(19)
(11)EP 1 448 617 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
01.07.2015 Bulletin 2015/27

(21)Application number: 03741567.6

(22)Date of filing:  07.07.2003
(51)International Patent Classification (IPC): 
C08F 132/08(2006.01)
C08F 4/80(2006.01)
C08F 232/08(2006.01)
(86)International application number:
PCT/KR2003/001350
(87)International publication number:
WO 2004/007564 (22.01.2004 Gazette  2004/04)

(54)

METHOD FOR PREPARING NORBORNENE BASED ADDITION POLYMER CONTAINING ESTER OR ACETYL FUNCTIONAL GROUP

VERFAHREN ZUR HERSTELLUNG VON POLYMERISAT AUF NORBORNEN-BASIS MIT ESTER- ODER ACETYLFUNKTIONELLER GRUPPE

PROCEDE DE PREPARATION D'UN POLYMERE ADDITIONNEL A BASE DE NORBORNENE CONTENANT UN GROUPE FONCTIONNEL ESTER OU ACETYLE


(84)Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

(30)Priority: 10.07.2002 KR 2002040044
24.06.2003 KR 2003041039

(43)Date of publication of application:
25.08.2004 Bulletin 2004/35

(73)Proprietor: LG Chem, Ltd.
Seoul 150-721 (KR)

(72)Inventors:
  • CHUN, Sung-Ho,
    Daejeon-city 305-340 (KR)
  • KIM, Won-Kook, 115-1203 Hwangsil Town
    Daejeon-city 302-280 (KR)
  • YOON, Sung-Cheol,
    Yuseong-gu, Daejeon-city 305-509 (KR)
  • LIM, Tae-Sun, 3-410 LG Chemical Sataek
    Daejeon-city 305-340 (KR)
  • KIM, Heon, 2-308 LG Chemical Employee's apt.
    Daejeon-city 305-340 (KR)
  • KIM, Kyoung-Hoon, 6-303 LG Chemical Employee's apt
    Daejeon-city 305-340 (KR)

(74)Representative: Chalk, Anthony John et al
HGF Limited Saviour House 9 St Saviourgate
York YO1 8NQ
York YO1 8NQ (GB)


(56)References cited: : 
EP-B1- 0 729 480
US-A- 5 468 819
US-A1- 2002 052 454
JP-A- 2000 169 517
US-A1- 2002 040 115
US-B1- 6 350 832
  
  • HENNIS A D ET AL: "NOVEL, EFFICIENT, PALLADIUM-BASED SYSTEM FOR THE POLYMERIZATION OF NORBORNENE DERIVATIVES: SCOPE AND MECHANISM" ORGANOMETALLICS, ACS, COLUMBUS, OH, US, vol. 20, no. 13, 25 June 2001 (2001-06-25), pages 2802-2812, XP001048893 ISSN: 0276-7333
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

BACKGROUND OF THE INVENTION


(a) Field of the Invention



[0001] The present invention relates to a method for preparing a cyclic olefin polymer, and more particularly to a method for preparing a cyclic olefin polymer by addition polymerization of a norbornene-based compound containing polar functional groups such as an ester or an acetyl.

(b) Description of the Related Art



[0002] Currently, PMMA (polymethylmethacrylate) or PC (polycarbonate) is widely used for a transparent polymer. Although PMMA has good transparency, it has poor dimensional stability due to its high hygroscopicity. Therefore, it is not suitable for material for precision optical devices or displays.

[0003] Until now, inorganic substances such as silicon oxide or silicon nitride have been predominantly used for insulation materials. However, with the increasing need of small-sized and highly efficient devices, new high functional materials are required. In this regard, polymers having a low dielectric constant and hygroscopicity, superior adhesion to metal, strength, thermal stability and transparency, and high glass transition temperature (Tg > 250 °C) attract a lot of attensions. Such polymers may be used for insulation films of semiconductor devices or TFT-LCDs, polarizer protection films for polaziers, multichip modules, integrated circuits (ICs), printed circuit boards, and molding compounds for electronic devices or optical materials for flat panel displays. Currently, polyimide, BCB (bis-benzocyclobutene), etc. are used as low dielectric materials for electronic devices.

[0004] Polyimide has long been used for electronic devices due to its thermal stability, oxidative stability, high glass transition temperature, and superior mechanical properties. However, it involves problems of corrosion due to high hygroscopicity, an increase in dielectric constant, its anisotropic electric property, a need for pre-treatment to reduce reaction with copper wire, its adhesion to metals, etc.

[0005] Although BCB has lower hygroscopicity and a lower dielectric constant than polyimide, its adhesion to metal is not good and curing at high temperature is required to obtain desired physical properties. Physical properties of BCB are affected by curing time and temperature.

[0006] Cyclic olefin copolymers are known to have low dielectric constants and hygroscopicity due to their low hydrocarbon content. Cyclic monomers can be polymerized by ROMP (ring opening metathesis polymerization), HROMP (ring opening metathesis polymerization followed by hydrogenation), or copolymerization with ethylene and homogeneous polymerization, as shown in the following Scheme 1.



[0007] Polymers synthesized by ROMP have poor thermal stability and oxidative stability due to unsaturation of the main chain, and are used as thermoplastic resins or thermosetting resins. Tenny et al. discloses in US Patent No. 5,011,730 that a thermosetting resin prepared by the above method can be used as a circuit board by reaction injection molding. However, as mentioned above, it has problems of thermal stability, oxidative stability, and low glass transition temperature.

[0008] There has been an attempt to stabilize the main chain of the polymer by hydrogenation. Although a polymer prepared by this method has improved oxidative stability, the thermal stability is reduced. In general, hydrogenation increases the glass transition temperature of a ROMP polymer by about 50°C, but because of the ethylene groups located between the cyclic monomers, the glass transition temperature is still low (Metcon 99). Moreover, a cost increase due to increased polymerization steps and weak mechanical properties of the polymer are hindering its commercial use.

[0009] From addition co-polymerization with ethylene, a product called Apel was obtained using a homogeneous vanadium catalyst. However, this method has problems of low catalytic activity and generation of excessive oligomers.

[0010] A zirconium based metallocene catalyst has been reported to give a polymer having a narrow molecular weight distribution and a large molecular weight (Plastic News, Feb. 27, 1995, p.24). However, the activity of the catalyst decreases with the increase of cyclic monomer concentration, and the obtained copolymer has a low glass transition temperature (Tg < 200°C). In addition, although the thermal stability increases, mechanical strength is weak and chemical resistance against solvents such as halogenated hydrocarbon solvents is poor.

[0011] Gaylord et al. have reported addition polymerization of norbornene in 1977 (Gaylord, N.G.; Deshpande, A.B.; Mandal, B.M.; Martan, M. J. Macromol. Sci.-Chem. 1977, A11(5), 1053-1070). [Pd(C6H5CN)Cl2]2 was used as a catalyst and the yield was 33%. Later, a norbornene polymer was prepared using a [Pd(CH3CN)4][BF4]2 catalyst (Sen, A.; Lai, T.-W. J. Am. Chem. Soc. 1981, 103, 4627-4629).

[0012] Kaminsky et al. have reported homogeneous polymerization of norbornene using a zirconium-based metallocene catalyst (Kaminsky, W.; Bark, A.; Drake, I. Stud. Surf. Catal. 1990, 56,425). However, since a polymer obtained by this method is very crystalline and is hardly soluble in organic solvent, and thermal decomposition occurs without showing glass transition temperature, further studies could not be conducted.

[0013] Like the above-explained polyimide or BCB, the cyclic polymers also have poor adhesion to metal. For a polymer to be used for electronic devices, it should have good adhesion to a variety of surfaces, such as silicon, silicon oxide, silicon nitride, alumina, copper, aluminum, gold, silver, platinum, titanium, nickel, tantalum, chromium, and other polymers.

[0014] The following method has been introduced to increase adhesion of polyimide, BCB, etc. to metal. A substrate is treated with an organic silicon coupling agent having two functional groups such as aminopropyltriethoxysilane or triethoxyvinylsilane. Then, the substrate is reacted with a polymer or polymer precursor. In this reaction, it is believed that the hydrolyzed silyl group reacts with the hydroxy group on the substrate surface to form a covalent bond.

[0015] A cyclic polymer can be used for insulating electronic devices, replacing inorganic materials such as silicon oxide or silicon nitride. For a functional polymer to be used for electronic devices, it should have a low dielectric constant and hygroscopicity, superior adhesion to metal, strength, thermal stability and transparency, and a high glass transition temperature (Tg > 250°C).

[0016] Such a polymer can be used for insulation films of semiconductor devices or TFT-LCDs. Here, amino groups on the substrate surface react with functional groups of the polymer or polymer precursor to form bridges linking the substrate and the polymer. This technique has been disclosed in US Patent No. 4,831,172. However, this method is a multi-step process and requires a coupling agent.

[0017] Introduction of functional groups to a polymer comprising hydrocarbons is a useful method for the control of chemical and physical properties of the polymer. However, introduction of functional groups is not easy because unshared electron pairs of the functional groups tend to react with active catalytic sites. A polymer obtained by polymerizing cyclic monomers having functional groups has a low molecular weight (US Patent No. 3,330,815).

[0018] In order to overcome this problem, a method of adding the monomers having functional groups at a later step of polymerization (US Patent No. 5,179,171) has been proposed. However, thermal stability of the polymer has not increased by this method. Also, physical and chemical properties and adhesion to metal did not improve significantly.

[0019] As an alternative, a method of reacting functional groups with a base polymer in the presence of a radical initiator has been introduced. However, this method involves problems in that the grafting site of the substituents cannot be controlled and only a small amount of radicals are grafted. The excessive radicals cut the polymers to decrease molecular weight of the polymer. Or, they are not grafted to the base polymer but polymerize with other radicals.

[0020] When a polycyclic compound having a silyl group is used for an insulation film, it adheres to metal and by-products such as water or ethanol are produced, which are not completely removed to increase dielectric constant or cause corrosion of another metal.

[0021] Polymerization or copolymerization of norbornene having an ester or acetyl group has attracted continuous attentions (Risse, et al., Macromolecules, 1996, Vol. 29, 2755-2763; Risse, et al., Makromol. Chem. 1992, Vol. 193, 2915-2927; Sen, et al., Organometallics 2001, Vol. 20, 2802-2812; Goodall, et al., US Patent No. 5,705,503; Lipian, et al., WO 00/20472). Risse et al. activated a [(η3-ally)PdCl]2 palladium compound with a cocatalyst such as AgBF4 or AgSbF6, or used a catalyst such as [Pd(RCN)4][BF4]2. Sen, et al. activated [(1,5-cyclooctadiene)(CH3)Pd(Cl)] with a phosphine such as PPh3 and a cocatalyst such as Na+[3,5-(CF3)2C6H3]4B-. US Patent No. 5,705,503 used a catalyst system similar to that reported by Risse, et al. ([(η3-ally)PdCl]2 was activated with AgBF4 or AgSbF6.).

[0022] In addition polymerization or addition copolymerization of norbornene having an ester or acetyl group, excessive catalyst, as much as 1/100 to 1/400 moles of norbornene, has been used. Lipian, et al. reported polymerization of a norbornene-based monomer using a small amount of catalyst (WO 00/20472). However, most of the preferred embodiments refer to polymerization of alkyl norbornene or copolymerization of alkyl norbornene and silyl norbornene. Although Example 117 refers to polymerization of ester norbornene, the initial addition amount of ester norbornene is only 5% of that of butyl norbornene, suggesting that this method is not efficient for polymerization of ester norbornene. Although the content of ester norbornene in the prepared polymer is not presented, it is expected to be very small. Also, polymerization of norbornene having an acetyl group in Example 134 shows only about a 5% polymerization yield, indicating that the catalyst system is inefficient.

[0023] In addition, the literature reported by the inventors of WO 00/20472 in 2001 (Sen, et al., Organometallics 2001, Vol. 20, 2802-2812) shows that the polymerization yield of ester norbornene was below 40%, and an excessive amount of catalyst of as much as about 1/400 moles of the amount of the monomer was used.

[0024] It is believed that the reason why such a large amount of catalyst should be used is that catalytic activity decreases due to interaction with a polar group of norbornene such as an ester or acetyl group (Sen, et al., Organometallics 2001, Vol. 20, 2802-2812). Specifically, when polymerizing norbornene having an ester or acetyl group, an exo isomer is more stable thermodynamically, but an endo isomer is stabilized kinetically to generate more endo isomers than exo isomers.

[0025] This can be explained by interaction of oxygen lone-pair electrons and π-orbital of a diene in a Diels-Alder reaction or by steric interaction of a methyl group and an ester group of diene, as shown in the following Scheme 2 and Scheme 3.





[0026] The endo isomer is known to reduce catalytic activity in the subsequent polymerization steps (Risse, et al., Macromolecules, 1996, Vol. 29, 2755-2763; Risse, et al., Makromol. Chem. 1992, Vol. 193, 2915-2927). Therefore, in polymerization of a norbornene monomer having an ester or an acetyl group, it is desirable that more exo isomers exist in the polymerization solution, if possible. Also, a method of introducing a ligand designed to prevent a decrease in polymerization activity in the presence of endo isomers is required.

