KR101142687B1 - Preparation method of polynobornene including polar substituents - Google Patents

Abstract

The present invention relates to a method for producing a norbornene-based resin comprising a polar functional group, by providing a method for producing a norbornene-based resin comprising the step of polymerizing a norbornene-based monomer having a polar functional group in the presence of a solvent and a nickel-based catalyst In addition, there is an effect that the norbornene-based polymer containing a polar functional group can be produced in high yield by using a small amount of a catalyst having a simple structure and low cost.

Norbornene, catalyst, nickel

Description

Preparation method of norbornene-based resin containing a polar functional group {Preparation method of polynobornene including polar substituents}

The present invention relates to a method for producing a norbornene-based resin comprising a polar functional group, and more particularly to a method for producing a norbornene-based resin to polymerize a norbornene-based compound containing a polar group using a nickel catalyst under a polar solvent.

In general, inorganic materials such as silicon oxide and silicon nitride have been mainly used as materials for insulating materials. However, there is an increasing need for a smaller and more efficient device. Accordingly, a polymer having low dielectric constant and hygroscopicity, excellent metal adhesion, strength, thermal stability, light transmittance, and high glass transition temperature is required.

Currently, polyimide and BCB (bis-benzocyclobutenes) are used as low dielectric materials for electronic materials. The polyimide is widely used as an electronic material because of its excellent thermal stability and oxidation stability, high glass transition temperature, and excellent mechanical properties. However, the corrosion of the material due to the high water absorption rate, increased dielectric constant, anisotropic electrical properties, the need for pretreatment to reduce the reaction with copper wire and adhesion to the metal has been a problem. In addition, the BCB has a moisture hygroscopicity and a dielectric constant lower than that of polyimide, but has a problem in that metal adhesion is not good and curing at high temperature is required.

Cyclic olefin polymer is a polymer produced by polymerization of cyclic olefin monomers such as norbornene, and has excellent transparency, heat resistance, and chemical resistance, and has low birefringence and water absorption rate as compared with existing olefin polymers. Therefore, this is an insulating film of a semiconductor or TFT-LCD, a polarizer protective film, multichip modules, an integrated circuit (IC), a printed circuit board, an encapsulant of an electronic material or a flat panel display. Alternatively, the present invention may be used as a low dielectric coating agent, film, and packaging for optics, and may also be used as a material of a plastic substrate for implementing flexible displays.

Polymerization technology of the cyclic olefin polymer may include Ring Opening Metathesis Polymerization (ROMP), Ring opening metathesis polymerization followed by hydrogenation (HROMP), copolymerization and homopolymerization with ethylene, metallocene compounds, Ni, Pd- Transition metal catalysts such as compounds are used. These catalysts show different polymerization characteristics and polymer structure through the change of core metal, ligand, and catalyst composition.

However, the polymer produced by the ROMP has a problem that the glass transition temperature is low, thermal stability and oxidative stability is greatly reduced because it contains one double bond per monomer repeat unit. Accordingly, there have been attempts to make a stable main chain by hydrogenating the ROMP polymer with a catalyst such as Pd or Raney-Ni, but this also has a limit of decreasing thermal stability and an increase in manufacturing cost.

In the case of using a metallocene catalyst-based zirconium-based catalyst, it has been reported that a polymer having a small molecular weight distribution is produced in copolymerization with an ethylene-based monomer (Plastic News, Feb. 27, 1995, p24). The higher the content of the cyclic monomer, the lower the activity of the catalyst, thereby reducing the molecular weight.

On the other hand, when considering as a candidate material of the substrate material of the flexible display in the future using the excellent optical properties of the norbornene-based resin, in addition to the above-mentioned thermal stability, it should be excellent in adhesion with the metal. That is, the adhesion to metal materials such as silicon, nitride, alumina, copper, aluminum, gold, silver, platinum, titanium, nickel and the like should be excellent. Therefore, a research into introducing a substituent having a polarity in the polymer structure as a method for improving this performance is being actively conducted.

In the case where the cyclic olefin monomer contains a polar functional group such as an ester group, the polar functional group increases the intermolecular packing and increases the adhesion to the metal substrate or other polymers. Polymerization or copolymerization of norbornene containing ester groups has been of constant interest because it can be usefully used in the US (US Pat. No. 3,330,815, EP 045755A2, US Pat. No. 5,705,503, US Pat. No. 6,455,650).

Norbornene-based monomers incorporating polar functional groups have two structural isomers, endo isomers and exo isomers, as shown in Chemical Formulas 6 and 7.

