KR100503374B1 - Addition polymers derived from pauson-khand type norborbene monomers and preparation method therof - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to cyclic olefin polymers, in particular cyclic olefin addition polymers of norbornene-based compounds comprising norbornene derivatives made using the poson-cant reaction, and methods for their preparation, in particular of the phoson-cant type novo Provided are a cyclic olefin addition polymer of a nene compound and a norbornene compound and a process for producing the same.

Description

Polycyclic olefin polymer having a poson-cant-type norbornene-based monomer and a method for preparing the same {{ADDITION POLYMERS DERIVED FROM PAUSON-KHAND TYPE NORBORBENE MONOMERS AND PREPARATION METHOD THEROF}

FIELD OF THE INVENTION The present invention relates to cyclic olefin polymers, and more particularly to cyclic olefin addition polymers of norbornene-based compounds comprising norbornene derivatives made using a poson-cant reaction and methods for their preparation.

The copolymer of norbornene-based compound has low dielectric constant and hygroscopicity, excellent transparency, and high glass transition temperature (Tg> 200 ℃), so it can be used for insulating films, multichip modules, and integrated circuits of semiconductors and TFT-LCDs. (IC), an encapsulant for electronic materials, a flat panel display or a low dielectric coating for optical applications, or a film or packaging. Currently, polyimide, bis-benzocyclobutenes (BCB), and the like are used as low dielectric materials for electronic materials, and polymethylmethacrylate (PMMA) and polycarbonate (PC) are used for optical materials.

However, polyimide, despite thermal stability and oxidation stability, high glass transition temperature, and good mechanical properties, pretreatment to reduce corrosion and increase of dielectric constant, anisotropic electrical properties, and reaction with copper wire due to high water absorption. The necessity and the adhesion to metal are pointed out as problems. BCB has a moisture hygroscopicity and a dielectric constant lower than that of polyimide, but has poor metal adhesion, and has a problem of curing at high temperature to obtain desired physical properties. In this case, physical properties are affected by curing time and temperature.

Copolymers of the cyclic olefins have a high hydrocarbon content and have a low dielectric constant and low hygroscopic properties. Methods of polymerizing cyclic monomers include ring opening metathesis polymerization (ROMP), ring opening metathesis polymerization followed by hydrogenation (HROMP), copolymerization with ethylene, and homogeneous polymerization.

The copolymer of the cyclic olefin synthesized by ROMP has a disadvantage in that thermal stability and oxidative stability are greatly decreased due to the unsaturation of the main chain, and the use thereof is a thermoplastic resin or a thermosetting resin, especially a reaction injection molding to a circuit board. It is known to be used (US Pat. No. 5,011,730).

In order to overcome the disadvantages of resins synthesized by ROMP, a method of hydrogenating resins is known. Hydrogenation generally increases the glass transition temperature of the ROMP polymer by about 50 ° C. However, the increased cost and the weak mechanical properties of the polymers, which result from the increased synthesis stages, are hindering the commercial application of these polymers.

In the case of addition polymerization through copolymerization with ethylene, a product called Topas was introduced by a company called Ticona, Germany, using a metallocene catalyst, and apel (Apel) using a homogeneous vanadium catalyst. The product was launched by Mitsui in Japan. However, this method has a disadvantage in that the copolymer thus produced does not have a functional group and thus has low hardness and metal adhesion. In addition, the use of zirconium-based metallocene catalysts have been reported to yield high molecular weight polymers with a low molecular weight distribution (Plastic News, Feb. 27, 1995, p. 24). However, as the concentration of the cyclic monomer increases, the activity decreases, and the copolymer shows a disadvantage of low glass transition temperature (Tg <240 ° C). In addition, even if the thermal stability is increased, the mechanical strength is weak, there is a disadvantage that the chemical resistance to a hydrocarbon solvent or a halogenated hydrocarbon solvent is low.

Since 1990, a homopolymerization of norbornene using a zirconium-based metallocene catalyst has been reported by Kaminsky, but the norbornene polymer produced at this time has very high crystallinity, does not dissolve in general organic solvents, shows no glass transition temperature, and pyrolysis. No further studies have been conducted (Kaminsky, W .; Bark, A .; Drake, I. Stud. Surf. Catal. 1990, 56, 425). Polymerization of norbornene-based monomers using post-transition metal catalysts has already been reported in 1977 (Gaylord, NG; Deshpande, AB; Mandal, BM; Martan, MJ Macromol. Sci.-Chem. 1977, A11 (5), 1053- 1070). In the case of polymerizing norbornene using a post-transition metal, an appropriate functional group may be introduced into the copolymer, and the resulting copolymer is soluble in an organic solvent and has high glass transition temperature and high transparency.

However, since there is a limitation in the synthesis of norbornene-based monomers through the organic chemical synthesis method, the production of norbornene copolymers having various functional groups is not easy. In addition, when introducing a functional group through a Diels Alder reaction, as shown in Scheme 1, the introduced functional group generates an indistinguishable mixture of endo / exo. In this case, norbornene having an endo structure is known to be significantly less reactive than a monomer having an exo structure depending on the catalyst, so that a substituent may be selectively introduced at the exo position. I need a way.

