Cycloolefin composition as well as polymer hydride and low-haze optical film thereof

Abstract

The invention relates to the technical field of optical materials, in particular to a cycloolefin composition, a polymer hydride thereof and a low-haze optical film. The cycloolefin composition comprises a compound C1, and the retention time of the compound C1 in high performance gas chromatography measurement ranges from 16.0 minutes to 20.0 minutes. According to the invention, a proper amount of cycloolefin compound C1 is added into the cycloolefin composition, so that the size of spherocrystals in cycloolefin polymer products can be reduced, and the formation of crystal forms which contribute greatly to haze can be destroyed, so that the haze of a polymer film is effectively improved.

Description

Technical Field

[0001] The invention relates to the technical field of optical materials, in particular to a cycloolefin composition and a polymer hydride thereof and a low-haze optical film. Background Art

[0002] As electronic and display technologies continue to develop towards high speed, high integration, high density and ultra-thinness, higher and higher requirements are placed on the heat resistance, high temperature dimensional stability, water and oxygen barrier, low haze and other properties of polymer optical materials. Therefore, the research on low haze, colorless, transparent and high temperature resistant polymer optical films has received widespread attention.

[0003] Cyclic olefin copolymers have high transparency, high refractive index, low birefringence, and excellent heat resistance, chemical resistance, melt fluidity, dimensional stability, etc. They are widely used in the manufacture of various optical, information, electrical, and medical materials.

[0004] Haze is one of the important optical properties of film products. There are many factors that affect the haze of crystalline polymer films, which can be simply attributed to two aspects: materials and processing technology. Material factors include molecular structural parameters such as the relative molecular mass and its distribution of polymers, the content and distribution of comonomers, the content and distribution of branches of different lengths, and the presence of various additives. Processing technology factors include process parameters such as film making method, film thickness, melt temperature, cooling rate, and pulling rate. Haze reflects the scattering ability of the film for visible light, and the following three factors will lead to the enhancement of scattered light—greater refractive index difference, more scattering micro-areas, and larger scattering micro-area particle size. The haze of the film can be divided into surface haze and internal haze. The surface haze comes from the surface undulations of the film, and the internal haze mainly comes from the scattering of polymer spherulites and other crystal particles and phase separation structures.

[0005] The prior art has an optical film in which a hard coating is provided on one side of a light-transmitting substrate to suppress the haze of the film, but this solution does not solve the haze problem from the perspective of chemical structure. Summary of the invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a cycloolefin composition and a polymer hydride thereof and a low-haze optical film, thereby improving the haze of the optical film.

[0007] To achieve the above object, the present invention provides a cycloolefin composition, which includes a compound C1, and the retention time of the compound C1 in high performance gas chromatography determination is 16.0 minutes to 20.0 minutes.

[0008] Preferably, the retention time of compound C1 in high performance gas chromatography determination is 16.0 minutes to 17.0 minutes.

[0009] In some specific embodiments of the present invention, the retention time of compound C1 in high performance gas chromatography determination is 16.135 minutes.

[0010] The peak area of ​​the compound C1 in the high performance gas chromatography measurement is 0.001 to 0.5, preferably 0.001 to 0.3, relative to the total peak area 100 of the compounds contained in the cycloolefin composition.

[0011] The conditions for the above-mentioned high performance gas chromatography determination are preferably as follows:

[0012] Injection volume: 0.1 μL;

[0013] Inlet temperature: 220°C;

[0014] Program temperature rise: 50°C (1min) → 10°C / min → 170°C → 20°C / min → 300°C (5min);

[0015] As the column, Agilent 19091J-413 (HP-5), 30 m*320 μm*0.25 μm was used;

[0016] Carrier gas flow rate: 2 ml / min, split ratio: 200:1, tail gas flow: 25 ml / min;

[0017] As the measurement solution, a mixed solution of 1 ml of the cycloolefin composition and 10 mL of acetonitrile was used;

[0018] The injection volume was 2 μL.

[0019] Preferably, the molecular weight of the cycloolefin compound represented by C1 is 160.

