JP4615248B2 - Method for producing polar group-containing cyclic olefin copolymer - Google Patents

Description

  The present invention relates to a cyclic olefin-alkenyldialkylaluminum copolymer, a cyclic olefin copolymer having a polar group, and a method for producing the same.

  Polynorbornene is one of the most important transparent plastic materials because it has superior heat resistance compared to conventional polyolefin materials, exhibits high transparency and low birefringence, and is used in optical materials such as optical lenses, disks, and optical fibers. It is used in many fields.

  However, while chemically stable, there is a problem such as poor adhesion to other plastic materials and metal thin films due to nonpolarity. In order to solve this problem, many attempts have been made to produce polymers in which polar groups are introduced into polynorbornene.

First, it has been proposed to directly polymerize polar group-containing norbornene in the presence of a ring-opening metathesis polymerization catalyst (see, for example, Patent Documents 1 to 3).
However, the norbornene polymer obtained by such ring-opening metathesis polymerization requires a step of hydrogenation, and the polymerization activity is considerably low and there is room for improvement.

  Next, Non-Patent Document 1 proposes copolymerization of a norbornene derivative and methyl acrylate by atom transfer radical polymerization. The obtained copolymer was a random copolymer, but had a problem of low norbornene content and low molecular weight.

In recent years, attempts have been made to directly polymerize polar monomers without a protecting group by using a late transition metal complex having a low oxygen affinity. For example, Grubbs et al. Copolymerize polar group-containing norbornene and ethylene using a chelate-type complex of nickel (Non-patent Document 2). However, this approach can only yield polyethylene analogs with low norbornene content.
Further, in copolymerization with 1-alkene monomers such as propylene, direct copolymerization of polar monomers is extremely difficult from the viewpoint of copolymerization performance.

  Regarding the copolymerization of polar group-containing norbornene derivatives, there are Non-Patent Document 3, Non-Patent Document 4 and the like using nickel complexes, and Non-Patent Document 5 and the like for palladium complexes. However, the main chain of the copolymer obtained by these methods is composed only of a norbornene skeleton, so that it is difficult to control physical properties.

JP 9-120002 A JP-A-9-221577 JP-A-9-316179 Sharon Elyashiv-Barad, Nils Greinert, and Ayusman Sen.Macromolecules.2002,35,7521 Grubbs, R.Sceience 2000,287,460-462 Guillermo C.Bazan.Macromolecules 2003,36,9731-9735 Brian L. Goodall, Larry F. Rhodes. Macromolecules 2003, 36, 2623-2632 Ayusman Sen.Organomitallics 2001,20,2802-2812

As a result of studying in view of such a situation, the present inventors copolymerized alkenyldialkylaluminum synthesized by various methods with a cyclic olefin such as norbornene to obtain a cyclic olefin-alkenyldialkylaluminum copolymer. Further, by subjecting this copolymer to a post-reaction such as oxidative decomposition using a decomposing agent such as oxygen, a cyclic olefin-based copolymer containing a polar group, preferably a norbornene-based copolymer ( That is, it was found that a norbornene-1-alkene copolymer) can be produced.
The cyclic olefin copolymer containing a polar group obtained by the present invention is not limited to imparting polarity to the cyclic olefin copolymer, but varies depending on the reaction in the polymer side chain using the introduced polar group. It is a very useful copolymer that can be modified with a polymer and can be used to produce a new copolymer.

（式中、Ｒ¹，Ｒ²は炭素数１〜２０のアルキル基、ｎは１〜２０の整数を示す。）

化学式（Ｃ）

（式中，ｎは１〜２０の整数を示す。）

化学式（Ｄ）

（式中、ｎは１〜２０の整数、ＸはＯＨ、ＣＯＯＨ、ＳＯＯＨ又はＳＯＯＯＨ基を示す。） That is, the present invention decomposes a cyclic olefin-alkenyldialkylaluminum copolymer obtained by copolymerizing a cyclic olefin and an alkenyldialkylaluminum compound represented by the chemical formula (A) using a metallocene catalyst or a half metallocene catalyst. A cyclic olefin unit, a unit represented by the chemical formula (C), and a unit represented by the chemical formula (D), wherein the dialkylaluminum group in the copolymer is converted into a polar group by reacting with the agent. And a method for producing a polar group-containing cyclic olefin copolymer having a weight average molecular weight of 1,000 to 1,000,000 .
Chemical formula (A)

(Wherein, R ^1, R ² is an alkyl group having 1 to 20 carbon atoms, n is an integer of 1-20.)

