CN102731721A - Cycloolefin copolymer and preparation method thereof - Google Patents

Abstract

The present invention provides a cycloolefin copolymer, which has the structure of formula (I), wherein m and n are the degree of polymerization, m:n≥1.5; R ₁ and R ₂ are independently selected from hydrogen or the number of carbon atoms is 1 to 10 of saturated aliphatic hydrocarbons. In the present invention, the cycloolefin monomer having the structure of formula (II) and α-olefin are used as polymerized monomers, and they are polymerized in an inert solvent under the condition of the presence of a catalyst to obtain the cycloolefin copolymer having the structure of formula (I) things. In the present invention, the cycloolefin monomer having the structure of formula (II) is a bulky cycloolefin, and due to steric hindrance, under the condition of low insertion rate, a cycloolefin copolymer with a high glass transition temperature is obtained, With the structure of formula (I), the flexible α-olefin unit in the copolymer is increased, so that the rigidity of the cyclic olefin copolymer chain is reduced, and the entanglement between the chains is enhanced, thereby improving the tear resistance of the cyclic olefin copolymer. improve its brittleness.

Description

A kind of cyclic olefin copolymer and preparation method thereof

technical field

The invention relates to the technical field of polymers, in particular to a cycloolefin copolymer and a preparation method thereof. the

Background technique

Cyclic olefin copolymer (COC) is prepared by the addition copolymerization reaction of α-olefin and cycloolefin, which has such advantages as low density, high transparency, good thermal stability, high optical refractive index and strong chemical corrosion resistance. and other excellent performance. Since it was first synthesized in the 1990s, COC has become one of the important engineering plastics and is used in heat-resistant and optical materials. At present, Japan's Mitsui Chemicals Corporation (Mitsui) and the United States' Ticona Corporation (Ticona) have launched commercialized COCs with trade names of APEL and Topas, respectively. the

The research results published in the prior art show that: when the glass transition temperature (T _g ) of COC is greater than 150° C., the obtained COC has high practical value. In order to obtain a COC with a T _g greater than 150°C, the prior art improves the glass transition temperature of the cycloolefin copolymer obtained by increasing the insertion rate of the cycloolefin in the copolymer, such as the ethylene-norbornene disclosed in the prior art ( NB) copolymers, when the insertion rate of norbornene exceeds 50 mol%, the cycloolefin copolymer with T _g greater than 150 ° C can be obtained. However, at a high cycloolefin insertion rate, the obtained COC molecules are more rigid, making the copolymers more brittle, which hinders the application of COCs.

In order to improve the brittleness of COC molecules under the premise of maintaining a relatively high glass transition temperature, many methods have been disclosed in the prior art. For example, in 1995, German scientist Kaminsky used a metallocene catalyst to catalyze the copolymerization of ethylene and dimethyloctahydronaphthalene (DMON), and synthesized COC with the highest _Tg of 143°C, in which the insertion rate of DMON was 44mol% (Angew.Chem., Int. Ed. 1995, 34, 2273.). However, the catalytic activity of the ferrocene metal catalyst in this method is low, so that the activity of the polymerization reaction is 4.0×10 ^-10 ~ 0.94×10 ^-6 g/mol _Zr h, and the obtained copolymer is a semi-crystalline structure. Not much value. In order to obtain a COC with high application value, Korean scientist Lee used tricyclopentadiene (TCPD) as a comonomer in 2010 to prepare a catalyst with a _Tg of up to 177 ℃ of COC, in which the insertion rate of TCPD is 45mol% (Macromolecules 2010, 43, 725.), the tensile test results of the obtained COC show that when the insertion rate of TCPD is 37mol% and T _g is 154℃, the elongation at break The rate is 2.8%, the brittleness of the obtained COC is not significantly improved, and it still has serious brittleness, which is not conducive to its application.

Contents of the invention

The object of the present invention is to provide a cyclic olefin copolymer and a preparation method thereof. The cyclic olefin copolymer provided by the present invention has a relatively high elongation at break, and its brittleness is obviously improved, which is beneficial to its application. the

The present invention provides a cycloolefin copolymer having the structure of formula (I):

式（I）； 

Formula (I);

Among them, m and n are polymerization degree, m:n≥1.5;

R ₁ and R ₂ are independently selected from hydrogen or saturated aliphatic hydrocarbon groups with 1 to 10 carbon atoms.

Preferably, 20≥m:n≥2.3. the

Preferably, said R ₁ and R ₂ are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or hydrogen.

The present invention provides a kind of preparation method of cycloolefin copolymer described in above-mentioned technical scheme, comprises the following steps:

In an inert solvent, the cycloolefin monomer having the structure of formula (II) is polymerized with α-olefin in the presence of a catalyst to obtain a cycloolefin copolymer having the structure of formula (I);

式（II）； 

式（I）； 

Formula (II);

Formula (I);

In formula (I), m and n are degrees of polymerization, m:n≥1.5;

R ₁ and R ₂ are independently selected from hydrogen or saturated aliphatic hydrocarbon groups with 1 to 10 carbon atoms.

Preferably, the molar ratio of the α-olefin to the cycloolefin monomer having the structure of formula (II) is (2.3-20):1. the

Preferably, the α-olefin is ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene. the

Preferably, the molar ratio of the catalyst to the cycloolefin monomer having the structure of formula (II) is 1:(1~20). the

Preferably, the catalyst includes a main catalyst and a cocatalyst;

The main catalyst is (tert-butylamino)-dimethyl-(tetramethyl-η ⁵ -cyclopentadienyl)-silane titanium dichloride;

The cocatalyst is triisobutylaluminum and triphenylcarbon tetrakis-(pentafluorophenyl) borate. the

Preferably, the molar ratio of the main catalyst to the triisobutylaluminum in the cocatalyst is 1: (200~2500);

The molar ratio of the main catalyst to the triphenylcarbontetra-(pentafluorophenyl) borate in the co-catalyst is 1: (1-10). the

Preferably, the inert solvent is a linear hydrocarbon compound, a cyclic hydrocarbon compound or an aromatic compound;

The temperature of the polymerization reaction is 0°C to 100°C;

