Cyclic olefin ring-opening polymer and hydride thereof

Abstract

The invention relates to the field of optical materials, in particular to a cyclic olefin ring-opening polymer and hydride thereof. The ring-opening polymer comprises a structural unit (A) from a formula I and a structural unit (B) from other norbornene monomers, and the content (in percentage by mass) of the structural unit (A) accounts for 10-40% of all the structural units. The polymer has excellent thermal yellowing resistance, dimensional stability at high temperature and formability. According to the present invention, a cyclic olefin ring-opening polymer hydride having excellent thermal yellowing resistance, dimensional stability at high temperatures, and moldability can be provided; a resin molded article obtained using the cyclic olefin ring-opening polymer hydride and an optical member formed from the resin molded article also have the advantages of thermal yellowing resistance, dimensional stability at high temperatures, moldability, and the like.

Description

Technical Field

[0001] The invention relates to the field of optical materials, and in particular to a cyclic olefin ring-opening polymer and a hydride thereof. Background Art

[0002] In recent years, cyclic olefin ring-opening polymers, especially hydrogenated cyclic olefin ring-opening polymers (hereinafter, cyclic olefin ring-opening polymers, hydrogenated cyclic olefin ring-opening polymers and copolymers are also referred to as cyclic olefin ring-opening polymers) have attracted much attention as thermoplastic transparent resins with high Abbe numbers and excellent heat resistance. The polymers are widely used in the fields of optical lenses, medical bag materials, optical films and other materials. In order to make the material perform excellent functions even when it is small or thin, it is required to have higher linear transmittance and yellowing resistance.

[0003] Therefore, the present invention provides a cycloolefin ring-opening polymer hydrogenate having high linear transmittance, excellent yellowing resistance and excellent molding performance, a resin molded body and an optical component prepared using the ring-opening polymer hydrogenate. Summary of the invention

[0004] According to the problems of the prior art, the present invention provides a cyclic olefin ring-opening polymer and a hydride thereof. The cyclic olefin ring-opening polymer comprises a structural unit formed by ring opening of formula I. The polymer has excellent heat yellowing resistance, dimensional stability at high temperature and formability. A cyclic olefin ring-opening polymer hydride having excellent heat yellowing resistance, dimensional stability at high temperature and formability can be provided, and a resin molded body obtained by using the cyclic olefin ring-opening polymer hydride and an optical component formed by the resin molded body also have advantages such as heat yellowing resistance, dimensional stability at high temperature and formability.

[0005] In order to achieve the above technical effects, the technical solution of the present invention includes:

[0006] A cyclic olefin ring-opening polymer, comprising a structural unit (A) from formula I and a structural unit (B) from other norbornene-based monomers, wherein the content of the structural unit (A) (by mass percentage) accounts for 10% to 40% of all structural units.

[0007]

[0008] In Formula I, R1 to R4 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms; R5 to R 12They independently represent a hydrogen atom, a hydrocarbon group having 1-10 carbon atoms, a polar group consisting of a halogen atom or / and an alkoxy group or / and a hydroxyl group or / and an ester group or / and a cyano group or / and an amide group or / and an imide group or / and a silyl group, a group having an aromatic or heterocyclic ring, or a group in which an aromatic or heterocyclic ring is combined with an alkylene group having 1-5 carbon atoms; m represents an integer of 0 to 2, and n represents an integer of 0 to 10.

[0009] Preferably, R6 and R9, R9 and R 11 , R 10 With R 12 , R 12 and R8 may bond to each other to form a carbocyclic ring or a heterocyclic ring, and the carbocyclic ring or the heterocyclic ring may be a monocyclic structure or a polycyclic structure or an aromatic ring.

[0010] Preferably, the proportion of the syndiotactic dyad from the structural unit of formula I in the ring-opening polymer structural unit to the total mass of the polymer is less than 30%. Reducing the regularity of the polymer is more conducive to improving the linear transmittance and transparency of the formed body.