Chemical formula (C)

(In the formula, n represents an integer of 1 to 20.)

Chemical formula (D)

(In the formula, n represents an integer of 1 to 20, and X represents an OH, COOH, SOOH or SOOOH group.)

Moreover, this invention is a manufacturing method of said polar group containing cyclic olefin type copolymer whose n of said Chemical formula (C) and Chemical formula (D) is 2-6, and X of Chemical formula (D) is OH group. Is to provide.
In particular, a copolymer having a polar group content (that is, a unit of the chemical formula D) of 0.1 to 3 mol% or 20 to 50 mol% is also preferable.

  Furthermore, the present invention provides a method for producing the above polar group-containing cyclic olefin copolymer, wherein the decomposition agent is oxygen, carbon dioxide, sulfur dioxide or sulfur trioxide.

  According to the present invention, a polar group-containing cyclic olefin copolymer (preferably a norbornene-alkene copolymer) can be easily produced without using expensive reagents and harsh reaction conditions.

As the polar group of the polar group-containing cyclic olefin copolymer, a hydroxyl group, a carboxyl group, a sulfinyl group or the like can be introduced, and the cyclic olefin unit, the alkene unit, and the content of the alkene unit having a polar group in the copolymer Can be arbitrarily adjusted, and a copolymer suitable for various applications can be provided.
Furthermore, various polymer modifications are possible using the introduced polar group.

[Cyclic olefins]
In the present invention, the cyclic olefin is a monocycloalkene such as cyclopentene or norbornene, and is widely exemplified in, for example, Japanese Patent No. 2868569. In the present invention, norbornene-based cyclic olefin is preferably used. In addition, preferable specific monomers include norbornene, tetracyclododecene, dicyclopentadiene, ethylidene norbornene, 5-methyl-2-norbornene, and the like. Among these, norbornene is preferable.
[Alkenyldialkylaluminum compounds]
In the present invention, the alkenyldialkylaluminum compound copolymerized with the cyclic olefin is represented by the chemical formula (A).
Chemical formula (A)

Wherein, R ^1, R ² is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms. N is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 4 or 6.
Specifically, propenyldiethylaluminum, propenyldiisobutylaluminum, pentenyldiethylaluminum, pentenyldiisobutylaluminum, hexenyldiisobutylaluminum, hexenyldiethylaluminum, octenyldiisobutylaluminum, octenyldiethylaluminum, decenyldiisobutylaluminum, dodecenyldiisobutylaluminum, An example is undecenyl diisobutylaluminum. Among these, hexenyl diisobutylaluminum, hexenyldiethylaluminum, octenyldiisobutylaluminum, and octenyldiethylaluminum are preferable.

[Method for producing alkenyldialkylaluminum compound]
The alkenyldialkylaluminum used in the present invention is a known compound. A commercial item can also be utilized and the compound of Chemical formula (A) can be manufactured by a well-known method. For example, there are hydroalumination reaction of non-conjugated dienes, cross-coupling reaction of alkenyl halide and organoaluminum compound, transmetalation reaction between organometallic compound such as alkenyl lithium and alkenyl magnesium and organoaluminum compound. Among these, a preferred method is a hydroalumination reaction of a nonconjugated diene, and an alkenyldialkylaluminum can be produced by reacting a nonconjugated diene and a dialkylaluminum hydride under mild conditions.