Scheme 1

In view of the above problems, the present invention has a low dielectric constant, low hygroscopicity, high glass transition temperature, excellent thermal stability and oxidation stability, excellent chemical resistance and toughness, and excellent metal adhesion. An object is to provide an olefin addition polymer and a method for producing the same.

It is still another object of the present invention to provide a cyclic olefin addition polymer having excellent optical properties and a process for producing the same.

It is still another object of the present invention to provide a cyclic olefin addition polymer used in a film such as a low dielectric coating agent constituting an electronic material such as an integrated circuit or a multi-chip module or a packaging requiring a barrier property, and a manufacturing method thereof It is.

It is still another object of the present invention to provide a cyclic olefin addition polymer that adheres well to a substrate of an electronic material and a method for preparing the same.

In order to achieve the above object, the present invention provides a cyclic olefin addition homopolymer of a poson-cant type norbornene-based compound, and a cyclic olefin addition copolymer of a norsonene-based compound and a norbornene-based compound of the poson-cant type and these It provides a method for producing.

Hereinafter, the present invention will be described in detail.

The present invention relates to an addition homopolymer of a poson-cant-type norbornene-based compound (cyclic monomer), and a norsonene-based compound (cyclic monomer) of poson-cant type and another norbornene-based compound (cyclic type) It is to provide an addition copolymer (monomer).

A cyclic norbornene-based compound or norbornene-based derivative means a monomer including at least one norbornene unit such as Chemical Formula 3a.

[Formula 3a]

Thus, the simplest monomer of the present invention is bicyclo [2,2,1] hept-2-ene called norbornene.

The norsonene-based compound (cyclic monomer) of the poson-cant type of the present invention means a monomer represented by the following formula (1) or (2).

[Formula 1]

In the formula of Formula 1,

k is an integer from 0 to 4;

R ¹ and R ² are each independently or simultaneously hydrogen; halogen; Linear or branched alkyl of 1 to 20 carbon atoms, alkoxy, alkoxy alkyl, alkoxy silyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, vinyl; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Alkynyl having 3 to 20 carbon atoms; Or a radical comprising sulfur;

When R ¹ and R ² are not hydrogen or halogen, they are connected to each other to form an alkylidene group having 1 to 10 carbon atoms; Saturated or unsaturated cyclic groups of 3 to 12 carbon atoms; Or an aromatic cyclic compound having 6 to 17 carbon atoms;

Radicals containing sulfur include SR ″, R′SR ″, SSR ″, R'SSR ″, S (═O) R ″, R ′S (═O) R ″, , , R'C (= S) R ", R'C (= S) SR", R'SO ₃ H, R'N = C = S, R'NNC (= S) R ", , , , , , or Is,

Indicated on the radical containing each of said sulfur

R 'and R' '' are each independently linear or branched alkyl having 1 to 20 carbon atoms, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, or vinyl ; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms;

Each R ″ is independently hydrogen; halogen; linear or branched alkyl of 1 to 20 carbon atoms, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, or vinyl; hydrocarbon Cycloalkyl of 5 to 12 carbon atoms, substituted or unsubstituted, aryl of 6 to 40 carbon atoms, substituted or unsubstituted, aralkyl of 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; or Alkynyl having 3 to 20 carbon atoms;

When R ″ is not hydrogen or halogen, it may be linked to R ′ to form a cyclic group, where each n is 0 or 1 and each n ′ and n ″ are an integer from 1 to 10; .

[Formula 2]

In Chemical Formula 2,

Each L is, independently or simultaneously, an integer from 0 to 4;

R ⁶ is alkyl diradical; Aryl diradicals; Alkoxy alkyl diradicals; Alkoxy silyl diradicals; Or alkenyl diradical;

R ⁴ , and R ⁵ are each independently or simultaneously hydrogen; halogen; Linear or branched alkyl of 1 to 20 carbon atoms, alkoxy, alkoxy alkyl, alkoxy silyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, vinyl; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl substituted or unsubstituted with hydrocarbon having 7 to 15 carbon atoms; Alkynyl having 3 to 20 carbon atoms; Or a radical containing sulfur,

R ⁴ and R ⁵ , when not hydrogen or halogen, are connected to each other to form an alkylidene group having 1 to 10 carbon atoms; Saturated or unsaturated cyclic groups of 3 to 12 carbon atoms; Or may form an aromatic cyclic compound having 6 to 17 carbon atoms,

The radical containing sulfur is as defined in Formula 1 above.

The addition polymer of the present invention includes an addition homopolymer of a monomer represented by Formula 1 or 2, and a random copolymer of a monomer represented by Formula 1 or 2 and a monomer represented by Formula 3 below.