[0011] Preferably, the formula I as described above can specifically be a bicyclo-2-heptene derivative (bicyclohept-2-ene derivative), a tricyclo-3-decene derivative, a tricyclo-3-undecene derivative, a tetracyclo-3-dodecene derivative, a pentacyclo-4-pentadecaene derivative, a pentacyclopentadecadiene derivative, a pentacyclo-3-pentadecaene derivative, a pentacyclo-4-hexadecene derivative, a pentacyclo-3-hexadecene derivative, a hexacyclo-4-heptadecaene derivative, a heptadecaene derivative, a heptadecaene derivative, Heptacyclic-4-eicosene derivatives, heptacyclic-5-heneicosene derivatives, octacyclic-5-hexadecene derivatives, nonacyclic-5-pentadecene derivatives, nonacyclic-6-hexadecene derivatives, derivatives of cyclopentadiene-acenaphthene adducts, 1,4-methylene-1,4,4a,9a-tetrahydrofluorene (Formula II) derivatives, 1,4-methylene-1,4,4a,5,10,10a-hexahydroanthracene (Formula III) derivatives, cycloolefin derivatives having 3 to 20 carbon atoms, and the like.

[0012] More preferably, the formula I can be a tetracyclic [4.4.0.1 2,5 .1 7,10 ]-3-dodecene derivatives, hexacyclo[6.6.1.1 3,6 .1 10,13 .0 2,7 .0 9,14]-4-heptadecene derivatives, 1,4-methylene-1,4,4a,9a-tetrahydrofluorene derivatives, 1,4-methylene-1,4,4a,5,10,10a-hexahydroanthracene derivatives, acenaphthene-norbornene (Formula IV) derivatives, cyclopentadiene-benzyne adduct (benzonorbornene) (Formula V) derivatives, benzonorbornene (Formula VI) derivatives.

[0013]

[0014]

[0015] Particularly preferably, the formula I can be 1,4-methylene-1,4,4a,9a-tetrahydrofluorene, 1,4-methylene-1,4,4a,5,10,10a-hexahydroanthracene, cyclopentadiene-benzyne adduct, cyclopentadiene-acenaphthene adduct, and most preferably 1,4-methylene-1,4,4a,9a-tetrahydrofluorene.

[0016] Cyclic olefins shown in formula I as described above can be manufactured by making cyclopentadiene and olefins with corresponding structures undergo Diels-Alder reaction. These structural units (A) derived from cyclic olefins shown in formula I all contain two or more isomers. In addition, the material obtained by polymerization using the above-mentioned monomers can be changed as needed, and the structure of the structural unit derived from the monomer can be changed at this time. For example, the benzene ring in the structural unit derived from the monomer can be changed into a cyclohexyl ring according to the conditions by hydrogenation treatment.

[0017] Preferably, in the ring-opening polymer, the other norbornene-based monomers constituting the structural unit (B) are compounds having a norbornene ring structure, without particular limitation. Specifically, they may have polar or non-polar substituents, and may have ring structures other than the norbornene ring.