SUMMARY OF THE INVENTION



[0027] It is an object of the present invention to provide a catalyst system capable of preparing a cyclic olefin polymer having a low dielectric constant, low hygroscopicity, a high glass transition temperature, superior thermal stability and oxidative stability, good chemical resistance and toughness, and superior adhesion to metal, and a method for preparing a cyclic olefin polymer using the same.

[0028] It is another object of the present invention to provide a method for preparing a cyclic olefin polymer having superior optical characteristics that can be used for an optical film, a retardation film, a protection film of a polarizer, etc.

[0029] It is still another object of the present invention to provide a method for preparing a cyclic olefin polymer that can be used for electronic devices, such as integrated circuits, printed circuit boards, and multichip modules.

[0030] It is still another object of the present invention to provide a method for preparing a cyclic olefin polymer that can be attached to a substrate of an electronic device without using a coupling agent.

[0031] It is still another object of the present invention to provide a method for preparing a cyclic olefin polymer that has good adhesion to a substrate made of copper, silver, or gold.

[0032] It is still another object of the present invention to provide a method for preparing a homopolymer or copolymer of a norbornene-based compound having an ester or acetyl group.

[0033] It is still another object of the present invention to provide a method for preparing a copolymer of norbornene-based compound having an ester or acetyl group, which exhibits superior polymerization activity even under endo- rich conditions that endo isomers hold a great part of the norbornene-based monomers (50 mole% or more).

[0034] In order to achieve these objects, the present invention provides a catalyst system for preparing a norbornene-based addition polymer having a polar group of ester or acetyl, which comprises:
  1. (a) a group X transition metal compound;
  2. (b) a compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160°; and
  3. (c) dimethylanilinium tetrakis(pentafluorophenylborate),
wherein the norbornene-based addition polymer comprises 50 mole% or more of norbornene-based monomer having a polar group of ester or acetyl, and
wherein the (a) compound of a Group X transition metal is represented by Chemical Formula 1:

        M(R)2     [Chemical Formula 1]

wherein,

M is a Group X metal; and

R is a ligand selected from the group consisting of acetate and acetylacetonate (R"C(O)CHC(O)R") (wherein R" is hydrogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl having hetero atom; C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; or C3 to C20 alkynyl),

wherein the (b) compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160° is represented by Chemical Formula 2 or Chemical Formula 3:

        P(R5)3-c[X(R5)d]c     [Chemical Formula 2]

wherein,

X is oxygen, sulphur, silicon, or nitrogen;

c is an integer of 0 to 3;

d is 1 if X is oxygen or sulphur, 3 if X is silicon, and 2 if X is nitrogen;

if c is 3 and X is oxygen, two or three R5 groups may be connected with each other through oxygen to form a cyclic group; and if c is 0, two R5 groups may be connected with each other to form a phosphacycle; and

R5 is hydrogen; a C1 to C20 linear or branched alkyl, alkoxy, allyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C40 aryl substituted with hydrocarbon or unsubstituted; a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; a C3 to C20 alkynyl; a tri(C1 to C10 linear or branched alkyl)silyl; a tri(C1 to C10 linear or branched alkoxy)silyl; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryloxy substituted with hydrocarbon or unsubstituted)silyl; a tri(C1 to C10 linear or branched alkyl)siloxy; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)siloxy; or a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)siloxy, wherein each substituent can be further substituted with a linear or branched haloalkyl or halogen; and

        (R5)2P - (R6)-P(R5)2     [Chemical Formula 3]

wherein,

R5 is the same as defined in the Chemical Formula 2; and R6 is a C1 to C5 linear or branched alkyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C20 aryl substituted with hydrocarbon or unsubstituted; or a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted.



[0035] The present invention also provides a method for preparing a catalyst for preparing a norbornene-based addition polymer having a polar group of ester or acetyl, comprising the step of mixing:
  1. (i) a group X transition metal compound;
  2. (ii) a compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160°, and
  3. (iii) dimethylanilinium tetrakis(pentafluorophenylborate),
in a solvent,

wherein the (a) compound of a Group X transition metal is represented by Chemical Formula 1:

        M(R)2     [Chemical Formula 1]

wherein,

M is a Group X metal; and

R is a ligand selected from the group consisting of acetate and acetylacetonate (R"C(O)CHC(O)R") (wherein R" is hydrogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl having hetero atom; C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; or C3 to C20 alkynyl),

wherein the (b) compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160° is represented by Chemical Formula 2 or Chemical Formula 3:

        P(R5)3-c[X(R5)d]c     [Chemical Formula 2]

wherein,

X is oxygen, sulphur, silicon, or nitrogen;

c is an integer of 0 to 3;

d is 1 if X is oxygen or sulphur, 3 if X is silicon, and 2 if X is nitrogen;

if c is 3 and X is oxygen, two or three R5 groups may be connected with each other through oxygen to form a cyclic group; and if c is 0, two R5 groups may be connected with each other to form a phosphacycle; and

R5 is hydrogen; a C1 to C20 linear or branched alkyl, alkoxy, allyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C40 aryl substituted with hydrocarbon or unsubstituted; a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; a C3 to C20 alkynyl; a tri(C1 to C10 linear or branched alkyl)silyl; a tri(C1 to C10 linear or branched alkoxy)silyl; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryloxy substituted with hydrocarbon or unsubstituted)silyl; a tri(C1 to C10 linear or branched alkyl)siloxy; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)siloxy; or a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)siloxy, wherein each substituent can be further substituted with a linear or branched haloalkyl or halogen; and

        (R5)2P - (R6)-P(R5)2     [Chemical Formula 3]

wherein,

R5 is the same as defined in the Chemical Formula 2; and R6 is a C1 to C5 linear or branched alkyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C20 aryl substituted with hydrocarbon or unsubstituted; or a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted.


BRIEF DESCRIPTION OF THE DRAWINGS



[0036] 

Fig. 1 is a schematic diagram showing interaction of an endonorbornene ester and palladium metal.

Fig. 2 is a schematic diagram showing interaction of an exo-norbornene ester and palladium metal.

Fig. 3a is a schematic diagram of a structure wherein both the catalyst and the ester group are in exo positions to norbornene, showing structural stability according to the position of the catalyst and the ester group in case phosphine group does not exist.

Fig. 3b is a schematic diagram of a structure wherein the catalyst is in an exo position but the ester group is in an endo position to norbornene, showing structural stability according to the position of the catalyst and the ester group in case phosphine group does not exist.

Fig. 3c is a schematic diagram of a structure wherein both the catalyst and the ester group are in endo positions to norbornene, showing structural stability according to the position of the catalyst and the ester group in case phosphine group does not exist.

Fig. 4a is a schematic diagram of a structure wherein both the catalyst and the ester group are in exo positions to norbornene, showing structural stability according to the position of the catalyst and the ester group in case a PH3 ligand exists.

Fig. 4b is a schematic diagram of a structure wherein the catalyst is in an exo position but the ester group is in an endo position to norbornene, showing structural stability according to the position of the catalyst and the ester group in case a PH3 ligand exists.

Fig. 4c is a schematic diagram of a structure wherein both the catalyst and the ester group are in endo positions to norbornene, showing structural stability according to the position of the catalyst and the ester group in case a PH3 ligand exists.

Fig. 5a is a schematic diagram of a structure wherein both the catalyst and the ester group are in exo positions to norbornene, showing structural stability according to the position of the catalyst and the ester group in case a PPh3 ligand exists.

Fig. 5b is a schematic diagram of a structure wherein the catalyst is in an exo position but the ester group is in an endo position to norbornene, showing structural stability according to the position of the catalyst and the ester group in case a PPh3 ligand exists.

Fig. 5c is a schematic diagram of a structure wherein both the catalyst and the ester group are in endo positions to norbornene, showing structural stability according to the position of the catalyst and the ester group in case a PPh3 ligand exists.

Fig. 6a is a schematic diagram of a structure wherein both the catalyst and the ester group are in exo positions to norbornene, showing structural stability according to the position of the catalyst and the ester group in case a P(cyclohexyl)3 ligand exists.

Fig. 6b is a schematic diagram of a structure wherein the catalyst is in an exo position but the ester group is in an endo position to norbornene, showing structural stability according to the position of the catalyst and the ester group in case a P(cyclohexyl)3 ligand exists.

Fig. 6c is a schematic diagram of a structure wherein both the catalyst and the ester group are in endo positions to norbornene, showing structural stability according to the position of the catalyst and the ester group in case a P(cyclohexyl)3 ligand exists.


DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS



[0037] Hereinafter, the present invention is described in more detail.

[0038] The present inventors have discovered that a norbornene-based addition polymer having a polar group of ester or acetyl group, which has high molecular weight and high yield regardless of the fact that the monomers are exo- or endo- isomer, can be prepared by an addition polymerization of norbornene-based monomers having polar group of ester or acetyl group in the presence of a catalyst into which a suitable ligand is introduced, and completed the present invention

[0039] The present invention provides a highly active catalyst system for polymerization of norbornene-based polymer, which comprises a cocatalyst and a catalyst into which a suitable ligand capable of avoiding catalytic activity deterioration due to the ester group or acetyl group of an endo-isomer is introduced. And, the present invention also provides a method for preparing a norbornene-based addition polymer comprising norbornene-based monomers having an ester or acetyl group without loss of yield and molecular weight by addition polymerization of norbornene-based monomers having ester or acetyl group using the above catalyst system.

[0040] The catalyst system of the present invention can polymerize a norbornene-based compound having an ester or acetyl functional group using a much smaller amount of catalyst than that of prior art. Specifically, superior polymerization result can be obtained with a catalyst amount of only 1/2500 to 1/100,000 based on the weight of the norbornene monomer having an ester or acetyl group.

[0041] The catalyst system comprises:
  1. (a) a group X transition metal compound;
  2. (b) a compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160°; and
  3. (c) dimethylanilinium tetrakis(pentafluorophenylborate),
wherein the norbornene-based addition polymer comprises 50 mole% or more of norbornene-based monomer having a polar group of ester or acetyl, and

wherein the (a) compound of a Group X transition metal is represented by Chemical Formula 1:

        M(R)2     [Chemical Formula 1]

wherein,

M is a Group X metal; and

R is a ligand selected from the group consisting of acetate and acetylacetonate (R"C(O)CHC(O)R") (wherein R" is hydrogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl having hetero atom; C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; or C3 to C20 alkynyl),

wherein the (b) compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160° is represented by Chemical Formula 2 or Chemical Formula 3:

        P(R5)3-c[X(R5)d]c     [Chemical Formula 2]

wherein,

X is oxygen, sulphur, silicon, or nitrogen;

c is an integer of 0 to 3;

d is 1 if X is oxygen or sulphur, 3 if X is silicon, and 2 if X is nitrogen;

if c is 3 and X is oxygen, two or three R5 groups may be connected with each other through oxygen to form a cyclic group; and if c is 0, two R5 groups may be connected with each other to form a phosphacycle; and

R5 is hydrogen; a C1 to C20 linear or branched alkyl, alkoxy, allyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C40 aryl substituted with hydrocarbon or unsubstituted; a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; a C3 to C20 alkynyl; a tri(C1 to C10 linear or branched alkyl)silyl; a tri(C1 to C10 linear or branched alkoxy)silyl; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryloxy substituted with hydrocarbon or unsubstituted)silyl; a tri(C1 to C10 linear or branched alkyl)siloxy; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)siloxy; or a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)siloxy, wherein each substituent can be further substituted with a linear or branched haloalkyl or halogen; and

        (R5)2P - (R6)-P(R5)2     [Chemical Formula 3]

wherein,

R5 is the same as defined in the Chemical Formula 2; and R6 is a C1 to C5 linear or branched alkyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C20 aryl substituted with hydrocarbon or unsubstituted; or a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted.



[0042] Specifically, said components may be mixed in a solvent to prepare an activated catalyst solution to be used for polymerization, or they may be added respectively in a polymerization solution. The norbornene-based addition polymer may be a norbornene-based homopolymer having an ester or acetyl group, a copolymer of a norbornene-based monomer having a different ester or acetyl group, or a copolymer of a norbornene-based monomer having an ester or acetyl group and a norbornene-based monomer that does not comprise an ester or acetyl group.

[0043] The norbornene-based polymer having an ester or acetyl group of the present invention is prepared by homopolymerizing a norbornene-based monomer having at least one ester or acetyl group (represented by the following Chemical Formula 7) in the presence of a Group X metal catalyst, or by copolymerizing a norbornene-based monomer having an ester or acetyl group with norbornene in the presence of a catalyst system comprising the Group X metal catalyst.

wherein

m is an integer of 0 to 4;

at least one of R1, R2, R3 and R4 is a radical having an ester or acetyl group; and

each of the other R1, R2, R3 and R4 is hydrogen; linear or branched C1 to C20 alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl substituted with hydrocarbon or unsubstituted; C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; C3 to C20 alkynyl; or halogen.

If R1, R2, R3 and R4 are not radical having an ester or acetyl group, hydrogen or halogen, R1 and R2, or R3 and R4 may be connected to form a C1 to C10 alkylidene group, or R1 or R2 may be connected with one of R3 and R4 to form a C4 to C12 saturated or unsaturated cyclic group or a C6 to C17 aromatic group.



[0044] A cyclic norbornene-based monomer or norbornene derivative refers to a monomer having at least one norbornene (bicyclo[2,2,1]hept-2-ene (bicyclo[2.2.1 hept-2-ene)) unit, which is represented by the following Chemical Formula 8.