[0020] Preferably, the compound C1 has the following structure:

[0021]

[0022] Wherein, m is an integer of 1-7, and when m is 7, the number of double bonds in the chemical formula is not greater than 4;

[0023] R1-R6 are independently a hydrogen atom, or a halogen atom other than a fluorine atom, or a hydrocarbon group with 1-20 carbon atoms which can be substituted by a halogen atom other than a fluorine atom; and R1 and R4, R2 and R3, R5 and R6 can form a ring together or form a bond individually, and the ring formation does not include a five-membered ring.

[0024] The cycloolefin compound represented by C1 contains double bonds in its structure, and the number of the double bonds is not greater than 4, and can be 1, 2, 3 or 4 double bonds.

[0025] The m can be 1, 2, 3, 4, 5, 6 or 7. Further, the m is 1, 2, 5, 6 or 7.

[0026] Preferably, the above ring formation includes a saturated or unsaturated ring.

[0027] Preferably, the ring is a 3-8-membered saturated or unsaturated ring, excluding a five-membered ring, and preferably a four-membered ring or a six-membered ring.

[0028] The above-mentioned hydrocarbon groups include saturated hydrocarbon groups and unsaturated hydrocarbon groups, including but not limited to alkyl groups, alkenyl groups and alkynyl groups.

[0029] Preferably, the R1-R6 are independently hydrogen atoms, chlorine atoms, bromine atoms, iodine atoms, or hydrocarbon groups with 1 to 10 carbon atoms that can be substituted by chlorine atoms, bromine atoms or iodine atoms. R1 and R4, R2 and R3, R5 and R6 can form a ring together or form a bond separately, and the ring is a four-membered or six-membered saturated or unsaturated ring.

[0030] More preferably, the R1-R6 are independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; further preferably, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a vinyl group, a propenyl group, a butenyl group, or a butadienyl group. R1 and R4, R2 and R3, and R5 and R6 can form a ring together or form a bond alone, and the ring is a four-membered or six-membered saturated or unsaturated ring.

[0031] Further preferably, the R1-R6 are independently hydrogen atoms or hydrocarbon groups with 1 to 4 carbon atoms; and R1 and R4 together form a four-membered or six-membered saturated or unsaturated ring, and R2 and R3, R5 and R6 are hydrogen atoms, alkyl groups with 1 to 4 carbon atoms, or together form a four-membered or six-membered saturated or unsaturated ring. The hydrocarbon group with 1 to 4 carbon atoms is preferably methyl, ethyl, propyl, vinyl, propenyl, butenyl, butadienyl.

[0032] In some specific embodiments of the present invention, R1-R6 are independently a hydrogen atom, an alkyl group or an alkenyl group having 1 to 4 carbon atoms; and R1 and R4 together form a four-membered or six-membered saturated or unsaturated ring, and R2 and R3 or R5 and R6 together form a four-membered or six-membered saturated or unsaturated ring.

[0033] In some specific embodiments of the present invention, R1-R6 are independently a hydrogen atom, an alkyl group or an alkenyl group having 1 to 4 carbon atoms; and R1 and R4 together form a four-membered or six-membered saturated or unsaturated ring, and R2, R3, R5, and R6 are independently a hydrogen atom, an alkyl group or an alkenyl group having 1 to 4 carbon atoms.

[0034] In some specific embodiments of the present invention, R1-R6 are independently a hydrogen atom, an alkyl group or an alkenyl group having 1 to 4 carbon atoms.

[0035] The alkyl group or alkenyl group having 1 to 4 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, a vinyl group, a propenyl group, a butenyl group or a butadienyl group.

[0036] The above R1-R6 can be connected to the mother core via a single bond or a double bond.

[0037] In some specific embodiments of the present invention, the compound C1 preferably comprises at least one of the following compounds (C1-a), (C1-b), (C1-c), (C1-d), (C1-e), (C1-f), (C1-g), (C1-h), (C1-i), (C1-j), (C1-k) and (C1-l):

[0038]

[0039] In the present invention, the cycloolefin compound represented by C1 and other cycloolefin compounds are combined to form a composition.

[0040] Preferably, the other cycloolefin compounds include one or more of norbornene cycloolefin compounds and tetracyclododecene cycloolefin compounds, and more preferably include both norbornene cycloolefin compounds and tetracyclododecene cycloolefin compounds.