[Copolymerization of cyclic olefin and alkenyldialkylaluminum]
The catalyst for obtaining a copolymer of a cyclic olefin and an alkenyldialkylaluminum is not particularly limited, but a coordination anion type catalyst usually used for polymerization of norbornene can be used.
For example, so-called metallocene catalysts or half metallocenes can be used. Among these, in the present invention, it is preferable to use a half metallocene catalyst from the viewpoint of copolymerization of norbornene and alkenyldialkylaluminum which are bulky cyclic olefins.

Here, the half metallocene catalyst is composed of the following components (a) and (b) and, if necessary, the component (c).
Component (a): a transition metal compound of Groups 4 to 6 of the periodic table having a conjugated five-membered ring ligand and the like.
Component (b): an activator for activating component (a), and examples include (b-1) to (b-4) below.
(B-1) Aluminum oxy compound (b-2) An ionic compound capable of reacting with component (a) to convert component (a) into a cation (b-3) Lewis acid (b-4) Ion exchange layered Silicate component (c): an organoaluminum compound.

（式中、Ｒ¹、Ｒ²およびＲ³は炭素数１〜５のアルキル基を、Ｒ⁴およびＲ⁵は炭素数１〜３のアルキル基もしくはハロゲンを示し、それぞれ同じでも異なっても良い。ＭはＴｉ、ＺｒもしくはＨｆを示す。）
具体的な化合物としては、（ｉ−ＰｒＮＳｉＭｅ₂Ｆｌｕ）ＴｉＭｅ₂、（ｉ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＴｉＭｅ₂、（ｔ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＴｉＭｅ₂、（ｉ−ＰｒＮＳｉＭｅ₂Ｆｌｕ）ＴｉＣｌ₂、（ｉ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＴｉＣｌ₂、（ｔ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＴｉＣｌ₂、（ｉ−ＰｒＮＳｉＭｅ₂Ｆｌｕ）ＺｒＭｅ₂、（ｉ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＺｒＭｅ₂、（ｔ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＺｒＭｅ₂、（ｉ−ＰｒＮＳｉＭｅ₂Ｆｌｕ）ＺｒＣｌ₂、（ｉ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＺｒＣｌ₂、（ｔ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＺｒＣｌ₂、（ｉ−ＰｒＮＳｉＭｅ₂Ｆｌｕ）ＨｆＭｅ₂、（ｉ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＨｆＭｅ₂、（ｔ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＨｆＭｅ₂、（ｉ−ＰｒＮＳｉＭｅ₂Ｆｌｕ）ＨｆＣｌ₂、（ｉ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＨｆＣｌ₂、（ｔ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＨｆＣｌ₂などが挙げられ、好ましくは（ｔ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＴｉＭｅ₂、（ｔ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＺｒＭｅ₂、（ｔ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＨｆＭｅ₂である。本発明において、特に好ましくは下記式（２）で表されるチタニウム錯体［（ｔ−ＢｕＮＳｉＭｅ₂Ｆｌｕ）ＴｉＭｅ₂］である。該チタニウム錯体は、例えば、「Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ、第３１巻、３１８４頁、１９９８年」の記載に基づき、容易に合成することができる。
式（２）

（式中、Ｍｅはメチル基を、ｔ−Ｂｕはターシャリーブチル基を示す。） In the present invention, the metallocene compound represented by the following formula (1) is preferable as the component (a) of the half metallocene catalyst.





Formula (1)