The time of the polymerization reaction is 1 minute to 60 minutes. the

The present invention provides a cycloolefin copolymer having a structure of formula (I), wherein m and n are degrees of polymerization, m:n≥1.5; R ₁ and R ₂ are independently selected from hydrogen or carbon atoms with 1 to 10 Saturated aliphatic hydrocarbon group. In the present invention, α-olefins and cycloolefin monomers having the structure of formula (II) are used as polymerization monomers, and they are polymerized in an inert solvent under the action of a catalyst to obtain a cycloolefin copolymer having the structure of formula (I) . The cyclic olefin monomer used in the present invention has a structure of formula (II), which is a large-volume cyclic olefin. During the polymerization reaction, due to steric hindrance, at a relatively low insertion rate of the cyclic olefin monomer, the obtained ring The olefin copolymer has a higher glass transition temperature, and the flexible α-olefin unit in the copolymer increases, so that the rigidity of the cyclic olefin copolymer chain is reduced, and the entanglement between the chains is enhanced, thereby improving the cyclic olefin copolymer. The tear resistance improves its brittleness, and a cycloolefin copolymer with a higher glass transition temperature and improved brittleness is obtained. Experimental results show that the insertion ratio of the cycloolefin monomer in the cycloolefin copolymer provided by the present invention is less than or equal to 30.0mol%, and its glass transition temperature can reach 207.0°C. The higher glass transition temperature makes the cycloolefin copolymer have a higher High practicability; tensile test results show that when its glass transition temperature is 160.4°C, its elongation at break is 7.6%, and its tensile strength is 55.0MPa.

And, the cyclic olefin copolymer that the present invention obtains has higher transparency and better molecular weight distribution, and in the preparation method of cyclic olefin copolymer provided by the invention, the polymerization reaction of cyclic olefin monomer and α-olefin has higher reactivity. Experimental results show that the molecular weight of the cyclic olefin copolymer obtained in the present invention is 173kg/mol~439kg/mol, and the molecular weight distribution index is 1.67~2.80; the light transmittance of the cyclic olefin copolymer provided by the present invention in the visible region>80%; The reactivity is (6.0×10 ⁶ ~20.0×10 ⁶ ) g/mol _Ti ·h.

Description of drawings

Fig. 1 is the ¹³ C NMR spectrogram of the cycloolefin copolymer obtained in Example 2 and Example 8 of the present invention;

Fig. 2 is the DSC curve of the cycloolefin copolymer that embodiment of the present invention 5～8 obtains;

Fig. 3 is the stress-strain curve of the cycloolefin copolymer that embodiment of the present invention 6～8 obtains;

Fig. 4 is the light transmittance curve of the ultraviolet-visible spectrum region of the cyclic olefin copolymer that embodiment of the present invention 7～8 obtains;

Fig. 5 is the ¹ H NMR spectrum of the cycloolefin copolymer obtained in Example 8 of the present invention.

Detailed ways

The present invention provides a cycloolefin copolymer having the structure of formula (I):

Formula (I);

Among them, m and n are polymerization degree, m:n≥1.5;

R ₁ and R ₂ are independently selected from hydrogen or saturated aliphatic hydrocarbon groups with 1 to 10 carbon atoms.

The present invention provides a cycloolefin copolymer having a structure of formula (I), wherein m and n are degrees of polymerization, m:n≥1.5, preferably 2.3≤m:n≤20, more preferably 3≤m:n≤ 15. The weight average molecular weight of the cycloolefin copolymer obtained in the present invention is preferably 150kg/mol~800kg/mol, more preferably 170kg/mol~500kg/mol. In the cyclic olefin copolymer provided by the present invention, the value of n is small, which shows that the content of cyclic olefin monomer is small, and the proportion of corresponding flexible α-olefin polymerized units increases, thereby providing a cyclic olefin copolymer molecule The flexibility of the chain improves its tear resistance and significantly improves its brittleness. the

In the formula (I), the R ₁ and R ₂ are independently selected from hydrogen or saturated aliphatic hydrocarbon groups with 1 to 10 carbon atoms, preferably independently selected from methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl or hydrogen, most preferably hydrogen.

The cyclic olefin monomer in the cyclic olefin copolymer provided by the present invention has the structure of formula (II), which is a bulky comonomer. During the copolymerization process with α-olefin, due to the steric hindrance effect, the cyclic olefin copolymer chain The increase of the content of α-olefin in the polymer chain reduces the rigidity of the polymer chain and strengthens the entanglement between the chains, thereby obtaining a cycloolefin copolymer with higher flexibility, and at a lower Under the insertion rate of cycloolefin monomer, the obtained cycloolefin copolymer has a higher glass transition temperature and has higher practical value. Experimental results show that in the cycloolefin copolymer provided by the present invention, the insertion rate of the cycloolefin monomer having the structure of formula (II) can be adjusted between 0mol% and 30.4mol%, and its glass transition temperature can reach 207.0°C ; When the T _g of the cycloolefin copolymer is 164.0°C, the elongation at break is 7.6%, the tensile strength is 55.0MPa, and the tensile modulus is 2590MPa; when the T _g of the cycloolefin copolymer is 154.0°C, Its elongation at break is 2.8%, and its tensile modulus is 2100MPa. A cycloolefin copolymer with high performance at a high glass transition temperature has been successfully obtained.

The present invention provides a kind of preparation method of cycloolefin copolymer described in above-mentioned technical scheme, comprises the following steps:

In an inert solvent, the cycloolefin monomer having the structure of formula (II) is polymerized with α-olefin in the presence of a catalyst to obtain a cycloolefin copolymer having the structure of formula (I);

式（II）； 

式（I）； 

Formula (II);

Formula (I);

In formula (I), m and n are degrees of polymerization, m:n≥1.5;

R ₁ and R ₂ are independently selected from hydrogen or saturated aliphatic hydrocarbon groups with 1 to 10 carbon atoms.

The preparation method of the cyclic olefin copolymer provided by the present invention is carried out in an inert solvent. The inert solvent is preferably a linear hydrocarbon compound, a cyclic hydrocarbon compound or an aromatic compound, more preferably a benzene compound, and most preferably toluene. the

In the inert solvent, in the present invention, the cycloolefin monomer having the structure of formula (II) is polymerized with α-olefin in the presence of a catalyst to obtain the cycloolefin copolymer having the structure of formula (I). In the present invention, there is no special limitation on the source of the cycloolefin monomer having the structure of formula (II), which may be a commercially available product or a self-made product. The present invention has no special limitation on the preparation method of the cycloolefin monomer having the structure of formula (II). In the present invention, the cycloolefin monomer having the structure of formula (II) is preferably as described in the following scientific papers Method for preparation: Michael N. Paddon-Row and Robert Hartcher. Orbital Interactions. 7. The birch reduction as a tool for exploring orbital interactions through bonds. Through-Four-,-Five-, and-Six-Bond Interactions ¹ .Journal of the American Chenzicul Society, 1980, 102:671~678. Specifically:

