferred to a distillation apparatus. Distillation under reduced pressure at 1 torr using a vacuum pump gave the product at 50 ° C. (yield: 57.6%, exo / endo = 58/42).
¹ H-NMR (600 MHz, CDCl ₃ ), End: δ 6.17 (dd, 1H), 5.91 (dd, 1H), 3.60 (s, 3H), 3.17 (b, 1H), 2 .91 (m, 1H), 2.88 (b, 1H), 1.90 (m, 1H), 1.42 (m, 2H), 1.28 (m, 1H); Exo: δ 6.09 ( m, 2H), 3.67 (s, 3H), 3.01 (b, 1H), 2.88 (b, 1H), 2.20 (m, 1H), 1.88 (m, 1H), 1.51 (d, 1H), 1.34 (m, 2H).

Production Example 2: Production of allyl 5-norbornene-2-acetate DCPD (Aldrich 248 mL, 1.852 mol), allyl acetate (Aldrich 500 mL, 4.63 mol), hydroquinone (0 0.7 g, 0.006 mol), the temperature was raised to 190 ° C. This was reacted for 5 hours while stirring at 300 rpm, and when completed, the reaction product was cooled and transferred to a distillation apparatus. A vacuum distillation was performed at 1 torr using a vacuum pump over the second time to obtain the product at 56 ° C. (yield: 30%, exo / endo = 57/43).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 6.17 to 5.91 (m, 2H), 4.15 to 3.63 (m, 2H), 2.91 to 2.88 (m, 2H), 2.38 (m, 1H), 2.05 (s, 3H), 1.83 (m, 1H), 1.60 to 1.25 (m, 2H), 0.57 (m, 1H).

Cocatalyst production
Production Example 3: Production of [HP (Cy) ₃ ] [Cl] P (Cy) ₃ (2.02 g, 7.2 mmol, Cy is cyclohexyl) was put into a 250 mL Schlenk flask, and diethyl ether (150 ml) was added. And dissolved. Next, HCl (14.4 mL, 1.0 M in ether) is added at room temperature, and a white precipitate is formed while the reaction proceeds. The white precipitate is allowed to react for about 20 minutes and filtered through a glass filter. After washing with diethyl ether (80 ml) about 3 times, the solvent was removed under vacuum at room temperature to obtain [HP (Cy) ₃ ] [Cl] (86%, 1.95 g).
_{^{1 H-NMR (600MHz, CD}} 2 Cl 2): δ7.02~6.23 (d, 1H, J H-P = 470Hz), 2.56~1.30 (m, 33H); 13 C-NMR (600 MHz, CD ₂ Cl ₂ ): δ 28.9 (d), 28.5 (d), 26.8 (d), 25.6 (s). ³¹ P-NMR (600 MHz, CD ₂ Cl ₂ ): δ 22.98 (d, J _P-H = 470 Hz).

Production Example 4: Production of [HP (n-Bu) ₃ ] [Cl] (n-Bu) ₃ P (2.0 g, 10.0 mmol) was charged into a 250 mL Schlenk flask, and diethyl ether (150 ml) was added. And dissolved. Next, HCl (20.0 mL, 1.0 M in ether) is added at room temperature, and a white precipitate is formed while the reaction proceeds. The white precipitate is allowed to react for about 20 minutes through a glass filter. After filtration and washing with diethyl ether (80 ml) about 3 times, the residual solvent was removed at room temperature under vacuum to remove [HP (n-Bu) ₃ ] [Cl] (90%, 2.15 g). Obtained.

Production Example 5: Production of [HP (Cy) ₃ ] [B (C ₆ F ₅ ) ₄ ] [HP (Cy) ₃ ] [Cl] (0.56 g, 1.G) obtained in Production Example 3 in a glove box. 75 mmol) and [Li] [B (C ₆ F ₅ ) ₄ ] (1.0 g, 1.46 mmol) were placed in a 100 mL Schlenk flask, respectively, and dichloromethane (20 ml) was added and dissolved. Next, the [HP (Cy) ₃ ] [Cl] solution was gradually added dropwise to the [Li] [B (C ₆ F ₅ ) ₄ ] solution side at room temperature. After the reaction for about 1 hour, the unreacted material is filtered through a glass filter, and after removing the solvent under vacuum until the solvent becomes about 5 ml, the temperature is lowered to −78 ° C. and diethyl ether (30 ml) is added for recrystallization. did. Finally, after washing about three times with diethyl ether (30ml) was poured the solution, the remaining solvent at room temperature the solvent was removed under _{vacuum, [HP (Cy) 3]} [B (C 6 F 5) 4 ] (90%, 1.26 g) (tricyclohexylphosphonium (tetrakispentafluorophenyl) boric acid).
¹ H-NMR (600 MHz, CD ₂ Cl ₂ ): δ 5.32 to 4.65 (d, 1H, J _H-P = 440 Hz), 2.43 to 1.33 (m, 33H); ¹³ C-NMR (600 MHz, CD ₂ Cl ₂ ): δ 149.7, 148.1, 139.7, 139.2, 138.1, 138.0, 137.8, 136.2, 125.1, 124.9, 29 1.0 P, 28.8, 26.7 (d), 25.4 (s); ³¹ P-NMR (600 MHz, CD ₂ Cl ₂ ): 31.14 (d, J _PH = 440 Hz); ¹⁹ F _{-NMR (600MHz, CD 2 Cl 2} ): - 130.90, -161.51, -163.37.