[Formula 3]

In the formula (3),

m is an integer from 0 to 4,

R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently or simultaneously hydrogen; halogen; Linear or branched alkyl of 1 to 20 carbon atoms, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, or vinyl; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms,

When R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are not hydrogen or halogen, R ¹¹ and R ¹² , or R ¹³ and R ¹⁴ may be connected to each other to form an alkylidene group having 1 to 10 carbon atoms. Or R ¹¹ , or R ¹² is R ¹³ , and R ¹⁴ A saturated or unsaturated cyclic group having 4 to 12 carbon atoms connected to any one of the groups; Or an aromatic cyclic compound having 6 to 17 carbon atoms.

Such additive polymers are prepared using post-transition metal catalysts such as nickel or palladium.

The polymers of the invention comprise monomers of the poson-cant type and the amount is from 0.1 to 100 mol%.

The polymer system for preparing the addition polymer of the present invention comprises a poson-cant type monomer, or at least one type of poson-cant type monomer and the norbornene-based monomer of Formula 3 as a catalyst of a group VIII metal compound. Prepared by polymerization under a catalyst system. The polymer system is prepared by mixing a monomer to be polymerized in a solvent, a catalyst, and a cocatalyst if necessary, and polymerizing it from the reaction mixture as in a conventional polymerization method.

The temperature at which the polymerization reaction of the present invention proceeds is -100 to 200 ° C, preferably -60 ° C to 90 ° C, or more preferably -10 to 80 ° C. At this time, it is preferable to select a solvent whose boiling point is higher than the polymerization temperature.

The molecular weight (Mn) of the polymer of the present invention is preferably between 10,000 and 1,000,000.

The present invention provides an addition polymer comprising a exo-selective monomer of the poson-cant type, so that various functional groups can be introduced when preparing the polymer according to the present invention. More importantly, in general, when the introduced functional group is an endo, it is known that the polymerization or copolymerization yield is remarkably reduced when polymerizing or copolymerizing monomers having functional groups substituted with these endo. Since the monomer of the poson-cant type according to the present invention provides exo-selective monomers, it is possible to significantly increase the degree of polymerization or copolymerization when polymerizing or copolymerizing them.

To explain the method for synthesizing the monomer of the poson-cant type of the present invention is shown in Scheme 2.

Scheme 2

Norbonadiene and various alkynes were used to synthesize the norbornene derivatives of Formula 1a to Formula 1i in high yield using a poson-cant reaction. This material has one functional group, and the pentagram has a form of cyclopentenone. The addition of a second functional group in 1,4-addition by attacking the lithium copper nucleophile is possible in high yield.

The advantages of the method used in the present invention are firstly, because the reaction is a catalytic reaction, which is advantageous for experiments on a large scale. Second, various alkyne and nucleophiles can be used for various changes. And third, norbornene monomer derivatives are in exo conformation, which is known to favor norbornene polymerization.

Examples of monomers synthesized according to the present invention are as follows.

[Formula 1a] [Formula 1b]

[Formula 1c] [Formula 1d]

[Formula 1e] [Formula 1f]

[Formula 1g] [Formula 1h]

Formula 1i]

According to the method of the present invention, an alkyl or a polar functional group can be easily introduced into a monomer according to the purpose, and thus a polymer having new physical properties can be synthesized. In other words, the norbornene-based derivatives obtained by the poson-cant reaction according to the present invention can introduce various functional groups, and by controlling these functional groups, the cyclic olefin copolymers can be prepared without adding additional norbornene-based derivatives during copolymerization. It can increase the physical properties (hardness, metal adhesion, etc.).

Therefore, the cyclic olefin addition polymer of the present invention has a low dielectric constant, low hygroscopicity, high glass transition temperature, excellent thermal stability and oxidative stability, excellent chemical resistance and toughness, Excellent metal adhesion. In addition, it has excellent optical properties, can be attached to substrates of electronic materials without coupling agents, and has low dielectric coating or barrier properties that make up electronic materials such as integrated circuits or multichip modules. It can also be used for such necessary packaging.

The present invention will be described in more detail with reference to the following examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

All operations dealing with air or water sensitive compounds were carried out using standard Schlenk techniques or dry box techniques.

Nuclear magnetic resonance spectra were obtained using a Bruker 300 spectrometer, ¹ H NMR at 300 MHz and ¹³ C NMR at 75 MHz.

IR spectra were recorded using Shimadzu IR-470.

The molecular weight and molecular weight distribution of the copolymer were measured using gel permeation chromatography (GPC), in which polystyrene samples were used as standard.

Thermal analyzes such as TGA and DSC were performed using a TA Instrument (TGA 2050) (heating rate 10 K / min). HRMS was measured at the Interuniversity center natural science facility at Seoul National University.

Toluene was purified by distillation in potassium / benzophenone (potassium / benzophenone), CH ₂ Cl ₂ was dried in P ₂ O ₅ and purified by CaH ₂ again.