Under the protection of an inert gas, anthracene and norbornadiene are reacted to obtain a cycloolefin monomer having a structure of formula (II). In the present invention, the molar ratio of the anthracene to the norbornadiene is preferably (0.1-0.5): 1, more preferably (0.15-0.3): 1; the inert gas is preferably nitrogen; the present invention is preferably In an autoclave, anthracene and norbornadiene are reacted; the reaction temperature of the anthracene and norbornadiene is preferably 150°C to 200°C, more preferably 160°C to 190°C; the reaction temperature of the anthracene and norbornadiene The reaction time is preferably 20 hours to 40 hours, more preferably 25 hours to 30 hours. the

After the reaction between the anthracene and the norbornadiene is completed, the present invention preferably lowers the reaction system to room temperature, and then distills unreacted norbornadiene to obtain a reaction product, which is a light yellow solid. After the reaction product is obtained, in the present invention, the reaction product is preferably extracted, recrystallized, filtered and dried to obtain the cycloolefin monomer having the structure of formula (II). The present invention has no special limitations on the extraction, recrystallization, filtration and drying methods, and the technical solutions of extraction, recrystallization, filtration and drying well known to those skilled in the art can be used. The present invention preferably uses petroleum ether as a solvent, extracts with a Soxhlet extractor for 20 hours to 30 hours, then recrystallizes the obtained concentrated extract, separates out white crystals, and then filters the product obtained by recrystallization to obtain The solid is preferably vacuum-dried at 40° C. to 60° C. to obtain a cycloolefin monomer having a structure of formula (II). the

The preparation method of the cycloolefin monomer with the structure of formula (II) adopted in the present invention has simple synthesis and purification and high yield. Experimental results show that the yield of the cycloolefin monomer with the structure of formula (II) obtained by the preparation method adopted in the present invention is as high as 80.0%. the

After obtaining the cycloolefin monomer with the structure of formula (II), the present invention polymerizes the cycloolefin monomer with the structure of formula (II) and α-olefin in the presence of a catalyst in an inert solvent to obtain A cyclic olefin copolymer with a structure of formula (I). The present invention preferably provides a cycloolefin monomer solution and a catalyst solution having a structure of formula (II) dissolved in an inert solvent, and the cycloolefin monomer solution having a structure of formula (II), the catalyst solution and α-olefin are added to an inert After polymerization in a solvent, a cycloolefin copolymer having a structure of formula (I) is obtained. In the present invention, the α-olefin is preferably ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1- Hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, more preferably ethylene, propylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, most preferably ethylene; said α-olefin and said The molar ratio of the cycloolefin monomer having the structure of formula (II) is preferably (2.3~20):1, more preferably (3.0~15):1; the catalyst and the ring having the structure of formula (II) The molar ratio of olefin monomers is preferably 1:(1~20), more preferably 1:(5~10). In the present invention, when the α-olefin is ethylene, since ethylene is in a gaseous state, the present invention preferably fills the reaction solution with ethylene gas, and continuously feeds ethylene gas into the reactor to keep the pressure of ethylene preferably at 0.5 atmospheric pressure ~ 2 atmospheric pressure, more preferably 1 atmospheric pressure ~ 1.5 atmospheric pressure;

In the present invention, the catalyst can be a catalyst well known to those skilled in the art for the copolymerization of cycloolefin monomers and α-olefins, preferably including a main catalyst and a cocatalyst, and the main catalyst includes but is not limited to (tert-butyl amino)-dimethyl-(tetramethyl-η ⁵ -cyclopentadienyl)-silane titanium dichloride (CGC), the cocatalysts include but are not limited to triisobutylaluminum (TIBA) and Triphenylcarbon tetra-(pentafluorophenyl) borate [Ph ₃ CB(C ₆ F ₅ ) ₄ ]; the mol ratio of the main catalyst and the triisobutylaluminum in the cocatalyst is preferably 1: (200 ~ 2500), more preferably 1: (250 ~ 2000); the molar ratio of the main catalyst and the triphenylcarbon tetra-(pentafluorophenyl) borate in the cocatalyst is preferably 1: ( 1~10), more preferably 1:(3~6).

In the present invention, when the cycloolefin monomer, α-olefin and catalyst with the (II) structure are mixed in an inert solvent, it is preferably carried out in the following order:

In the present invention, the solution of the cycloolefin monomer having the (II) structure, the α-olefin and the solution of the inert solvent of the cocatalyst are first added to the inert solvent; then the main catalyst is added to the obtained mixed solution A solution in an inert solvent, after polymerization, a cycloolefin copolymer having a structure of formula (I) is obtained. In the present invention, the molar concentration of the cycloolefin monomer solution having the structure of formula (II) is preferably 0.1mol/L~5mol/L, more preferably 1.0mol/L~3mol/L; The molar concentration of triisobutyl aluminum solution is preferably 0.1mol/L～5mol/L, more preferably 0.3mol/L～3mol/L, most preferably 0.5mol/L～1mol/L; The molar concentration of benzocarbotetra-(pentafluorophenyl) borate solution is preferably 1 μmol/mL～10 μmol/mL, more preferably 5 μmol/mL～8 μmol/mL; the molar concentration of the main catalyst solution is preferably 0.1 μmol /mL~5μmol/mL, more preferably 0.5μmol/mL~2μmol/mL. In the present invention, the temperature of the polymerization reaction is preferably 0°C to 100°C, more preferably 20°C to 90°C, most preferably 40°C to 80°C; the time of the polymerization reaction is preferably 1 minute to 60 minutes , more preferably 5 minutes to 30 minutes. the

During the polymerization reaction, the cycloolefin monomer having the structure of formula (II) has a large volume, and due to the influence of the steric hindrance effect, under the lower insertion rate of the cycloolefin monomer, a higher The glass transition temperature of the cyclic olefin copolymer has the structure of formula (I), and the proportion of flexible α-olefin units in the copolymer is increased, so that the rigidity of the resulting cyclic olefin copolymer chain is reduced and the entanglement between the chains is enhanced , thereby improving the tear resistance of the cycloolefin copolymer, so that its brittleness is improved. Further, the present invention uses (tert-butylamino)-dimethyl-(tetramethyl-η ⁵ -cyclopentadienyl)-silane titanium dichloride as the main catalyst, and during the polymerization reaction, The procatalyst replaces the bridging group (SiMe ₂ ) on the cyclopentadiene to limit the geometric configuration of the metal atom space, so that the active sites of the metal atoms in the procatalyst are more exposed, so that it has excellent copolymerization catalytic ability , promote the copolymerization reaction of the cycloolefin monomer having the structure of formula (II) and α-olefin, so that the polymerization reaction of the present invention has higher reactivity.

