JP2010511072A5 - - Google Patents

Description

Norbornene polymer or copolymer

  The present invention relates to a polymer or copolymer of a norbornene monomer and a linear olefin compound.

A copolymer of a cyclic olefin monomer such as norbornene and a linear olefin compound is superior in transparency, heat resistance, chemical resistance, mechanical strength and refractive index as compared with existing olefin polymers. Therefore, this copolymer can be used as a camera or DVD pick-up lens, semiconductor or TFT-LCD insulating film, polarizing plate protective film, multichip module, integrated circuit (IC), PCB (printed circuit board; printed circuit board). circuit board), sealing material for electronic materials, or low dielectric coating agent for flat display or optics, film and packaging, etc. It can also be used as material of plastic substrate for realizing flexible display.

  However, in order to use a norbornene copolymer obtained by copolymerizing a norbornene monomer and a linear olefin compound for the above-mentioned applications, high optical properties, refractive index and thermal stability must be ensured. I must. Since the currently known linear olefin-norbornene copolymer has a refractive index of less than 1.5 and a low glass transition temperature (Tg), the physical properties for use in the above-mentioned applications are effectively improved. Not satisfied.

  In general, polymers composed of monomers with a bulky structure tend to have a low glass transition temperature, which has undesirable thermal stability problems and is unsuitable for use as an electronic material. It is considered to be. However, when the present inventors have produced a copolymer with a linear olefin compound by introducing a bulky substituent to a norbornene-based monomer, the glass transition temperature becomes high on the contrary, It was confirmed that the material was excellent in optical characteristics and thermal characteristics, and the present invention was completed.

  That is, the present invention provides a norbornene-based polymer or copolymer having high heat resistance and excellent optical properties even when copolymerized with a linear olefin compound.

  The present invention also provides an optical material excellent in refractive index and light transmittance.

According to one embodiment of the present invention, the norbornene-based copolymer includes a repeating unit represented by the following chemical formula 1.

［式中、Ｒ_１、Ｒ_２およびＲ_３は互いに同じでも異なってもよく、水素原子、炭素数１〜１０の直鎖状もしくは分岐状アルキル基、または炭素数５〜１２の環状アルキル基であるが、Ｒ_１、Ｒ_２およびＲ_３の少なくとも一つは水素原子ではなく、Ｒ_４は

から選ばれ、ここで、Ｒ_５は水素原子、炭素数１〜１０の直鎖状もしくは分岐状アルキル基、または炭素数５〜１２の環状アルキル基であり、ｎは０以上の整数であり、ｍは１、３、４、又は５である。］ <Chemical Formula 1>

[Wherein R ₁ , R ₂ and R ₃ may be the same or different from each other, and are a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 5 to 12 carbon atoms. But at least one of R ₁ , R ₂ and R ₃ is not a hydrogen atom and R ₄ is

Wherein R ₅ is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 5 to 12 carbon atoms, n is an integer of 0 or more, m is 1, 3, 4, or 5 . ]

  In the above aspect, the molar ratio of the norbornene monomer to the linear olefin compound may be 10:90 to 99: 1.

  The norbornene homopolymer or copolymer according to the above embodiment has a glass transition temperature (Tg) of 120 ° C. or higher, a weight average molecular weight (Mw) of 10,000 or higher, and a molecular weight distribution of 1.0 to 4. 0.0.

According to another preferred aspect of the present invention, the optical material includes the norbornene-based copolymer .

The optical material according to the aspect has a refractive index of 1.5 to 1.7, a light transmittance (T) according to the following formula 1 of 0.9 or more , and a thickness of 50 to 500 μm. Can do.

ｌ_０＝基材に対する光の垂直入射強度
ｌ_ａ＝基材による光の吸収強度
ｌ_ｒ＝基材による光の反射強度 <Formula 1>

l ₀ = normal incident intensity of light to the substrate l _a = light absorption intensity by the substrate l _r = light reflection intensity by the substrate

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

  In the present invention, the norbornene-based polymer is a homopolymer or a copolymer containing the repeating unit represented by the chemical formula 1. The norbornene polymer is a polymer of a cyclic norbornene monomer introduced with an ester group and a bulky substituent and a linear olefin compound, and has a weight average molecular weight of 10,000 or more, and a molecular weight distribution. Is 1.0 to 4.0, and the glass transition temperature (Tg) is 120 ° C. or higher.