Preparation Example 1

(Synthesis of Monomer (3-butyl-2-pentyl-2,3,3a, 4,7,7a-hexahydro-4,7-methano-inden-1-one) of Formula 1b)

1-heptine (1-heptyne; 2.0 ml, 15 mmol), norbornadien (2.5 ml, 2.25 mmol), Co ₂ (CO) ₈ (35 mg, 1 mol%) and CH ₂ Cl ₂ 20 ML was added to a stainless steel reactor. The reactor was filled with carbon monoxide, pressurized to 30 atm, and reacted at 130 ° C. for 18 hours. After cooling the reactor to room temperature, carbon monoxide was discharged and the solution was filtered. The filtered solution was evaporated to dryness and separated using a chromatography method on a silica gel column. At this time, the developing solution (eluting solution) was used a mixed solution of hexane / ethyl acetate (v / v 10: 1). The developing solution was removed to yield 3.0 g of product (yield: 92%).

This product was dissolved in 5 ml of ether and then placed in ⁿ Bu ₂ CuLi (prepared by reacting 14.5 ml of 2.5 M ⁿ BuLi with 3.5 g CuI) dissolved in 30 ml ether at -78 ° C. The reaction was stirred for 5 hours while heating to room temperature. 5 ml of cold water was added to the reactant, and the organic layer was separated after passing through a Celite pad. The water layer again extracted the remaining product using 20 mL of ether. The ether solution thus extracted and the ether solution separated previously were combined, and the combined solution was dried using anhydrous magnesium sulfate. The dried solution was evaporated, and then separated by chromatography on silica gel using nucleic acid / ethyl acetate (v / v 15: 1) as a developing solution to obtain a compound of formula 1b as a final product in a yield of 85%.

1 H NMR (CDCl ₃ ) 6.19 (m, 1 H), 6.13 (m, 1 H), 3.12 (br s, 1 H), 2.71 (br s, 1 H), 2.30 (m, 1 H), 2.20 ( br, 1H), 1.89 (br, 1H), 1.70 (br, 1H), 1.56 (m, 2H), 1.41-1.20 (m, 11H), 1.10 (m, 1H), 0.96 ( m, 3H), 0.89 (m, 3H) ppm;

13 C NMR (CDCl ₃ ) 219.1, 138.7, 137.8, 59.7, 54.8, 48.6, 47.4, 45.1, 45.0, 36.8, 30.1, 29.6, 27.9, 23.5, 23.4, 14.5, 14.3 ppm;

IR CO 1730 cm −1;

HRMS M + calcd. 261.2218, obsd. 261.2216.

Manufacture example 2-9

In the same manner to prepare a compound of Formula 1a and Formulas 1c to 1i with the remaining compounds.

(Compound of Formula 1a)

¹ H NMR (CDCl ₃ ) 6.10 (m, 1 H), 6.05 (m, 1 H), 3.02 (br s, 1 H), 2.65 (br s, 1 H), 2.07 (m, 1 H), 1.74 (t, 8.0 Hz, 1 H), 1.50 (m, 1 H), 1.36-1.18 (m, 7 H), 1.15 (d, 6.5 Hz, 3 H), 0.99 (d, 9.3 Hz, 1 H), 0.82 (t, 6.7 Hz, 3 H) ppm; ¹³ C NMR (CDCl ₃ ) 216.0, 137.5, 136.6, 59.8, 53.3, 48.0, 45.9, 44.2, 43.6, 39.4, 28.5, 26.4, 22.4, 20.3, 13.3 ppm; IR CO 1730 cm −1; HRMS M + calcd. 219.1749, obsd. 219.1742.

(Compound of Formula 1c)

¹ H NMR (CDCl ₃ ) 6.19 (m, 1 H), 6.12 (m, 1 H), 3.11 (br s, 1 H), 2.70 (br s, 1 H), 2.29 (d, 9.1 Hz, 1 H ), 2.19 (br, 1 H), 1.89 (br, 1 H), 1.69 (br, 1 H), 1.56 (m, 2 H), 1.44-1.25 (m, 13 H), 1.07 (d, 9.1 Hz , 1 H), 0.95 (t, 6.8 Hz, 3 H), 0.88 (t, 6.8 Hz, 3 H) ppm; ¹³ C NMR (CDCl ₃ ) 218.7, 138.2, 137.3, 59.3, 54.3, 48.1, 46.9, 44.6, 44.5, 36.3, 32.1, 29.6, 27.6, 26.6, 22.9, 22.4, 14.0, 13.9 ppm; IR CO 1732 cm-1; HRMS M + calcd. 275.2375, obsd. 275.2372.