[0041] The norbornene-based cycloolefin compound preferably includes one or more of methyl dicyclopentadiene, dimethyl dicyclopentadiene, ethyl dicyclopentadiene, vinyl dicyclopentadiene, acryl dicyclopentadiene, and dicyclopentadiene.

[0042] The tetracyclododecene cycloolefin compounds preferably include tetracyclo[4.4.0.12,5.17,10]-3-dodecene (tetracyclododecene), 8-methyltetracyclo[4.4.0.12,5.17,10]-3-dodecene (8-methyltetracyclododecene), 8-ethyltetracyclo[4.4.0.12,5.17,10]-3-dodecene, 8-ethylidenetetracyclo[4.4.0.12,5.17,10]-3- One or more of dodecene, 8,9-dimethyltetracyclo[4.4.0.12,5.17,10]-3-dodecene, 8-ethyl-9-methyltetracyclo[4.4.0.12,5.17,10]-3-dodecene, 8-ethylidene-9-methyltetracyclo[4.4.0.12,5.17,10]-3-dodecene, and 8-methyl-8-carboxymethyltetracyclo[4.4.0.12,5.17,10]-3-dodecene.

[0043] The mass ratio of the norbornene-based cycloolefin compound to the tetracyclododecene-based cycloolefin compound is preferably 5-9:1-5, more preferably 7:3.

[0044] The mass content of the cycloolefin compound represented by C1 in the cycloolefin composition is preferably 0.001% to 0.5%, more preferably 0.005% to 0.5%, and further preferably 0.005% to 0.3%.

[0045] The present invention provides a polymer hydrogenate, which is prepared by the above-mentioned cycloolefin composition through ring-opening copolymerization and hydrogenation.

[0046] The present invention has no particular limitation on the process and conditions of the above-mentioned ring-opening copolymerization reaction, which may be the ring-opening copolymerization reaction conditions of polyolefin compounds well known to those skilled in the art.

[0047] The ring-opening copolymerization reaction may be added with a solvent as long as it does not inhibit the reaction. The solvent includes, but is not limited to, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, saturated hydrocarbons such as hexane, heptane, octane, nonane, halogens such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene, etc. The above solvents can be used alone or in combination of two or more.

[0048] The present invention does not specifically limit the amount of the solvent. As the ring-opening copolymerization reaction proceeds, the concentration of the polymer generated by the polymerization increases continuously, the viscosity of the solution also increases, and the fluidity of the monomer decreases. Preferably, after the polymerization reaction is completed, the concentration of the polymer in the solvent is 0.1% to 50% by weight, more preferably 0.5% to 30% by weight, and further preferably 1% to 25% by weight.

[0049] Preferably, the ring-opening polymerization reaction is carried out under the catalytic action of a catalyst. The catalyst is mainly composed of a transition metal compound catalyst component and a metal compound co-catalyst component. The transition metal compound catalyst component is a transition metal compound of Groups 3-11 of the periodic table of elements. Including but not limited to halides, halides, alkoxy halides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, their derivatives, or complex products of their derivatives and complexing agents.

[0050] The transition metal compound catalyst component includes but is not limited to: TiCl4, TiBr4, VOCl3, WBr3, WCl6, WOCl4, MoCl5, MoOCl4, WO2, H2WO4, etc. In order to obtain higher polymerization activity, the catalyst is preferably a compound of W, Mo, Ti, V, preferably a halide, oxyhalide or alkoxy halide of W, Mo, Ti, V. Particularly preferred are compounds of W, and further preferred are halides of W, such as WBr3, WCl 6、 WOCl4, MoCl5, the above preferred catalysts have excellent reaction efficiency and can make the monomers containing alicyclic structures in the reaction raw materials almost completely polymerize, so that the designed polymer can be easily obtained.

[0051] The components of the metal compound co-catalyst are preferably metal compounds of Groups 1-2 and 12-14 of the periodic table, preferably having at least one metal element-carbon bond or metal element-hydrogen bond. More preferably, they include organic compounds containing elements such as Al, Sn, Li, Na, Mg, Zn, Cd, and B. The co-catalysts can be used alone or in combination of two or more.