  At this time, from the viewpoint of the thermal stability of the copolymer, the molar ratio of the norbornene-based monomer to the linear olefin in the produced homopolymer or copolymer is 10:90 to 99: 1, preferably Is 20: 80-95: 5. In particular, the higher the molar ratio of the norbornene monomer, the higher the thermal stability, thereby increasing the glass transition temperature.

  Such a norbornene polymer of the present invention is obtained by copolymerization of a monomer having a structure of the following chemical formula 2 and a linear olefin compound.

［式中、Ｒ_１、Ｒ_２およびＲ_３は、互いに同じでも異なってもよく、水素原子、炭素数１〜１０の直鎖状もしくは分岐状アルキル基、または炭素数５〜１２の環状アルキル基であるが、Ｒ_１、Ｒ_２およびＲ_３の少なくとも一つは水素原子ではなく、Ｒ_４は

から選ばれ、ここで、Ｒ_５は水素原子、炭素数１〜１０の直鎖状もしくは分岐状アルキル基、または炭素数５〜１２の環状アルキル基であり、ｎは０以上の整数である。］ <Chemical formula 2>

[Wherein R ₁ , R ₂ and R ₃ may be the same or different from each other, and are a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 5 to 12 carbon atoms. Wherein at least one of R ₁ , R ₂ and R ₃ is not a hydrogen atom, and R ₄ is

Here, R ₅ is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 5 to 12 carbon atoms, and n is an integer of 0 or more. ]

  The norbornene monomer of formula 2 and the linear olefin compound are charged into an organic solvent together with a catalyst for polymerization.

  At this time, the norbornene monomer of formula 2 and the linear olefin were adjusted so as to satisfy the molar ratio of the norbornene monomer to the linear olefin in the homopolymer or copolymer produced. And put it in.

  The organic solvent is a hydrocarbon solvent. Alternatively, in order to dissolve the adamantyl group-containing norbornene derivative, the alcohol can be used alone or mixed with an organic solvent other than alcohol such as water or tetrahydrofuran, and the alcohol includes methanol, ethanol, Isopropanol, butanol and the like can be used.

  A known metallocene compound can be used as the catalyst.

  The catalyst and the reaction monomer, that is, the monomer of Formula 2 and the linear olefin compound are preferably mixed at a molar concentration ratio of 1: 100 to 1: 10,000.

  In addition to the catalyst, a metallocene compound can be further used as a co-catalyst if necessary.

The polymerization reaction temperature between the linear olefin compound and the norbornene monomer represented by Chemical Formula 2 is maintained at −50 to 100 ° C., preferably −30 to 80 ° C. The polymerization reaction time varies depending on the kind of raw material to be polymerized, the concentration of the catalyst component and the reaction temperature, but is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours. The pressure is preferably set to 0 to ²⁰ kg / cm ² .

  The norbornene-based polymer including the repeating unit represented by Formula 1 manufactured as described above has a weight average molecular weight (Mw) of 10,000 or more. Under normal polymerization conditions, the weight average molecular weight (Mw) is 20,000 to 1,000,000, and the molecular weight distribution is 1.0 to 4.0.

  Since the norbornene-based polymer of the present invention has a glass transition temperature of 120 ° C. or higher, a material having excellent thermal stability can be provided. Since the higher the glass transition temperature, the better the thermal stability, there is no point in limiting the upper limit.

  In the present invention, the “norbornene monomer” includes at least a norbornene (bicyclo [2,2,1] hept-2-ene) unit represented by the following chemical formula 3. Means a monomer containing one.

<Chemical formula 3>

  The norbornene-based monomer represented by Chemical Formula 2 includes, for example, an alkyl group-substituted or unsubstituted cyclopentadiene (CPD), dicyclopentadiene (DCPD), or a mixture thereof, and an alkyl acrylate having an adamantyl group It may be obtained by the Diels-Alder reaction.

  Specifically, an alkyl group-substituted or unsubstituted CPD, DCPD or a mixture thereof and an alkyl acrylate having an adamantyl group are in a molar ratio of 1: 0.5 to 10, preferably 1: 0. It is made to react so that it may become a molar ratio of 5-4.

  At this time, the reaction temperature is 180 to 220 ° C., and the reaction pressure is normal pressure or higher.

  When synthesizing the monomer of Formula 2, a polymerization inhibitor can be added to adjust n to the target value in Formula 2. Specific examples of the polymerization inhibitor include aniline, cyclohexane, phenol, 4-epoxyphenol, nitrobenzene, hydroquinone, benzoquinone, copper dichloride, and 2,2-di (4-tert-octylphenyl) -1-picryl. It is selected from the group consisting of hydrazyl, preferably hydroquinone or benzoquinone, but is not limited thereto.