<Formula 6>

<Formula 7>

Generally, however, endo isomers are mainly present than exo isomers, and the endo isomers tend to reduce the activity of the catalyst used in the polymerization. Therefore, it is not easy to introduce polar functional groups into a polymer composed of hydrocarbons.

U.S. Patent No. 3,330,815 discloses that the polymer obtained when polymerizing a cyclic monomer with substituents has a low molecular weight. In order to solve this problem, US Pat. No. 5,179,171 describes a method of introducing a monomer having a substituent later in the polymerization process, but thermal stability, physical and chemical properties, and adhesion are not improved. In addition, a method of reacting a substituent with the base polymer has been devised, but it is difficult to control the substituents introduced into the base polymer.

On the other hand, when the norbornene or norbornene-ester monomers were prepared by cationic [Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ catalysts, the polymerization yield was low and only exo isomers tended to be selectively polymerized. (Sen, A .; Lai, T.-WJAm. Chem. Soc. 1981, 103, 4627-4629).

As a polymerization method of either after activation of the palladium compound as co-catalyst, or was used as a catalyst, such as _{[Pd (RCN) 4] [} BF 4] 2, U.S. Patent No. 5,705,503 discloses activating a palladium compound as AgBF ₄ or AgSbF ₆ This is described.

In the case of polymerizing norbornene containing such an ester group, the catalyst has a complicated structure, and the catalyst should be used in an excess of about 1/100 to 1/400 of the monomer, and the polymerization yield is low. It is difficult to remove the residue.

Therefore, the conventional polymerization method of the norbornene-based polymer containing a polar functional group shows a low polymerization yield and a low molecular weight, there is a problem that an excess catalyst should be used to increase the yield.

In view of the above problems, an object of the present invention is to provide a polymerization method capable of producing a norbornene-based polymer containing a polar functional group in high yield.

Another object of the present invention is to provide a polymerization method which can be easily polymerized by using a small amount of a catalyst having a simpler structure and a cheaper structure in order to polymerize a norbornene-based polymer including a polar functional group.

The present invention for achieving the above object is a method for producing a norbornene-based resin comprising the step of polymerizing a solvent and a norbornene-based monomer having a polar functional group in the presence of a catalyst selected from the nickel-based catalyst represented by the formula (1) to To provide.

<Formula 1>

NiX ₂

(Wherein, X is a halogen atom or an alkyl group having 1 to 10 carbon atoms.)

<Formula 2>

(R ¹ NiX) ₂

(In the above formula, wherein X is a halogen atom or an alkyl group having 1 to 10 carbon atoms, and R ¹ is an allyl group having 3 to 12 carbon atoms.)

<Formula 3>

R ² _m NiX ₂

(Wherein, X is a halogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a nitrile group or a cyclodiene group, m is 1 or 2.)

The catalyst is characterized in that the content of 0.1 ~ 1mol% relative to the norbornene monomer content.

The solvent is characterized in that the alcohol alone or a mixed solvent with water or an organic solvent other than alcohol.

The volume ratio of the alcohol and water or an organic solvent other than alcohol and alcohol is 1: 0.1 to 10.

The norbornene-based monomer having a polar functional group is characterized by having a structure of the formula (4).

<Formula 4>

,

,

,

,

및

중 선택된 구조이되, R³, R⁴, R⁵ 및 R⁶ 중 적어도 하나는

,

,

,

,

및

중에서 선택된 구조이고, 여기서 R은 수소 원자 또는 탄소수 1~10의 사슬형 또는 고리형 알킬기를 의미한다.)(Wherein n is an integer of 1 to 5, R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different hydrogen atoms, linear or cyclic alkyl groups having 1 to 20 carbon atoms, aromatic substituents,

,

,

,

,

And

Selected structure, wherein at least one of R ³ , R ⁴ , R ⁵ and R ⁶

,

,

,

,

And

Wherein R is a hydrogen atom or a chain or cyclic alkyl group having 1 to 10 carbon atoms.)

The polymerization reaction is characterized in that for 1 to 24 hours to react at 20 ~ 100 ℃.

Hereinafter, the present invention will be described in more detail.

The norbornene-based resin of the present invention is prepared by adding a solvent to the catalyst, adding a norbornene-based monomer having a polar group while maintaining the temperature at 20 to 100 ° C, and reacting for 1 to 24 hours.