After the polymerization reaction is completed, the present invention preferably carries out post-treatment to the reaction solution obtained by the polymerization reaction, specifically:

In the present invention, the reaction solution can be mixed with the ethanol solution of hydrochloric acid to terminate the growth of the polymerization chain to obtain a reaction product; the reaction product is separated from solid and liquid and then dried to obtain a cycloolefin copolymer. In the present invention, the method for terminating the growth of the polymer chain is not particularly limited, and the above-mentioned method of mixing the reaction solution with the ethanol solution of hydrochloric acid can be adopted, and the volume fraction of the ethanol solution of hydrochloric acid is preferably 5% to 15%; the present invention The reaction product is preferably separated from solid and liquid by filtration, and the filtered product is washed. In the present invention, the washing reagent is preferably acetone, and the number of times of washing is preferably 2 to 5 times. Second; the present invention has no special limitation to the method of described drying, adopts the technical solution of drying well-known to those skilled in the art to get final product, in the present invention, described drying is vacuum drying, and the temperature of described drying is 50 ℃～ 80°C, the drying time is preferably 20 hours to 30 hours. the

After obtaining the cyclic olefin copolymer, the present invention carries out structural identification and performance testing to the cyclic olefin copolymer, and the specific process is as follows:

The present invention carries out nuclear magnetic resonance (NMR) detection on the cycloolefin copolymer obtained, including ¹ H NMR spectrum, ¹³ C NMR spectrum and distortion-free polarization transfer enhanced (DEPT) spectrum. The results show that the cycloolefin copolymer provided by the invention It has the structure of formula (I), and the insertion rate of the cycloolefin monomer with the structure of formula (II) is between 0mol%~30.4mol%, and the insertion rate of the cycloolefin monomer with the structure of formula (II) is reduced, and the Improve the rigidity of the obtained cyclic olefin copolymer, thereby improving the tear resistance of the cyclic olefin copolymer;

The present invention carries out tensile test to the cycloolefin copolymer obtained, and the result shows that the elongation at break of the cycloolefin copolymer obtained by the present invention is between 2.1%～7.6%, and the tensile strength is between 44MPa～63.3MPa, The tensile modulus is 2390MPa ~ 2680MPa, which shows that the cyclic olefin copolymer provided by the present invention has higher tensile properties, and its tear resistance has been improved, so that its brittleness has been significantly improved;

The present invention uses differential scanning calorimetry (DSC) to measure the glass transition temperature of the obtained cycloolefin copolymer, and the results show that the glass transition temperature of the cycloolefin copolymer provided by the present invention can reach 207°C, which shows that the present invention The invention has prepared a cycloolefin copolymer with a higher glass transition temperature and improved brittleness, and the cycloolefin copolymer obtained by the present invention has higher practicability;

The present invention has measured the molecular weight of cyclic olefin copolymer, and the result shows, the weight average molecular weight of the cyclic olefin copolymer thing prepared by the embodiment of the present invention is 173kg/mol～439kg/mol, and molecular weight distribution index is 1.60～2.80, has good molecular weight Adjustability;

The present invention measures the light transmittance of the cyclic olefin copolymer, and the result shows that the cyclic olefin copolymer provided by the present invention has high transparency, and the light transmittance in the visible light region is greater than 80%. the

The present invention provides a cyclic olefin copolymer and a preparation method thereof. The cyclic olefin copolymer provided by the present invention has a structure of formula (I), wherein m and n are, m:n≥1.5; R ₁ and R ₂ are independently selected from Hydrogen or a saturated aliphatic hydrocarbon group with 1 to 10 carbon atoms. In the present invention, α-olefin and cycloolefin monomer having the structure of formula (II) are used as polymerization monomers, which are polymerized under the action of a catalyst to obtain the cycloolefin copolymer having the structure of formula (I). The cycloolefin monomer selected in the present invention has the structure of formula (II), which is a bulky cycloolefin. During the polymerization reaction, due to the steric hindrance effect, at a lower insertion rate of the cycloolefin monomer, a higher High glass transition temperature cyclic olefin copolymer, the flexible α-olefin unit in the cyclic olefin copolymer increases, so that the rigidity of the cyclic olefin copolymer chain is reduced, and the entanglement between the chains is enhanced, thereby improving the cyclic olefin copolymer Excellent tear resistance, so that its brittleness is improved, and a cycloolefin copolymer with a higher glass transition temperature and improved brittleness is obtained. And, the cyclic olefin copolymer that the present invention obtains has higher transparency and better molecular weight distribution, and in the preparation method of cyclic olefin copolymer provided by the invention, the polymerization reaction of cyclic olefin monomer and α-olefin has higher reactivity. Experimental results show that the insertion rate of the cycloolefin monomer in the cycloolefin copolymer provided by the present invention is less than or equal to 30.0mol%, and its glass transition temperature can reach 207.0°C. The higher glass transition temperature makes the cycloolefin copolymer have Higher practicability; Tensile test result shows, when its glass transition temperature is 160.4 ℃, its elongation at break is 7.6%. Tensile strength is 55.0MPa; The molecular weight of the cyclic olefin copolymer that the present invention obtains is 173kg/mol~439kg/mol, the molecular weight distribution index is 1.67~2.80; the light transmittance of the cycloolefin copolymer provided by the invention in the visible light region is >80%; the reactivity is as high as 2.0×10 ⁷ g/mol _Ti ·h.

In order to further illustrate the present invention, the cycloolefin copolymer provided by the present invention and its preparation method are described in detail below in conjunction with examples, but they should not be interpreted as limiting the protection scope of the present invention. the

Example 1

42 g of anthracene and 108 g of norbornadiene were sequentially added into a 150 mL autoclave. Under nitrogen atmosphere, anthracene and norbornanol were reacted by heating at 180°C for 27 hours. After the reaction was completed, the temperature of the reaction system was lowered to room temperature, and the unreacted norbornadiene was evaporated to obtain a light yellow solid. Using petroleum ether as a solvent, the obtained light yellow solid was extracted with a Soxhlet extractor for 24 hours to obtain a concentrated extract. The concentrated extract was recrystallized to precipitate white crystals, and then filtered, and the resulting solid was vacuum-dried at 50° C. to obtain a cycloolefin monomer. the

The cycloolefin monomer obtained in the present invention is a white crystal, the mass of the cycloolefin monomer obtained by weighing is 50.2 g, and the calculated yield is 80.0%. the