[0018] The compounds of the norbornene ring structure constituting the other norbornene-based monomers used in the present invention may specifically be 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-n-butyl-2-norbornene, 5-n-hexyl-2-norbornene, 5-n-decyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclo[9.2.1.02,10.03,8]tetradeca-3,5,7,12-tetraene, tetracyclo[10.2.1.0 2,11 .0 4,9 ] penta-4,6,8,13-tetraene and other unsubstituted or hydrocarbon-containing bicyclo[2.2.1]hept-2-enes; tetracyclo[6.2.1.1 3,6 .02,7 ] dodeca-4-ene, 9-methyltetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-4-ene, 9-ethyltetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-4-ene, 9-n-butyltetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-4-ene, 9-cyclohexyltetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-4-ene, 9-ethylenetetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-4-ene, 9-vinyltetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-4-ene, 9-phenyltetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-4-ene or other unsubstituted or hydrocarbon-containing tetracyclic [6.2.1.1 3,6 .0 2,7 ] dodecanes; bicyclo[2.2.1]hept-2-enes having an alkoxycarbonyl group, such as methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, n-butyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, ethyl 2-methyl-5-norbornene-2-carboxylate, n-butyl 2-methyl-5-norbornene-2-carboxylate, methyl 5-norbornene-2,3-dicarboxylate, and ethyl 5-norbornene-2,3-dicarboxylate; tetracyclo[6.2.1.1 3,6 .0 2,7 ] methyl dodecan-9-ene-4-carboxylate, tetracyclo[6.2.1.1 3,6 .0 2,7 ] ethyl dodecyl-9-ene-4-carboxylate, 4-methyltetracyclo[6.2.1.1 3,6 .0 2,7 ] methyl dodecan-9-ene-4-carboxylate, tetracyclo[6.2.1.1 3,6 .0 2,7 ] methyl dodecan-9-ene-4,5-dicarboxylate, tetracyclo[6.2.1.1 3,6 .0 2,7 ] tetracyclic [6.2.1.1] having an alkoxycarbonyl group, such as ethyl dodecan-9-ene-4,5-dicarboxylate 3,6 .0 2,7 ] dodeca-9-enes; bicyclo[2.2.1]hept-2-enes having a hydroxycarbonyl group, such as 5-norbornene-2-carboxylic acid and 5-norbornene-2,3-dicarboxylic acid; tetracyclo[6.2.1.1 3,6 .02,7 ]Dodec-9-ene-4-carboxylic acid, tetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene-4,5-dicarboxylic acid and other tetracyclic [6.2.1.1 3,6 .0 2,7 ] dodeca-9-enes; bicyclo[2.2.1]hept-2-enes having a hydroxyl group, such as 2-hydroxy-5-norbornene, 2-hydroxymethyl-5-norbornene, 2,2-bis(hydroxymethyl)-5-norbornene, and 2,3-bis(hydroxymethyl)-5-norbornene; tetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-en-4-ol, tetracyclo[6.2.1.1 3,6 .0 2,7 ]Dodec-9-ene-4-methanol, tetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene-4,5-dimethanol and other tetracyclic [6.2.1.1 3,6 .0 2,7 ] dodeca-9-enes; bicyclo[2.2.1]hept-2-enes having an acetoxy group, such as 2-acetoxy-5-norbornene, 2-acetoxymethyl-5-norbornene, 2,2-bis(acetoxymethyl)-5-norbornene, and 2,3-bis(acetoxymethyl)-5-norbornene; 4-acetoxytetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene, 4-acetoxymethyltetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene, 4,5-bis(acetoxymethyl)tetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene and other tetracyclic rings having an acetoxy group [6.2.1.1 3,6 .0 2,7 ] dodeca-9-enes; bicyclo[2.2.1]hept-2-enes having a functional group containing a nitrogen atom, such as 5-norbornene-2-carbonitrile and 5-norbornene-2-carboxamide; tetracyclo[6.2.1.1 3,6 .0 2,7 ]Dodec-9-ene-4-carbonitrile, tetracyclo[6.2.1.1 3,6 .0 2,7 ] tetracyclic [6.2.1.1] having a functional group containing a nitrogen atom, such as dodeca-9-ene-4-carboxamide 3,6 .0 2 ,7] dodeca-9-enes; bicyclo[2.2.1]hept-2-enes having halogen atoms such as 2-chloro-5-norbornene and 2-fluoro-5-norbornene; 4-chlorotetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene, 4-fluorotetracyclo[6.2.1.1 3,6 .0 2,7 ] tetracyclic rings having halogen atoms such as dodec-9-ene [6.2.1.1 3,6 .0 2,7 ] dodeca-9-enes; bicyclo[2.2.1]hept-2-enes having a functional group containing a silicon atom, such as 2-trimethylsilyloxy-5-norbornene, 2-trimethoxysilyl-5-norbornene, and 2-tris(trimethoxysilyloxy)silyl-5-norbornene; 4-trimethylsilyloxytetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene, 4-trimethoxysilyltetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene, 4-tris(trimethoxysilyloxy)silyltetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene and the like having a tetracyclic [6.2.1.1 3,6 .0 2,7 ] dodeca-9-enes; bicyclo[2.2.1]hept-2-enes having anhydride structures, carbonate structures, or dithiocarbonate structures, such as 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2,3-carbonate, and 5-norbornene-2,3-dithiocarbonate; tetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene-4,5-dicarboxylic anhydride, tetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene-4,5-carbonate, tetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-9-ene-4,5-dithiocarbonate and the like having anhydride structure, carbonate structure, dithiocarbonate structure [6.2.1.1 3,6 .0 2,7 These norbornenes may be used alone or in combination of two or more.