[0052] The metal compound co-catalyst includes, but is not limited to, organic aluminum compounds such as trimethylaluminum, triisobutylaluminum, diethylaluminum monochloride, methylaluminum sesquichloride, and ethylaluminum dichloride; organic tin compounds such as tetramethyltin, diethyldimethyltin, tetrabutyltin, and tetraphenyltin; organic lithium compounds such as n-butyllithium; organic sodium compounds such as n-pentylsodium; organic magnesium compounds such as methylmagnesium iodide; organic zinc compounds such as diethylzinc; organic cadmium compounds such as diethylcadmium; organic boron compounds, etc. Among them, compounds of Group 13 metals are preferred, and organic compounds of Al are particularly preferred.

[0053] In the present invention, when the above-mentioned ring-opening polymerization reaction is carried out, in addition to the transition metal catalyst and the metal co-catalyst, a third component can also be added to enhance the metathesis polymerization activity. The third component preferably includes Lewis acids such as aliphatic tertiary amines, aromatic tertiary amines, molecular oxygen, alcohols, ethers, peroxides, carboxylic acids, acid anhydrides, acid chlorides, esters, ketones, nitrogen-containing compounds, and halogen-containing compounds, preferably alcohols. The above-mentioned third components can be used alone or in combination of two or more.

[0054] The weight ratio of the transition metal catalyst to the metal promoter is preferably 1:0.1 to 1:100, more preferably 1:0.1 to 1:10.

[0055] The weight ratio of the transition metal catalyst to the third component is preferably 1:0.05 to 1:50, more preferably 1:0.05 to 1:10.

[0056] In the present invention, the amount of catalyst added during the ring-opening polymerization reaction, calculated as the weight ratio of the transition metal in the polymerization, the mass ratio of the transition metal to the total monomers participating in the reaction is preferably 1:100-1:2000000, more preferably 1:500-1:20000, and further preferably 1:500-1:10000.

[0057] In the present invention, a chain transfer agent may be added during the ring-opening polymerization reaction, and the chain transfer agent preferably includes cis-olefins, including but not limited to one or more of cis-2-butene, cis-3-hexene, cis-4-octene, cis-4-decene, 1-hexene and 1-octene. In view of availability, economy and operability, one or more of cis-2-butene, cis-3-hexene, cis-4-octene, 1-hexene and 1-octene are more preferred.

[0058] In the present invention, the amount of the chain transfer agent used depends on the target molecular weight, and the added amount is preferably 1 mol / 100,000 mol to 1 mol / 10 mol, and more preferably 1 mol / 10,000 mol to 1 mol / 20 mol.

[0059] In the present invention, the ring-opening polymerization reaction can be carried out by batch reaction or by continuously supplying raw materials by a plug flow method or the like.

[0060] The ring-opening polymerization reaction is preferably carried out under normal pressure, but may be carried out under pressure as required, or may be carried out under an inert gas in consideration of safety.

[0061] The temperature of the ring-opening polymerization reaction is preferably 20°C to 100°C, more preferably 25°C to 90°C.

[0062] The polymerization conversion rate of the polymer obtained by polymerization is preferably 95 wt % or more, more preferably 97 wt % or more, particularly preferably 99.5 wt % or more.

[0063] In the present invention, the above-mentioned polymerization conversion rate is a value obtained by subtracting the weight of unreacted monomers from the weight of monomers used and dividing the result by the weight of monomers used.

[0064] After the ring-opening copolymerization reaction, a hydrogenation catalyst is added to the system to carry out a hydrogenation reaction.

[0065] The present invention has no particular limitation on the above hydrogenation catalyst, and it can be a hydrogenation catalyst commonly used for olefin compounds and aromatic compounds well known to those skilled in the art.

[0066] The hydrogenation catalyst may be a homogeneous catalyst or a heterogeneous catalyst; a homogeneous catalyst can suppress the amount of catalyst added because it is easy to disperse in the hydrogenation reaction liquid. In addition, since it has sufficient activity even when not under high temperature and high pressure, it is not easy to cause decomposition and gelation of cyclic olefin ring-opening polymers and their hydrogenates. Therefore, considering the cost and the quality of the product, it is preferred to use a homogeneous catalyst.

[0067] The homogeneous catalyst includes, but is not limited to: Wilkinson coordination compound [tri(triphenylphosphine)rhodium chloride (I)]; catalysts formed by a combination of transition metal compounds and alkyl metal compounds, such as combinations of cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, dichlorotitanocene / n-butylaluminum, dichlorozirconocene / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, etc.