(Wherein R ¹ , R ² and R ³ represent an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ represent an alkyl group having 1 to 3 carbon atoms or halogen, and may be the same or different. M represents Ti, Zr or Hf.)
Specific compounds include (i-PrNSiMe ₂ Flu) TiMe ₂ , (i-BuNSiMe ₂ Flu) TiMe ₂ , (t-BuNSiMe ₂ Flu) TiMe ₂ , (i-PrNSiMe ₂ Flu) TiCl ₂ , (i- BuNSiMe ₂ Flu) TiCl ₂ , (t-BuNSiMe ₂ Flu) TiCl ₂ , (i-PrNSiMe ₂ Flu) ZrMe ₂ , (i-BuNSiMe ₂ Flu) ZrMe ₂ , (t-BuNSiMe ₂ Flu) ZrMe ₂ Flu PrNSiMe ₂ Flu) ZrCl ₂ , (i-BuNSiMe ₂ Flu) ZrCl ₂ , (t-BuNSiMe ₂ Flu) ZrCl ₂ , (i-PrNSiMe ₂ Flu) HfMe ₂ , (i-BuNSiMe ₂ Flu) HfMe ₂ Flu _{BuNSiMe 2 Flu) HfMe 2, (} i-PrN _{iMe 2 Flu) HfCl 2, (} i-BuNSiMe 2 Flu) HfCl 2, is like _{(t-BuNSiMe 2 Flu) HfCl} 2, preferably _{(t-BuNSiMe 2 Flu) TiMe} 2, (t-BuNSiMe 2 Flu) ZrMe _2, a _{(t-BuNSiMe 2 Flu) HfMe} 2. In the present invention, a titanium complex [(t-BuNSiMe ₂ Flu) TiMe ₂ ] represented by the following formula (2) is particularly preferable. The titanium complex can be easily synthesized based on, for example, the description of “Macromolecules, Vol. 31, page 3184, 1998”.
Formula (2)

(In the formula, Me represents a methyl group, and t-Bu represents a tertiary butyl group.)

  The component (b) is preferably alumoxane, borate or borane compound.

  In the present invention, since an alkenyldialkylaluminum compound is used as a comonomer, a polymerization method in which no other organoaluminum compound is used except for the (b-1) aluminumoxy compound used as an activator is also possible. That is, the alkenyldialkylaluminum acts both as a conomer and as an organoaluminum compound of component (c).

[Polymerization method]
In obtaining the copolymer of the present invention, the amount ratio of each monomer in the reaction system does not need to be constant over time, and it is convenient to supply each monomer at a constant mixing ratio. It is also possible to change the mixing ratio over time.
Also, any of the monomers can be added in portions in consideration of the copolymerization reaction ratio.
The object of the present invention is to introduce a unit represented by the chemical formula (B), that is, an alkenyldialkylaluminum unit up to 50 mol%. Here, the raw material charging ratio for obtaining a copolymer containing a large amount of such alkenyldialkylaluminum units will be described. This charging ratio varies depending on the copolymerizability of the catalyst used in the polymerization reaction and the chain length (carbon number) of the aluminum compound. The molar ratio of cyclic olefin to alkenyldialkylaluminum for introducing up to 50 mol% of alkenyldialkylaluminum units is 1: 0.001-1: 10, preferably 1: 0.001-1: 5, More preferably, it is 1: 0.001-1: 2.

As the polymerization mode, any polymerization mode can be adopted as long as the catalyst component and each monomer come into efficient contact. Specifically, a solution polymerization method using an inert solvent or a bulk polymerization method using a cyclic olefin as a solvent can be employed. Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.
In the case of solution polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, and toluene is used alone or as a polymerization solvent. The polymerization temperature is 0 to 200 ° C., and hydrogen can be used as an auxiliary molecular weight regulator.

（式中、Ｒ¹，Ｒ²は炭素数１〜２０のアルキル基、ｎは１〜２０の整数を示す。） [Cyclic olefin-alkenyldialkylaluminum copolymer]
The cyclic olefin-alkenyldialkylaluminum copolymer of the present invention is a structural unit derived from a cyclic olefin in which structural units derived from the alkenyldialkylaluminum represented by the chemical formula (B) are randomly distributed. The unit is 50 to 99.9 mol%, preferably 60 to 99.9 mol%, more preferably 65 to 99.9 mol%, and the unit represented by the chemical formula (B) is 0.1 to 50 mol%, preferably Is a cyclic olefin-alkenyldialkylaluminum copolymer comprising 0.1 to 40 mol%, more preferably 0.1 to 35 mol%. When the number of structural units derived from aluminum is less than 0.1 mol%, it is difficult to obtain the effects (improved dyeability, adhesion, etc.) when dialkylaluminum groups are converted to polar groups. Moreover, when larger than 50 mol%, there exists a problem that the original performance of a polycyclic olefin cannot be taken out.
Chemical formula (B)

(Wherein, R ^1, R ² is an alkyl group having 1 to 20 carbon atoms, n is an integer of 1-20.)