[0045] The polymer of the present invention has cyclic repeating units having an ester or acetyl group, of which content is 0.1 to 100 mol%.

[0046] According to the present invention, a norbornene-based monomer comprising at least one ester or acetyl group and a norbornene-based monomer that does not comprise ester or acetyl group are polymerized in a catalyst system comprising a Group X metal compound. As in the conventional polymerization process, the monomers and catalyst are mixed in a solvent, and the reaction mixture is polymerized. And, the norbornene-based monomers are used without separating endo-and exo-isomers.

[0047] Hereinafter, the catalyst system of the present invention is described in more detail.

[0048] The a) Group X transition metal is represented by the following Chemical Formula 1:

        [Chemical Formula 1]     M(R)2

wherein

M is a Group X metal; and

R is a ligand selected from the group consisting of acetate and acetylacetonate (R"C(O)CHC(O)R"),

wherein R" is hydrogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl having hetero atom; C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; or C3 to C20 alkynyl.



[0049] The b) compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160° is represented by Chemical Formula 2 or Chemical Formula 3:

        P(R5)3-c[X(R5)d]c     [Chemical Formula 2]

wherein,

X is oxygen, sulphur, silicon, or nitrogen;

c is an integer of 0 to 3;

d is 1 if X is oxygen or sulphur, 3 if X is silicon, and 2 if X is nitrogen;

if c is 3 and X is oxygen, two or three R5 groups may be connected with each other through oxygen to form a cyclic group; and if c is 0, two R5 groups may be connected with each other to form a phosphacycle; and

R5 is hydrogen; a C1 to C20 linear or branched alkyl, alkoxy, allyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C40 aryl substituted with hydrocarbon or unsubstituted; a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; a C3 to C20 alkynyl; a tri(C1 to C10 linear or branched alkyl)silyl; a tri(C1 to C10 linear or branched alkoxy)silyl; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryloxy substituted with hydrocarbon or unsubstituted)silyl; a tri(C1 to C10 linear or branched alkyl)siloxy; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)siloxy; or a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)siloxy, wherein each substituent can be further substituted with a linear or branched haloalkyl or halogen; and

        (R5)2P - (R6)-P(R5)2     [Chemical Formula 3]

wherein,

R5 is the same as defined in the Chemical Formula 2; and R6 is a C1 to C5 linear or branched alkyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C20 aryl substituted with hydrocarbon or unsubstituted; or a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted.



[0050] The c) salt is dimethylanilinium tetrakis(pentafluorophenylborate). However, the relative stability changes if the cone angle of the phosphine ligand is larger than 160°, as in P(cyclohexyl)3. Fig. 6a, Fig. 6b, and Fig. 6c compare structural stability according to the position of the catalyst and the ester group in case a P(cyclohexyl)3 ligand (cone angle = 180°) exists in the catalyst. Fig. 6a shows the structure wherein both the catalyst and the ester group are in the exo position to norbornene, Fig. 6b shows the structure wherein the catalyst is in the exo position but the ester group is in the endo position to norbornene, and Fig. 6c shows the structure wherein both the catalyst and the ester group are in the endo position to norbornene. Among the three structures, the structure of Fig. 6a is stable by about 1.61 kcal/mol compared to the structure of Fig. 6c, and the structure of Fig. 6b is unstable by about 1.41 kcal/mol compared to the structure of Fig. 6c. Therefore, the structure having both the catalyst and the ester group in the endo position to norbornene is not stabilized, and a decrease of polymerization activity due to the endo isomer is prevented.

[0051] Accordingly, when a ligand having a large cone angle, such as a phosphine, is introduced in the catalyst, a decrease in catalytic activity due to the endo isomer can be avoided, and catalyst with improved activity can be designed. This catalytic activity improvement effect can also be seen in an anionic ligand offering σ- and-π-bonding, such as acetylacetonate or acetate, as well as in an allyl ligand.

[0052] With regard to catalytic activity, a catalytic system comprising Pd(acac)2 or Pd(acetate)2, dimethylanilinium tetrakis(pentafluorophenylborate), and tricyclohexylphosphine is more effective than a catalyst system comprising [(allyl)Pd(Cl)]2, borate, and phosphine, as will be shown in the Examples. The reason is believed that the acetylacetonate group is easily released from palladium to form a large space around the palladium, so a large norbornene monomer can access easily.

[0053] Accordingly, the present invention provides a catalyst system comprising:
  1. (a) a group X transition metal compound;
  2. (b) a compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160°; and
  3. (c) dimethylanilinium tetrakis(pentafluorophenylborate),
wherein the norbornene-based addition polymer comprises 50 mole% or more of norbornene-based monomer having a polar group of ester or acetyl, and

wherein the (a) compound of a Group X transition metal is represented by Chemical Formula 1:

        M(R)2     [Chemical Formula 1]

wherein,

M is a Group X metal; and

R is a ligand selected from the group consisting of acetate and acetylacetonate (R"C(O)CHC(O)R") (wherein R" is hydrogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl having hetero atom; C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; or C3 to C20 alkynyl),

wherein the (b) compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160° is represented by Chemical Formula 2 or Chemical Formula 3:

        P(R5)3-c[X(R5)d]c     [Chemical Formula 2]

wherein,

X is oxygen, sulphur, silicon, or nitrogen;

c is an integer of 0 to 3;

d is 1 if X is oxygen or sulphur, 3 if X is silicon, and 2 if X is nitrogen;

if c is 3 and X is oxygen, two or three R5 groups may be connected with each other through oxygen to form a cyclic group; and if c is 0, two R5 groups may be connected with each other to form a phosphacycle; and

R5 is hydrogen; a C1 to C20 linear or branched alkyl, alkoxy, allyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C40 aryl substituted with hydrocarbon or unsubstituted; a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; a C3 to C20 alkynyl; a tri(C1 to C10 linear or branched alkyl)silyl; a tri(C1 to C10 linear or branched alkoxy)silyl; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryloxy substituted with hydrocarbon or unsubstituted)silyl; a tri(C1 to C10 linear or branched alkyl)siloxy; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)siloxy; or a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)siloxy, wherein each substituent can be further substituted with a linear or branched haloalkyl or halogen; and

        (R5)2P - (R6)-P(R5)2     [Chemical Formula 3]

wherein,

R5 is the same as defined in the Chemical Formula 2; and R6 is a C1 to C5 linear or branched alkyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C20 aryl substituted with hydrocarbon or unsubstituted; or a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted.



[0054] For this purpose, the catalyst system comprises: i) 1 mol of a Group X transition metal compound; ii) 1 to 3 mols of a compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160°C; and iii) 1 to 2 mols of dimethylanilinium tetrakis(pentafluorophenylborate.

[0055] Preferably, the catalyst system is used in an amount of 1/2500 to 1/100,000 based on the weight of the norbornene monomer having an ester or acetyl group, for polymerization of the norbornene having an ester or acetyl group.

[0056] Preferably, polymerization of the present invention is carried at a temperature range of -100°C to 200°C, more preferably at -60°C to 150°C, and most preferably at -10°C to 150°C. The polymerization solvent is preferably selected from those having a boiling point higher than the polymerization temperature.

[0057] Preferably, the molecular weight (Mn) of the polymer of the present invention is in the range of 10,000 to 1,000,000.

[0058] The cyclic olefin addition polymer having an ester or acetyl group according to the present invention does not generate by-products because the ester or acetyl group is directly attached to metal.

[0059] The conventional polycyclic compounds having silyl groups are attached to metal to generate water or alcohol (e.g. ethanol) by-products, which are not completely removed during process to decrease dielectric constant or corrode metals. However, the cyclic olefin addition polymer having an ester or acetyl group of the present invention does not generate by-products when attached to metal, and rather it is strongly attached to metal, therefore there is no concern of decrease in dielectric constant or corrosion of metals.

[0060] Accordingly, the cyclic olefin addition polymer of the present invention has a low dielectric constant and hygroscopicity, a high glass transition temperature, superior thermal stability and oxidative stability, good chemical resistance and toughness, and superior adhesion to metal. Also, it has superior optical characteristics and can be attached to a substrate for electronic devices without a coupling agent. Since it is attached to a copper, silver or gold substrate very well, it can be used for a low dielectric coating agent or film comprising electronic devices such as integrated circuits and multichip modules.

[0061] Hereinafter, the present invention is described in more in detail through Examples. However, the following Examples are only for the understanding of the present invention, and the present invention is not limited by the following Examples.

EXAMPLES



[0062] All procedures treating compounds sensitive to air or water were carried out by the standard Schlenk technique or using a dry box. Nuclear magnetic resonance (NMR) spectrums were obtained using a Bruker 300 spectrometer. 1H NMR was measured at 300MHz, and 13C NMR was measured at 75MHz. Molecular weight and molecular weight distribution of polymers were measured by GPC (gel permeation chromatography) using a polystyrene sample as a standard. Thermal analysis, such as TGA and DSC, was carried out using a TA Instrument (TGA 2050; heating rate = 10K/min).

[0063] Toluene was purified by distillation in potassium/benzophenone, and CH2Cl2 was purified by distillation in CaH2.

[0064] The BLYP(Becke-Lee-Yang-Parr) gradient corrected DFT(density functional theory) (Hohenberg, et al., Phys. Rev. B., 1964, Vol. 136, 864; Kohn, et al., J. Phys. Rev. A., 1965, Vol. 140, 1133) was employed to optimize all of the molecules, using the Dmol3 program(Delley, J. Chem. Phys. 1990, Vol. 92, 508; J. Quant. Chem. 1998, Vol. 69, 423).

[0065] ECP(The energy adjusted effective core potential) (Dolg, et al., J. Chem. Phys. 1987, Vol. 86, 866; Bergner, et al., Mol. Phys. 1993, Vol. 80, 1431) was used for Pd atom. DND(double numerical plus d-functional) was used for C,H,O,P atoms, and the valence electrons for Pd were expanded with the DND basis set.

[0066] No structural constraint was given in GO (geometry optimization) for calculating the minimum energy of isomers. Because every system has an OS (open shell) with a +1 charge and a doublet, SUOS-WF (spin-unrestricted open shell wave function) was used for calculation.

[0067] A medium grid was used for numerical integration, and the 0.005-hartree thermal smearing algorithm was applied for quick SCF convergence. In SCF, the density convergence criterion was set at 1×10-5. In structure optimization, energy convergence and gradient convergence criterion were set at 2×10-5 and 4×10-5, respectively.

Preparation Example 1: Synthesis of exo-rich norbornene carboxylic acid methyl ester



[0068] DCPD (dicyclopentadiene, Aldrich, 256.5mL, 1.9 mol), methylacrylate (Aldrich, 405mL, 4.5mol), and hydroquinone (3.2g, 0.03 mol) were put in a 2L autoclave. After heating to 180°C, reaction was carried out for 6 hours while stirring at 300 rpm. After the reaction was completed, the reaction mixture was cooled down and transferred to a distillation unit. The reaction mixture was distilled at 1 torr using a vacuum pump at 50°C to obtain the product (yield: 86%). The mole ratio of exo-isomers to endo-isomers of the product was 52:48.

[0069] 1H-NMR (600MHz, CDCl3), endo: δ 6.17 (dd, 1 H), 5.91 (dd, 1 H), 3.60 (s, 3H), 3.17 (b, 1 H), 2.91 (m, 1 H), 2.88 (b, 1 H), 1.90 (m, 1 H), 1.42 (m, 2H), 1.28 (m, 1H); exo: δ 6.09 (m, 2H), 3.67 (s, 3H), 3.01 (b, 1 H), 2.88 (b, 1 H), 2.20 (m, 1 H), 1.88 (m, 1 H), 1.51 (d, 1 H), 1.34 (m, 2H).

[0070] 13C-NMR (600MHz, CDCl3), endo: δ 29.10 (CH2), 42.39 (CH), 43.03 (CH), 45.52(CH), 49.47(CH2), 51.28(CH3), 132.23(CH), 137.56(CH), 175.02(C); exo: δ 30.20(CH2), 41.49(CH), 42.83(CH), 46.21(CH2). 46.43(CH), 51.53(CH3), 135.59(CH), 139.90(CH), 176.52(C).

Preparation Example 2: Synthesis of endo-rich norbonene carbonxylic acid methylester



[0071] DCPD (dicyclopentadiene, Aldrich, 256.5mL, 1.9 mol), methylacrylate (Aldrich, 405mL, 4.5mol), and hydroquinone (3.2g, 0.03 mol) were put in a 2L autoclave. After heating to 180°C, reaction was carried out for 5 hours while stirring at 300 rpm. After the reaction was completed, the reaction mixture was cooled down and transferred to a distillation unit. The reaction mixture was distilled at 1 torr using a vacuum pump at 50°C to obtain the product (yield: 86%). The mole ratio (mol%) of exo-isomers to endo-isomers of the product was 41.1 : 58.9.

[0072] 1H-NMR (600MHz, CDCl3), endo: δ 6.17 (dd, 1 H), 5.91 (dd, 1 H), 3.60 (s, 3H), 3.17 (b, 1 H), 2.91 (m, 1 H), 2.88 (b, 1 H), 1.90 (m, 1 H), 1.42 (m, 2H), 1.28 (m, 1 H); exo: δ 6.09 (m, 2H), 3.67 (s, 3H), 3.01 (b, 1 H), 2.88 (b, 1 H), 2.20 (m, 1 H), 1.88 (m, 1 H), 1.51 (d, 1 H), 1.34 (m, 2H).