Production Example 6: Production of [HP (Cy) ₃ ] [B (C ₆ F ₅ ) ₄ ]
Except for using [Na] [B (C ₆ F ₅ ) ₄ ] or [MgBr] [B (C ₆ F ₅ ) ₄ ] instead of [Li] [B (C ₆ F ₅ ) ₄ ] Then, [HP (Cy) ₃ ] [B (C ₆ F ₅ ) ₄ ] (tricyclohexylphosphonium (tetrakispentafluorophenyl) borate) was produced by the same method as in Production Example 5. The synthesis yield was about 90% as in Production Example 5.

Production Example 7: Production of [HP (n-Bu) ₃ ] [B (C ₆ F ₅ ) ₄ ] [HP (n-Bu) ₃ ] [Cl] (0. 42 g, 1.75 mmol) and [Li] [B (C ₆ F ₅ ) ₄ ] (1.0 g, 1.46 mmol) were each put into a 100 mL Schlenk flask and dissolved in dichloromethane (20 ml). . Next, after gradually adding [HP (Cy) ₃ ] [Cl] solution to the [Li] [B (C ₆ F ₅ ) ₄ ] solution side at room temperature, unreacted substances are removed after reaction for about 1 hour. The solution was filtered through a glass filter, and the solvent was removed under vacuum until the solvent was about 5 ml. Next, the temperature was lowered to −78 ° C., diethyl ether (30 ml) was added and recrystallized, and then the solution was poured and washed with diethyl ether (30 ml) about 3 times. Finally, the residual solvent was removed under vacuum at room temperature, and [HP (Cy) ₃ ] [B (C ₆ F ₅ ) ₄ ] (87%, 1.12 g) (tri-n-butylphosphonium (tetrakispenta Fluorophenyl) borate).

Production Example 8: Production of [(t-Bu) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (t-Bu) ₃ P (0.35 g, 1.73 mmol, t-Bu is tert-butyl) The mixture was put into a 250 mL Schlenk flask and dissolved in diethyl ether (30 ml). Next, anhydrous HCl (1.9 mL, 1.0 M in ether) is added at room temperature, and a white precipitate is formed while the reaction proceeds. The white precipitate is allowed to react for about 20 minutes through a glass filter. After filtration and washing with diethyl ether (30 ml), the residual solvent was removed in vacuo at room temperature to obtain (t-Bu) ₃ PHCl as a white solid.
(T-Bu) ₃ PHCl was dissolved in dichloromethane (10 ml), and [Li] [B (C ₆ F ₅ ) ₄ ] (1.07 g, 1.56 mmol) was added to a 100 mL Schlenk flask in a glove box. Charge and dissolve in dichloromethane (20 ml). Next, the (t-Bu) ₃ PHCl solution was gradually added dropwise to the [Li] [B (C ₆ F ₅ ) ₄ ] solution side at room temperature. After the reaction for about 1 hour, the side reaction product LiCl was filtered through a glass filter, and the solvent was removed under vacuum, and then [(t-Bu) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (67 %, 1.05 g) (tri-t-butylphosphonium (tetrakispentafluorophenyl) borate).
¹ H-NMR (600 MHz, CD ₂ Cl ₂ ): δ 5.34 to 4.63 (d, 1H, J _H-P = 440 Hz), 1.61 (d, 27H); ¹³ C-NMR (600 MHz, CD ^{_{2 Cl 2): δ149.5,147.9,139.6,138.0,137.7,136.0,124.4,38.3,30.4; 31}} P-NMR (600MHz, CD 2 Cl ₂ ): 63.0 (d, J _P—H = 440 Hz); ¹⁹ F-NMR (600 MHz, CD ₂ Cl ₂ ): −133.3, −163.9, −167.8.

Production Example 9 Production of [(Et) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (Et) ₃ P (0.8 g, 6.77 mmol, Et is ethyl) was put into a 250 mL Schlenk flask, Diethyl ether (50 ml) was added and dissolved. Next, anhydrous HCl (7.4 mL, 1.0 M in ether) is added at room temperature, and a white precipitate is formed while the reaction proceeds. The reaction is performed for about 20 minutes, and the solvent is removed under vacuum. After washing with hexane (30 ml), the residual solvent was removed under vacuum at room temperature to give (Et) ₃ PHCl as a white solid.
(Et) ₃ PHCl was dissolved in dichloromethane (10 ml), and [Li] [B (C ₆ F ₅ ) ₄ ] (4.41 g, 6.43 mmol) was put into a 100 mL Schlenk flask in a glove box. Dichloromethane (50 ml) was added and dissolved. Next, the (Et) ₃ PHCl solution was gradually added dropwise to the [Li] [B (C ₆ F ₅ ) ₄ ] solution side at room temperature. After the reaction for about 1 hour, LiCl as a side reaction product was filtered through a glass filter, and after removing the solvent under vacuum, [(Et) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (54% 2.91) (triethylphosphonium (tetrakispentafluorophenyl) borate).
¹ H-NMR (600 MHz, CD ₂ Cl ₂ ): δ 6.06 (m, 0.5 H), 5.30 (m, 0.5 H), 2.28 (m, 6 H), 1.40 (m, 9H); ¹³ C-NMR (600 MHz, CD ₂ Cl ₂ ): δ 149.5, 147.9, 139.7, 138.0, 137.9, 137.7, 136.1, 124.6, 10. 6 (d), 6.8 (d); ³¹ P-NMR (600 MHz, CD ₂ Cl ₂ ): 26.3 (d); ¹⁹ F-NMR (600 MHz, CD ₂ Cl ₂ ): -133.5, -163.7, -167.8.