  The polymerization inhibitor is preferably 1 so that the molar ratio of the alkyl group-substituted or unsubstituted CPD, DCPD or a mixture thereof to the polymerization inhibitor is 1: 0.001 to 0.05. : It is added so that it may become 0.002-0.04.

The monomer thus obtained is represented by Chemical Formula 2, and in Chemical Formula 2, at least one of R _{1 to} R ₃ , particularly R ₁ is not a hydrogen atom. This monomer structure can play a role of increasing the amorphous property of the polymer containing this as a repeating unit and increasing the light transmittance.

  The norbornene-based polymer containing the repeating unit represented by Chemical Formula 1 of the present invention is dissolved in a solvent, and then manufactured into a film or a sheet by a solvent casting method. At this time, the polymer can be used by mixing at least one kind. The manufactured film has a thickness of 50 to 500 μm, and the light transmittance (T) represented by Equation 1 is 0.9 or more.

ｌ_０＝基材に対する光の垂直入射強度
ｌ_ａ＝基材による光の吸収強度
ｌ_ｒ＝基材による光の反射強度
また、前記フィルムまたはシートは、水分吸収率が低くて寸法安定性に優れる。 <Formula 1>

l ₀ = normal incident intensity of light to the substrate l _a = light absorption intensity by the substrate l _r = light reflection intensity by the substrate The film or sheet has a low moisture absorption rate and excellent dimensional stability. .

  Hereinafter, examples of the present invention will be described in more detail. However, these examples are only for explaining the present invention, and do not limit the scope of the present invention.

[Synthesis of norbornene-ester monomer (Synthesis Examples 1-2, Comparative Synthesis Example 1)]

<Synthesis Example 1> Synthesis of 2-methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate DCPD (dicyclopentadiene; Aldrich, 10.2 mL, 0.0757 mol) was added to a 0.25 L autoclave. ), 2-methyl-2-adamantyl methacrylate (42.6 g, 0.18 mol) and hydroquinone (0.83 g, 0.1 mol) were added and reacted at 180 ° C. for 12 hours, and then the reaction product was cooled and distilled. The product was obtained by distillation under reduced pressure at 1 torr using a vacuum pump at 110 ° C. (yield: 25%). The molar ratio (mol%) of exo isomer to endo isomer of this product is 48.5: 51.5.
¹ H-NMR (500MHz, CDCl ₃ ), endo: δ6.20 (dd, 1H), 6.18 (dd, 1H); exo: δ6.12 (m, 2H)

<Synthesis Example 2> Synthesis of 1-adamantyl-5-norbornene-2-methyl-2-carboxylate DCPD (dicyclopentadiene, Aldrich, 10.2 mL, 0.0757 mol), 1- After adding adamantyl methacrylate (40.0 g, 0.18 mol) and hydroquinone (0.83 g, 0.1 mol) and reacting at 200 ° C. for 12 hours, the reaction product was cooled and transferred to a distillation apparatus, and then a vacuum pump was used. The desired product was obtained at 100 ° C. by distillation under reduced pressure at 1 torr (yield: 85%). The molar ratio (mol%) of exo isomer to endo isomer of this product is 40.0: 59.1.
¹ H-NMR (500 MHz, CDCl ₃ ), endo: δ6.18 (dd, 1H), 6.04 (dd, 1H); exo: δ6.12 (dd, 1H), 6.04 (dd, 1H)

<Comparative Synthesis Example 1> Synthesis of norbornene-2-carboxylic acid methyl ester Into a 0.5 L autoclave, DCPD (dicyclopentadiene, Aldrich, 67 mL, 0.5 mol), methacrylate (Aldrich, 94.6 mL, 1.05 mol) and Hydroquinone (2.3 g, 0.02 mol) was added and reacted at 200 ° C. for 12 hours. The reaction product was cooled, transferred to a distillation apparatus, and then distilled at 1 torr using a vacuum pump at 50 ° C. (Yield: 89%). The molar ratio (mol%) of exo isomer to endo isomer of this product is 52.8: 47.2.
¹ H-NMR (500 MHz, CDCl ₃ ), endo: δ6.17 (dd, 1H), 5.91 (dd, 1H); exo: δ6.09 (m, 2H)

[Synthesis of linear olefin compound and norbornene polymer (Examples 1 to 10, Comparative Example 1)]