(Compound of Formula 1d)

¹ H NMR (CDCl ₃ ) 6.11 (m, 1 H), 6.03 (m, 1 H), 3.40 (br s, 1 H), 3.03 (br s, 1 H), 2.20 (d, 9.0 Hz, 1 H ), 2.15 (br, 1 H), 1.85 (m, 1 H), 1.63 (m, 1 H), 1.48 (m, 2 H), 1.40-1.14 (m, 15 H), 0.98 (d, 9.1 Hz , 1 H), 0.87 (t, 6.6 Hz, 3 H), 0.80 (t, 6.5 Hz, 3 H) ppm; ¹³ C NMR (CDCl ₃ ) 218.1, 138.1, 137.2, 59.2, 54.2, 48.0, 46.9, 44.5, 36.3, 31.6, 29.0, 27.6, 26.9, 22.9, 22.5, 13.9, 13.8 ppm; IR CO 1732 cm-1; HRMS M + calcd. 289.2531, obsd. 289.2525.

(Compound of Formula 1e)

¹ H NMR (CDCl ₃ ) 7.32 (t, 5.9 Hz, 2 H), 7.25 (t, 5.9 Hz, 1 H), 7.04 (d, 6.0 Hz, 2 H), 6.25 (m, 1 H), 6.19 ( m, 1 H), 3.43 (d, 12.0 Hz, 1 H), 3.26 (br s, 1 H), 2.82 (br s, 1 H), 2.48 (d, 9.1 Hz, 1 H), 2.05 (t, 8.3 Hz, 1 H), 1.79 (m, 1 H), 1.6201.22 (m, 8 H), 0.86 (t, 6.8 Hz, 3 H) ppm; ¹³ C NMR (CDCl ₃ ) 215.4, 138.4, 137.6, 137.4, 128.8, 128.5, 127.0, 67.1, 54.6, 48.0, 47.9, 46.5, 44.9, 44.7, 35.8, 29.6, 22.9, 13.9 ppm; IR CO 1732 cm-1; HRMS M + calcd. 281.1905, obsd. 281.1913.

(Compound of Formula 1f)

¹ H NMR (CDCl ₃ ) 6.18 (m, 1 H), 6.13 (m, 1 H), 4.11 (m, 1 H), 3.60 (d, 4.5 Hz, 2 H), 3.09 (br s, 1 H) , 2.97 (br, 1 H), 2.70 (br s, 1 H), 2.29 (d, 8.1 Hz, 1 H), 2.20 (br, 1 H), 2.02 (d, 4.1 Hz, 2 H), 1.91 ( br, 1H), 1.70 (br, 1H), 1.54-0.88 (m, 14H) ppm; ¹³ C NMR (CDCl ₃ ) 218.7, 138.0, 137.0, 125.7, 61.9, 60.1, 59.1, 54.1, 47.2, 46.7, 44.5, 44.4, 44.2, 36.0, 32.6, 29.4, 26.9, 22.9, 22.7, 13.8 ppm; IR CO 1723 cm −1; HRMS M + calcd. 277.2168, obsd. 277.2173.

(Compound 1 g)

¹ H NMR (CDCl ₃ ) 7.77 (d, 8.3 Hz, 2 H), 7.33 (d, 8.2 Hz, 2 H), 6.19 (m, 1 H), 6.12 (m, 1 H), 4.01 (t, 6.4 Hz, 2 H), 3.10 (br s, 1 H), 2.70 (br s, 1 H), 2.45 (s, 3 H), 2.28 (d, 8.9 Hz, 1 H), 2.20 (br, 1 H) , 1.89-0.95 (m, 19 H) ppm; ¹³ C NMR (CDCl ₃ ) 218.3, 144.6, 138.2, 137.2, 133.0, 129.7, 127.8, 70.3, 58.9, 54.2, 47.9, 46.8, 44.6, 44.5, 44.4, 36.2, 29.5, 29.1, 26.9, 22.9, 22.8, 21.5 , 14.0 ppm; IR CO 1724 cm −1; HRMS M + calcd. 431.2256, obsd. 431.2250.

(Compound of Formula 1h)

¹ H NMR (CDCl ₃ ) 7.57 (d, 6.0 Hz, 4 H), 7.25 (m, 6 H), 6.11, m, 1 H), 6.03 (m, 1 H), 3.58 (t, 5.5 Hz, 2 H), 3.03 (br s, 1 H), 2.62 (br s, 1 H), 2.20 (d, 9.1 Hz, 1 H), 2.10 (br, 1 H), 1.80 (m, 1 H), 1.62 ( m, 1H), 1.48-1.18 (m, 14H), 0.96 (s, 9H), 0.86 (t, 6.5 Hz, 3H) ppm; ¹³ C NMR (CDCl ₃ ) 219.2, 138.7, 137.7, 135.9, 134.5, 129.9, 128.0, 64.1, 59.8, 54.8, 48.7, 47.5, 45.3, 45.1, 36.9, 33.3, 30.2, 28.0, 27.3, 23.7, 23.5, 19.6 , 14.6 ppm; IR CO 1728 cm −1; HRMS M + calcd. 515.3345, obsd. 515.3333.