[0073] 13C-NMR (600MHz, CDCl3), endo: δ 29.10 (CH2), 42.39 (CH), 43.03 (CH), 45.52(CH), 49.47(CH2), 51.28(CH3), 132.23(CH), 137.56(CH), 175.02(C); exo: δ 30.20(CH2), 41.49(CH), 42.83(CH), 46.21(CH2), 46.43(CH), 51.53(CH3), 135.59(CH), 139.90(CH), 176.52(C).

Preparation Example 3: Synthesis of exo-rich norbornene carboxylic acid butyl ester



[0074] DCPD (dicyclopentadiene, Aldrich, 180mL, 1.34 mol), butylacrylate (Junsei, 500mL, 3.49 mol), and hydroquinone (2.7g, 0.025 mol) were put in a 2L autoclave. After heating to 190°C, reaction was carried out for 5 hours while stirring at 300 rpm. After the reaction was completed, the reaction mixture was cooled down and transferred to a distillation unit. The reaction mixture was distilled at 1 torr using a vacuum pump at 80°C to obtain the product (yield: 78%). The mole ratio (mol%) of the exo-isomers to endo-isomers of the product was 56.2 : 43.8.

[0075] 1H-NMR (600MHz, CDCl3), endo: δ 6.17 (dd, 1H), 5.86 (dd, 1H), 3.97 (t, 2H), 3.15 (b, 1 H), 2.88 (m, 1 H), 2.85 (b, 1 H), 1.86 (m, 1 H), 1.57 (m, 2H), 1.35 (m, 4H), 1.21 (m, 1 H), 0.89 (t, 3H); exo: δ 6.09 (m, 2H), 4.05 (t, 2H), 2.98 (b, 1H), 2.86 (b, 1 H), 2.20 (m, 1 H), 1.88 (m, 1H), 1.58 (m, 2H), 1.50 (d, 1 H), 1.34 (m, 4H), 0.89 (t, 3H).

[0076] 13C-NMR (600MHz, CDCl3), endo: δ 13.57(CH3), 19.04 (CH2), 29.00 (CH2), 30.63 (CH2), 42.39 (CH), 43.20 (CH), 45.56 (CH), 49.45 (CH2), 63.83 (CH2), 132.21 (CH), 137.50 (CH), 174.05 (C); exo: δ 13.57(CH3), 19.04 (CH2), 30.14 (CH2), 30.63 (CH2), 41.48 (CH), 43.04 (CH), 46.19 (CH2), 46.48 (CH), 64.07 (CH2), 135.61 (CH), 137.84 (CH), 176.05 (C).

Preparation Example 4 : Synthesis of endo-rich allylacetate norbonene



[0077] DCPD (dicyclopentadiene, Aldrich, 248mL, 1.852 mol), allylacetate (Aldrich, 500mL, 4.63 mol), and hydroquinone (0.7g, 0.006 mol) were put in a 2L autoclave. After heating to 180°C, reaction was carried out for 5 hours while stirring at 300 rpm. After the reaction was completed, the reaction mixture was cooled down and transferred to a distillation unit. The reaction mixture was distilled twice at 1 torr using a vacuum pump at 56 °C to obtain the product (yield: 30%). The mole ratio (mol%) of the exo-isomers to endo-isomers of the product was 17 : 83.

[0078] 1H-NMR (300MHz, CDCl3) : δ 6.17 ∼5.91 (m, 2H), 4.15 ~ 3.63 (m, 2H), 2.91 ∼ 2.88 (m, 2H), 2.38 (m, 1H), 2.05 (s, 3H), 1.83 (m, 1 H), 1.60 ~ 1.25 (m, 2H), 0.57 (m, 1 H)

Example 1: Preparation of norbornene carboxylic acid methyl ester addition homopolymer using tricyclohexylphosphine and Pd(acac)2 as catalyst



[0079] 10g (65.7 mmol) of exo-rich norbornene carboxylic acid methyl ester synthesized in Preparation Example 1 and 15mL of purified toluene were introduced into a 250mL Schlenk flask, as monomer and solvent, respectively. Then, 2 mg of palladium (II) acetylacetonate dissolved in 5 ml of toluene and 1.84 mg of tricyclohexyl phosphine as a catalyst, and 10.6 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 2 ml of CH2Cl2 as a cocatalyst were introduced into the flask, and reaction was carried out at 90°C for 18 hours while stirring.

[0080] After the reaction was completed, the reaction mixture was added to excess ethanol to obtain a white copolymer precipitate. The precipitate was filtered with a glass funnel and dried in a vacuum oven at 65°C for 24 hours to obtain 3.34 g of norbornene carboxylic acid methyl ester homopolymer (yield: 33.4 mol% of total monomer input). Number average molecular weight (Mn) of the polymer was 31,700, and weight average molecular weight (Mw) of the polymer was 71,400.

Example 2: Preparation of norbornene carboxylic acid butyl ester addition homopolymer using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0081] 10g (51.47 mmol) of exo-rich norbornene carboxylic acid butyl ester prepared in the Preparation Example 3 and 5mL of purified toluene solvent were introduced into a 250mL Schlenk flask. Then, 3.14mg of palladium(II) acetylacetonate (Pd(acac)2) and 2.89mg of tricyclohexylphosphine dissolved in 5 mL of toluene, and 16.5mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 2 mL of CH2Cl2 were added to the flask, as catalyst and cocatalyst, respectively. Then, reaction was carried out at 90°C for 17 hours while stirring the flask.

[0082] After the reaction was completed, the reaction mixture was added to excess ethanol to obtain a white copolymer precipitate. The precipitate was filtered with a glass funnel and dried in a vacuum oven at 65°C for 24 hours to obtain 4.83 g of norbornene carboxylic acid butyl ester homopolymer (yield: 48.3wt% of total monomer input). Number average molecular weight of the polymer was 45,000, and weight average molecular weight was 84,000.

Comparative Example 1: Preparation of norbonene carboxylic acid methylester addition homopolymer using triphenyl phosphine and Pd(acac)2 as a catalyst]



[0083] 5 g (32,90 mmol) of the exo-rich norbonene carboxylic acid methylester prepared in the Preparation Example 1 as monomers and 5 ml of purified toluene were introduced in 250 ml Schlenk flask. To the flask, 1.00 mg of Pd(acac)2 dissolved in 5 ml of toluene and 0.92 mg of triphenyl phosphine as a catalyst, and 5.26 mg of dimethylanilinium tetrakiss(pentafluorophenyl)borate dissolved in 2 ml of CH2Cl2 as a cocatalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0084] After the reaction was completed, the reactant was introduced into an excessive ethanol. However, copolymer precipitate could not be obtained.

Example 3: Preparation of norbornene carboxylic acid methyl ester addition homopolymer using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0085] 10.46 g (68.7 mmol) of norbornene carboxylic acid methyl ester synthesized in Preparation Example 1 and 20mL of purified toluene solvent were put in a 250mL Schlenk flask, as monomer and solvent, respectively. Then, 1.54mg of Pd(acac)2 and 1.93mg of tricyclohexyl phosphine dissolved in 5mL of toluene, and 11.01 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 2 mL of CH2Cl2 were added to the flask, as catalyst and cocatalyst, respectively. Then, reaction was carried out at 90°C for 18 hours while stirring.

[0086] After the reaction was completed, the reaction mixture was added to excess ethanol to obtain a white copolymer precipitate. The precipitate was filtered with a glass funnel and dried in a vacuum oven at 65°C for 24 hours to obtain 3.33 g of norbornene carboxylic acid methyl ester homopolymer (yield: 31.8 mol% of total monomer input). Number average molecular weight of the polymer was 27,500, and weight average molecular weight was 78,300.

Example 4: Preparation of addition copolymer of norbonene carboxylic acid methylester / norbonene using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0087] Into a 250 ml Schlenk flask, 16.74 mg (110.0 mmol) of the exo-rich norbonene carboxylic acid methylester prepared in the Preparation Example 1 and 4.44 g (47.13 mmol) of norbonene as monomers, and 37 ml of purified toluene solvent were introduced. Into the flask, 4.79 mg of Pd(acac)2 and 4.41 mg of tricyclohexyl phosphine dissolved in 5 ml of toluene as a catalyst, and 25.2 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 2 ml of CH2Cl2 as a cocatalyst were added. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0088] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain white copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried in a vacuum oven at 65 °C for 24 hours to obtain 12.96 g of copolymer of norbonene and norbonene carboxylic acid methylester (yield : 61.2 mol% of total monomer input). Number average molecular weight of the polymer was 81,000, and weight average molecular weight was 164,000.

Example 5: Preparation of addition copolymer of norbonene carboxylic acid methylester/ butyl norbonene using tricyclohexyl phosphine and Pd(acac)2 as a catalsyt



[0089] Into a 250 ml Schlenk flask, 10.46 mg (68.73 mmol) of the exo-rich norbonene carboxylic acid methylester prepared in the Preparation Example 1 and 10.24 g (6.73 mmol) of butyl norbonene as monomers, and 39 ml of purified toluene solvent were introduced. To the flask, 4.17 mg of Pd(acac)2 and 3.86 mg of tricyclohexyl phosphine dissolved in 5 ml of toluene as a catalyst, and 22.1 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 2 ml of CH2Cl2 as a cocatalyst were added. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0090] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain white copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried in a vacuum oven at 65 °C for 24 hours to obtain 15.15 g of copolymer of butyl norbonene and norbonene carboxylic acid methylester (yield : 73.2 mol% of total monomer input). Number average molecular weight of the polymer was 62,000, and weight average molecular weight was 140,000.

Example 6: Preparation of addition copolymer of norbonene carboxylic acid methylester/ hexyl norbonene using tricyclohexyl phosphine and Pd(acac)2 as a catalsyt



[0091] Into a 250 ml Schlenk flask, 9.41 mg (61.85 mmol) of the exo-rich norbonene carboxylic acid methylester prepared in the Preparation Example 1 and 11.03 g (61.85 mmol) of hexyl norbonene as monomers, and 39 ml of purified toluene solvent were introduced. To the flask, 3.8 mg of Pd(acac)2 and 3.5 mg of tricyclohexyl phosphine dissolved in 5 ml of toluene as a catalyst, and 20.8 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 2 ml of CH2Cl2 as a cocatalyst were added. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0092] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain white copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried in a vacuum oven at 65 °C for 24 hours to obtain 18.02 g of copolymer of hexyl norbonene and norbonene carboxylic acid methylester (yield : 78.4 mol% of total monomer input). Number average molecular weight of the polymer was 50,000, and weight average molecular weight was 136,000.

Example 7: Preparation of norbornene carboxylic acid butyl ester addition homopolymer using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0093] 40g (205.9 mmol) of norbornene carboxylic acid butyl ester prepared in the Preparation Example 3 as monomers and 70mL of purified toluene solvent were introduced into a 250mL Schlenk flask. Then, 12.5 mg of Pd(acac)2 and 11.6mg of tricyclohexyl phosphine dissolved in 10mL of toluene, and 66.0mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 5mL of CH2Cl2 were added to the flask, as catalyst and cocatalyst, respectively. Then, reaction was carried out at 80°C for 90 hours while stirring.

[0094] After the reaction was completed, the reaction mixture was added to excess ethanol to obtain a white copolymer precipitate. The precipitate was filtered with a glass funnel and dried in a vacuum oven at 65 °C for 24 hours to obtain 29.9 g of norbornene carboxylic acid butyl ester homopolymer (yield: 74.8 mol% of total monomer input). Number average molecular weight of the polymer was 47,000, and weight average molecular weight was 92,000.

Example 8: Preparation of norbornene carboxylic acid butyl ester addition homopolymer using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0095] 100g (514.7 mmol) of norbornene carboxylic acid butyl ester prepared in the Preparation Example 3 and 180mL of purified toluene were put in a 250mL Schlenk flask, as monomer and solvent, respectively. Then, 32.36mg of Pd(acac)2 and 28.86mg of tricyclohexylphosphine dissolved in 20mL of toluene, and 164.9mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 10mL of CH2Cl2 were added to the flask, as catalyst and cocatalyst, respectively. Then, reaction was carried out at 80°C for 90 hours while stirring the flask.

[0096] After the reaction was completed, the reaction mixture was added to excess ethanol to obtain a white copolymer precipitate. The precipitate was filtered with a glass funnel and dried in a vacuum oven at 65 °C for 24 hours to obtain 73.7g of norbornene carboxylic acid butyl ester homopolymer (yield: 73.7 mol% of total monomer input). Number average molecular weight of the polymer was 47,200, and weight average molecular weight was 91,800.

Example 9: Preparation of addition copolymer of norbonene/norbonene carboxylic acid butyl ester using tricylcohexylphosphine and Pd(acac)2 as a catalyst



[0097] To a 250 ml Schlenk flask, 10 g (51.47 mmol) of the exo-rich norbonene carboxylic acid butyl ester prepared in the Preparation Example 3 and 4.85 g (51.47 mmol) of norbonene as monomers, and 25 ml of purified toluene solvent were introduced. To the flask, 6.27 mg of Pd(acac)2 and 5.77 mg of tricyclohexyl phosphine dissolved in 5 ml of purified toluene as a catalyst, and 33.0 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 2 ml of CH2Cl2 were added. Then, reaction was carried out at 80 °C for 17 hours.