<Example 1>
On the top of a 1 L glass polymerization vessel having a stirrer, the concentration of 2-methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate obtained in Synthesis Example 1 was 7.0 mol / L. A catalyst (eg, 7.0 × 10 ⁻³ mol / L of a toluene solution of Cp ₂ ZrCl ₂ ) is supplied to the toluene solution, and an auxiliary catalyst (eg, 0.2 mol / L of methylaluminum oxane (MAO)) is supplied. Of toluene solution) was continuously fed. 15 L of ethylene was supplied to the upper part of the polymerization vessel over 1 hour, and polymerization was carried out for 1 hour while maintaining the polymerization temperature at 30 ° C.
Table 1 below shows the yield, composition, molecular weight and molecular weight distribution of the obtained polymer, and the glass transition temperature measured with TGA (Thermogravimetric Analyzer) and DSC (Differential Scanning Calorimeter). Indicated.

<Example 2>
Polymerization was performed in the same manner as in Example 1 except that 30 L of ethylene was supplied over 1 hour.
The yield, composition, molecular weight (Mw) and molecular weight distribution of the obtained polymer, and glass transition temperature (Tg) measured by TGA (thermal mass analyzer) and DSC (differential calorimeter) are shown in Table 1 below. It was.

<Example 3>
Polymerization was carried out in the same manner as in Example 1 except that 60 L of ethylene was supplied over 1 hour.
The yield, composition, molecular weight and molecular weight distribution of the obtained polymer, and the glass transition temperature measured by TGA (thermal mass analyzer) and DSC (differential calorimeter) are shown in Table 1 below.

<Example 4>
Instead of 2-methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate, 1-adamantyl-5-norbornene-2-methyl-2-carboxylate obtained in Synthesis Example 2 was used. Except for the above, polymerization was carried out in the same manner as in Example 1.
The yield, composition, molecular weight (Mw) and molecular weight distribution of the obtained polymer, and glass transition temperature (Tg) measured by TGA (thermal mass analyzer) and DSC (differential calorimeter) are shown in Table 1 below. It was.

<Example 5>
Polymerization was carried out in the same manner as in Example 4 except that 30 L of ethylene was supplied over 1 hour.
The yield, composition, molecular weight (Mw) and molecular weight distribution of the obtained polymer, and glass transition temperature (Tg) measured by TGA (thermal mass analyzer) and DSC (differential calorimeter) are shown in Table 1 below. It was.

<Example 6>
Polymerization was carried out in the same manner as in Example 4 except that 60 L of ethylene was supplied over 1 hour.
The yield, composition, molecular weight (Mw) and molecular weight distribution of the obtained polymer, and glass transition temperature (Tg) measured by TGA (thermal mass analyzer) and DSC (differential calorimeter) are shown in Table 1 below. It was.

<Example 10>
On the top of a 1 L glass polymerization vessel having a stirrer, the concentration of 2-methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate obtained in Synthesis Example 1 was 7.0 mol / L. A toluene solution of norbornene-2,3-dicarboxylic acid anhydride (manufactured by Aldrich) having a concentration of 7.0 mol / L and each norbornene monomer are mixed in a 1: 1 ratio with the toluene solution, and a catalyst (for example, , 7.0 × 10 ⁻³ mol / L Cp ₂ ZrCl ₂ in toluene solution) and cocatalyst (for example, 0.2 mol / L methylaluminum oxide (MAO) in toluene solution) are continuously fed. did. 15 L of ethylene was supplied to the upper part of the polymerization vessel over 1 hour, and polymerization was carried out for 1 hour while maintaining the polymerization temperature at 30 ° C.
The yield, composition, molecular weight (Mw) and molecular weight distribution of the obtained polymer, and the glass transition temperature (Tg) measured by TGA (thermal mass analyzer) and DSC (differential calorimeter) are shown in Table 1 below. .

<Comparative Example 1>
The same as Example 1 except that norbornene-2-carboxylic acid methyl ester synthesized in Comparative Synthesis Example 1 was used instead of 2-methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate Polymerization was carried out by the method.
The yield, composition, molecular weight (Mw) and molecular weight distribution of the obtained polymer, and the glass transition temperature (Tg) measured by TGA (thermal mass analyzer) and DSC (differential calorimeter) are shown in Table 1 below. .

注：^１）１Ｈ−ＮＭＲの積分値による結果である。
^２）ポリスチレンを標準として、溶媒はＴＨＦを使用する。
^３）重量平均分子量を数平均分子量で割った値である。

Notes: ¹⁾ Results are based on ¹ H-NMR integration.
^{2) Using} polystyrene as a standard, the solvent is THF.
³⁾ A value obtained by dividing the weight average molecular weight by the number average molecular weight.