Production of addition polymers
Example 1: Polymerization of 5-norbornene-2-allyl acetate Allyl 5-norbornene-2-acetate (NB—CH ₂ —O—C (O) —CH ₃ ) (5 mL, 30.9 mmol, NB is norbornene) Toluene (18 ml) was charged into a 250 mL Schlenk flask. Palladium acetate (Pd (OAc) ₂ ) (OAc = acetate, 0.46 mg, 2.06 μmol) and tricyclohexylphosphonium (tetrakispentafluorophenyl) borate ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ]) (5.0 mg, 5.2 μmol) and 1 mL of dichloromethane were dissolved and dissolved.
Charged to the monomer solution. The reaction temperature was raised to 90 ° C. and stirred for 18 hours. After 18 hours of reaction, 100 mL of toluene was added to thin the polymer solution with high viscosity, and this was poured into an excessive amount of ethanol to obtain a white copolymer precipitate. The copolymer recovered by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to give 4.73 g of 5-norbornene-2-allyl acetate polymer (based on the total amount of monomers charged). 92.2% by weight) was obtained. The weight average molecular weight _{M w} of the polymer was 250,071, Mw / Mn was 2.70.

Example 2: The polymerization catalyst amount of allyl 5-norbornene-2-acetate was adjusted to palladium acetate (Pd (OAc) ₂ ) (0.14 mg, 0.62 μmol) and tricyclohexylphosphonium (tetrakispentafluorophenyl) borate. ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ]) (1.2 mg, 1.24 μmol) and 5-norbornene-like the method of Example 1 at a polymerization temperature of 100 ° C. 2-Allyl acetate was polymerized. As a result of the polymerization, 4.00 g of the polymer was obtained (78% by weight based on the total amount of monomers charged). The weight average molecular weight _{M w} of the polymer was 262,149, Mw / Mn was 2.09.

Example 3: 5-norbornene-2-allyl acetate copolymerized with 5-norbornene-2-allyl acetate and butyl norbornene _{(NB-CH 2 -O-C} (O) -CH 3) (5mL, 30.9mmol) , Butylnorbornene (1.3 mL, 7.7 mmol) and toluene (7.3 mL) were charged into a 250 mL Schlenk flask. Palladium acetate (Pd (OAc) ₂ ) (0.17 mg, 0.77 μmol) and tricyclohexylphosphonium (tetrakispentafluorophenyl) borate ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ] ) (1.48 mg, 1.55 μmol) was dissolved in 1 mL of dichloromethane and then charged into the monomer solution. The reaction temperature was raised to 90 ° C. and stirred for 18 hours. After 18 hours of reaction, 120 mL of toluene was added to thin the polymer solution with high viscosity, and this was poured into an excessive amount of ethanol to obtain a white copolymer precipitate. The copolymer recovered by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours, and 4.35 g of a 5-norbornene-2-acetic acid / butylnorbornene copolymer was added (single charged monomer). 69.2% by weight based on the total mass). The weight-average molecular weight _{M w} of the polymer is 303,550, Mw / Mn was 2.16.

Example 4: The amount of copolymerization catalyst of 5-norbornene-2-acetic acid allyl and butylnorbornene was adjusted to palladium acetate (Pd (OAc) ₂ ) (0.09 mg, 0.39 μmol) and tricyclohexylphosphonium (tetrakispentane). Fluorophenyl) borate ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ]) (0.74 mg, 0.77 μmol) and 5-norbornene as in Example 3 2-Allyl acetate and butyl norbornene were copolymerized. As a result of the polymerization, 2.9 g of a polymer (46% by weight based on the total amount of monomers charged) was obtained. The weight average molecular weight _{M w} of the polymer was 362.680, Mw / Mn was 1.96.

Example 5: Copolymerization of 5-norbornene-2-acetic acid allyl, butylnorbornene , 5-norbornene-2-carboxylic acid methyl ester 5-norbornene-2-acetic acid allyl (5 mL, 30.9 mmol), butylnorbornene (1. 2 mL, 6.6 mmol), 5-norbornene-2-carboxylic acid methyl ester (1 mL, 6.6 mmol); toluene (12.4 mL) was charged into a 250 mL Schlenk flask. Palladium acetate (Pd (OAc) ₂ ) (0.66 mg, 2.94 μmol) and tricyclohexylphosphonium (tetrakispentafluorophenyl) borate ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ]) (5.65 mg, 5.88 μmol) was dissolved in 1 mL of dichloromethane and then charged into the monomer solution. The reaction temperature was raised to 90 ° C. and stirred for 18 hours. After 18 hours of reaction, 120 mL of toluene was added to thin the polymer solution with high viscosity, and this was poured into an excessive amount of ethanol to obtain a white copolymer precipitate. The copolymer recovered by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to give 5-norbornene-2-acetic acid / butylnorbornene / 5-norbornene-2-carboxylic acid methyl ester. 6.45 g of copolymer (90.5% by weight based on the total amount of monomers charged) was obtained. The weight average molecular weight _{M w} of the polymer was 211,891, Mw / Mn was 2.67.