  The preferred range of the structural unit amount derived from aluminum varies depending on the use of the copolymer of the present invention. For applications requiring heat resistance, the content of the unit represented by the chemical formula (B) is preferably not too large, and may be preferably 0.1 to 5 mol%, more preferably 0.1 to 0.1 mol%. It may be 3 mol%. On the other hand, when used as a soft material or a resin additive, it may be preferable that the content of the unit represented by the chemical formula (B) is large, and 20 to 50 mol% may be preferable. .

The content of the alkenyldialkylaluminum compound is determined using C ¹³ -NMR. The measurement conditions are as follows. NMR apparatus: JEOL-La-500 manufactured by JEOL Ltd., measurement temperature: 120 ° C., solvent: 1,1,2,2-tetrachloroethane-d ₂ , pulse angle: 45 °, scan frequency: 10,000, pulse interval 7 seconds. Regarding the determination of the chemical shift of each absorption spectrum, 1,1,2,2-tetrachloroethane can be determined as an internal standard. The chemical shift of 1,1,2,2-tetrachloroethane is 74.47 ppm.

  The cyclic olefin-alkenyldialkylaluminum copolymer of the present invention is very unstable and easily decomposes with moisture or oxygen in the air. Therefore, in the present invention, the polymerization product is reacted with methanol in a nitrogen atmosphere to convert the carbon-aluminum bond to a carbon-hydrogen bond, so that a methine moiety derived from norbornene (around 46 to 54 ppm) and an alkenyldialkyl are obtained. The copolymerization amount of the alkenyldialkylaluminum unit was identified from the area ratio of the absorption spectrum of the methyl group derived from aluminum (around 12 to 15 ppm).

The molecular weight of the cyclic olefin-alkenyldialkylaluminum copolymer represented by the norbornene-alkenyldialkylaluminum copolymer of the present invention is 1,000 to 1,000,000, preferably 3,000 to 800, in terms of weight average molecular weight. 000, more preferably 5,000 to 600,000. The ratio of the weight average molecular weight to the number average molecular weight is not particularly limited, and a wide range can be produced depending on the polymerization conditions, but is generally about 2 to 8.
The weight average molecular weight and number average molecular weight are measured as follows. That is, measurement is performed by a gel permeation chromatography method using 150C manufactured by Waters. Conditions are measurement temperature: 140 ° C., solvent: orthodichlorobenzene, column: two Shodex 80M / S, and calculation of molecular weight is determined from standard polystyrene.

[Polyolefin-containing cyclic olefin copolymer]
The polar group-containing cyclic olefin copolymer of the present invention will be specifically described. This copolymer can be produced by reacting a cyclic olefin-alkenyldialkylaluminum copolymer with various decomposition agents. That is, it can be obtained by converting a dialkylaluminum group (carbon-aluminum bond) in the copolymer into a carbon-polar group bond.
The reaction with the decomposing agent can be carried out according to a known method relating to the reaction between the low molecular weight organoaluminum compound and the inorganic compound. Examples of the decomposing agent include oxygen, peroxide, carbon dioxide, and sulfur oxide.