[0068] On the other hand, since heterogeneous catalysts show particularly excellent activity under high temperature and high pressure, they can hydrogenate cyclic olefin ring-opening polymers in a short time.

[0069] The heterogeneous catalyst includes, but is not limited to, a heterogeneous catalyst in which a metal such as nickel (Ni), palladium (Pd), platinum (Pt), ruthenium (Ru), or rhodium (Rh) is supported on a carrier. In particular, in order to reduce the weight of impurities in the obtained hydride, an adsorbent such as alumina or diatomaceous earth is preferably used as the carrier.

[0070] The above-mentioned hydrogenation reaction is usually carried out in an organic solvent. As an organic solvent, there is no particular limitation as long as it is an organic solvent that is inactive in the hydrogenation reaction. As an organic solvent, a hydrocarbon solvent is preferably used from the viewpoint of being easy to dissolve the generated hydride. The hydrocarbon solvent includes, but is not limited to: aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, decalin, and bicyclononane.

[0071] The organic solvents may be used alone or in combination of two or more. In addition, solvents commonly used in ring-opening polymerization reactions are also suitable as solvents for hydrogenation reactions, so a hydrogenation catalyst may be directly added to the ring-opening polymerization reaction solution and then supplied to the hydrogenation reaction.

[0072] The temperature of the hydrogenation reaction is preferably -20 to 250°C, more preferably 50 to 220°C, and even more preferably 100 to 200°C.

[0073] The hydrogen pressure in the hydrogenation reaction is preferably 0.01 to 10.0 MPa, more preferably 0.05 to 8.0 MPa, and even more preferably 0.1 to 5.0 MPa.

[0074] The time of the hydrogenation reaction may be appropriately selected in order to control the hydrogenation rate. The time of the hydrogenation reaction is preferably 0.1 to 50 hours.

[0075] After the hydrogenation reaction is terminated, it is preferably centrifuged, filtered or the like to remove the catalyst residue. In addition, a catalyst inactivator such as water or alcohol, or an adsorbent such as activated clay or alumina may be added as needed.

[0076] Preferably, after the hydrogenation reaction is completed, the hydride is collected by precipitating the hydride in a poor solvent and filtering. The poor solvent is preferably isopropanol.

[0077] The degree of hydrogenation of the finally obtained cyclic olefin ring-opening polymer hydrogenate is measured by H-NMR spectroscopy using deuterated chloroform as a solvent. Preferably, the degree of hydrogenation is 98% or more, and more preferably, the degree of hydrogenation is 98.5% or more.

[0078] The weight average molecular weight of the hydrogenated cyclic olefin ring-opening polymer provided by the present invention is preferably 20,000 to 150,000, more preferably 20,000 to 100,000.

[0079] Preferably, in the present invention, additives may be added to the above polymer hydrogenate.

[0080] The additives preferably include antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, plasticizers, antistatic agents and other conventional additives in the art.

[0081] The mass content of the additive in the polymer hydrogenate is preferably 0.01% to 5%, more preferably 0.1% to 2%, and further preferably 0.2% to 1%.

[0082] The present invention provides application of the polymer hydride in preparing optical materials.

[0083] The invention provides a low-haze optical film, which is obtained by processing and molding the above-mentioned polymer hydrogenate.

[0084] The low-haze optical film provided by the present invention can be used as a light guide plate or polarizing film of an optical device.

[0085] The present invention has no special limitation on the processing and forming process of the low-haze optical film, and the film can be prepared by methods well known to those skilled in the art.

[0086] The present invention has no special limitation on the thickness and size of the low-haze optical film, which can be adjusted according to the product size.

[0087] Preferably, the thickness of the low haze optical film is 5 μm or more, more preferably 10 μm or more, preferably 200 μm or less, more preferably 170 μm or less.

[0088] In the present invention, the thickness of the film is preferably measured using a micrometer MDE-25MX manufactured by Mitutoyo Co., Ltd. Preferably, the center of the film is measured three times, and the average value is used as the thickness.