Example 6: The amount of copolymerization catalyst of allyl 5-norbornene-2-acetate, butyl norbornene, and 5-norbornene-2-carboxylic acid methyl ester was adjusted to palladium acetate (Pd (OAc) ₂ ) Pd (OAc) ₂ (0. 20 mg, 0.88 μmol) and tricyclohexylphosphonium (tetrakispentafluorophenyl) borate ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ]) (1.70 mg, 1.77 μmol) In the same manner as in Example 5, 5-norbornene-2-acetic acid allyl, butylnorbornene, and 5-norbornene-2-carboxylic acid methyl ester were copolymerized. As a result of the polymerization, 3.3 g of the polymer was obtained (46.7% by weight based on the total amount of monomers charged). The weight average molecular weight _{M w} of the polymer was 261,137, Mw / Mn was 2.01.

Examples 7 to 13: Polymerization of allyl 5-norbornene-2-acetate Tricyclohexylphosphonium (tetrakispentafluorophenyl) borate ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ]) Palladium acetate (Pd (OAc) ₂ ) molar ratio was changed to 2: 1, 1: 1, 2: 3, 1: 2, 1: 4, 1: 8, respectively, to polymerize allyl 5-norbornene-2-acetate did. 5-Norbornene-2-allyl acetate (4 mL, 24.7 mmol) and toluene (12 mL) were charged into a 100 mL Schlenk flask, and palladium acetate (Pd (OAc) ₂ ) (1.1 mg, 4.9 μmol) as a catalyst. And tricyclohexylphosphonium (tetrakispentafluorophenyl) borate ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ]), which were changed to various equivalent ratios, were dissolved in dichloromethane (1 ml). Then, it was put into the monomer solution and reacted for 4 hours at 90 ° C. with stirring. The polymerization reaction and the polymer recovery process were carried out in the same manner as in Example 1 to produce a polymer of allyl 5-norbornene-2-acetate. The results are shown in Table 1.

Examples 14 to 16: Polymerization of allyl 5-norbornene-2-acetate The amount of cyclopentene was changed to 10: 1, 5: 1 and 7: 3 respectively in terms of molar ratio of 5-norbornene-2-acetate to 5-norbornene. 2-Allyl acetate was polymerized. Allyl 5-norbornene-2-acetate (10 mL, 61.7 mmol) and toluene (20 ml) were charged into a 250 mL Schlenk flask, and the amount of palladium acetate (Pd (OAc) ₂ ) as a catalyst was changed between cyclopentene and monomer. The amount of tricyclohexylphosphonium (tetrakispentafluorophenyl) borate ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ]) is used in an amount of 5000: 1 with respect to the total number of moles. OAc) 2x was used in contrast to ₂ moles. The polymerization temperature was 90 ° C. and the reaction time was 18 hours. The polymerization reaction and the polymer recovery process were carried out in the same manner as in Example 1 to produce a polymer of allyl 5-norbornene-2-acetate. The results are shown in Table 2.

Example 17: Polymerization of allyl 5-norbornene-2-acetate Allyl 5-norbornene-2-acetate (10 mL, 61.7 mmol) and industrial toluene (35 mL) were exposed to air in a 250 mL Schlenk flask. I put it in. Palladium acetate (Pd (OAc) ₂ ) (0.92 mg, 4.11 μmol) and tricyclohexylphosphonium (tetrakispentafluorophenyl) borate ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ]) (7.9 mg, 8.23 μmol) was dissolved in 1 mL of dichloromethane, and then charged into the monomer solution. The reaction temperature was raised to 90 ° C. and stirred for 18 hours. After 18 hours of reaction, 280 mL of toluene was added to thin the polymer solution with high viscosity, and this was poured into an excessive amount of ethanol to obtain a white copolymer precipitate. The copolymer recovered by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain 9.74 g of an allyl 5-norbornene-2-acetate polymer (based on the total amount of monomers charged). 95% by weight). The weight average molecular weight _{M w} of the polymer was 271,010, Mw / Mn was 2.40.

Examples 18 to 20: Polymerization of allyl 5-norbornene-2-acetate Polymerization of allyl 5-norbornene-2-acetate was carried out in the same manner as in Example 17 except that the amount of industrial toluene and the amount of catalyst were changed as the solvent. It was. The polymerization results are shown in Table 3.

表４の結果から、トリシクロへキシルホスホニウム（テトラキスペンタフルオロフェニル）ホウ酸塩を含む触媒溶液は、４８時間の間黄色を維持し、これを重合した時に、４８時間の間重合収率面で９０％以上、分子量面で２５万ないし２９万程度に維持されることを観察できた。トリシクロへキシルホスホニウム（テトラキスペンタフルオロフェニル）ホウ酸塩を含む触媒は、一定時間が経過した場合にも触媒活性を保存して安定性に優れていた。 Examples 21 to 23: As a polymerization monomer of 5-norbornene-2-acetate, allyl 5-norbornene-2-acetate (3 mL, 18.5 mmol) was used, and toluene (11 ml) was used as a polymerization solvent. The amount of tricyclohexylphosphonium (tetrakispentafluorophenyl) borate ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ]) is twice as much as the amount of palladium acetate (Pd (OAc) ₂ ). The catalyst solution used was a yellow solution at a concentration of 1.23 mM using dichloromethane. After the catalyst solution was prepared, it was allowed to react for 24 to 48 hours (aging time). The reaction temperature was 90 ° C. and the reaction time was 18 hours. The polymerization reaction and the polymer recovery process were carried out in the same manner as in Example 1 to produce a polymer of allyl 5-norbornene-2-acetate. The results are shown in Table 4.