[0019] Furthermore, the present invention provides a cyclic olefin ring-opening polymer hydrogenate, which is obtained by hydrogenating the cyclic olefin ring-opening polymer of the present invention, wherein the hydrogenation rate is >99%.

[0020] The weight average molecular weight of the cyclic olefin ring-opening polymer hydrogenate is not particularly limited. Preferably, its weight average molecular weight Mn is 1000 to 500000, more preferably 10000 to 100000, and most preferably 15000 to 80000. The cyclic olefin ring-opening polymer hydrogenate of the present invention will not make the weight average molecular weight too high, thereby improving its bending strength. Therefore, the cyclic olefin ring-opening polymer hydrogenate of the present invention has excellent moldability. The cyclic olefin ring-opening polymer hydrogenate having the above-mentioned weight average molecular weight has excellent moldability and the obtained molded body has excellent heat resistance.

[0021] The molecular weight distribution (Mw / Mn) of the hydrogenated cyclic olefin ring-opening polymer is not particularly limited, but is preferably 1-5, and more preferably 1-4.

[0022] Preferably, the glass transition temperature of the cyclic olefin ring-opening polymer hydrogenate is above 120°C.

[0023] The yellowness difference (ΔYI) of the hydrogenated cyclic olefin ring-opening polymer of the present invention is usually 20 or less, preferably 15 or less.

[0024] The preparation method of the cyclic olefin ring-opening polymer hydrogenate of the present invention is not particularly limited. For example, the target cyclic olefin ring-opening polymer hydrogenate can be obtained by subjecting 1,4-methylene-1,4,4a,9a-tetrahydrofluorene and other norbornene-based monomers to a ring-opening polymerization reaction in the presence of a polymerization catalyst, and then hydrogenating the carbon-carbon double bonds of the obtained cyclic olefin ring-opening polymer in the presence of a hydrogenation catalyst.

[0025] The polymerization catalyst used is not particularly limited.

[0026] The polymerization of norbornene monomers can be carried out by bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, precipitation polymerization, etc. In the case of polymerization using a solvent, it is necessary to use a solvent that does not adversely affect the catalytic activity. As solvents that can be used, aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; ethers such as diethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate, n-propyl acetate, and n-butyl acetate; lactones such as δ-valerolactone and γ-butyrolactone, and water.

[0027] When the ring-opening polymerization reaction is carried out, a Lewis base may be added to the polymerization reaction system for the purpose of controlling the polymerization rate and the molecular weight distribution of the obtained ring-opening polymer.

[0028] The Lewis base is not particularly limited and can be selected from: ethers such as diethyl ether and tetrahydrofuran; ketones such as acetone and cyclohexanone; nitriles such as acetonitrile and benzonitrile; amines such as triethylamine and N,N-diethylaniline; pyridines such as pyridine and lutidine; phosphines such as triphenylphosphine; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; phosphine oxides such as triphenylphosphine oxide; esters such as ethyl acetate, etc. Among these, ethers, pyridines, and nitriles are preferred.