The present invention conducts structural characterization of the obtained cycloolefin monomer, and the result shows that the cycloolefin monomer prepared by the present invention has the structure of formula (II). the

Example 2

Under an ethylene atmosphere, 21.5 mL of anhydrous toluene, 1 mL of a toluene solution with a structure of formula (II) prepared in Example 1 with a molar concentration of 2 mol/L, 1.5 mL of anhydrous toluene, and 1.5 mL of molar A toluene solution of TIBA with a concentration of 0.5 mol/L and a toluene solution of [Ph ₃ CB(C ₆ F ₅ ) ₄ ] with a molar concentration of 6 μmol/mL in 3 mL, and the resulting mixed solution was stirred at 40° C. for 10 minutes, 3 mL of a toluene solution of CGC with a molar concentration of 1 μmol/mL was added thereto, ethylene was continuously fed into the reactor, and the pressure of ethylene was kept at 1 atmosphere, and the polymerization was carried out for 5 minutes. After the polymerization reaction is completed, the obtained reaction solution is poured into an ethanol solution of hydrochloric acid with a volume fraction of 10%, and the reaction product is precipitated; the obtained reaction product is filtered and washed 3 times with acetone, and the obtained product is placed in a vacuum oven , dried at 60°C for 24 hours to obtain a white cycloolefin copolymer.

The present invention carries out hydrogen nuclear magnetic resonance spectrum detection to the cycloolefin copolymer obtained, and the result is shown in Figure 1, and Fig. 1 is the ¹³ C NMR spectrogram of the cycloolefin copolymer obtained in Example 2 and Example 8 of the present invention, wherein ( a) is the ¹³ C NMR spectrum of the cycloolefin copolymer obtained in Example 2. It can be seen from Figure 1 (a) that the cycloolefin copolymer provided by the present invention has the structure shown in (I); It can be seen from the calculation of the ¹ HNMR spectrum that, in this example, the insertion rate of the cycloolefin monomer having the structure of formula (II) is 7.60 mol%.

The present invention uses differential scanning calorimetry (DSC) to detect the glass transition temperature of the cycloolefin copolymer obtained, and the results show that the glass transition temperature of the cycloolefin copolymer prepared in this example is 70.8°C. the

The present invention conducts a tensile test experiment on the obtained cycloolefin copolymer, and the results show that the cycloolefin copolymer prepared in this embodiment has better elongation at break, tensile strength and tensile modulus. the

The present invention weighs and obtains that the quality of the cycloolefin copolymer prepared in this embodiment is 3.70g; the relative weight average molecular weight of the cycloolefin copolymer prepared in this embodiment is 173kg/mol by using gel permeation chromatography detection, and the relative molecular weight distribution The index is 2.50. the

The present invention detects the catalytic activity of the polymerization reaction, and the result shows that the catalytic activity of the polymerization reaction in this example is 14.0×10 ⁶ g/mol _Ti ·h.

The present invention detects the light transmittance of the cycloolefin copolymer, and obtains its light transmittance curve in the ultraviolet-visible spectrum region, and the results show that the cycloolefin copolymer prepared in this embodiment has relatively high light transmittance. the

Example 3

Under an ethylene atmosphere, 21.5 mL of anhydrous toluene, 1.5 mL of the toluene solution of the cycloolefin monomer with the structure of formula (II) prepared in Example 1 with a molar concentration of 2 mol/L, and 1.5 mL of A toluene solution of TIBA with a molar concentration of 0.5 mol/L and 3 mL of a toluene solution of [Ph ₃ CB(C ₆ F ₅ ) ₄ ] with a molar concentration of 6 μmol/mL were stirred at 60°C for 10 minutes Finally, 3 mL of a toluene solution of CGC with a molar concentration of 1 μmol/mL was added thereto, ethylene was continuously fed into the reactor, and the pressure of ethylene was kept at 1.2 atmospheres, and the polymerization was carried out for 5 minutes. After the polymerization reaction is completed, the obtained reaction solution is poured into an ethanol solution of hydrochloric acid with a volume fraction of 10%, and the reaction product is precipitated; the obtained reaction product is filtered and washed 3 times with acetone, and the obtained product is placed in a vacuum oven , dried at 60°C for 24 hours to obtain a white cycloolefin copolymer.

The present invention carries out nuclear magnetic resonance spectrum detection to the cycloolefin copolymer obtained, and it can be seen from the ¹³ C NMR spectrogram of the cycloolefin copolymer that the cycloolefin copolymer provided by the invention has the structure shown in (I); According to the calculation of the ¹ H NMR spectrum of the copolymer, the insertion rate of the cycloolefin monomer having the structure of formula (II) is 9.50 mol%.

The present invention weighs and obtains that the mass of the cyclic olefin copolymer prepared in this embodiment is 5.40 g; the relative weight average molecular weight of the cyclic olefin copolymer prepared in this embodiment is 205 kg/mol by using gel permeation chromatography detection, and the relative molecular weight distribution The index was 1.84. the

The present invention conducts a tensile test experiment on the obtained cycloolefin copolymer, and the results show that the cycloolefin copolymer prepared in this embodiment has better elongation at break, tensile strength and tensile modulus. the

The present invention uses differential scanning calorimetry (DSC) to detect the glass transition temperature of the obtained cycloolefin copolymer, and the results show that the glass transition temperature of the cycloolefin copolymer prepared in this example is 78.0°C. the

The present invention detects the catalytic activity of the polymerization reaction, and the result shows that the catalytic activity of the polymerization reaction in this example is 21.6×10 ⁶ g/mol _Ti ·h.

The present invention detects the light transmittance of the cycloolefin copolymer, and obtains its light transmittance curve in the ultraviolet-visible spectrum region, and the results show that the cycloolefin copolymer prepared in this embodiment has relatively high light transmittance. the

Example 4

Under an ethylene atmosphere, 21.5 mL of anhydrous toluene, 2 mL of a toluene solution with a structure of formula (II) prepared in Example 1 with a molar concentration of 2 mol/L, 1.5 mL of anhydrous toluene, and 1.5 mL of molar A toluene solution of TIBA with a concentration of 0.6mol/L and a toluene solution of [Ph ₃ CB(C ₆ F ₅ ) ₄ ] with a molar concentration of 7 μmol/mL in 3 mL were stirred at 80°C for 10 minutes to obtain the mixed solution , 3 mL of a toluene solution of CGC with a molar concentration of 1 μmol/mL was added thereto, ethylene was continuously fed into the reactor, and the pressure of ethylene was kept at 1.1 atmospheric pressure, and the polymerization reaction was carried out for 15 minutes. After the polymerization reaction is completed, the obtained reaction solution is poured into an ethanol solution with a volume fraction of 10% hydrochloric acid to precipitate the reaction product; the obtained reaction product is filtered and washed 3 times with acetone, and then the obtained product is placed in a vacuum oven , dried at 60°C for 24 hours to obtain a white cycloolefin copolymer.