From the results of Table 4, the catalyst solution containing tricyclohexylphosphonium (tetrakispentafluorophenyl) borate maintains a yellow color for 48 hours, and when this is polymerized, it is 90% in terms of polymerization yield for 48 hours. It was observed that the molecular weight was maintained at about 250,000 to 290,000. The catalyst containing tricyclohexylphosphonium (tetrakispentafluorophenyl) borate preserved the catalytic activity even when a certain period of time passed and was excellent in stability.

Examples 24 and 25: Polymerization of allyl 5-norbornene-2-acetate Allyl 5-norbornene-2-acetate (5 mL, 30.9 mmol) and toluene (18 ml) were charged into a 250 mL Schlenk flask. Palladium acetate (Pd (OAc) ₂ ) (0.46 mg, 2.06 μmol) and tricyclohexylphosphonium (tetrakispentafluorophenyl) borate ([(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ]) (5.0 mg, 5.2 μmol) was dissolved in 1 mL of dichloromethane, and then dissolved in the monomer solution and reacted for 18 hours while changing the polymerization temperature to 80 ° C. and 150 ° C. The polymerization method and the polymer recovery process were the same as in Example 1. The results are shown in Table 5 below. The results of Example 1 are also shown for reference.

表６の結果から、ジメチルアニリウム（テトラキスペンタフルオロフェニル）ホウ酸塩を含む触媒溶液は、１０分程度の経過後にオレンジ色から緑色に変わり、このような緑色の触媒溶液を使用して重合テストを行った場合、触媒製造後の経過時間が２４時間程度で８０％の重合収率を維持する一方、それ以後には重合収率が次第に減少して４８時間には１０％以下の収率を示した。結果として、ジメチルアニリウム（テトラキスペンタフルオロフェニル）ホウ酸塩を含む比較例１ないし３の触媒溶液は、トリシクロへキシルホスホニウム（テトラキスペンタフルオロフェニル）ホウ酸塩を含む実施例２１ないし２３の触媒溶液に比べて不安定であるということを示す。 Comparative Examples 1 to 3: The polymerization catalyst system of 5-norbornene-2-allyl acetate is palladium acetate (Pd (OAc) ₂ ), dimethylanilium (tetrakis-pentafluorophenyl) borate ([(PhNMe ₂ H) [B (C ₆ F ₅ ) ₄ ]]), tricyclohexylphosphine (P (Cy) ₃ ). The amount of dimethylanilium (tetrakispentafluorophenyl) borate ([(PhNMe ₂ H) [B (C ₆ F ₅ ) ₄ ]] is twice that of Pd (OAc) ₂ mol, and P (Cy) ₃ was used as a Pd (OAc) ₂ molar ratio, and the catalyst solution was an orange solution at a concentration of 1.23 mM using dichloromethane. Polymerization was carried out under conditions similar to those of Example 23. The results are shown in Table 6 below.

From the results in Table 6, the catalyst solution containing dimethylanilium (tetrakispentafluorophenyl) borate changes from orange to green after about 10 minutes, and a polymerization test is performed using such a green catalyst solution. In this case, the polymerization yield of 80% is maintained for about 24 hours after the production of the catalyst, while the polymerization yield gradually decreases after that, and the yield of 10% or less is obtained for 48 hours. Indicated. As a result, the catalyst solutions of Comparative Examples 1 to 3 containing dimethylanilium (tetrakispentafluorophenyl) borate are the catalyst solutions of Examples 21 to 23 containing tricyclohexylphosphonium (tetrakispentafluorophenyl) borate. It shows that it is unstable compared to.

Comparative Example 4: Polymerization of allyl 5-norbornene-2-acetate In a Schlenk flask, allyl 5-norbornene-2-acetate (5.0 g, 30 mmol) and [Li] [B (C ₆ F ₅ ) ₄ ] (20.6 mg , 0.0030 mmol). [(Allyl) PdCl] ₂ (0.55 mg, 0.0015 mmol) and P (Cy) ₃ (0.84 mg, 0.0030 mmol) were dissolved in 0.1 mL of toluene and added dropwise to the monomer side. After the reaction at 90 ° C. for 18 hours, the reaction solution was added to an excessive amount of ethanol, but no polymer was obtained.

Comparative Example 5: 5-norbornene-2-carboxylic acid polymer of 5-norbornene-2-carboxylic acid methyl ester methyl ester _{(MENB (NB-C (O} ) -O-CH 3), 5mL, 34.4mmol) and toluene 18 ml was put into a 250 ml Schlenk flask, and palladium acetate (Pd (OAc) ₂ ) (0.772 mg, 3.44 μmol) and [ PhN (CH ₃ ) ₂ H ] [B (C ₆ F ₅ ) ₄ ] ( 6.61 mg, 6.88 μmol) was added to another 100 ml flask, and 1 mL of dichloromethane was added and dissolved. Next, the catalyst solution was added dropwise to the monomer solution through a syringe at 90 ° C. and reacted at 90 ° C. for 18 hours. After the reaction, the reaction solution was added to an excessive amount of ethanol to obtain a white polymer precipitate. The polymer collected by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain 0.8 g of 5-norbornene-2-carboxylic acid methyl ester polymer (the charged monomer). 15% by weight based on the total amount) was obtained.