[0089] The internal haze of the low haze optical film prepared by the present invention is less than 1%, more preferably less than 0.5%, and further preferably less than 0.3%. The prepared film has higher transparency and is more suitable for optical films such as polarizer protective films.

[0090] In the present invention, the internal haze of the film can be measured using, for example, a haze meter ("NDH5000" manufactured by Nippon Denshoku Industries, Ltd.).

[0091] Compared with the prior art, the present invention provides a cycloolefin composition, including the cycloolefin compound shown in C1 and other cycloolefin compounds. The present invention helps to reduce the size of spherulites in cycloolefin polymer products and destroy the formation of crystal forms that contribute greatly to haze by adding an appropriate amount of the cycloolefin compound shown in C1 to the cycloolefin composition, thereby effectively improving the haze of the polymer film. DETAILED DESCRIPTION

[0092] In order to further illustrate the present invention, the following is a detailed description in conjunction with the embodiments. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the invention.

[0093] All raw materials of the present invention have no particular limitation on their sources, and can be purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0094] In the following description, "%" and "parts" representing amounts are by weight unless otherwise noted. In addition, the operations described below are performed at room temperature and pressure unless otherwise noted.

[0095] Evaluation Method

[0096] Measurement methods of weight average molecular weight and number average molecular weight

[0097] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymers dissolved in tetrahydrofuran (THF) or trifluorotoluene (TFT) were determined using a gel permeation chromatography (GPC) system (Agilent) with molecular weight calibrated by polystyrene standards;

[0098] Detector: Agilent 1260 Infinity II, serially connected columns: PL1110-6300, column temperature 35°C, flow rate 1 ml / min, sample concentration: 3.0 to 9.0 mg / ml.

[0099] Method for measuring internal haze of thin films.

[0100] The internal haze of the film is measured as follows:

[0101] First, a test piece of 50 mm×50 mm in size was cut out from the film, and the haze of the sample was measured using a haze meter ("NDH5000" manufactured by Nippon Denshoku Industries).

[0102] Examples 1-6

[0103] Methyl dicyclopentadiene, 8-methyltetracyclo[4.4.0.12,5.17,10]-3-dodecene and 1-hexene were mixed in a weight ratio of 7:3:0.05 to obtain a composition B;

[0104] Compound C1-a tricyclo[6.2.2.0(2,7)]dodeca-6,9-diene was added to composition B in a certain amount to obtain a composition mixture having a C1 content of 0.001wt% to 0.5wt% (as shown in Table 1 below), and then 0.05wt% of a catalyst was added. After reacting in toluene at room temperature for 2 hours, 0.4 weight parts of isopropanol was added to each 100 weight parts of the obtained polymerization reaction solution to deactivate the ring-opening polymerization catalyst and terminate the polymerization reaction. The polymerization conversion rate of the polymerization reaction was found to be 99.8%.

[0105] Compound C1-a was prepared according to the method described in the literature, which is Reactions of 1-halocyclohexenes and methyl substituted 1-halocyclohexenes with potassium t-butoxide, Tetrahedron, Volume 28, Issue 19, 1972, Pages 4883-4904, ISSN 0040-4020, https: / / doi.org / 10.1016 / 0040-4020(72)88141-9.

[0106] Compound C1-e was prepared according to the method described in the literature: Bonjouklian R, Ruden RA. Versatile allene and carbon dioxide equivalents for the Diels-Alder reaction [J]. The Journal of Organic Chemistry, 1977, 42 (25): 4095-4103.

[0107] Compound C1-g was prepared according to the method described in the literature: Brudermüller M, Musso H. Synthesis of all-cis-1,4,7,10-Cyclododecatetraene [J]. Angewandte Chemie International Edition in English, 1988, 27 (2): 298-299.

[0108] Compound C1-1 was prepared according to the method described in the literature: Binger P, Germer A. Research on Methylencyclopropane, V1) Palladium (0)-katalysierte [2σ + 2π]-Cycloadditionen des 1-Methylen-2-vinylcyclopropans [J]. Chemische Berichte, 1981, 114 (10): 3325-3335.