The present invention carries out nuclear magnetic resonance spectrum detection to the cycloolefin copolymer obtained, and it can be seen from the ¹³ C NMR spectrogram of the cycloolefin copolymer that the cycloolefin copolymer provided by the invention has the structure shown in (I); From the calculation of the ¹ H NMR spectrum of the copolymer, it can be concluded that the insertion rate of the cycloolefin monomer having the structure of formula (II) is 11.40 mol%.

The present invention uses differential scanning calorimetry (DSC) to detect the glass transition temperature of the obtained cycloolefin copolymer, and the results show that the glass transition temperature of the cycloolefin copolymer prepared in this example is 80.0°C. the

The present invention conducts a tensile test experiment on the obtained cycloolefin copolymer, and the results show that the cycloolefin copolymer prepared in this embodiment has better elongation at break, tensile strength and tensile modulus. the

The present invention weighs and obtains that the quality of the cycloolefin copolymer prepared in this embodiment is 1.55g; the relative weight average molecular weight of the cycloolefin copolymer prepared in this embodiment is 173kg/mol by using gel permeation chromatography detection, and the relative molecular weight distribution The index was 1.67. the

The present invention detects the catalytic activity of the polymerization reaction, and the result shows that the catalytic activity of the polymerization reaction in this example is 6.0×10 ⁶ g/mol _Ti ·h.

The present invention detects the light transmittance of the cycloolefin copolymer, and obtains its light transmittance curve in the ultraviolet-visible spectrum region, and the results show that the cycloolefin copolymer prepared in this embodiment has relatively high light transmittance. the

Example 5

Under an ethylene atmosphere, 20.5mL of anhydrous toluene, 2mL of the toluene solution of the cycloolefin monomer with the structure of formula (II) prepared in Example 1 with a molar concentration of 3mol/L, 1.5mL of molar A toluene solution of TIBA with a concentration of 0.7 mol/L and 3 mL of a toluene solution of [Ph ₃ CB(C ₆ F ₅ ) ₄ ] with a molar concentration of 6.5 μmol/mL were stirred at 60°C for 10 minutes Finally, 3 mL of a toluene solution of CGC with a molar concentration of 1 μmol/mL was added thereto, ethylene was continuously fed into the reactor, and the pressure of ethylene was kept at 1 atmosphere, and the polymerization was carried out for 20 minutes. After the polymerization reaction is completed, the obtained reaction solution is poured into an ethanol solution containing 10% hydrochloric acid by volume fraction to precipitate the reaction product; the obtained reaction product is filtered and washed 3 times with acetone, and then the obtained product is put into a vacuum In an oven, dry at 60° C. for 24 hours to obtain a white cycloolefin copolymer.

The present invention carries out nuclear magnetic resonance spectrum detection to the cycloolefin copolymer obtained, and it can be seen from the ¹³ C NMR spectrogram of the cycloolefin copolymer that the cycloolefin copolymer provided by the invention has the structure shown in (I); According to the calculation of the ¹ H NMR spectrum of the copolymer, the insertion rate of the cycloolefin monomer having the structure of formula (II) is 12.40 mol%.

The present invention uses differential scanning calorimetry (DSC) to detect the glass transition temperature of the cycloolefin copolymer, and the results are shown in Figure 2, and Figure 2 is the DSC curve of the cycloolefin copolymer obtained in Examples 5 to 8 of the present invention, Wherein, curve a is the DSC curve of the cycloolefin copolymer obtained in Example 5, as can be seen from curve a in Figure 2, the glass transition temperature of the cycloolefin copolymer prepared in the present embodiment is 83.5°C.

The present invention conducts a tensile test experiment on the obtained cycloolefin copolymer, and the results show that the cycloolefin copolymer prepared in this embodiment has better elongation at break, tensile strength and tensile modulus. the

The present invention weighs and obtains that the mass of the cycloolefin copolymer prepared in this embodiment is 3.10 g; the relative weight average molecular weight of the cycloolefin copolymer prepared in this embodiment is detected by gel permeation chromatography to be 330 kg/mol, and the relative molecular weight distribution The index is 2.25. the

The present invention detects the catalytic activity of the polymerization reaction, and the result shows that the catalytic activity of the polymerization reaction in this example is 12.4×10 ⁶ g/mol _Ti ·h.

The present invention detects the light transmittance of the cycloolefin copolymer, and obtains its light transmittance curve in the ultraviolet-visible spectrum region, and the results show that the cycloolefin copolymer prepared in this embodiment has relatively high light transmittance. the

Example 6

Under an ethylene atmosphere, 18.75 mL of anhydrous toluene, 3.75 mL of the toluene solution of the cycloolefin monomer with the structure of formula (II) prepared in Example 1 with a molar concentration of 2 mol/L, and 1.5 mL of A toluene solution of TIBA with a molar concentration of 0.5 mol/L and 3 mL of a toluene solution of [Ph ₃ CB(C ₆ F ₅ ) ₄ ] with a molar concentration of 6 μmol/mL were stirred at 60°C for 10 minutes Finally, 3 mL of a toluene solution of CGC with a molar concentration of 1 μmol/mL was added thereto, ethylene was continuously fed into the reactor, and the pressure of ethylene was kept at 1 atmosphere, and the polymerization was carried out for 5 minutes. After the polymerization reaction is completed, the obtained reaction solution is poured into an ethanol solution of hydrochloric acid with a volume fraction of 10%, and the reaction product is precipitated; the obtained reaction product is filtered, and after being washed 3 times with acetone, the obtained product is put into a vacuum oven , dried at 60°C for 24 hours to obtain a white cycloolefin copolymer.

The present invention carries out nuclear magnetic resonance spectrum detection to the cycloolefin copolymer obtained, and it can be seen from the ¹³ C NMR spectrogram of the cycloolefin copolymer that the cycloolefin copolymer provided by the invention has the structure shown in (I); According to the calculation of the ¹ H NMR spectrum of the copolymer, the insertion rate of the cycloolefin monomer having the structure of formula (II) is 15.0 mol%.