Comparative Example 6: 5-norbornene-2-polymerizing 5-norbornene-2-carboxylic acid butyl ester of carboxylic acid butyl ester _{(MENB (NB-C (O} ) -O-CH 2 CH 2 CH 2 CH 3), 5mL, 34.4 mmol) and 17 mL of toluene were put into a 250 mL Schlenk flask, and palladium acetate (Pd (OAc) ₂ ) (0.56 mg, 2.51 μmol) and [ PhN (CH ₃ ) ₂ H ] [B (C ₆ F ₅ ) ₄ ] (4.82 mg, 5.02 μmol) was charged into another 100 ml flask, and 1 ml of dichloromethane was added and dissolved. Next, the catalyst solution was added dropwise to the monomer solution through a syringe at 90 ° C. and reacted at 90 ° C. for 18 hours. After the reaction, the reaction solution was added to an excessive amount of ethanol, but no polymer was obtained.

Comparative Example 7: Polymerization of allyl 5-norbornene-2-acetate Allyl 5-norbornene-2-acetate (5 mL, 30.9 mmol) and toluene (18 ml) were charged into a 100 mL Schlenk flask. Palladium acetate (Pd (OAc) ₂ ) (0.69 mg, 3.09 μmol) and [ PhN (CH ₃ ) H ] [B (C ₆ F ₅ ) ₄ ] (5.94 mg, 6.18 μmol) were used as catalysts. After dissolving in dichloromethane (1 mL), AlEt ₃ (18.5 μl, 18.5 μmol) was added. At this time, the catalyst solution turns black. A black catalyst solution was added to the monomer solution and allowed to react with stirring at 90 ° C. After reacting for 18 hours, precipitation was performed using an ethanol solvent, but almost no polymer was obtained.

Comparative Example 8: Polymerization of allyl 5-norbornene-2-acetate Allyl 5-norbornene-2-acetate (5 mL, 30.9 mmol) and toluene (18 ml) were charged into a 100 mL Schlenk flask. Palladium acetate (Pd (OAc) ₂ ) (0.69 mg, 3.09 μmol) and dimethylanilium (tetrakispentafluoro) borate ([PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ]) as catalysts (5.94 mg, 6.18 μmol) was dissolved in dichloromethane (1 mL) and then prepared with (Cy) ₃ P (0.87 mg, 3.09 μmol) and AlEt ₃ (3.09 μl, 3.09 μmol). (Cy) ₃ P · AlEt ₃ colorless complex solution was added. At this time, the catalyst solution turned black. A black catalyst solution was added to the monomer solution and allowed to react with stirring at 90 ° C. After reacting for 18 hours, the reaction solution was poured into an excessive amount of ethanol to obtain a white polymer precipitate. The polymer collected by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain 0.5 g of a polymer (10 wt% based on the total amount of monomers charged).

Comparative Examples 9 and 10: Polymerization of allyl 5-norbornene-2-acetate Allyl 5-norbornene-2-acetate (5 mL, 30.9 mmol) and toluene (18 ml) were charged into a 250 mL Schlenk flask. Palladium acetate (Pd (OAc) ₂ ) (0.46 mg, 2.06 μmol) and tricyclohexylphosphonium (tetrakispentafluorophenyl) borate ([ PhN (CH ₃ ) ₂ H ] [B (C ₆ F _{5 4} ]) (5.0 mg, 5.2 μmol) was dissolved in 1 mL of dichloromethane, and then dissolved in the monomer solution and reacted for 18 hours while changing the polymerization temperature to 50 ° C. and 170 ° C. The polymerization method and the polymer recovery process were the same as in Example 1. The results are shown in Table 7.

Comparative Example 11: Polymerization of 5-norbornene-2-carboxylic acid 10 g of 5-norbornene-2-carboxylic acid and 100 mg of [Pd (C ₆ H ₅ CN) Cl ₂ ] ₂ were filled in a reaction flask, and 10. The mixture was reacted for 5 hours to obtain 5.75 g of a polymer. The molecular weight was 1129.

Comparative Example 12: Polymerization of 5-norbornene-2-methyl-decanyl acetate 5-norbornene-2-methyl-decanyl acetate (1.03 g, 3.7 mmol) was placed in a Schlenk flask, and [(allyl) PdCl ] ₂ (13.15 mg, 3.60 × 10 ⁻² mmol) and AgSbF ₆ (35 mg, 10.1 × 10 ⁻² mmol) were added, and 2 mL of chlorobenzene was added and dissolved. The AgCl precipitate was filtered, added dropwise to the monomer side at room temperature, and reacted for 24 hours. The polymerization yield was 1.01 g (98%), and the weight average molecular weight was 58,848.

Comparative Example 13: Polymerization of allyl 5-norbornene-2-acetate Li [B (C ₆ F ₅ ) ₄ ] was charged into allyl 5-norbornene-2-acetate (5.0 g, 30 mmol) in a Schlenk flask. [(Allyl) PdCl] ₂ (0.55 mg, 0.0015 mmol) and P (Cy) ₃ (0.84 mg, 0.0030 mmol) were dissolved in 0.1 mL of toluene and added dropwise to the monomer side. Reaction was performed at 65 ° C. for 4 hours to obtain 0.25 g (5%) of a polymer.