(Compound of Formula 1i)

¹ H NMR (CDCl ₃ ) 6.12 (m, 4 H), 6.04 (m, 4 H), 3.03 (br s, 4 H), 2.63 (br s, 4 H), 2.20 (d, 9.0 Hz, 4 H ), 2.10 (br, 4H), 1.81 (m, 4H), 1.61-1.18 (m, 14H), 0.98 (d, 9.0 Hz, 4H), 0.90-0.85 (m, 6H) ppm; ¹³ C NMR (CDCl ₃ ) 218.6, 138.2, 137.3, 59.2, 54.3, 48.0, 46.8, 44.6, 44.5, 44.4, 36.3, 30.3, 29.6, 27.6, 27.5, 26.8, 26.7, 22.9, 14.0 ppm; IR CO 1729 cm −1; HRMS M + calcd.477.3733, obsd.477.3736.

Example 1

(Polymerization of Compound of Formula 1b-Preparation of Homopolymer)

In a dry box, the compound of Formula 1b (1.2 g, 4.6 mmol) prepared in Preparation Example 1 was dissolved in 5 ml of a mixed solution of CH ₂ Cl ₂ and toluene (v / v. 1: 1). 8.4 mg of [(C ₃ H ₅ ) PdCl] ₂ and 10 mg of AgBF ₄ were reacted in a mixed solution of 4 ml of CH ₂ Cl ₂ and toluene (v / v. 1: 1), followed by filtering to prepare a palladium catalyst. It was.

The monomer solution was added to this palladium catalyst. After the solution was stirred at room temperature for 18 hours, methanol was added to stop the reaction. The resulting polymer was separated by a filter, washed with methanol and dried in vacuo to yield 1.18 g of polymer.

The analysis result of this homopolymer is as follows.

¹ H NMR (CDCl ₃ ) 2.9-1.7 (br m), 1.7-1.28 (max.)-1.1 (br m), 0.88 (br s) ppm; ¹³ C NMR (CDCl ₃ ) 225-215 (br m), 60-25 (br m), 22.5 (br s), 14.1 (br s) ppm.

Examples 2-9

In the same manner as in Example 1, the homopolymer was prepared by polymerizing the remaining compounds of Formula 1a and the compounds of Formulas 1c to 1i.

Analysis results of each homopolymer are as follows.

(Homopolymer of Formula 1a)

¹ H NMR (CDCl ₃ ) 2.9-1.7 (br m), 1.7-1.30 (max.)-1.1 (br m), 0.89 (br s) ppm; ¹³ C NMR (CDCl ₃ ) 225-215 (br m), 60-25 (br m), 23.1 (br s), 13.9 (br s) ppm.

(Homopolymer of Formula 1c)

¹ H NMR (CDCl ₃ ) 2.9-1.7 (br m), 1.7-1.26 (max.)-1.1 (br m), 0.87 (br s) ppm; ¹³ C NMR (CDCl ₃ ) 225-215 (br m), 60-25 (br m), 22.7 (br s), 14.1 (br s) ppm.

(Homopolymer of Formula 1d)

¹ H NMR (CDCl ₃ ) 2.9-1.7 (br m), 1.7-1.29 (max.)-1.1 (br m), 0.89 (br s) ppm; ¹³ C NMR (CDCl ₃ ) 225-215 (br m), 60-25 (br m), 23.1 (br s), 14.0 (br s) ppm.

(Homopolymer of Formula 1e)

¹ H NMR (CDCl ₃ ) 7.6-7.25 (max.)-7.1 (br m), 7.1-6.97 (max) -6.5 (br m), 3.6-1.6 (br m), 1.6-1.21 (max.)- 0.9 (br m), 0.9-0.83 (max.)-0.5 (br s) ppm; ¹³ C NMR (CDCl ₃ ) 225-215 (br m), 60-25 (br m), 22.9 (br s), 14.1 (br s) ppm.

(1 g of homopolymer)

¹ H NMR (CDCl ₃ ) 7.64 (br s), 7.34 (br s), 3.8-3.63 (max.)-3.4 (br m), 2.9-1.7 (br m), 1.7-1.33 (max.)-1.1 (br m), 1.03 (br s) ppm; ¹³ C NMR (CDCl ₃ ) 225-215 (br m), 135.5 (br s), 133.9 (br s), 129.5 (br s), 127.5 (br s), 65-62 (br m), 60-20 (br m), 26.8 (br s), 19.2 (br s), 14.1 (br s) ppm.

(Homopolymer of Formula 1h)

¹ H NMR (CDCl ₃ ) 7.75 (br s), 7.33 (br s), 4.203.98 (max.)-1.7 (br m), 3.46 (br s), 1.7-1.35 (max.)-1.1 (br m), 0.93 (br s) ppm; ¹³ C NMR (CDCl ₃ ) 225-215 (br m), 60-25 (br m), 25-23.2 (max.)-20, 21.6 (br s), 14.1 (br s) ppm.