The present invention uses differential scanning calorimetry (DSC) to detect the glass transition temperature of the cycloolefin copolymer, and the results are shown in Figure 2, and Figure 2 is the DSC curve of the cycloolefin copolymer obtained in Examples 5 to 8 of the present invention, Wherein, curve b is the DSC curve of the cycloolefin copolymer prepared in Example 6, and it can be seen from curve b in Figure 2 that the glass transition temperature of the cycloolefin copolymer prepared in this example is 125.5°C. the

The present invention carries out tensile test experiment to the obtained cyclic olefin copolymer, and the result is as shown in Figure 3, and Fig. 3 is the stress-strain curve of the cyclic olefin copolymer that the embodiment of the present invention 6～8 obtains, and wherein, curve a is implementation The stress-strain curve of the cycloolefin copolymer prepared by example 6, as can be seen from the curve a in Fig. 3, the elongation at break of the cycloolefin copolymer prepared by the present embodiment is 14.0%, and the tensile strength is 63.3MPa, The tensile modulus is 2680MPa. the

The present invention weighs and obtains that the quality of the cycloolefin copolymer prepared in this embodiment is 3.75g; the relative weight average molecular weight of the cycloolefin copolymer prepared in this embodiment is detected by gel permeation chromatography to be 360kg/mol, and the relative molecular weight distribution The index was 1.97. the

The present invention detects the catalytic activity of the polymerization reaction, and the result shows that the catalytic activity of the polymerization reaction in this example is 15.0×10 ⁶ g/mol _Ti ·h.

The present invention detects the light transmittance of the cycloolefin copolymer, and obtains the light transmittance curve in the ultraviolet-visible spectrum region. The result shows that the light transmittance of the cycloolefin copolymer prepared in this embodiment is 78%. the

Example 7

Under an ethylene atmosphere, 17.5 mL of anhydrous toluene, 5.0 mL of the toluene solution of the cycloolefin monomer with the structure of formula (II) prepared in Example 1 with a molar concentration of 2 mol/L, and 1.5 mL of A toluene solution of TIBA with a molar concentration of 0.5 mol/L and 3 mL of a toluene solution of [Ph ₃ CB(C ₆ F ₅ ) ₄ ] with a molar concentration of 6 μmol/mL were stirred at 60°C for 10 minutes. , 3 mL of a toluene solution of CGC with a molar concentration of 1 μmol/mL was added thereto, ethylene was continuously fed into the reactor, and the pressure of ethylene was kept at 1 atmosphere, and the polymerization was carried out for 25 minutes. After the polymerization reaction is completed, the obtained reaction solution is poured into an ethanol solution of hydrochloric acid with a volume fraction of 10%, and the reaction product is precipitated; the obtained reaction product is filtered and washed 3 times with acetone, and the obtained product is placed in a vacuum oven , dried at 60°C for 24 hours to obtain a white cycloolefin copolymer.

The present invention carries out nuclear magnetic resonance spectrum detection to the cycloolefin copolymer obtained, and it can be seen from the ¹³ C NMR spectrogram of the cycloolefin copolymer that the cycloolefin copolymer provided by the invention has the structure shown in (I); According to the calculation of ^{the 1} H NMR spectrum of the copolymer, the insertion rate of the cycloolefin monomer having the structure of formula (II) is 20.2 mol%.

The present invention uses differential scanning calorimetry (DSC) to detect the glass transition temperature of the obtained cycloolefin copolymer, and the results are shown in Figure 2, and Figure 2 is the DSC of the cycloolefin copolymer obtained in Examples 5 to 8 of the present invention Curve, wherein, curve c is the DSC curve of the cyclic olefin copolymer prepared in embodiment 7, can find out that the glass transition temperature of the cyclic olefin copolymer prepared by the present embodiment is 160.4 ℃ by the curve c in Fig. 2. the

The present invention carries out tensile test experiment to the cycloolefin copolymer that obtains, and the result is as shown in Figure 3, and Fig. 3 is the stress-strain curve of the cycloolefin copolymer that the embodiment of the present invention 6～8 obtains, and wherein, curve b is the implementation The stress-strain curve of the cyclic olefin copolymer that example 7 obtains, can find out that the elongation at break of the cyclic olefin copolymer prepared by the present embodiment is 7.6%, tensile strength is 55.0MPa, tensile strength is 55.0MPa by the curve b in Fig. 3 The tensile modulus is 2590MPa. the

The present invention weighs and obtains that the mass of the cyclic olefin copolymer prepared in this embodiment is 4.70 g; the relative weight average molecular weight of the cyclic olefin copolymer prepared in this embodiment is 407 kg/mol by using gel permeation chromatography detection, and the relative molecular weight distribution The index is 2.80. the

The present invention detects the catalytic activity of the polymerization reaction, and the result shows that the catalytic activity of the polymerization reaction in this example is 18.8×10 ⁶ g/mol _Ti ·h.

The present invention has detected the light transmittance of cyclic olefin copolymer, and the result is as shown in Figure 4, and Figure 4 is the light transmittance curve of its ultraviolet-visible spectral region of the cyclic olefin copolymer that embodiment 7～8 of the present invention obtains, wherein , curve A is the light transmittance curve of the cycloolefin copolymer prepared in Example 7 in the ultraviolet-visible spectrum region, as can be seen from curve A in Fig. 4, the light transmittance of the cycloolefin copolymer prepared in this embodiment> 80%. the

Example 8

Under an ethylene atmosphere, add 12.5mL of anhydrous toluene, 10.0mL of the toluene solution of the cycloolefin monomer with the structure of formula (II) prepared in Example 1 with a molar concentration of 2mol/L, and 1.5mL of A toluene solution of TIBA with a molar concentration of 0.5 mol/L and 3 mL of a toluene solution of [Ph ₃ CB(C ₆ F ₅ ) ₄ ] with a molar concentration of 6 μmol/mL were stirred at 60°C for 10 minutes. , 3 mL of a toluene solution of CGC with a molar concentration of 1 μmol/mL was added thereto, ethylene was continuously fed into the reactor, and the pressure of ethylene was kept at 1 atmosphere, and the polymerization reaction was carried out for 30 minutes. After the polymerization reaction is completed, the obtained reaction solution is poured into an ethanol solution of hydrochloric acid with a volume fraction of 10%, and the reaction product is precipitated; the obtained reaction product is filtered and washed 3 times with acetone, and the obtained product is placed in a vacuum oven , dried at 60°C for 24 hours to obtain a white cycloolefin copolymer.