[0029] The ring-opening polymerization reaction is usually carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not affect the polymerization reaction and dissolves or disperses the obtained polymer under predetermined conditions.

[0030] More specifically, the organic solvent can be selected from: aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decalin, bicycloheptane, tricyclodecane, hexahydroindenecyclohexane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile; ether solvents such as diethyl ether and tetrahydrofuran; aromatic ether solvents such as anisole and phenethyl ether, etc. Among these, preferred are aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents, and aromatic ether solvents commonly used in industry.

[0031] The molecular weight of the obtained ring-opening polymer can be adjusted during the ring-opening polymerization reaction. Specifically, an appropriate amount of a molecular weight regulator such as a vinyl compound or a diene compound can be added to the polymerization reaction system.

[0032] The vinyl compound used for molecular weight adjustment is not particularly limited as long as it is an organic compound having a vinyl group. It can be selected from: α-olefins such as 1-butene, 1-pentene, 1-hexene, and 1-octene; styrenes such as styrene and vinyl toluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylamide, etc.

[0033] The diene compound used for molecular weight adjustment can be selected from non-conjugated dienes such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, and conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like.

[0034] When a molecular weight modifier is used, the amount thereof added is preferably in the range of 0.1 to 10% by weight relative to the norbornene-based monomer.

[0035] The concentration of the norbornene-based monomer in the ring-opening polymerization reaction is not particularly limited, but is usually 1 to 50% by weight, preferably 2 to 45% by weight, and more preferably 3 to 40% by weight.

[0036] The polymerization temperature is not particularly limited, and is generally -100 to 150° C., preferably -50 to 120° C. If the temperature is lower than -100° C., the polymerization rate is slow, and if the temperature is higher than 150° C., the activity of the catalyst may be reduced. By selecting the polymerization temperature within the above range, the polymerization rate, molecular weight, etc. can be adjusted.

[0037] The polymerization time is not particularly limited, and is, for example, 1 minute to 100 hours. In addition, the polymerization is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

[0038] After the polymerization reaction is completed, the produced norbornene-based polymer may be post-treated by a known operation or treatment method (for example, reprecipitation) as necessary, separated by filtration, and then dried to be isolated.

[0039] The content of the monomer unit represented by formula I can be determined by dissolving the separated copolymer in an appropriate deuterated solvent and measuring its 1 H-NMR was calculated from its integrated value.

[0040] In addition, the position of the signal may be slightly different from the above depending on the type of structural unit (B) and the measurement conditions, but can basically be calculated by the above-mentioned method.

[0041] The hydrogenated cyclic olefin ring-opening polymer of the present invention can be obtained by hydrogenating the carbon-carbon double bonds of the cyclic olefin ring-opening polymer obtained by the above-mentioned ring-opening polymerization reaction in the presence of a hydrogenation catalyst.

[0042] The hydrogenation catalyst may be a homogeneous catalyst or a heterogeneous catalyst.

[0043] Homogeneous catalysts can reduce the amount of catalyst added because they are easily dispersed in the hydrogenation reaction liquid. In addition, since they have sufficient activity even without high temperature and high pressure, they are less likely to cause decomposition and gelation of cyclic olefin ring-opening polymers and their hydrogenates. Therefore, from the perspective of cost and product quality, it is preferred to use homogeneous catalysts.

[0044] 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.

[0045] The homogeneous catalyst may be a catalyst formed by a combination of a transition metal compound and an alkyl metal compound, and may be specifically selected from: Wilkinson coordination compound [tri(triphenylphosphine)rhodium chloride (I)], cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, dichlorotitacenes / n-butylaluminum, dichlorozirconocene / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, etc.