In this case, a nickel catalyst having a structure selected from NiX ₂ , (R ¹ NiX) _2, and R ² _m NiX ₂ is used, wherein X is a halogen atom or an alkyl group having 1 to 10 carbon atoms, and R ¹ is carbon number. It is an allyl group of 3-12, R <^2> is a nitrile group or a cyclodiene group, and m is 1 or 2. Specific examples of such a catalyst include nickel chloride (NiCl ₂ ), nickel bromide (NiBr ₂ ), nickel iodide (NiI ₂ ), allyl nickel chloride dimer (allyNiCl) ₂ , and dichlorobisacetonitrile nickel (NiCl ₂ (CH _2). CN) ₂ ), dichlorobisbenzonitrile nickel (NiCl ₂ (C ₆ H ₅ CN) ₂ ), and the like.

The content of the catalyst is preferably 0.1 to 1 mol% based on the norbornene-based monomer content.

Norbornene-based monomer having a polar group used in the present invention has a structure of formula (4).

<Formula 4>

,

,

,

,

및

중 선택된 구조로서, 여기서 R은 수소 원자 또는 탄소수 1~10의 사슬형 또는 고리형 알킬기를 의미한다.Wherein n is an integer of 1 to 5, R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different hydrogen atoms, linear or cyclic alkyl groups of 1 to 20 carbon atoms, aromatic substituents,

,

,

,

,

And

Wherein R is a hydrogen atom or a chain or cyclic alkyl group having 1 to 10 carbon atoms.

Herein, 'norbornene-based monomer' means a norbornene (bicyclo [2,2,1] hept-2-ene) unit as shown in Formula 5 below. It means a compound containing at least one.

<Formula 5>

The norbornene-based monomer represented by Formula 4 is obtained by, for example, reacting a cyclopentadiene (CPD), a dicyclopentadiene (DCPD) or a mixture thereof with an alkyl group substituted or unsubstituted with an acrylate compound having 1 to 20 carbon atoms. Can be.

On the other hand, the solvent used in the present invention may be used alone or by mixing alcohol with an organic solvent such as water or tetrahydrofuran, methanol, ethanol, isopropanol, butanol and the like can be used as the alcohol. In the case where the alcohol and the organic solvent are mixed and used, the volume ratio of the alcohol and the organic solvent is preferably 1: 0.1 to 10.

The norbornene-based resin prepared may have a number average molecular weight (Mn) of 10,000 or more, the molecular weight distribution is 1.0 to 3.0, the yield is 40% or more.

Hereinafter, examples of the present invention will be described in more detail, but the scope of the present invention is not limited to these examples.

&Lt; Example 1 >

As a catalyst, 3 ml of ethanol was added to 0.13 g (1.0 mmol) of nickel chloride (NiCl ₂ ), and 50 g of 5-norbornene-2-carboxylic acid methyl ester was added and reacted for 12 hours while maintaining the temperature at 60 ° C. After cooling the temperature of the reactor to room temperature, the reaction mixture was added dropwise to excess methanol dropwise to precipitate a precipitate. The precipitated precipitate was filtered off and dried in a vacuum oven at 60 ° C. for 24 hours to obtain a homopolymer of 5-norbornene-2-carboxylic acid methyl ester. The obtained polymer was dissolved in 5 ml of ethanol, and again added dropwise into excess methanol to precipitate a precipitate, which was then filtered and purified through vacuum drying. The result was 40g (80%), molecular weight 50,000 and MWD 1.7.

<Example 2>

The polymerization was carried out in the same manner as in Example 1, except that 0.26 g (2.0 mmol) of nickel chloride (NiCl ₂ ) was used as the catalyst. The result was 42 g (84%), molecular weight 35,000 and MWD 2.0.

<Example 3>

Polymerization was carried out in the same manner as in Example 1, except that 0.22 g (1.0 mmol) of nickel bromide (NiBr ₂ ) was used as the catalyst. As a result, the yield was 41 g (82%), molecular weight 52,000 and MWD 1.8.

<Example 4>

Allyl nickel chloride dimer ((allyNiCl) ₂ ) as a catalyst in Example 1 Polymerization was carried out in the same manner, except that 0.106 g (0.58 mmol) was used. The result was 43 g (86%), molecular weight 43,500 and MWD 2.0.

Example 5

Polymerization was carried out in the same manner as in Example 1, except that 0.15 g (0.58 mmol) of dichlorobisacetonitrile nickel (NiCl ₂ (CH ₂ CN) ₂ ) was used as a catalyst. The result was 43 g (86%), molecular weight 52,000 and MWD 1.92.

<Example 6>

Polymerization was carried out in the same manner as in Example 1, except that 50 g of 5-norbornene-2-methyl-2-carboxylic acid methyl ester was used instead of 5-norbornene-2-carboxylic acid methyl ester. The result was 42 g (84%), molecular weight 45,000 and MWD 1.6.