The present invention carries out proton nuclear magnetic resonance spectrum detection to the cycloolefin copolymer obtained, and the results are shown in Figure 1 and Figure 5, and Figure 1 is the ¹³ C NMR spectrogram of the cycloolefin copolymer obtained in Example 2 and Example 8 of the present invention , wherein the curve b is the ¹³ C NMR spectrum of the cycloolefin copolymer prepared in Example 8, and the curve c is the distortion-free polarization transfer enhanced (DEPT) spectrum of the cycloolefin copolymer prepared in Example 8, from the It can be seen from curve b and curve c that the ^cyclic olefin copolymer provided by the present invention has the structure shown in (I); It is calculated from ^{the 1} HNMR spectrum that the insertion rate of the cycloolefin monomer having the structure of formula (II) is 30.4 mol%.

The present invention uses differential scanning calorimetry (DSC) to detect the glass transition temperature of the obtained cycloolefin copolymer, and the results are shown in Figure 2, and Figure 2 is the DSC of the cycloolefin copolymer obtained in Examples 5 to 8 of the present invention Curve, wherein, curve d is the DSC curve of the cycloolefin copolymer prepared in Example 8 of the present invention, as can be seen from the curve d in Figure 2, the glass transition temperature of the cycloolefin copolymer prepared in this embodiment is 207.0 ° C . the

The present invention carries out tensile test experiment to the obtained cyclic olefin copolymer, and the result is as shown in Figure 3, and Fig. 3 is the stress-strain curve of the cyclic olefin copolymer that the embodiment of the present invention 6～8 obtains, and wherein, curve c is this The stress-strain curve of the cycloolefin copolymer prepared in the embodiment of the invention 8 can be seen from the curve c in Fig. 3, the elongation at break of the cycloolefin copolymer prepared in the present embodiment is 2.4%, and the tensile strength is 44.2MPa , the tensile modulus is 2390MPa. the

The present invention weighs and obtains that the mass of the cycloolefin copolymer prepared in this embodiment is 5.00 g; the relative weight average molecular weight of the cycloolefin copolymer prepared in this embodiment is detected by gel permeation chromatography to be 439 kg/mol, and the relative molecular weight distribution The index was 1.97. the

The present invention detects the catalytic activity of the polymerization reaction, and the result shows that the catalytic activity of the polymerization reaction in this example is 20.0×10 ⁶ g/mol _Ti ·h.

The present invention has detected the light transmittance of cyclic olefin copolymer, and the result is as shown in Figure 4, and Fig. 4 is the light transmittance curve of its ultraviolet-visible spectrum region of the cyclic olefin copolymer that the embodiment of the present invention 7～8 obtains, wherein , Curve B is the transmittance curve of the cycloolefin copolymer prepared in Example 8 in the ultraviolet-visible spectrum region, as can be seen from the curve B in Figure 6, the transmittance of the cycloolefin copolymer prepared in this embodiment> 85%. the

The present invention provides a cycloolefin copolymer having a structure of formula (I), wherein m and n are degrees of polymerization, m:n≥1.5; R ₁ and R ₂ are independently selected from hydrogen or carbon atoms with 1 to 10 Saturated aliphatic hydrocarbon group. In the present invention, α-olefins and cycloolefin monomers having the structure of formula (II) are used as polymerization monomers, and they are polymerized in an inert solvent under the action of a catalyst to obtain a cycloolefin copolymer having the structure of formula (I) . The cycloolefin monomer selected in the present invention has the structure of formula (II), which is a bulky cycloolefin. During the polymerization reaction, due to the influence of steric hindrance, high vitrification can be obtained under the condition of low insertion rate Cyclic olefin copolymers with transition temperature, in which the flexible α-olefin units increase, so that the rigidity of the cyclic olefin copolymer chains is reduced, and the entanglement between the chains is enhanced, thereby improving the tear resistance of the cyclic olefin copolymers , so that its brittleness is improved, and a cycloolefin copolymer with a higher glass transition temperature and improved brittleness is obtained. Experimental results show that the insertion rate of the cycloolefin monomer in the cycloolefin copolymer provided by the present invention is less than or equal to 30.0mol%, and its glass transition temperature can reach 207.0°C. The higher glass transition temperature makes the cycloolefin copolymer have Higher practicability; tensile test results show that when its glass transition temperature is 160.4°C, its elongation at break is 7.6%, and its tensile strength is 55.0MPa.

The above is only a preferred embodiment of the present invention, it should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications are also It should be regarded as the protection scope of the present invention. the

Claims (10)

1. cyclic olefine copolymer has formula (I) structure:

formula (I);

Wherein, m and n are the polymerization degree, m:n >=1.5;

R ₁And R ₂Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl.

2. cyclic olefine copolymer according to claim 1 is characterized in that, 20 >=m:n >=2.3.

3. cyclic olefine copolymer according to claim 1 is characterized in that, said R ₁And R ₂Be independently selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or hydrogen.

4. the preparation method of any described cyclic olefine copolymer of claim 1 ~ 3 may further comprise the steps:

In inert solvent, cycloolefin monomers and the terminal olefin that will have formula (II) structure carry out polyreaction under the condition that catalyzer exists, the cyclic olefine copolymer of (I) structure that obtains having formula;

formula (II);

formula (I);

In the formula (I), m and n are the polymerization degree, m:n >=1.5;

R ₁And R ₂Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl.

5. preparation method according to claim 4 is characterized in that, said terminal olefin and said mol ratio with cycloolefin monomers of formula (II) structure are (2.3 ~ 20): 1.

6. preparation method according to claim 4; It is characterized in that said terminal olefin is ethene, propylene, 1-butylene, iso-butylene, 1-amylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 1-hexene, 2-Methyl-1-pentene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butylene.

7. preparation method according to claim 4 is characterized in that, said catalyzer and said mol ratio with cycloolefin monomers of formula (II) structure are 1: (1 ~ 20).

8. preparation method according to claim 4 is characterized in that said catalyzer comprises Primary Catalysts and promotor;

Said Primary Catalysts is (tertiary butyl amido)-dimethyl--(tetramethyl--η ⁵-cyclopentadienyl moiety)-the silane titanium dichloride;

Said promotor is triisobutyl aluminium and triphen carbon four-(pentafluorophenyl group) borate.

9. preparation method according to claim 4 is characterized in that, the mol ratio of the triisobutyl aluminium in said Primary Catalysts and the said promotor is 1: (200 ~ 2500);

Triphen carbon four in said Primary Catalysts and the said promotor-(pentafluorophenyl group) boratory mol ratio is 1: (1 ~ 10).

10. preparation method according to claim 4 is characterized in that, said inert solvent is straight chain hydrocarbon compound, cyclic hydrocar-bons compound or arene compounds;

The temperature of said polyreaction is 0 ℃ ~ 100 ℃;

The time of said polyreaction is 1 minute ~ 60 minutes.

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