[Production of film]

<Examples 11 to 20, Comparative Example 2>
Films were produced using the polymers obtained in Examples 1 to 10 and Comparative Example 1, respectively. Specifically, an organic solvent was mixed with each of the polymers obtained from Examples 1 to 10 and Comparative Example 1 according to the composition shown in Table 2 to prepare a coating solution. The coating solution was cast on a glass substrate using an applicator (YOSHMITSUYBA-4), dried at room temperature for 1 hour, and further dried at 100 ° C. for 18 hours in a nitrogen atmosphere. After drying, the film was placed at −10 ° C. for 10 seconds, and then the film on the glass substrate was peeled off with a knife. Examples 11 to 20 having a thickness shown in Table 2 and a uniform thickness with a deviation of less than 5% And the transparent film of the comparative example 2 was obtained.

<Physical property evaluation>
(1) Light transmittance Each of the films obtained in Examples 11 to 20 and Comparative Example 2 was measured using a haze meter (NIPPONDENSHOKU 300A), the normal incident intensity of light to the substrate at 400 to 800 nm, Absorption intensity and reflection intensity were measured, and the light transmittance (T) was determined from Equation 1. The results are shown in Table 3.

ｌ_０＝基材に対する光の垂直入射強度
ｌ_ａ＝基材による光の吸収強度
ｌ_ｒ＝基材による光の反射強度
（２）屈折率 <Formula 1>

l ₀ = normal incident intensity of light to the substrate l _a = light absorption intensity by the substrate l _r = light reflection intensity by the substrate (2) Refractive index

  The refractive index of each film obtained in Examples 11 to 20 and Comparative Example 2 was measured with an Abbe refractometer at 25 ° C. using a sodium light source. The measurement results are shown in Table 3.

上記評価結果より、バルキーな置換基を含むノルボルネン系単量体と直鎖状オレフィン化合物とを共重合した共重合体の場合、バルキーな置換基を有さないノルボルネン系単量体を使用した比較例の場合よりガラス転移温度が増加したことが分かる。重合体におけるノルボルネン系単量体のモル比が高いほどガラス転移温度が増加した。

From the above evaluation results, in the case of a copolymer obtained by copolymerizing a norbornene monomer containing a bulky substituent and a linear olefin compound, a comparison using a norbornene monomer having no bulky substituent is used. It can be seen that the glass transition temperature has increased compared to the example. The higher the molar ratio of norbornene monomer in the polymer, the higher the glass transition temperature.

  In addition, the film produced by copolymerizing a norbornene monomer containing a bulky substituent and a linear olefin compound is compared to the case where a norbornene monomer having no bulky substituent is used. It can be seen that light transmission and refractive index increase.

  Therefore, even when a linear olefin compound and a norbornene monomer are copolymerized, thermal stability can be increased and more excellent optical properties can be provided.

  As described above, the present invention provides a norbornene homopolymer or copolymer obtained by copolymerizing a norbornene monomer having a bulky substituent and a linear olefin compound. Accordingly, the norbornene-based homopolymer or copolymer is excellent in heat resistance and optical properties, and is suitable for use as a heat resistant optical component material and an electronic component material.

Claims (6)

Norbornene copolymer containing a repeating unit represented by the following chemical formula 1:
<Chemical Formula 1>

[Wherein R ₁ , R ₂ and R ₃ may be the same or different from each other, and are a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 5 to 12 carbon atoms. Wherein at least one of R ₁ , R ₂ and R ₃ is not a hydrogen atom, and R ₄ is

Wherein R ₅ is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 5 to 12 carbon atoms, n is an integer of 0 or more, m is 1 , 3, 4 or 5. ]. The norbornene-based copolymer according to claim 1, wherein the molar ratio of the norbornene-based monomer to the linear olefin compound is 10:90 to 99: 1. The norbornene copolymer according to claim 1, wherein the glass transition temperature (Tg) is 120 ° C or higher. The optical material containing the norbornene-type copolymer of any one of Claims 1-3 . The optical material according to claim 4 , wherein the refractive index is 1.5 to 1.7. The optical material according to claim 5, wherein the light transmittance (T) according to the following formula 1 satisfies 0.9 or more and the thickness is 50 to 500 µm.
<Formula 1>

l ₀ = normal incident intensity of light on the substrate l _a = light absorption intensity by the substrate l _r = light reflection intensity by the substrate.