[0109] Among them, compound C1-a was detected by the gas phase detection method of "injection volume: 0.1μL; injection port temperature: 220℃; program temperature: 50℃(1min)→10℃ / min→170℃→20℃ / min→300℃(5min); using Agilent 19091J-413 (HP-5), 30m*320μm*0.25μm as column; carrier gas flow rate: 2ml / min, split ratio: 200:1, tail blow: 25ml / min, using a mixed solution of 1ml of cyclic olefin composition and 10mL of acetonitrile as the measurement solution; injection volume is 2μL" and its retention time was detected to be 16.135min.

[0110] Among them, compound C1-e was detected by gas phase detection method "injection volume: 0.1μL; injection port temperature: 220℃; program temperature: 50℃(1min)→10℃ / min→170℃→20℃ / min→300℃(5min); using Agilent 19091J-413 (HP-5), 30m*320μm*0.25μm as column; carrier gas flow rate: 2ml / min, split ratio: 200:1, tail blow: 25ml / min, using a mixed solution of 1ml of cyclic olefin composition and 10mL of acetonitrile as the measurement solution; injection volume is 2μL" and its retention time was detected to be 16.178min.

[0111] Among them, compound C1-g was detected by gas phase detection method "injection volume: 0.1μL; injection port temperature: 220℃; program temperature: 50℃(1min)→10℃ / min→170℃→20℃ / min→300℃(5min); using Agilent 19091J-413 (HP-5), 30m*320μm*0.25μm as column; carrier gas flow rate: 2ml / min, split ratio: 200:1, tail blow: 25ml / min, using a mixed solution of 1ml of cyclic olefin composition and 10mL of acetonitrile as the measurement solution; injection volume is 2μL" and its retention time was detected to be 16.384min.

[0112] Among them, compound C1-1 was detected by gas phase detection method "injection volume: 0.1μL; injection port temperature: 220℃; program temperature: 50℃(1min)→10℃ / min→170℃→20℃ / min→300℃(5min); using Agilent 19091J-413 (HP-5), 30m*320μm*0.25μm as column; carrier gas flow rate: 2ml / min, split ratio: 200:1, tail blow: 25ml / min, using a mixed solution of 1ml of cyclic olefin composition and 10mL of acetonitrile as the measurement solution; injection volume is 2μL" and its retention time was detected to be 16.425min.

[0113] The catalyst adopts a main catalyst, a co-catalyst and an activator composition, the main catalyst adopts WOCl4, the co-catalyst adopts diethylaluminum chloride, the activator adopts n-butanol, and the main catalyst: co-catalyst: activator = 1:2:1.5 (molar ratio).

[0114] For every 100 parts by weight of the polymerization reaction solution obtained in the previous step, 1.2 parts by weight of a diatomaceous earth-supported nickel catalyst (manufactured by Zudochemy Catalyst; G-96D, nickel loading rate 58 wt%) and 200 parts by weight of cyclohexane were added to a hydrogenation reactor, and the hydrogenation reaction was carried out at 170° C. and a hydrogen pressure of 4.5 MPa for 8 hours; the solution after the reaction was filtered through a pressure filter (manufactured by Ishikawajima Harima Heavy Industries, Ltd., leaf filter) using diatomaceous earth as a filter aid to remove the catalyst.

[0115] The reaction solution containing the obtained polymer hydrogenate was poured into 3000 parts by weight of isopropanol under stirring to precipitate the hydrogenate, and the mixture was collected by filtration. After washing with 500 parts by weight of acetone, it was dried at 100° C. for 24 hours in a vacuum dryer under reduced pressure of 0.1 kPa or less to obtain a cyclic olefin ring-opening polymer hydrogenate product.

[0116] Sample preparation

[0117] The hydrogenated cyclic olefin ring-opening polymer was clamped by a SUS metal plate heated to 250°C, and a pressure of 100 kgf was applied by a punch for 3 minutes. A pressure of 100 kgf was further applied by a punch set at 25°C for 5 minutes to produce a film with a thickness of 100 μm, which was then cut into a test piece of 50*50 mm. The results of the physical property measurement of the film are shown in Table 1.

[0118] Comparative Examples 1-3

[0119] The contents of compound C1 were 0%, 1% and 2% respectively, and the other conditions were the same as those in Example 1. The results of the measurement of the physical properties of the obtained films are shown in Tables 1-4.