[0098] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain white copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried in a vacuum oven at 65 °C for 24 hours to obtain 10.14 g of copolymer of norbonene and norbonene carboxylic acid butyl ester (yield: 68.3 mmol% of total monomer input). Number average molecular weight of the polymer was 126,000, and weight average molecular weight was 266,000.

Example 10: Preparation of addition copolymer of norbonene catboxylic acid butyl ester / butyl norbonene using tricyclohexylphosphine and Pd(acac)2 as a catalyst



[0099] To a 250 ml Schlenk flask, 15.55 g (80.0 mmol) of the exo-rich norbonene carboxylic acid butyl ester prepared in the Preparation Example 3 and 11.93 g (80.0 mmol) of butyl norbonene as monomers, and 55 ml of purified toluene solvent were introduced. To the flask, 4.9 mg of Pd(acac)2 and 4.5mg of tricyclohexyl phosphine dissolved in 5 ml of purified toluene as a catalyst, and 25.6 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 2 ml of CH2Cl2 were added. Then, reaction was carried out at 90 °C for 18 hours.

[0100] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain white copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried in a vacuum oven at 65 °C for 24 hours to obtain 18.1 g of copolymer of butyl norbonene and norbonene carboxylic acid butyl ester (yield: 65.9 mol% of total monomer input). Number average molecular weight of the polymer was 56,000, and weight average molecular weight was 132,000.

Example 11: Preparation of norbonene carboxylic acid butyl ester addition homopoly_mer using endo isomers only and using trichlcohexylphosphine and Pd(acac)2 as a catalyst



[0101] To a 250 ml Schlenk flask, 5.0 g (25.73 mmol) of norbonene carboxylic acid butyl ester endo isomers as monomers and 9 ml of purified toluene solvent were introduced. To the flask, 7.84mg of Pd(acac)2 and 7.22mg of tricyclohexyl phosphine dissolved in 1 ml of toluene as a catalyst, and 41.2 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 1 ml of CH2Cl2 were added. Then, reaction was carried out at 90 °C for 18 hours. After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain white copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried in a vacuum oven at 65 °C for 24 hours to obtain 2.57 g of norbonene carboxylic acid butyl ester homopolymer (yield: 51.4 mol% of total monomer input). Number average molecular weight of the polymer was 31,000, and weight average molecular weight was 81,000.

Example 12: Preparation of norbonene carboxylic acid butyl ester homopolymer using exo isomers only and using tricclohexyl phosphine and Pd(acac)2 as a catalyst



[0102] To a 250 ml Schlenk flask, 2.7 g (13.90 mmol) of norbonene carboxylic acid butyl ester exo isomers as monomers and 4.6 ml of purified toluene solvent were introduced. To the flask, 8.47mg of Pd(acac)2 and 7.8mg of tricyclohexyl phosphine dissolved in 1 ml of toluene as a catalyst, and 44.5 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 1 ml of CH2Cl2 were added. Then, reaction was carried out at 80 °C for 2 hours while stirring.

[0103] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain white copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried in a vacuum oven at 65 °C for 24 hours to obtain 1.53 g of norbonene carboxylic acid butyl ester homopolymer (yield: 56.7 mol% of total monomer input). Number average molecular weight of the polymer was 52,000, and weight average molecular weight was 97,000.

Example 13: Preparation of a copolymer of norbonene carboxylic acid methylester / norbonene carboxylic acid butylester using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0104] Into a 500 ml Schlenk flask, 63.8 g (328.5 mmol) of the exo-rich norbonene carboxylic acid butyl ester prepared in the Preparation Example 3 and 50.0 g (328.5 mmol) of the exo-rich norbonene carboxylic acid methylester prepared in the Preparation Example 1 as monomers and 210 ml of purified toluene solvent were introduced. Into the flask, 40.0 mg of Pd(acac)2 and 36.9 mg of tricyclohexyl phosphine dissolved in 20 ml of toluene as a catalyst and 210.6 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 10 ml of CH2Cl2 as a co-catalyst were introduced. Then, reaction was carried out at 80 °C for 90 hours while stirring.

[0105] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 89.94 g of copolymer of norbonene carboxylic acd butyl ester and norbonene carboxylic acid methyl ester (yield: 79.0 wt% of total monomer input). Number average molecular weight of the polymer was 50,000, and weight average molecular weight is 97,000.

Example 14: Preparation of 5-norbonene-2-yl acetate addition homopolymer using tricylcohexyl phosphine and Pd(acac)2 as a catalyst



[0106] Into a 250 ml Schlenk flask, 5 g (32.85 mmol) of the exo-rich 5-norbonene-2-yl acetate (containing 88 mol% of exo) as monomers and 9 ml of purified toluene solvent were introduced. Into the flask, 20.6 mg of Pd(acac)2 and 18.93 mg of tricyclohexyl phosphine dissolved in 1 ml of toluene as a catalyst and 18.93 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 2 ml of CH2Cl2 as a co-catalyst were introduced. Then, reaction was carried out at 80 °C for 17 hours while stirring.

[0107] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 4.69 g of 5-norbonene-2-yl acetate homopolymer (yield: 93.8 wt% of total monomer input). Number average molecular weight of the polymer was 36,000, and weight average molecular weight is 88,000.

Example 15: Preparation of allyl acetate norbonene addition homopolymer using tricyclohexylphosphine and Pd(acac)2 as a catalyst



[0108] Into a 250 ml Schlenk flask, 5 g (30.1 mmol) of the endo-rich allyl acetate norbonene prepared in the Preparation Example 4 as monomers and 10 ml of purified toluene solvent were introduced. Into the flask, 1.83 mg of Pd(acac)2 and 1.69 mg of tricyclohexyl phosphine dissolved in 3 ml of CH2Cl2 as a catalyst and 9.64 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0109] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 4.79 g of allyl acetate norbonene homopolymer (yield: 95.8 mol% of total monomer input). Number average molecular weight of the polymer was 78,000, and weight average molecular weight is 203,000.

Example 16: Preparation of alkyl acetate norbonene addition homopolymer using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0110] Into a 250 ml Schlenk flask, 10.0 g (60.2 mmol) of the endo-rich allyl acetate norbonene prepared in the Preparation Example 4 as monomers and 20 ml of purified toluene solvent were introduced. Into the flask, 1.35 mg of Pd(acac)2 and 1.69 mg of tricyclohexyl phosphine dissolved in 3 ml of CH2Cl2 as a catalyst and 12.03 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0111] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 4.72 g of allyl acetate norbonene homopolymer (yield: 47.2 mol% of total monomer input). Number average molecular weight of the polymer was 70,000, and weight average molecular weight is 140,000.

Example 17: Preparation of addition copolymer of norbonene carboxylic acid methylester / norbonene allyl acetate using tricyclohexyl phospine and Pd(acac)2 as a catalyst



[0112] Into a 250 ml Schlenk flask, 9.16 g (60.2 mmol) of the exo-rich norbonene carboxylic acid methyl ester prepared in the Preparation Example 1 and 10.0 g (60.2 mmol) of the endo-rich norbonene allyl acetate prepared in the Preparation Example 4 as monomers and 38 ml of purified toluene solvent were introduced. Into the flask, 2.7 mg of Pd(acac)2 and 3.37 mg of tricyclohexyl phosphine dissolved in 5 ml of CH2Cl2 as a catalyst and 19.2 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0113] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 5.56 g of copolymer of norbonene carboxylic acd methyl ester and norbonene allyl acetate (yield: 29.0 mol% of total monomer input). Number average molecular weight of the polymer was 53,000, and weight average molecular weight is 122,000.

Example 18: Preparation of addition copolymer of norbonene carboxylic acid methylester / norbonene allyl acetate using a tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0114] Into a 250 ml Schlenk flask, 14.96 g (98.3 mmol) of the exo-rich norbonene carboxylic acid methylester prepared in the Preparation Example 1 and 7.0 g (42.1 mmol) of the endo-rich norbonene allyl acetate prepared in the Preparation Example 4 as monomers and 43 ml of purified toluene solvent were introduced. Into the flask, 3.15 mg of Pd(acac)2 and 3.94 mg of tricyclohexyl phosphine dissolved in 5 ml of CH2Cl2 as a catalyst and 22.49 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0115] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 8.81 g of copolymer of norbonene carboxylic acd methyl ester and norbonene allyl acetate (yield: 40.1 mol% of total monomer input). Number average molecular weight of the polymer was 41,000, and weight average molecular weight is 100,000.

Example 19: Preparation of addition copolymer of norbonene carboxylic acid methyl ester / norbonene allyl acetate using tricyclohexyl phosphoine and Pd(acac)2 as a catalyst



[0116] Into a 250 ml Schlenk flask, 5.89 g (38.7 mmol) of the exo-rich norbonene carboxylic acid methyl ester prepared in the Preparation Example 1 and 15.0 g (90.2 mmol) of the endo-rich norbonene allyl acetate prepared in the Preparation Example 4 as monomers and 41 ml of purified toluene solvent were introduced. Into the flask, 2.89 mg of Pd(acac)2 and 3.62 mg of tricyclohexyl phosphine dissolved in 5 ml of CH2Cl2 as a catalyst and 20.66 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0117] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 10.48 g of copolymer of norbonene carboxylic acid methyl ester and norbonene allyl acetate (yield: 50.2 mol% of total monomer input). Number average molecular weight of the polymer was 59,000, and weight average molecular weight is 144,000.

Example 20: Preparation of addition copolymer of norbonene carboxylic acid butylester / norbonene allyl acetate using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0118] Into a 250 ml Schlenk flask, 9.35 g (48.1 mmol) of the exo-rich norbonene carboxylic acid butyl ester prepared in the Preparation Example 3 and 8.0 g (48.1 mmol) of the endo-rich norbonene allyl acetate prepared in the Preparation Example 4 as monomers and 35.24 ml of purified toluene solvent were introduced. Into the flask, 2.16 mg of Pd(acac)2 and 2.70 mg of tricyclohexyl phosphine dissolved in 5 ml of CH2Cl2 as a catalyst and 15.42 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0119] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 2.89 g of copolymer of norbonene carboxylic acd butyl ester and norbonene allyl acetate (yield: 16.4 mol% of total monomer input). Number average molecular weight of the polymer was 52,000, and weight average molecular weight is 97,000.

Example 21: Preparation of addition copolymer of norbonene carboxylic acid butyl ester / norbonene allyl acetate using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0120] Into a 250 ml Schlenk flask, 15.0 g (77.2 mmol) of the exo-rich norbonene carboxylic acid butyl ester prepared in the Preparation Example 3 and 5.5 g (33.1 mmol) of the endo-rich norbonene allyl acetate prepared in the Preparation Example 4 as monomers and 41.9 ml of purified toluene solvent were introduced. Into the flask, 2.48 mg of Pd(acac)2 and 3.09 mg of tricyclohexyl phosphine dissolved in 5 ml of CH2Cl2 as a catalyst and 17.67 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0121] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 4.63 g of copolymer of norbonene carboxylic acd butyl ester and norbonene allyl acetate (yield: 22.6 mol% of total monomer input). Number average molecular weight of the polymer was 48,000, and weight average molecular weight is 91,000.

Example 22: Preparation of addition copolymer of norbonene carboxylic acid butyl ester / norbonene allyl acetate using tricyclohexyl phosphine and Pd(acac)2



[0122] Into a 250 ml Schlenk flask, 6.51 g (33.5 mmol) of the exo-rich norbonene carboxylic acid butyl ester prepared in the Preparation Example 3 and 13.0 g (78.2 mmol) of the endo-rich norbonene allyl acetate prepared in the Preparation Example 4 as monomers and 39.4 ml of purified toluene solvent were introduced. Into the flask, 2.51 mg of Pd(acac)2 and 3.13 mg of tricyclohexyl phosphine dissolved in 5 ml of CH2Cl2 as a catalyst and 17.90 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0123] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 6.65 g of copolymer of norbonene carboxylic acd butyl ester and norbonene allyl acetate (yield: 34.1 mol% of total monomer input). Number average molecular weight of the polymer was 56,000, and weight average molecular weight is 113,000.

Example 23: Preparation of copolymer of butyl norbonene and 5-norbonene-2-yl acetate using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0124] Into a 250 ml Schlenk flask, 9.40 g (61.37 mmol) of the exo-rich 5-norbonene-2-yl acetate (containing 88 mol% of exo) and 9.20 g (61.37 mmol) of butyl norbonene as monomers and 35 ml of purified toluene solvent were introduced. Into the flask, 3.76 mg of Pd(acac)2 and 3.46 mg of tricyclohexyl phosphine dissolved in 5 ml of toluene as a catalyst and 19.8 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0125] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 12.18 g of copolymer of 5-norbonene-2-yl acetate and butyl norbonene (yield: 65.5 mol% of total monomer input). Number average molecular weight of the polymer was 93,000, and weight average molecular weight is 207,000.