Comparative Example 14: Polymerization of allyl 5-norbornene-2-acetate Allyl 5-norbornene-2-acetate (5 mL, 30.9 mmol) and toluene (15 ml) were charged into a 250 mL Schlenk flask. As a catalyst dissolved in dichloromethane (1 mL) in this flask, Pd (OAc) ₂ (1.4 mg, 6.2 mol), dimethylanilium tetrakis (pentafluorophenyl) borate (10.9 mg, 13.6 mol), And reacted with stirring at 90 ° C. for 18 hours. After reacting for 18 hours, the reaction product was added to an excessive amount of ethanol, but no polymer precipitate was obtained.

前記表８で、ＴＨＦはテトラヒドロフランであり、ＭＣは塩化メチレンである。 Production of optically anisotropic film
Examples 26 and 27
After the polymers obtained in Examples 1 and 3 were mixed as shown in Table 8 below to prepare a coating solution, the coating solution was cast on a glass substrate using a knife coater or a bar coater. The film was dried at room temperature for 1 hour, and further dried at 100 ° C. for 18 hours under a nitrogen atmosphere. After drying, the film was stored at −10 ° C. for 10 seconds, and then the film on the glass substrate was peeled off with a knife to obtain a transparent film having a uniform thickness with a thickness deviation of less than 2%. The thicknesses for these films and the translucency at 400 to 700 nm are shown together in Table 8 below.

In Table 8, THF is tetrahydrofuran and MC is methylene chloride.

またＲ_ｅ及びＲ_ｔｈ値でフィルムの厚さを割って屈折率差（ｎ_ｘ−ｎ_ｙ）と屈折率差（ｎ_ｙ−ｎ_ｚ）とを求めた。下記の表９にそれぞれの透明フィルムの（ｎ_ｘ−ｎ_ｙ）、Ｒ_θ、Ｒ_ｔｈ、（ｎ_ｙ−ｎ_ｚ）を示した。
また、Ｒ_ｅ及びＲ_ｔｈ値でフィルムの厚さを割って屈折率差（ｎ_ｘ−ｎ_ｙ）と屈折率差（ｎ_ｙ−ｎ_ｚ）とを求めた。下記表９にそれぞれの透明フィルムの（ｎ_ｘ−ｎ_ｙ）、Ｒ_θ、Ｒ_ｔｈ、（ｎ_ｙ−ｎ_ｚ）を示した。

また、ｎ_ｙ＞ｎ_ｚであるトリアセテートセルロースフィルムを重ねてＲ_θを測定した場合、いずれの環状オレフィン系フィルムのＲ_θ値も増大し、これは、環状オレフィン系フィルムのＲ_ｔｈは、厚さ方向にネガティブ複屈折率（ｎ_ｙ＞ｎ_ｚ）によるものであることを示す。 Optical anisotropy measurement
Test Examples 1 and 2
The transparent films according to Examples 26 and 27 each measured the refractive index n using an Abbe refractometer, and using an automatic birefringence system (manufactured by Oji Scientific Instruments; KOBRA-21 ADH). measuring the retardation value R _e in the plane, the incident light and the angle between the film surface is measured retardation value R _theta when there 50 °, the film thickness direction and an in-plane x-axis by the following equation 2 And a phase difference value R _th were obtained.

Also determine the refractive index difference by dividing the thickness of the film _{R e} and _{R th} value _(n x -n _y) and the refractive index difference _(n y -n _z). Each of the transparent film are shown in Table 9 below _{(n x -n y), R} θ, R th, showed _(n y -n _z).
Further, to determine the refractive index difference by dividing the thickness of the film _{R e} and _{R th} value _(n x -n _y) and the refractive index difference _(n y -n _z). Each of the transparent film in the following Table _{9 (n x -n y),} R θ, R th, showed _(n y -n _z).

Further, when overlapping the triacetate cellulose film is n _y> n _z were measured R _theta, also increases R _theta value of any cyclic olefin-based film, which is, R _th cycloolefin film thickness It shows that it is based on a negative birefringence index ( _ny > _nz ) in a direction.

It is a photograph which shows the structure of a tricyclohexyl phosphonium (tetrakis pentafluorophenyl) borate) compound.

Claims (14)

A catalyst composition for producing a cyclic olefin polymer containing a polar functional group,
A group 10 metal-containing pre-catalyst having a ligand containing a heteroatom directly coordinated to a metal and represented by the following chemical formula 3a:
A catalyst composition for producing a cyclic olefin polymer containing a polar functional group, comprising a promoter which is a phosphonium salt compound represented by the following chemical formula 4.