[0046] As a heterogeneous catalyst, it can be: a heterogeneous catalyst in which a metal such as nickel (Ni), palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh) is loaded on a carrier. Preferably, in order to reduce the amount of impurities in the obtained hydride, the carrier is preferably an adsorbent such as alumina and diatomaceous earth.

[0047] The hydrogenation reaction is usually carried out in an organic solvent, and the organic solvent is not particularly limited as long as it is an organic solvent that is inactive in the hydrogenation reaction. As the organic solvent, a hydrocarbon solvent is usually used from the viewpoint of being easy to dissolve the generated hydride. The hydrocarbon solvent can be: an aromatic hydrocarbon solvent such as benzene, toluene, and xylene; an aliphatic hydrocarbon solvent such as n-pentane, n-hexane, and n-heptane; an alicyclic hydrocarbon solvent such as cyclohexane, methylcyclohexane, decalin, and bicyclononane.

[0048] These organic solvents can be used alone or in combination of two or more. In addition, solvents generally used for ring-opening polymerization are also suitable as solvents for hydrogenation, so after adding a hydrogenation catalyst to the ring-opening polymerization reaction liquid, it can be supplied to the hydrogenation reaction.

[0049] The hydrogenation reaction conditions may be conventionally selected according to the type of hydrogenation catalyst used. The reaction temperature is usually 100 to 250°C.

[0050] The hydrogen pressure is usually 0.1 to 10.0 MPa, preferably 0.8 to 8.0 MPa, and more preferably 1 to 5.0 MPa.

[0051] The hydrogenation reaction time may be selected to appropriately control the hydrogenation rate, and is usually in the range of 0.1 to 50 hours.

[0052] After the hydrogenation reaction is completed, the catalyst residue is removed by centrifugation, filtration, etc. In addition, a catalyst inactivator such as water or alcohol, or an adsorbent such as activated clay or alumina may be added as needed.

[0053] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydrogenated cyclic olefin ring-opening polymer are standard isoprene-equivalent values ​​obtained by gel permeation chromatography (GPC) using cyclohexane as an eluent.

[0054] The hydrogenated cyclic olefin ring-opening polymer of the present invention has a relatively high glass transition temperature and is excellent in fluidity and mechanical strength when molten.

[0055] The heat yellowing resistance of the hydrogenated cyclic olefin ring-opening polymer can be evaluated by conducting a test based on ASTM E313 (the details of the test are described in Examples) and determining the yellowness difference (ΔYI).

[0056] The cyclic olefin ring-opening polymer hydrogenate of the present invention has excellent yellowing resistance because all double bonds in the polymer are completely hydrogenated and the material will no longer be oxidized and yellowed.

[0057] Furthermore, the present invention provides a resin molded body obtained by molding a resin composition containing the hydrogenated cyclic olefin ring-opening polymer of the present invention.

[0058] The resin composition used may contain other components such as additives within a range that does not hinder the effects of the present invention.

[0059] The other ingredients may be antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, plasticizers, antistatic agents, etc. The content of these ingredients can be appropriately determined according to the purpose. The content is usually in the range of 0.001 to 5 parts by weight, preferably in the range of 0.01 to 1 part by weight, relative to 100 parts by weight of the hydrogenated cyclic olefin ring-opening polymer.

[0060] The antioxidant may be a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, or the like.

[0061] The phenolic antioxidant may be: 3,5-di-tert-butyl-4-hydroxytoluene, dibutylhydroxytoluene, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylidenebis(3-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), α-tocopherol, 2,2,4-trimethyl-6-hydroxy-7-tert-butylchroman, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc. Among these, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is particularly preferred.

[0062] When the resin composition contains a phenolic antioxidant, the content of the phenolic antioxidant is 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, and more preferably 0.2 to 1 part by weight, based on 100 parts by weight of the hydrogenated cyclic olefin ring-opening polymer.

[0063] The phosphorus antioxidant can be selected from distearoyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenyl diphosphite, trisnonylphenyl phosphite and the like.