Example 24: Preparation of copolymer hexyl norbonene and 5-norbonene-2-yl acetate using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0126] Into a 250 ml Schlenk flask, 9.40 g (61.37 mmol) of the exo-rich 5-norbonene-2-yl acetate (containing 88 mol% of exo) and 11.01 g (61.37 mmol) of hexyl norbonene as monomers and 39 ml of purified toluene solvent were introduced. Into the flask, 3.76 mg of Pd(acac)2 and 3.46 mg of tricyclohexyl phosphine dissolved in 5 ml of toluene as a catalyst and 19.8 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate dissolved in 2 ml of CH2Cl2 as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0127] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 14.31 g of copolymer of 5-norbonene-2-yl acetate and hexyl norbonene (yield: 70.1 mol% of total monomer input). Number average molecular weight of the polymer was 104,000, and weight average molecular weight is 243,000.

Example 25: Preparation of copolymer of phenyl norbonene and norbonene carboxylic acid butylester using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0128] Into a 250 ml Schlenk flask, 7.0 g (41.1 mol) of phenyl norbonene and 6.13 g (41.1 mol) of the exo-rich norbonene carboxylic acid butylester prepared in the Preparation Example 3 as monomers and 28 ml of purified toluene solvent were introduced. Into the flask, 1.85 mg of Pd(acac)2 and 2.31 mg of tricyclohexyl phosphine dissolved in 3 ml of CH2Cl2 as a catalyst and 13.18 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0129] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 9.5 g of copolymer of phenyl norbonene and norbonene carboxylic acid butylester (yield: 72.4 mol% of total monomer input). Number average molecular weight of the polymer was 109,000, and weight average molecular weight is 265,000.

Example 26: Preparation of copolymer of norbonene carboxylic acid methylester and norbonene allyl acetete using tricyclohexyl phosphine and Pd(acac)2 as a catalyst



[0130] Into a 250 ml Schlenk flask, 9.16 (60.2 mmol) of the exo-rich norbonene carboxylic acid methylester prepared in the Preparation Example 1 and 10.0 g (60.2 mmol) of endo-rich norbonene allyl acetate prepared in the Preparation Example 4 as monomers and 38 ml of purified toluene solvent were introduced. Into the flask, 2.7 mg of Pd(acac)2 and 3.37 mg of tricyclohexyl phosphine dissolved in 5 ml of CH2Cl2 as a catalyst and 19.2 mg of dimethylanilinium tetrakis(pentafluorophenyl)borate as a co-catalyst were introduced. Then, reaction was carried out at 90 °C for 18 hours while stirring.

[0131] After the reaction was completed, the reactant was introduced into an excessive ethanol to obtain a copolymer precipitate. The precipitate was filtered with a glass funnel and the recovered copolymer was dried at 65 °C for 24 hours to obtain 5.56 g of copolymer of norbonene carboxylic acid methylester and norbonene allyl acetate (yield: 29.0 mol% of total monomer input). Number average molecular weight of the polymer was 53,000, and weight average molecular weight is 122,000.

Example 27: Surface tension measurement of butylester norbonene homopolymer



[0132] In order to measure surface tension of butyl ester norbornene polymer prepared in Example 2, it was dissolved in toluene2 to 20wt% and cast on a petri dish. After 3 hours at room temperature, the dish was dried at 120°C for 6 hours to obtain a film having a thickness of 120µm. Surface tension of the film was calculated from contact angles of H2O and CH2l2, by the following Equation 1 (Wu, S. J. Polym. Sci. C Vol 34, p19, 1971).



[0133] In Equation 1, γs is the surface tension of the film; γLV is the surface tension of the liquid; γSL is the interfacial tension of film and liquid; θ is the contact angle; γd is the distribution (dispersion) term of surface tension; and γp is the polar term of surface tension.

[0134] For water (γd = 44.1mN/m, γp = 6.7mN/m), the contact angle was 74.3°, and for diiodomethane (γd = 22.1mN/m, γp = 50.7 mN/m), 33.5°. From these values, the surface tension was calculated to be 49.5mN/m.

Example 28: Metal adhesivity test of butylester norbonene homopolymer



[0135] In order to test metal adhesivity of butyl ester norbornene homopolymer prepared in Example 2, it was dissolved in toluene to 10wt% and coated on glass plates respectively having chrome, aluminum and tungsten patterns to a thickness of ∼2µm. Horizontal and vertical lines were drawn to form lattice patterns on the glass plate with 5mm spacing, and a 180° taping test was carried out. None of the three lattice patterns were separated from the glass plate.

Example 29: Adhesivity to PVA polarizer of butylester norbonene homopolymer



[0136] A PVA polarizer was treated with a butyl ester norbornene film that was cast in Example 27. The film was corona surface-treated 3 times with an 8mA current at a line speed of 6m/min. Contact angles were 20.7° for water and 22° for diiodomethane. Surface tension was calculated to be 76.9mN/m.

[0137] Within 30 minutes after the corona treatment, the fully dried PVA polarizer (iodine type; transmissivity = 44%) was roll-pressed with a 10wt% PVA aqueous solution, and then dried at 80 °C for 10 minutes. The PVA polarizer roll-pressed with butyl ester norbornene had very superior adhesivity.

[0138] The present invention prepares a cyclic olefin addition polymer using a catalytic system capable of avoiding a decrease of catalytic activity due to an ester or acetyl group of an endo isomer. According to the present invention, superior polymerization result can be obtained with a very small amount of catalyst. An addition polymer of norbornene having an ester or acetyl group prepared by the present invention is a cyclic olefin addition polymer which is transparent, has good adhesivity to metal or polymers having other polar groups, generates no byproducts when attached to metal, has a low dielectric constant so that it can be used for insulating electronic devices, and has superior thermal stability and mechanical strength.

[0139] While the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that various modifications and substitutions can be made thereto without departing from the spirit and scope of the present invention as set forth in the appended claims.


Claims

1. A catalyst system for preparing a norbornene-based addition polymer having a polar group of ester or acetyl, which comprises:

(a) a group X transition metal compound;

(b) a compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160°; and

(c) dimethylanilinium tetrakis(pentafluorophenylborate),

wherein the norbornene-based addition polymer comprises 50 mole% or more of norbornene-based monomer having a polar group of ester or acetyl, and

wherein the (a) compound of a Group X transition metal is represented by Chemical Formula 1:

        M(R)2     [Chemical Formula 1]

wherein,

M is a Group X metal; and

R is a ligand selected from the group consisting of acetate and acetylacetonate (R"C(O)CHC(O)R") (wherein R" is hydrogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl having hetero atom; C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; or C3 to C20 alkynyl),

wherein the (b) compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160° is represented by Chemical Formula 2 or Chemical Formula 3:

        P(R5)3-c[X(R5)d]c     [Chemical Formula 2]

wherein,

X is oxygen, sulphur, silicon, or nitrogen;

c is an integer of 0 to 3;

d is 1 if X is oxygen or sulphur, 3 if X is silicon, and 2 if X is nitrogen;

if c is 3 and X is oxygen, two or three R5 groups may be connected with each other through oxygen to form a cyclic group; and if c is 0, two R5 groups may be connected with each other to form a phosphacycle; and

R5 is hydrogen; a C1 to C20 linear or branched alkyl, alkoxy, allyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C40 aryl substituted with hydrocarbon or unsubstituted; a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; a C3 to C20 alkynyl; a tri(C1 to C10 linear or branched alkyl)silyl; a tri(C1 to C10 linear or branched alkoxy)silyl; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryloxy substituted with hydrocarbon or unsubstituted)silyl; a tri(C1 to C10 linear or branched alkyl)siloxy; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)siloxy; or a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)siloxy, wherein each substituent can be further substituted with a linear or branched haloalkyl or halogen; and

        (R5)2P - (R6)- P(R5)2     [Chemical Formula 3]

wherein,

R5 is the same as defined in the Chemical Formula 2; and R6 is a C1 to C5 linear or branched alkyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C20 aryl substituted with hydrocarbon or unsubstituted; or a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted.


 
2. The catalyst system according to Claim 1, which comprises:

(a) 1 mol of the compound of a Group X transition metal;

(b) 1 to 3 mols of the compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160°; and

(c) 1 to 2 mols of dimethylanilinium tetrakis(pentafluorophenylborate).


 
3. The catalyst system according to Claim 1 or 2, wherein the catalyst is introduced in an amount of 1/2500 to 1/100,000, based on the moles of the introduced monomers.
 
4. A method for preparing a catalyst for preparing a norbornene-based addition polymer having a polar group of ester or acetyl, comprising the step of mixing:

(i) a group X transition metal compound;

(ii) a compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160°, and

(iii) dimethylanilinium tetrakis(pentafluorophenylborate),

in a solvent,

wherein the (a) compound of a Group X transition metal is represented by Chemical Formula 1:

        M(R)2     [Chemical Formula 1]

wherein,

M is a Group X metal; and

R is a ligand selected from the group consisting of acetate and acetylacetonate (R"C(O)CHC(O)R") (wherein R" is hydrogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl having hetero atom; C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; or C3 to C20 alkynyl),

wherein the (b) compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160° is represented by Chemical Formula 2 or Chemical Formula 3:

        P(R5)3-c[X(R5)d]c     [Chemical Formula 2]

wherein,

X is oxygen, sulphur, silicon, or nitrogen;

c is an integer of 0 to 3;

d is 1 if X is oxygen or sulphur, 3 if X is silicon, and 2 if X is nitrogen;

if c is 3 and X is oxygen, two or three R5 groups may be connected with each other through oxygen to form a cyclic group; and if c is 0, two R5 groups may be connected with each other to form a phosphacycle; and

R5 is hydrogen; a C1 to C20 linear or branched alkyl, alkoxy, allyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C40 aryl substituted with hydrocarbon or unsubstituted; a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; a C3 to C20 alkynyl; a tri(C1 to C10 linear or branched alkyl)silyl; a tri(C1 to C10 linear or branched alkoxy)silyl; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)silyl; a tri(C6 to C40 aryloxy substituted with hydrocarbon or unsubstituted)silyl; a tri(C1 to C10 linear or branched alkyl)siloxy; a tri(C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted)siloxy; or a tri(C6 to C40 aryl substituted with hydrocarbon or unsubstituted)siloxy, wherein each substituent can be further substituted with a linear or branched haloalkyl or halogen; and

        (R5)2P - (R6)- P(R5)2     [Chemical Formula 3]

wherein,

R5 is the same as defined in the Chemical Formula 2; and R6 is a C1 to C5 linear or branched alkyl, alkenyl, or vinyl; a C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; a C6 to C20 aryl substituted with hydrocarbon or unsubstituted; or a C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted.


 
5. A method for preparing a norbornene-based addition polymer having a polar group of ester or acetyl, which comprises the step of contacting a norbomene-based monomer having an ester or acetyl group with a catalyst system according to any one of Claims 1 to 3, in solvent to conduct an addition polymerisation.
 
6. The method according to Claim 5, wherein the norbornene-based addition polymer is selected from a norbornene-based homopolymer comprising an ester or acetyl group; a copolymer of norbornene-based monomers comprising different ester or acetyl groups; or a copolymer of a norbornene-based monomer comprising an ester or acetyl group and a norbornene-based monomer that does not comprise an ester or acetyl group.
 
7. The method for preparing a norbornene-based addition polymer according to Claim 5 or 6, wherein the norbornene-based monomer having an ester or acetyl group is represented by Chemical Formula 7:

wherein

m is an integer of 0 to 4;

at least one of R1, R2, R3, and R4 is a radical having an ester or acetyl group;

each of the other R1, R2, R3, and R4 is hydrogen; linear or branched C1 to C20 alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted with hydrocarbon or unsubstituted; C6 to C40 aryl substituted with hydrocarbon or unsubstituted; C7 to C15 aralkyl substituted with hydrocarbon or unsubstituted; C3 to C20 alkynyl; or halogen; and

if R1, R2, R3, and R4 are not radical having an ester or acetyl group, a hydrogen or a halogen, R1 and R2, or R3 and R4 may be connected to form a C1 to C10 alkylidene group, or R1 or R2 may be connected with R3 or R4 to form a C4 to C12 saturated or unsaturated cyclic group or a C6 to C17 aromatic group.


 
8. A norbornene-based addition polymer comprising an ester or acetyl group prepared by the method of any one of Claims 5 to 7.
 
9. The norbornene-based addition polymer according to Claim 8, which is selected from a norbornene-based homopolymer comprising an ester or acetyl group; a copolymer of norbornene-based monomers comprising different ester or acetyl groups; or a copolymer of a norbornene-based monomer comprising an ester or acetyl group and a norbornene-based monomer that does not comprise an ester or acetyl group.
 
10. The norbornene-based addition polymer according to Claim 8 or 9, wherein the polymer has a molecular weight (Mn) of 10,000 to 1,000,000.
 
11. The catalyst system according to any one of Claims 1 to 3 which comprises:

(a) Pd(acetylacetonate)2 or Pd(acetate)2;

(b) tricyclohexylphosphine; and

(c) dimethylanilinium tetrakis(pentafluorophenylborate).


 
12. The method for preparing a catalyst according to Claim 4, wherein the catalyst system comprises:

(a) Pd(acetylacetonate)2 or Pd(acetate)2;

(b) tricyclohexylphosphine; and

(c) dimethylanilinium tetrakis(pentafluorophenylborate).