  Specifically, the dialkylaluminum group can be converted into a hydroxyl group by contacting with oxygen or peroxide and then hydrolyzing, and a hydroxyl group-containing cyclic olefin copolymer can be obtained (example of literature: R. Rienacker and G. Ohloff, Angew. Chem., 1961, 73, 240, P. Tesseire and M. Plattier, Recherches, 1963, 13, 34 [Chem.] Bstr., 1964, 60, 1591). Moreover, it is possible to convert a dialkylaluminum group into a carboxyl group by contacting with carbon dioxide and then hydrolyzing, and a norbornene-based copolymer containing a carboxyl group can be obtained (reference example: K. Zieglar, F. Krupp, K. Weyer and W. Larbig, Liebugs Ann. Chem., 1960, 629, 251). In addition, dialkylaluminum groups can be converted into sulfinyl (SOOH) groups and sulfonyl (SOOOOH) groups by contacting with sulfur dioxide and sulfur trioxide, respectively, and then hydrolyzing. Norbornene copolymers are obtained (examples: K. Zieglar, F. Krupp, K. Weyer and W. Larbig, Liebugs Ann. Chem., 1960,629,251, AJKunchin, LIAkhmetov, VPYur'ev and GATolstikov, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 420, AJRutkowski and AFTurbak, US Pat. 3121737 [Chem. Abstr., 1964, 60, 10550]).

By the way, in this decomposition reaction, the ratio which converts a dialkylaluminum group into a polar group does not necessarily need to be 100%. If necessary, a component having a structure of the chemical formula (C) in which a carbon-aluminum bond is simply hydrolyzed (converted to a carbon-hydrogen bond) can be contained. As a method for such partial decomposition, alcohol or water is mixed when oxygen or carbon dioxide and norbornene-alkenyldialkylaluminum copolymer are brought into contact, and oxygen or carbon dioxide is mixed with alkenyldialkylaluminum. It can be achieved by bringing the content into contact with the content or less (equivalent or less), or changing the temperature or time during the reaction. Furthermore, the structure of (C) can also be introduced by copolymerization of the corresponding 1-alkene.
In the present invention, in the copolymer of cyclic olefin and alkenyldialkylaluminum, the copolymer with 100% of component (C) and 0% of component D due to termination of polymerization with methanol / HCl, that is, does not contain a polar group. A cyclic olefin copolymer can be produced. Moreover, the polar group containing cyclic olefin copolymer which has (C) component and (D) component can be manufactured in one step by stopping superposition | polymerization with oxygen.

The polar group-containing cyclic olefin copolymer of the present invention is a structural unit derived from a cyclic olefin in which structural units represented by chemical formula (C) and chemical formula (D) are randomly distributed. The unit is 50 to 99.9 mol%, preferably 60 to 99.9 mol%, more preferably 65 to 99.9 mol%, and the unit represented by the chemical formula (C) is 0 to 49.9 mol%, preferably Is 0 to 40 mol%, more preferably 0 to 30 mol%, 0.1 to 50 mol%, preferably 0.1 to 40 mol%, more preferably 0.1 to 0.1% by mole of the unit represented by the chemical formula (D). A polar group-containing cyclic olefin copolymer comprising ˜35 mol%.
When the structural unit represented by the chemical formula (D) is less than 0.1 mol%, the effect of the polar group on the dyeability and adhesiveness cannot be obtained. Moreover, when larger than 50 mol%, there exists a problem that the original performance of a polycyclic olefin cannot be taken out.

  By the way, it is considered that the content of the structural unit represented by the chemical formula (C) greatly affects the heat resistance of the copolymer. For this reason, as for content of the structural unit represented by Chemical formula (C), a preferable range changes with uses. For applications requiring high heat resistance, the content of the unit represented by the chemical formula (C) is preferably not too large, and a copolymer of 20 mol% or less, more preferably 10 mol% or less is preferred. There is. If it is larger than 20 mol%, the heat resistance may be adversely affected. However, when used as a soft material or a resin additive, it is preferable that the content of the unit represented by the chemical formula (C) is large, and the content of the unit represented by the chemical formula (C) is 20 A copolymer of ˜50 mol%, preferably 20 to 40 mol% may be preferred.