Physical properties of each homopolymer are shown in Table 1 below.

division Mw Mn Mw / Mn IR (CO) yield(%) Example 2 Homopolymer of Formula 1a 28400 15100 1.88 1731 98 Example 1 Homopolymer of Formula 1b 22400 12800 1.75 1730 93 Example 3 Homopolymer of Formula 1c 17800 10500 1.70 1728 90 Example 4 Homopolymer of Formula 1d 27300 15400 1.77 1729 82 Example 5 Homopolymer of Formula 1e 15200 9600 1.58 1733 87 Example 6 Homopolymer of Formula 1f - - - - n.r. Example 7 Homopolymer of Formula 1g 12500 8400 1.49 1727 92 Example 8 Homopolymer of Formula 1h 17200 11200 1.54 1726 80 Example 9 Homopolymer of Formula 1i - Insoluable - - 98

(Metal adhesion test)

In order to test the metal adhesion of the homopolymers of Formulas 1a, 1b, 1c, 1d, 1g, and 1h in the polymers polymerized in Examples 1 to 9, each polymer was dissolved in mesitylene at 5% by weight, followed by chromium. A glass plate coated with a pattern of, aluminum, and tungsten was coated to a thickness of 0.317 μm. The thin films were separated into square lattice shapes of 5 x 5 mm in width and length, followed by a 180 ° tape test. Test results showed that one of the nine gratings was not liberated by the tape from the patterned glass plate.

Examples 10-11

(Copolymerization of Compound of Formula 1b and Compound of Formula 3a-Preparation of Copolymer)

As shown in Table 2, a copolymer was obtained in the same manner as in Example 1 except that the copolymer of the poson-cant-type monomer and norbornene was changed only in the monomer.

Here, Example 10 polymerized a compound of Formula 1b and a compound of Formula 3a in a molar ratio of 1: 1, and Example 11 polymerized a compound of Formula 1b and a compound of Formula 3a in a molar ratio of 1: 5. Physical properties of each copolymer are shown in Table 2 below.

division Molar ratio Mw Mn Mw / Mn IR (CO) yield(%) Example 10 Copolymers of Formula 1b and Formula 3a 1: 1 65700 12500 5.27 1727 98 Example 11 Copolymers of Formula 1b and Formula 3a 1: 5 153800 25400 6.06 1726 98

The analysis results of each copolymer are as follows.

(Copolymer obtained by polymerizing the compound of Formula 1b of Example 3 and the compound of Formula 3a in a molar ratio of 1: 1)

¹ H NMR (CDCl ₃ ) 2.9-1.7 (br m), 1.7-1.33 (max) -1.1 (br m), 0.89 (br s) ppm; ¹³ C NMR (CDCl 3) 225-215 (br m), 60-25 (br m), 23.1 (br s), 13.9 (br s) ppm.

(Copolymer obtained by polymerizing the compound of Formula 1b of Example 4 and the compound of Formula 3a in a molar ratio of 1: 5)

¹ H NMR (CDCl ₃ ) 2.9-2.36 (max) -1.7 (br m), 1.7-1.33 (max) -1.1 (br m), 0.89 (br s) ppm; 13 C NMR (CDCl 3) 225-215 (br m), 60-25 (br m), 23.1 (br s), 13.9 (br s) ppm.

(Metal adhesion test)

In the polymers polymerized in Examples 10 to 11, 5 wt% of the polymer prepared for testing metal adhesion properties of the copolymers of Formulas 1a and 3a was dissolved in mesitylene, and then the patterns of chromium, aluminum, and tungsten were The coated glass plate was coated to a thickness of 0.317 μm. The thin films were separated into square lattice shapes of 5 x 5 mm in width and length, followed by a 180 ° tape test. As a result of the test, the copolymer of Example 11 having a low content of Formula 3a was not liberated by the tape from the lattice patterned glass plate of one of the nine lattice patterns. In addition, the copolymer of Example 10 having a high content of Formula 3a was liberated by a tape from a glass plate in which two of the nine gratings were patterned, but the remaining seven gratings were not released.

The polymer of the norbornene-based compound having a poson-cant-type functional group prepared according to the present invention has excellent transparency, excellent barrier properties, and can be applied as a transparent material and a packaging material, and an insulating electronic material. The dielectric constant is low enough to be used, and the like, and has excellent thermal stability and strength, and thus has excellent hardness and adhesion to metal.