 
13. The method according to any one of Claims 5 to 7 for preparing a norbornene-based addition polymer having a polar group of ester or acetyl, the catalyst system comprising:

(a) Pd(acetylacetonate)2 or Pd(acetate)2;

(b) tricyclohexylphosphine; and

(c) dimethylanilinium tetrakis(pentafluorophenylborate).


 
14. The use of the catalyst system according to any one of Claims 1 to 3 as a catalyst for polymerisation of a norbornene-based addition polymer having a polar group of ester or acetyl.
 


Ansprüche

1. Katalysatorsystem zur Herstellung eines Norbornen-basierten Zusatzpolymers, das eine polare Gruppe aus einem Ester oder Acetyl aufweist, welches Folgendes umfasst:

(a) eine Übergangsmetallverbindung der Gruppe X;

(b) eine Verbindung, die einen neutralen Elektronendonatorliganden der Gruppe XV umfasst, der einen Kegelwinkel von mindestens 160° aufweist; und

(c) Dimethylanilin-tetrakis(pentafluorphenylborat),

wobei das Norbornen-basierte Zusatzpolymer 50 Mol% oder mehr eines Norbornen-basierten Monomers umfasst, das eine polare Gruppe aus einem Ester oder Acetyl aufweist und

wobei die Verbindung (a) aus einem Übergangsmetall der Gruppe X durch die Chemische Formel 1 dargestellt wird:

        M(R)2     [Chemische Formel 1]

wobei

M ein Metall der Gruppe X ist; und

R ein Ligand ist, der aus der Gruppe ausgewählt wird, die sich aus Acetat und Acetylacetonat (R"C(O)CHC(O)R") (wobei R" Wasserstoff ist; lineares oder verzweigtes C1 bis C20-Alkyl, -Alkenyl oder -Vinyl; mit Kohlenwasserstoff substituiertes oder unsubstituiertes C5 bis C12-Cycloalkyl; mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C40-Aryl; C6 bis C40-Aryl, das ein Heteroatom aufweist; mit Kohlenwasserstoff substituiertes oder unsubstituiertes C7 bis C15-Aralkyl; oder C3 bis C20-Alkynyl) zusammensetzt,

wobei die Verbindung (b) die einen neutralen Elektronendonatorliganden der Gruppe XV umfasst, der einen Kegelwinkel von mindestens 160° aufweist, durch die Chemische Formel 2 oder die Chemische Formel 3 dargestellt wird:

        P(R5)3-c[X(R5)d]c     [Chemische Formel 2]

wobei

X Sauerstoff, Schwefel, Silicium oder Stickstoff ist;

c eine ganze Zahl von 0 bis 3 ist;

d 1 ist, wenn X Sauerstoff oder Schwefel ist; 3, wenn X Silicium ist und 2, wenn X Stickstoff ist;

wenn c 3 ist und X Sauerstoff ist, zwei oder drei R5-Gruppen miteinander durch Sauerstoff verbunden sein können, um eine zyklische Gruppe zu bilden; und wenn c 0 ist können zwei R5-Grupenn miteinander verbunden sein, um einen Phosphazyklus zu bilden; und

R5 Wasserstoff ist; ein lineares oder verzweigtes C1 bis C20-Alkyl, -Alkoxy, -Allyl, - Alkenyl oder -Vinyl; ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C5 bis C12-Cycloalkyl; ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C40-Aryl; ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C7 bis C15-Aralkyl, ein C3 bis C20-Alkynyl; ein tri(lineares oder verzweigtes C1 bis C10-Alkyl)Silyl; ein tri(lineares oder verzweigtes C1 bis C10-Alkoxy)Silyl; ein tri(mit Kohlenwasserstoff substituiertes oder unsubstituiertes C5 bis C12-Cycloalkyl)Silyl; ein tri(mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C40-Aryl)Silyl; ein tri(mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C40-Aryloxy)Silyl; ein tri(lineares oder verzweigtes C1 bis C10-Alkyl)Siloxy; ein tri(mit Kohlenwasserstoff substituiertes oder unsubstituiertes C5 bis C12-Cycloalkyl)Siloxy; oder ein tri(mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C40-Aryl)Siloxy, wobei jeder Substituent zusätzlich mit einem linearen oder verzweigten Haloalkyl oder Halogen substituiert werden kann; und

        (R5)2P - (R6) - P(R5)2     [Chemische Formel 3]

wobei,

R5 dem entspricht, was in der Chemischen Formel 2 definiert wurde; und R6 ein lineares oder verzweigtes C1 bis C5-Alkyl, -Alkenyl oder -Vinyl ist; ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C5 bis C12-Cycloalkyl; ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C20-Aryl, oder ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C7 bis C15-Aralkyl.


 
2. Katalysatorsystem nach Anspruch 1, das Folgendes umfasst:

(a) 1 mol der Verbindung eines Übergangsmetalls der Gruppe X;

(b) 1 bis 3 mol der Verbindung, die einen neutralen Elektronendonatorliganden der Gruppe XV umfasst, der einen Kegelwinkel von mindestens 160° aufweist; und

(c) 1 bis 2 mol von Dimethylanilin-tetrakis(pentafluorphenylborat).


 
3. Katalysatorsystem nach Anspruch 1 oder 2, wobei der Katalysator basierend auf den Molen der eingeführten Monomere in einer Menge von 1/2500 bis 1/100.000 eingeführt wird.
 
4. Verfahren zur Herstellung eines Katalysators zur Herstellung eines Norbornen-basierten Zusatzpolymers, das eine polare Gruppe aus einem Ester oder Acetyl aufweist, welches den Schritt des Vermischens des Folgenden umfasst:

(i) eine Übergangsmetallverbindung der Gruppe X;

(ii) eine Verbindung, die einen neutralen Elektronendonatorliganden der Gruppe XV umfasst, der einen Kegelwinkel von mindestens 160° aufweist und

(iii) Dimethylanilin-tetrakis(pentafluorphenylborat),

in einem Lösungsmittel

wobei die Verbindung (a) aus einem Übergangsmetall der Gruppe X durch die Chemische Formel 1 dargestellt wird:

        M(R)2     [Chemische Formel 1]

wobei

M ein Metall der Gruppe X ist; und

R ein Ligand ist, der aus der Gruppe ausgewählt wird, die sich aus Acetat und Acetylacetonat (R"C(O)CHC(O)R") (wobei R" Wasserstoff ist; lineares oder verzweigtes C1 bis C20-Alkyl, -Alkenyl oder -Vinyl; mit Kohlenwasserstoff substituiertes oder unsubstituiertes C5 bis C12-Cycloalkyl; mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C40-Aryl; C6 bis C40-Aryl, das ein Heteroatom aufweist; mit Kohlenwasserstoff substituiertes oder unsubstituiertes C7 bis C15-Aralkyl; oder C3 bis C20-Alkynyl) zusammensetzt,

wobei die Verbindung (b) die einen neutralen Elektronendonatorliganden der Gruppe XV umfasst, der einen Kegelwinkel von mindestens 160° aufweist, durch die Chemische Formel 2 oder die Chemische Formel 3 dargestellt wird:

        P(R5)3-c[X(R5)d]c     [Chemische Formel 2]

wobei

X Sauerstoff, Schwefel, Silicium oder Stickstoff ist;

c eine ganze Zahl von 0 bis 3 ist;

d 1 ist, wenn X Sauerstoff oder Schwefel ist; 3, wenn X Silicium ist und 2, wenn X Stickstoff ist;

wenn c 3 ist und X Sauerstoff ist, zwei oder drei R5-Gruppen miteinander durch Sauerstoff verbunden sein können, um eine zyklische Gruppe zu bilden; und wenn c 0 ist können zwei R5-Grupenn miteinander verbunden sein, um einen Phosphazyklus zu bilden; und

R5 Wasserstoff ist; ein lineares oder verzweigtes C1 bis C20-Alkyl, -Alkoxy, -Allyl, - Alkenyl oder -Vinyl; ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C5 bis C12-Cycloalkyl; ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C40-Aryl; ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C7 bis C15-Aralkyl; ein C3 bis C20-Alkynyl; ein tri(lineares oder verzweigtes C1 bis C10-Alkyl)Silyl; ein tri(lineares oder verzweigtes C1 bis C10-Alkoxy)Silyl; ein tri(mit Kohlenwasserstoff substituiertes oder unsubstituiertes C5 bis C12-Cycloalkyl)Silyl; ein tri(mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C40-Aryl)Silyl; ein tri(mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C40-Aryloxy)Silyl; ein tri(lineares oder verzweigtes C1 bis C10-Alkyl)Siloxy; ein tri(mit Kohlenwasserstoff substituiertes oder unsubstituiertes C5 bis C12-Cycloalkyl)Siloxy; oder ein tri(mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C40-Aryl)Siloxy, wobei jeder Substituent zusätzlich mit einem linearen oder verzweigten Haloalkyl oder Halogen substituiert werden kann; und

        (R5)2P - (R6) - P(R5)2     [Chemische Formel 3]

wobei,

R5 dem entspricht, was in der Chemischen Formel 2 definiert wurde; und R6 ein lineares oder verzweigtes C1 bis C5-Alkyl, -Alkenyl oder -Vinyl ist; ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C5 bis C12-Cycloalkyl; ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C20-Aryl; oder ein mit Kohlenwasserstoff substituiertes oder unsubstituiertes C7 bis C15-Aralkyl.


 
5. Verfahren zur Herstellung eines Norbornen-basierten Zusatzpolymers, das eine polare Gruppe aus einem Ester oder Acetyl aufweist, welches den Schritt des Kontaktierens eines Norbornen-basierten Monomers, das eine Ester- oder Acetylgruppe aufweist, mit einem Katalysatorsystem gemäß einem beliebigen der Ansprüche 1 bis 3 in einem Lösungsmittel umfasst, um eine Additionspolymerisation durchzuführen.
 
6. Verfahren nach Anspruch 5, wobei das Norbornen-basierte Zusatzpolymer aus Folgendem ausgewählt wird: einem Norbornen-basierten Homopolymer, das eine Ester- oder Acetylgruppe umfasst; einem Copolymer eines Norbornen-basierten Monomers, das verschiedene Ester- oder Acetylgruppen umfasst; oder einem Copolymer eines Norbornen-basierten Monomers, das eine Ester- oder Acetylgruppe umfasst und einem Norbornen-basierten Monomer, das keine Ester- oder Acetylgruppe umfasst.
 
7. Verfahren zur Herstellung eines Norbornen-basierten Zusatzpolymers nach Anspruch 5 oder 6, wobei das Norbornen-basierte Monomer, das eine Ester- oder Acetylgruppe aufweist, durch die Chemische Formel 7 dargestellt wird:

wobei

m eine ganze Zahl von 0 bis 4 ist;

mindestens eines von R1, R2, R3 und R4 ein Radikal ist, das eine Ester- oder Acetylgruppe aufweist;

jedes der anderen R1, R2, R3 und R4 Wasserstoff ist; lineares oder verzweigtes C1 bis C20-Alkyl, -Alkenyl oder -Vinyl; mit Kohlenwasserstoff substituiertes oder unsubstituiertes C5 bis C12-Cycloalkyl; mit Kohlenwasserstoff substituiertes oder unsubstituiertes C6 bis C40-Aryl; mit Kohlenwasserstoff substituiertes oder unsubstituiertes C7 bis C15-Aralkyl; oder C3 bis C20-Alkynyl; oder Halogen; und

wenn R1, R2, R3 und R4 kein Radikal, das eine Ester- oder Acetylgruppe aufweist, Wasserstoff oder ein Halogen sind, können R1, R2, R3 und R4 verbunden werden, um eine C1 bis C10-Alkylidengruppe zu bilden oder R1 oder R2 können mit R3 oder R4 verbunden werden, um eine gesättigte oder ungesättigte zyklische C4 bis C12-Gruppe oder eine aromatische C6 bis C17-Gruppe zu bilden.


 
8. Norbornen-basiertes Zusatzpolymer, das eine Ester- oder Acetylgruppe umfasst, welches mit dem Verfahren nach einem beliebigen der Ansprüche 5 bis 7 hergestellt wird.
 
9. Norbornen-basiertes Zusatzpolymer nach Anspruch 8, das aus Folgendem ausgewählt wird: einem Norbornen-basierten Homopolymer, das eine Ester- oder Acetylgruppe umfasst; einem Copolymer eines Norbornen-basierten Monomers, das verschiedene Ester- oder Acetylgruppen umfasst; oder einem Copolymer eines Norbornen-basierten Monomers, das eine Ester- oder Acetylgruppe umfasst und einem Norbornen-basierten Monomer, das keine Ester- oder Acetylgruppe umfasst.
 
10. Norbornen-basiertes Zusatzpolymer nach Anspruch 8 oder 9, wobei das Polymer ein Molekulargewicht (Mn) von 10.000 bis 1.000.000 aufweist.
 
11. Katalysatorsystem nach einem beliebigen der Ansprüche 1 bis 3, das Folgendes umfasst:

(a) Pd(acetylacetonat)2 oder Pd(acetat)2;

(b) Tricyclohexylphosphin; und

(c) Dimethylanilin-tetrakis(pentafluorphenylborat).