[0120] Table 1

[0121]

[0122]

[0123] Table 2

[0124]

[0125] Table 3

[0126]

[0127]

[0128] Table 4

[0129]

[0130]

[0131] According to the above embodiments and comparative examples, when the proportion of cycloolefin compound C1 in the entire cycloolefin composition (gas chromatography peak area percentage) is 0.001% to 0.5%, especially 0.005% to 0.3%, the haze of the film product is well improved.

[0132] The above embodiments are only used to help understand the method and core idea of ​​the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A cyclic olefin composition, comprising a compound C1, wherein the retention time of the compound C1 in a high performance gas chromatography determination is 16.0 minutes to 20.0 minutes.

2. The cyclic olefin composition according to claim 1, characterized in that The compound C1 has the following structure: Wherein, m is an integer of 1-7, and when m is 7, the number of double bonds in the chemical formula is not greater than 4; R1-R6 are independently a hydrogen atom, or a halogen atom other than a fluorine atom, or a hydrocarbon group with 1-20 carbon atoms which can be substituted by a halogen atom other than a fluorine atom; and R1 and R4, R2 and R3, R5 and R6 can form a ring together or form a bond individually, and the ring formation does not include a five-membered ring.

3. The cyclic olefin composition according to claim 2, characterized in that The m is 1, 2, 5, 6 or 7; The R1-R6 are independently a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms; and R1 and R4, R2 and R3, R5 and R6 can form a ring together or form a bond individually, and the ring is a 3-8-membered saturated or unsaturated ring, and does not include a five-membered ring.

4. The cyclic olefin composition according to claim 3, characterized in that R1-R6 are independently a hydrogen atom, an alkyl group or an alkenyl group having 1 to 4 carbon atoms; R1 and R4 together form a four-membered or six-membered saturated or unsaturated ring, and R2 and R3 or R5 and R6 together form a four-membered or six-membered saturated or unsaturated ring; Or R1-R6 are independently hydrogen atoms, alkyl or alkenyl groups with 1 to 4 carbon atoms; and R1 and R4 together form a four-membered or six-membered saturated or unsaturated ring, and R2, R3, R5, and R6 are independently hydrogen atoms, alkyl or alkenyl groups with 1 to 4 carbon atoms; Alternatively, R1-R6 are independently a hydrogen atom, an alkyl group or an alkenyl group having 1 to 4 carbon atoms.

5. The cyclic olefin composition according to claim 1, characterized in that The cyclic olefin composition also includes other cyclic olefin compounds; The other cycloolefin compounds include one or more of norbornene cycloolefin compounds and tetracyclododecene cycloolefin compounds; The norbornene-based cycloolefin compound includes one or more of methyl dicyclopentadiene, dimethyl dicyclopentadiene, ethyl dicyclopentadiene, vinyl dicyclopentadiene, acryl dicyclopentadiene, and dicyclopentadiene; The tetracyclododecene cycloolefin compounds include tetracyclo[4.4.0.12,5.17,10]-3-dodecene, 8-methyltetracyclo[4.4.0.12,5.17,10]-3-dodecene, 8-ethyltetracyclo[4.4.0.12,5.17,10]-3-dodecene, 8-ethyltetracyclo[4.4.0.12,5.17,10]-3-dodecene, 8,9-dimethyltetracyclo[4.4.0.12,5.17,10]-3-dodecene, One or more of 8-ethyl-9-methyltetracyclo[4.4.0.12,5.17,10]-3-dodecene, 8-ethylidene-9-methyltetracyclo[4.4.0.12,5.17,10]-3-dodecene, and 8-methyl-8-carboxymethyltetracyclo[4.4.0.12,5.17,10]-3-dodecene.

6. The cycloolefin composition according to any one of claims 1 to 5, characterized in that The mass content of the cycloolefin compound represented by C1 in the cycloolefin composition is 0.001% to 0.5%.

7. A polymer hydrogenate prepared by ring-opening copolymerization and hydrogenation of the cycloolefin composition according to any one of claims 1 to 6.

8. Use of the polymer hydride according to claim 7 in the preparation of optical materials.

9. A low haze optical film obtained by processing and molding the polymer hydrogenate according to claim 7.

10. The low haze optical film according to claim 9, characterized in that: The low-haze optical film is a light guide plate or a polarizing film of an optical device.

Images