Claims (6)

A cyclic olefin addition copolymer of a compound represented by the following formula (1) and a compound represented by the following formula (3): [Formula 1] In the formula of Formula 1, k is an integer from 0 to 4; R ¹ and R ² are each independently or simultaneously hydrogen; halogen; Linear or branched alkyl having 1 to 20 carbon atoms, alkoxy, alkoxy alkyl, alkoxy silyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, or vinyl; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Alkynyl having 3 to 20 carbon atoms; Or SR ", R'SR", SSR ", R'SSR", S (= O) R ", R'S (= O) R", , , R'C (= S) R ", R'C (= S) SR", R'SO ₃ H, R'N = C = S, R'NNC (= S) R ", , , , , , or Phosphorus containing radicals; When R ¹ and R ² are not each hydrogen or halogen, they are connected to each other to form an alkylidene group having 1 to 10 carbon atoms; Saturated or unsaturated cyclic groups of 3 to 12 carbon atoms; Or may form an aromatic cyclic compound having 6 to 17 carbon atoms, Each n indicated in the radical containing each sulfur defined in R ¹ and R ² is 0 or 1, each n ′, and n ″ are an integer from 1 to 10; R 'and R' '' are each independently linear or branched alkyl having 1 to 20 carbon atoms, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, or vinyl ; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms; Each R ″ is independently hydrogen; halogen; linear or branched alkyl of 1 to 20 carbon atoms, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, or vinyl; hydrocarbon Cycloalkyl of 5 to 12 carbon atoms, substituted or unsubstituted, aryl of 6 to 40 carbon atoms, substituted or unsubstituted, aralkyl of 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; or Alkynyl having 3 to 20 carbon atoms, When R ″ is not hydrogen or halogen, it may be linked to R ′ to form a cyclic group; [Formula 3] In the formula (3), m is an integer from 0 to 4; R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently or simultaneously hydrogen; halogen; Linear or branched alkyl of 1 to 20 carbon atoms, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, or vinyl; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms; When R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are not hydrogen or halogen, R ¹¹ and R ¹² , or R ¹³ and R ¹⁴ may be connected to each other to form an alkylidene group having 1 to 10 carbon atoms. Or R ¹¹ , or R ¹² is R ¹³ , and R ¹⁴ A saturated or unsaturated cyclic group having 4 to 12 carbon atoms connected to any one of the groups; Or an aromatic cyclic compound having 6 to 17 carbon atoms. The method of claim 1, The compound represented by Formula 1 is a compound represented by Formula 1a, a compound represented by Formula 1b, a compound represented by Formula 1c, a compound represented by Formula 1d, a compound represented by Formula 1e, A cyclic olefin addition copolymer selected from the group consisting of a compound represented by 1f, a compound represented by the following Chemical Formula 1g, and a compound represented by the compound represented by the following Chemical Formula 1h: [Formula 1a] [Formula 1b] [Formula 1c] [Formula 1d] [Formula 1e] [Formula 1f] [Formula 1g] [Formula 1h] delete delete In the method for producing a cyclic olefin addition copolymer of a compound represented by the formula (1) and a compound represented by the formula (3), a) at least one norbornene-based monomer selected from the group consisting of compounds represented by the following formula (1); And b) at least one norbornene-based monomer represented by formula (3) Copolymerizing under a catalyst system of a Group VIII metal compound Manufacturing method comprising: [Formula 1] In the formula of Formula 1, k is an integer from 0 to 4; R ¹ and R ² are each independently or simultaneously hydrogen; halogen; Linear or branched alkyl having 1 to 20 carbon atoms, alkoxy, alkoxy alkyl, alkoxy silyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, or vinyl; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Alkynyl having 3 to 20 carbon atoms; Or SR ", R'SR", SSR ", R'SSR", S (= O) R ", R'S (= O) R", , , R'C (= S) R ", R'C (= S) SR", R'SO ₃ H, R'N = C = S, R'NNC (= S) R ", , , , , , or Phosphorus containing radicals; When R ¹ and R ² are not each hydrogen or halogen, they are connected to each other to form an alkylidene group having 1 to 10 carbon atoms; Saturated or unsaturated cyclic groups of 3 to 12 carbon atoms; Or may form an aromatic cyclic compound having 6 to 17 carbon atoms, Each n indicated in the radical containing each sulfur defined in R ¹ and R ² is 0 or 1, each n ′, and n ″ are an integer from 1 to 10; R 'and R' '' are each independently linear or branched alkyl having 1 to 20 carbon atoms, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, or vinyl ; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms; Each R ″ is independently hydrogen; halogen; linear or branched alkyl of 1 to 20 carbon atoms, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, or vinyl; hydrocarbon Cycloalkyl of 5 to 12 carbon atoms, substituted or unsubstituted, aryl of 6 to 40 carbon atoms, substituted or unsubstituted, aralkyl of 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; or Alkynyl having 3 to 20 carbon atoms, When R ″ is not hydrogen or halogen, it may be linked to R ′ to form a cyclic group; [Formula 3] In the formula (3), m is an integer from 0 to 4; R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently or simultaneously hydrogen; halogen; Linear or branched alkyl of 1 to 20 carbon atoms, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, or vinyl; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms; When R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are not hydrogen or halogen, R ¹¹ and R ¹² , or R ¹³ and R ¹⁴ may be connected to each other to form an alkylidene group having 1 to 10 carbon atoms. Or R ¹¹ , or R ¹² is R ¹³ , and R ¹⁴ A saturated or unsaturated cyclic group having 4 to 12 carbon atoms connected to any one of the groups; Or an aromatic cyclic compound having 6 to 17 carbon atoms. delete