 
12. Verfahren zur Herstellung eines Katalysators nach Anspruch 4, wobei das Katalysatorsystem Folgendes umfasst:

(a) Pd(acetylacetonat)2 oder Pd(acetat)2;

(b) Tricyclohexylphosphin; und

(c) Dimethylanilin-tetrakis(pentafluorphenylborat).


 
13. Verfahren nach einem beliebigen der Ansprüche 5 bis 7 zur Herstellung eines Norbornen-basierten Zusatzpolymers, das eine polare Gruppe aus einem Ester oder Acetyl aufweist, wobei das Katalysatorsystem Folgendes umfasst:

(a) Pd(acetylacetonat)2 oder Pd(acetat)2;

(b) Tricyclohexylphosphin; und

(c) Dimethylanilin-tetrakis(pentafluorphenylborat).


 
14. Verwendung des Katalysatorsystems nach einem beliebigen der Ansprüche 1 bis 3 als ein Katalysator für die Polymerisation eines Norbornen-basierten Zusatzpolymers, das eine polare Gruppe aus einem Ester oder Acetyl aufweist.
 


Revendications

1. Système catalyseur pour la préparation d'un polymère d'addition à base de norbornène ayant un groupe polaire d'ester ou d'acétyle, comprenant:

(a) un composé de métal de transition du groupe X ;

(b) un composé comprenant un ligand donneur d'électrons de groupe XV neutre ayant un angle de cône d'au moins 160°; et

(c) du tétrakis (pentafluorophényle borate) de diméthylanilinium,

dans lequel le polymère d'addition à base de norbornène comprend 50% en moles ou plus d'un monomère à base de norbornène ayant un groupe polaire d'ester ou d'acétyle, et

dans lequel le composé (a) d'un métal de transition du groupe X est représenté par la formule chimique 1 :

        M(R)2     [Formule chimique 1]

où,

M est un métal de groupe X ; et

R est un ligand choisi dans le groupe constitué par l'acétate et l'acétylacétonate (R"C(O)CHC(O)R") (où R" est de l'hydrogène; un alkyle, alkényle ou vinyle linéaire ou ramifié C1 à C20 ; un cycloalkyle C5 à C12 substitué par un hydrocarbure ou non substitué; un aryle C6 à C40 substitué par un hydrocarbure ou non substitué; un aryle C6 à C40 ayant un hétéroatome; un aralkyle C7 à C15 substitué par un hydrocarbure ou non substitué; ou un alkynyle C3 à C20),

dans lequel le composé (b) comprenant un ligand donneur d'électrons de groupe XV neutre ayant un angle de cône d'au moins 160° est représenté par la Formule Chimique 2 ou la Formule Chimique 3 :

        P(R5)3.c[X(R5)d]c     [Formule chimique 2]

où,

X représente l'oxygène, le soufre, le silicium ou l'azote;

c est un nombre entier de 0 à 3;

d est 1 si X est l'oxygène ou le soufre, 3 si X est le silicium, et 2 si X est un azote ;

si c est égal à 3 et X représente l'oxygène, deux ou trois groupes R5 peuvent être reliés les uns aux autres par l'intermédiaire de l'oxygène pour former un groupe cyclique; et si c vaut 0, deux groupes R5 peuvent être reliés entre eux pour former un phosphacycle; et

R5 est un hydrogène; un alkyle, alkoxy, allyle, alkényle ou vinyle C1 à C20 linéaire ou ramifié; un cycloalkyle C5 à C12 substitué par un hydrocarbure ou non substitué; un aryle C6 à C40 substitué par un hydrocarbure ou non substitué; un aralkyle C7 à C15 substitué par un hydrocarbure ou non substitué; un alkynyle C3 à C20; un silyle tri (alkyle linéaire ou ramifié C1 à C10); un silyle tri (alkoxy linéaire ou ramifié C1 à C10); un silyle tri (cycloalkyle C5 à C12 substitué par un hydrocarbure ou non substitué); un silyle tri (un groupe aryle C6 à C40 substitué ou non substitué avec un hydrocarbure); un silyle tri (un aryloxy C6 à C40 substitué ou non substitué avec un hydrocarbure); un siloxy tri (alkyle C1 à C10 linéaire ou ramifié) ; un siloxy tri (cycloalkyle en C5 à C12 substitué ou non substitué avec un hydrocarbure); ou un siloxy tri (aryle C6 à C40 substitué ou non substitué avec un hydrocarbure), dans lequel chaque substituant peut être en outre substitué par un halogénoalkyle linéaire ou ramifié ou halogène; et

        (R5)2P - (R6)- P(R5)2     [Formule chimique 3]

où,

R5 est le même que défini dans la formule chimique 2; et R6 est un alkyle, alkényle, ou vinyle C1 à C5 linéaire ou ramifié; un cycloalkyle C5 à C12 substitué par un hydrocarbure ou non substitué; un aryle C6 à C20 substitué par un hydrocarbure ou non substitué; ou un aralkyle C7 à C15 substitué par un hydrocarbure ou non substitué.


 
2. Système catalyseur selon la revendication 1, qui comprend:

(a) 1 mole du composé d'un métal de transition du groupe X ;

(b) 1 à 3 moles du composé comprenant un ligand donneur d'électrons de groupe XV neutre ayant un angle de cône d'au moins 160°; et

(c) 1 à 2 moles de tétrakis (pentafluorophényle borate) de diméthylanilinium.


 
3. Système catalyseur selon les revendications 1 ou 2, dans lequel le catalyseur est introduit en une quantité de 1/2500-1/100.000, sur la base des moles des monomères introduits.
 
4. Procédé de préparation d'un catalyseur pour l'élaboration d'un polymère d'addition à base de norbornène ayant un groupe polaire d'ester ou d'acétyle, comprenant la phase consistant à mélanger:

(i) un composé de métal de transition du groupe X ;

(ii) un composé comprenant un ligand donneur d'électrons de groupe XV neutre ayant un angle de cône d'au moins 160°, et

(iii) du tétrakis (pentafluorophényle borate) de diméthylanilinium, dans un solvant,

dans lequel le composé (a) d'un métal de transition du groupe X est représenté par la formule chimique 1 :

        M(R)2     [Formule chimique 1]

où,

M est un métal de groupe X ; et

R est un ligand choisi dans le groupe constitué par l'acétate et l'acétylacétonate (R"C(O)CHC(O)R") (où R" est de l'hydrogène; un alkyle, alkényle ou vinyle C1 à C20 linéaire ou ramifié; un cycloalkyle C5 à C12 substitué par un hydrocarbure ou non substitué; un aryle C6 à C40 substitué par un hydrocarbure ou non substitué; un aryle C6 à C40 ayant un hétéroatome; un aralkyle C7 à C15 substitué par un hydrocarbure ou non substitué; ou un alkynyle C3 à C20),

dans lequel le composé (b) comprenant un ligand donneur d'électrons de groupe XV neutre ayant un angle de cône d'au moins 160° est représenté par la Formule Chimique 2 ou la Formule Chimique 3 :

        P(R5)3-c[X(R5)d]c     [Formule chimique 2]

X représente l'oxygène, le soufre, le silicium ou l'azote;

c est un nombre entier de 0 à 3 ;

d est 1 si X est de l'oxygène ou du soufre, 3 si X est du silicium, et 2 si X est de l'azote ;

si c est égal à 3 et X représente l'oxygène, deux ou trois groupes R5 peuvent être reliés les uns aux autres par l'intermédiaire de l'oxygène pour former un groupe cyclique; et si c vaut 0, deux groupes R5 peuvent être reliés entre eux pour former un phosphacycle; et

R5 est un hydrogène; un alkyle, alkoxy, allyle, alkényle ou vinyle C1 à C20 linéaire ou ramifié; un cycloalkyle C5 à C12 substitué par un hydrocarbure ou non substitué; un aryle C6 à C40 substitué par un hydrocarbure ou non substitué; un aralkyle C7 à C15 substitué par un hydrocarbure ou non substitué; un alkynyle C3 à C20; un silyle tri (alkyle C1 à C10 linéaire ou ramifié); un silyle tri (alkoxy C1 à C10 linéaire ou ramifié); un silyle tri (cycloalkyle C5 à C12 substitué par un hydrocarbure ou non substitué); un silyle tri (un aryle C6 à C40 substitué ou non substitué avec un hydrocarbure); un silyle tri (aryloxy C6 à C40 substitué ou non substitué avec un hydrocarbure); un siloxy tri (alkyle C1 à C10 linéaire ou ramifié); un siloxy tri (cycloalkyle C5 à C12 substitué ou non substitué avec un hydrocarbure); ou un siloxy tri (un aryle C6 à C40 substitué ou non substitué avec un hydrocarbure), dans lequel chaque substituant peut être en outre substitué par un halogénoalkyle linéaire ou ramifié ou halogène; et

        (R5)2P - (R6)- P(R5)2     [Formule chimique 3]

où,

R5 est le même que défini dans la formule chimique 2; et R6 est un alkyle, alkényle, ou vinyle C1 à C5 linéaire ou ramifié; un cycloalkyle C5 à C12 substitué par un hydrocarbure ou non substitué; un aryle C6 à C20 substitué par un hydrocarbure ou non substitué; ou un aralkyle C7 à C15 substitué par un hydrocarbure ou non substitué.


 
5. Procédé de préparation d'un polymère d'addition à base de norbornène ayant un groupe polaire d'ester ou d'acétyle comprenant la phase de mise en contact d'un monomère à base de norbornène ayant un groupe d'ester ou d'acétyle avec un système catalyseur selon l'une quelconque des revendications 1 à 3, dans le solvant pour réaliser une polymérisation par addition.
 
6. Procédé selon la revendication 5, où le polymère d'addition à base de norbornène est sélectionné parmi un homopolymère à base de norbornène comprenant un groupe d'ester ou d'acétyle ; un copolymère de monomères à base de norbornène comprenant différents groupes d'ester ou d'acétyle ; ou un copolymère de monomère à base de norbornène comprenant un groupe d'ester ou d'acétyle et un monomère à base de norbornène qui ne comprend pas de groupe d'ester ou d'acétyle.
 
7. Procédé de préparation d'un polymère d'addition à base de norbornène selon les revendications 5 ou 6, dans lequel le monomère à base de norbornène ayant un groupe d'ester ou d'acétyle est représenté par la formule chimique 7:

où,

m est un entier de 0 ou 4 ;

au moins l'un de Ri, R2, R3 et R4 est un radical ayant un groupe d'ester ou d'acétyle ;

chacun de l'autre R1, R2, R3 et R4 est de l'hydrogène; un alkyle, alkényle, ou vinyle C1 à C20 linéaire ou ramifié; un cycloalkyle C5 à C12 substitué par un hydrocarbure ou non substitué; un aryle C6 à C40 substitué par un hydrocarbure ou non substitué; un aralkyle C7 à C15 substitué par un hydrocarbure ou non substitué ; un alkynyle C3 à C20 ; ou un halogène ; et

si R1, R2, R3 et R4 ne sont pas des radicaux ayant un groupe d'ester ou d'acétyle, un hydrogène ou un halogène, R1 et R2, ou R3 et R4 peuvent être reliés pour former un groupe alkylidène C1 à C10, ou bien R1 ou R2 peuvent être reliés avec R3 ou R4 pour former un groupe cyclique C4 à C12, saturé ou insaturé ou un groupe aromatique C6 à C17.


 
8. Polymère d'addition à base de norbornène comprenant un groupe d'ester ou d'acétyle préparé selon le procédé selon l'une quelconque des revendications 5 à 7.
 
9. Polymère d'addition à base de norbornène selon la revendication 8, qui est choisi parmi un homopolymère à base de norbornène comprenant un groupe d'ester ou d'acétyle; un copolymère de monomères à base de norbornène comprenant différents groupes d'ester ou d'acétyle; ou un copolymère d'un monomère à base de norbornène comprenant un groupe d'ester ou d'acétyle et d'un monomère à base de norbornène qui ne comprend pas de groupe d'ester ou d'acétyle.
 
10. Polymère d'addition à base de norbornène selon les revendications 8 ou 9, dans lequel le polymère a un poids moléculaire (Mn) de 10.000 à 1.000.000.
 
11. Système catalyseur selon l'une quelconque des revendications 1 à 3, qui comprend:

(a) du Pd(acétylacetonate)2 ou Pd( acétate)2;

(b) de la tricyclohexylphosphine; et

(c) du tétrakis (pentafluorophényle borate) de diméthylanilinium.


 
12. Procédé de préparation d'un catalyseur selon la revendication 4, où le système catalyseur comprend:

(a) du Pd(acétylacétonate)2 ou Pd(acétate)2;

(b) de la tricyclohexylphosphine; et

(c) du tétrakis (pentafluorophényle borate) de diméthylanilinium.


 
13. Procédé selon l'une quelconque des revendications 5 à 7, pour la préparation d'un polymère d'addition à base de nobornène ayant un groupe polaire d'ester ou d'acétyle, le système catalyseur comprenant:

(a) du Pd(acétylacétonate)2 ou Pd(acétate)2;

(b) de la tricyclohexylphosphine; et

(c) du tétrakis (pentafluorophényle borate) de diméthylanilinium.


 
14. Utilisation du système catalyseur selon l'une quelconque des revendications 1 à 3 comme catalyseur pour la polymérisation d'un polymère d'addition à base de norbornène ayant un groupe polaire d'ester ou d'acétyle.
 




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Cited references

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