The content of the structural unit represented by the chemical formula (C) and the chemical formula (D) is the same as the measurement conditions of C ¹³ -N MR described above, and the methine site derived from norbornene (around 46 to 54 ppm), the chemical formula (C ) Derived from a structural unit represented by the formula (D), a methylene group (40 ppm or more) adjacent to the polar group X derived from the structural unit represented by the chemical formula (D). The content of each unit is identified from the area ratio of the absorption spectrum of the group carbon.
Furthermore, the molecular weight of the cyclic olefin copolymer having a polar group of the present invention preferably has a molecular weight in the range described for the cyclic olefin alkenyldialkylaluminum copolymer.

  Hereinafter, the present invention will be described more specifically based on examples. The present invention is not limited to these examples. The measurement of physical properties and reaction raw materials and auxiliaries in the following examples are as follows.

[Measurement method of physical properties]
(1) Measurement of molecular weight and molecular weight distribution Using 150C manufactured by Waters, the molecular weight and molecular weight distribution were measured by gel permeation chromatography. The conditions were measurement temperature: 140 ° C., solvent: orthodichlorobenzene, column: two Shodex 80M / S, and calculation of molecular weight was determined from standard polystyrene.

(2) Measurement of structure and reaction rate of alkenyldialkylaluminum
Measurement by ¹ H-NMR and ¹³ C-NMR: JEOL-La-300 manufactured by JEOL Ltd. was used and subjected to pulse Fourier transform at room temperature.
Measurement by gas chromatography: GC-353 manufactured by GL Sciences Inc. was used, injection sample: 1 μml, injection temperature: 250 ° C., detector: FID, detector temperature, column temperature: 40 ° C. Identification of the composition of the reaction mixture was calculated from the comparison with the retention time of the authentic sample and the peak area of the chromatogram.
(3) Measurement of comonomer content of copolymer
^It was determined by the method described above using ¹³ C-NMR. The measurement conditions are as follows. NMR apparatus: JEOL-La-500 manufactured by JEOL Ltd., measurement temperature: 120 ° C., solvent: 1,1,2,2-tetrachloroethane-d ₂ , pulse angle: 45 °, number of scans: 10,000, pulse interval 7 seconds.
All the reactions in this example were performed under a purified nitrogen atmosphere.

[Raw materials, auxiliaries]
(1) Norbornene: Aldrich Chemical Company, Inc. was dehydrated using calcium hydride and further distilled.
(2) 1,7-octadiene: Tokyo Kasei Co., Ltd. was dehydrated using calcium hydride and further distilled.
(3) Toluene: dehydrated using calcium hydride and further distilled.
(4) Nitrogen, argon: Trace amounts of oxygen and moisture were removed through a packed tower of manganese oxide and molecular sieve 4A.
(5) Diisobutylaluminum hydride: Tosoh Finechem Corporation was used as it was.

Half metallocene catalyst (a) component dimethylsilylfluorenylamide dimethyltitanium; [t-BuNSiMe ₂ Flu]
It was prepared based on the description of “Macromolecules, Vol. 31, 3184, 1998”. It refine | purified by recrystallizing in hexane at -20 degreeC, and it used for superposition | polymerization.
(B) Component Triphenylcarbenium tetrakis (pentafluorophenyl) borate; [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]: A commercial product manufactured by Tosoh Finechem Corporation was used as it was.

[Synthesis of octenyl diisobutylaluminum]
1,7-octadiene (20 ml: 0.14 mol) and diisobutylaluminum hydride (2.5 ml: 0.014 mol) were added to a 50 ml glass reactor equipped with a stirrer and reacted at 60 ° C. for 6 hours. Thereafter, the remaining 1,7-octadiene was removed under reduced pressure to obtain a reaction product. This reaction product was analyzed by gas chromatography and NMR. 0.5 ml of the reaction product was diluted with 2 ml of normal-decane (internal standard), then decomposed by adding distilled water and hydrochloric acid and used for analysis. As a result, it was confirmed that octenyl diisobutylaluminum was quantitatively produced.