[In Formula 3a,
R ₁ ′, R ₂ ′, R ₂ ″ and R ₂ ″ are each independently a linear or branched alkyl, alkenyl or vinyl having 1 to 20 carbon atoms; a hydrocarbon substituted or unsubstituted carbon A cycloalkyl having 5 to 12 carbon atoms; an aryl having 6 to 40 carbon atoms substituted or unsubstituted on a hydrocarbon; an aralkyl having 7 to 15 carbon atoms substituted or unsubstituted on a hydrocarbon; or an alkynyl having 3 to 20 carbon atoms ,
r and s are 0 to 2, and r + s is 2. ]
[HP (R ₄ ) ₃ ] [Ani] <Formula 4>
[In Formula 4 above,
R ₄ each independently represents a linear or branched alkyl having 1 to 20 carbon atoms; or a cycloalkyl having 3 to 12 carbon atoms substituted or unsubstituted on a hydrocarbon, wherein each of the above substituents Is halogen,
[Ani] is borate or aluminate. ] The cyclic olefin polymer containing a polar functional group according to claim 1, wherein the borate or aluminate represented by [Ani] in Chemical Formula 4 is an anion represented by the following Chemical Formula 2a or Chemical Formula 2b. Catalyst composition.
[M ′ (R ₆ ) ₄ ] <Chemical 2a>
[M ′ (OR ₆ ) ₄ ] <Chemical 2b>
[In Formula 2a and Formula 2b,
M ′ is boron or aluminum;
R ₆ is independently halogen; linear or branched alkyl or alkenyl having 1 to 20 carbon atoms substituted or unsubstituted with halogen; cycloalkyl having 3 to 12 carbon atoms substituted or unsubstituted with halogen; hydrocarbon A substituted or unsubstituted aryl having 6 to 40 carbon atoms; a linear or branched trialkylsiloxy having 3 to 20 carbon atoms or a linear or branched triarylsiloxy having 18 to 48 carbon atoms substituted with 6 carbon atoms An aryl having 7 to 40 carbon atoms; an aralkyl having 7 to 15 carbon atoms which is substituted or unsubstituted by halogen. ] In the pre-catalyst represented by Formula 3a,
The ligand containing a heteroatom directly coordinated to palladium (Pd) is acetylacetonate or acetate;
In the promoter of the salt compound having phosphonium represented by the chemical formula 4,
The catalyst composition for producing a cyclic olefin polymer containing a polar functional group according to claim 1, wherein R ₄ is cyclohexyl, isopropyl, t-butyl, n-butyl or ethyl.   The production of a cyclic olefin polymer containing a polar functional group according to claim 1, wherein the ratio of the cocatalyst to the precatalyst containing the Group 10 transition metal is 0.5 to 10 mol per mol of the precatalyst. Catalyst composition.   The catalyst composition for producing a cyclic olefin polymer containing a polar functional group according to claim 1, wherein the catalyst composition comprising the pre-catalyst and the co-catalyst is supported on a fine particle support.   8. The particulate support is silica, titania, silica / chromia, silica / chromia / titania, silica / alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite. A catalyst composition for producing a cyclic olefin polymer containing a polar functional group of   The polarity according to claim 1, wherein the catalyst composition comprising the pre-catalyst and the co-catalyst is used by being dissolved in an organic solvent selected from the group consisting of dichloromethane, dichloroethane, toluene, chlorobenzene and a mixture thereof. A catalyst composition for producing a cyclic olefin polymer containing a functional group.   The catalyst composition comprising the pre-catalyst and the co-catalyst comprises a metal catalyst complex compound comprising the pre-catalyst and the co-catalyst, for producing a cyclic olefin polymer having a polar functional group according to claim 1. Catalyst composition. A method for producing a cyclic olefin polymer containing a polar functional group,
Producing the catalyst composition according to any one of claims 1 to 8,
Addition polymerization of a monomer solution containing a cyclic olefin monomer containing a polar functional group at a temperature of 80 ° C. to 150 ° C. in the presence of the catalyst composition,
The manufacturing method of the cyclic olefin type polymer containing a polar functional group whose cyclic olefin monomer containing the said polar functional group is a compound represented by following Chemical formula 5.

[In Formula 5 above,
m is an integer from 0 to 4,
At least one of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ represents a polar functional group and the rest are non-polar functional groups;
The nonpolar functional group is hydrogen; halogen; linear or branched alkyl having 1 to 20 carbon atoms, haloalkyl, alkenyl, haloalkenyl; linear or branched alkynyl having 3 to 20 carbon atoms, haloalkynyl; alkyl, alkenyl. , Alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted Aryl having 6 to 40 carbon atoms; or alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted aralkyl having 7 to 15 carbon atoms;
The polar functional group is selected from the group consisting of —R ⁸ C (O) OR ⁹ , —C (O) OR ⁹ , —OC (O) R ⁹ , and —R ⁸ OC (O) R ^9. In the polar functional group,
Each R ⁸ is linear or branched alkylene having 1 to 20 carbons, and each R ⁹ is hydrogen or linear or branched alkyl having 1 to 20 carbons. ]   The method for producing a cyclic olefin-based polymer containing a polar functional group according to claim 9, wherein the total amount of the organic solvent in the reaction system is 50 to 800% relative to the total monomer weight in the monomer solution.   The method for producing a cyclic olefin-based polymer containing a polar functional group according to claim 9, wherein the catalyst composition is charged into the monomer solution in a solid phase.   The catalyst composition is charged into the reaction system in an amount of 1 / 2,500 to 1 / 200,000 relative to the total monomer molar amount in the monomer solution based on the pre-catalyst component. Item 10. A method for producing a cyclic olefin polymer containing the polar functional group according to Item 9.   The method for producing a cyclic olefin polymer containing a polar functional group according to claim 9, wherein the monomer solution further comprises a cyclic olefin compound containing no polar functional group.   The method for producing a cyclic olefin-based polymer containing a polar functional group according to claim 9, wherein the monomer solution further comprises a linear or branched olefin having 1 to 20 carbon atoms.

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