<Example 7>

Polymerization was carried out in the same manner as in Example 1, except that 50 g of N, N-dimethyl-5-norbornene-2-carboxylic acid amide was used instead of 5-norbornene-2-carboxylic acid methyl ester. The result was 37g (74%), molecular weight 47,000 and MWD 1.6.

<Example 8>

The polymerization was carried out in the same manner as in Example 1, except that isopropyl alcohol was used instead of ethanol as a solvent. As a result, the yield was 40 g (80%), molecular weight 51,500 and MWD 1.7.

Example 9

The polymerization was carried out in the same manner as in Example 1, except that ethanol and tetrahydrofuran were mixed in a ratio of 1: 2 instead of ethanol as a solvent. The result was 39 g (78%), molecular weight 49,500 and MWD 1.7.

<Example 10>

The polymerization was carried out in the same manner as in Example 1, except that the reaction temperature was 78 ° C. As a result, the yield obtained 30g (60%), molecular weight 35,500, and MWD 1.7.

Comparative Example 1

As a catalyst, ₂ ml (35 mmol) of ethanol (EtOH) was added to 0.104 (0.58 mmol) of palladium chloride (PdCl ₂ ), and 20 g of 5-norbornene-2-carboxylic acid methyl ester was added while maintaining the temperature at 50 ° C. The reaction was carried out for 12 hours. After the polymerization was completed the reaction mixture was added dropwise to excess methanol. The resulting precipitate was washed twice with methanol, filtered and dried in a vacuum oven at 60 ° C. for 12 hours to obtain a homopolymer of 5-norbornene-2-carboxylic acid methyl ester. As a result, the yield was 8.2 g (41%), the molecular weight was 34,000, and the MWD was 1.8.

Comparative Example 2

Polymerization was carried out in the same manner as in Comparative Example 1, except that 20 g of N, N-dimethyl-5-norbornene-2-carboxylic acid amide was used instead of 5-norbornene-2-carboxylic acid methyl ester, and N was used. A homopolymer of, N-dimethyl-5-norbornene-2-carboxylic acid amide was obtained. As a result, the yield was 7.4 g (37%), the molecular weight was 42,000 and the MWD was 2.1.

As a result of the experiment, it can be seen that when producing a norbornene-based polymer containing a polar functional group by the production method of the present invention, a high molecular weight polymer can be obtained in a higher yield than the comparative example.

As described above, the present invention is an invention having the effect of producing a high molecular weight and a high yield of a norbornene-based polymer containing a polar functional group by using a small amount of a simple and inexpensive catalyst.

Claims (6)

And polymerizing the norbornene-based monomer having a polar functional group in the presence of a solvent and a catalyst selected from the nickel-based catalysts represented by the following Chemical Formulas 1 to 3, The solvent is a method of producing a norbornene-based resin, characterized in that the solvent alone or a mixed solvent with water or an organic solvent other than alcohol. <Formula 1> NiX ₂ Wherein X is a halogen atom or an alkyl group having 1 to 10 carbon atoms. <Formula 2> (R ¹ NiX) ₂ Wherein X is a halogen atom or an alkyl group having 1 to 10 carbon atoms, and R ¹ is an allyl group having 3 to 12 carbon atoms. <Formula 3> R ² _m NiX ₂ In the above formula, X is a halogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a nitrile group or a cyclodiene group, and m is 1 or 2. The method of claim 1, The catalyst is a method for producing a norbornene-based resin, characterized in that the content of 0.1 ~ 1mol% with respect to the norbornene-based monomer content. delete The method of claim 1, A method of producing a norbornene-based resin, characterized in that the volume ratio of the alcohol with water or an organic solvent other than alcohol with alcohol is 1: 0.1 to 10. The method of claim 1, The norbornene-based monomer having a polar functional group has a structure of the formula (4) below. <Formula 4>

Wherein n is an integer of 1 to 5, R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different hydrogen atoms, linear or cyclic alkyl groups of 1 to 20 carbon atoms, aromatic substituents,

,

,

,

,

And

Selected structure, wherein at least one of R ³ , R ⁴ , R ⁵ and R ⁶

,

,

,

,

And

Wherein R is a hydrogen atom or a chain or cyclic alkyl group having 1 to 10 carbon atoms.) The method of claim 1, The polymerization reaction is a method for producing a norbornene-based resin, characterized in that carried out for 1 to 24 hours at 20 ~ 100 ℃.