[Example 1]
[Copolymerization of norbornene and octenyl diisobutylaluminum]
To a 100 ml glass reactor equipped with a stirrer, toluene and octenyl diisobutylaluminum (0.007 mol) and norbornene (0.036 mol) obtained by the above-described method were added. Here, the amount of toluene added was octenyl diisobutylaluminum and The volume of norbornene and toluene was adjusted so as to be 30 ml. The inside of the reactor was set to 40 ° C. Here, [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] is added as a toluene solution so as to be 20 μmol and [t-BuNSiMe ₂ Flu] is added as 20 μmol, and polymerization is carried out at a temperature of 40 ° C. for 10 minutes. did. Ten minutes later, a small amount of methanol / hydrochloric acid was directly added to terminate the polymerization reaction. The reaction product was filtered off and dried under reduced pressure at 60 ° C. for 6 hours to obtain a norbornene copolymer (norbornene-1-octene copolymer). The weight and physical properties of this copolymer are shown in Table 1.

[Examples 2-3]
The same operation as in Example 1 was carried out except that the amount of octenyl diisobutylaluminum added was changed as shown in Table 1. The yield of the obtained norbornene copolymer and the physical properties of the polymer are shown in Table 1. FIG. 1 (a) shows ¹³ CNMR of Example 3.

（式中、ｘ，ｙ，ｚは、各構成単位の重合度を表す数である。なお、各構成単位はランダムに共重合している。） [Examples 4 to 6]
After 10 minutes of polymerization by the method of Examples 1 to 3, 200 ml of dry oxygen was introduced at room temperature for 1.5 hours. Thereafter, the reaction product was filtered off and dried under reduced pressure at 60 ° C. for 6 hours / hour to obtain a hydroxyl group-containing norbornene copolymer. The physical properties of these copolymers are shown in Table 2.
The structures of these copolymers are as follows, and are copolymers in which a hydroxyl group is substituted at the terminal of a part of 1-octene of the norbornene-1-octene copolymer. FIG. 1 (b) shows ¹³ CNMR of Example 6.

(In the formula, x, y, and z are numbers representing the degree of polymerization of each structural unit. Each structural unit is randomly copolymerized.)

Polynorbornene is one of the most important transparent plastic materials because it has excellent heat resistance compared to conventional polyolefin materials, exhibits high transparency and low birefringence, and is used in optical materials such as optical lenses, disks, and optical fibers. It is used in many fields.
However, the conventional polynorbornene and norbornene-ethylene copolymer are chemically stable, but have problems such as poor adhesion to other plastic materials and metal thin films because they are nonpolar.
The norbornene-based copolymer obtained by the present invention is a cyclic olefin-based copolymer that solves the above-described problems and can be used for various applications that require polarity.

¹³ C-NMR spectra of Examples 3 and (a), a ¹³ C-NMR spectrum of Example 6 (b).

Claims (3)

A cyclic olefin- alkenyldialkylaluminum copolymer obtained by copolymerizing a cyclic olefin and an alkenyldialkylaluminum compound represented by the chemical formula (A) using a metallocene catalyst or a half metallocene catalyst, and a decomposition agent, A cyclic olefin unit, a unit represented by the chemical formula (C), and a unit represented by the chemical formula (D), characterized by converting a dialkylaluminum group in the copolymer into a polar group, and having a weight average A method for producing a polar group-containing cyclic olefin copolymer having a molecular weight of 1,000 to 1,000,000.
Chemical formula (A)

(Wherein, R ^1, R ² is an alkyl group having 1 to 20 carbon atoms, n is an integer of 1-20.)

Chemical formula (C)

(In the formula, n represents an integer of 1 to 20.)

Chemical formula (D)

(In the formula, n represents an integer of 1 to 20, and X represents an OH, COOH, SOOH or SOOOH group.) The method for producing a polar group-containing cyclic olefin copolymer according to claim 1, wherein the decomposing agent is oxygen, carbon dioxide, sulfur dioxide or sulfur trioxide . The manufacturing method of the polar group containing cyclic olefin type copolymer of Claim 1 whose n of the said Chemical formula (C) and Chemical formula (D) is 2-6, and X of Chemical formula (D) is OH group .

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