[0064] The sulfur-based antioxidant may be selected from distearoylthiodipropionate, dilauroylthiodipropionate and the like.

[0065] The ultraviolet absorber can be selected from: benzotriazole ultraviolet absorbers, benzoate ultraviolet absorbers, benzophenone ultraviolet absorbers, acrylate ultraviolet absorbers, metal coordination compound ultraviolet absorbers, etc.

[0066] The light stabilizer may be a hindered amine light stabilizer.

[0067] The near-infrared absorber can be selected from: cyanine near-infrared absorbers; pyrylium near-infrared absorbers; squarylium near-infrared absorbers; cretonium near-infrared absorbers; azulenium near-infrared absorbers; phthalocyanine near-infrared absorbers; dithiol metal coordination compound near-infrared absorbers; naphthoquinone near-infrared absorbers; anthraquinone near-infrared absorbers; indophenol near-infrared absorbers; azide near-infrared absorbers, etc.

[0068] The plasticizer may be selected from phosphate triester plasticizers, fatty acid monoester plasticizers, glycol ester plasticizers, oxygen-containing acid ester plasticizers, and the like.

[0069] The antistatic agent may be fatty acid ester of polyol or the like.

[0070] Resin composition is obtained by mixing each component according to a conventional method. As a mixing method, it can be: a method in which each component is mixed in a suitable solvent, a method of kneading in a molten state.

[0071] Kneading can be carried out using a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, a feeder Ruder or other melt kneading machine. The kneading temperature is preferably in the range of 200 to 400° C., more preferably in the range of 240 to 350° C. During kneading, each component may be added and kneaded at once, or may be added and kneaded in several portions.

[0072] Furthermore, the present invention provides an optical component formed of the resin molded body of the present invention.

[0073] The molding method when manufacturing the resin molded body of the present invention is not particularly limited, and may be injection molding, compression molding, extrusion molding, etc. Among these, when the resin molded body is an optical component, etc., injection molding is preferred from the viewpoint of being able to obtain a resin molded body of high precision.

[0074] The melting temperature during molding varies depending on the resin composition used, but is generally 200 to 400° C., preferably 210 to 350° C. When the glass transition temperature of the resin composition is defined as Tg, the mold temperature in the case of using a mold is generally from 20° C. to (Tg+15)° C., preferably from (Tg-30)° C. to (Tg+10)° C., and more preferably from (Tg-20)° C. to (Tg+5)° C.

[0075] As described above, the hydrogenated cyclic olefin ring-opening polymer of the present invention used as a raw material for producing the resin molded article of the present invention is excellent in heat yellowing resistance, dimensional stability at high temperatures, and moldability, and the resin molded article of the present invention is also excellent in these properties.

[0076] For the resin molded product of the present invention, the glass transition temperature is preferably 140 to 165°C, the melt flow rate measured at a temperature of 280°C and a load of 2.16 kg is preferably 8 g / 10 minutes or more according to ASTM D3835, and the flexural strength measured in a flexural test at a speed of 2 mm / minute according to GB / T9341-2008 is preferably 60 MPa or more.

[0077] Preferably, the resin molded body of the present invention can be used in the field of optical materials. The resin molded body of the present invention is suitable for use as optical components such as optical lenses, prisms, and light guides. In particular, the resin molded body of the present invention is suitable for use in fields such as optical lenses, medical bag materials, and optical films that require high light linear transmittance. Among them, it is particularly preferred to be used as an optical component such as a lens for a camera installed in a car.

[0078] In summary, the cyclic olefin ring-opening polymer and its hydrogenate of the present invention have excellent heat yellowing resistance, dimensional stability at high temperature and moldability. The resin molded body obtained by using the cyclic olefin ring-opening polymer hydrogenate and the optical component formed by the resin molded body also have advantages such as heat yellowing resistance, dimensional stability at high temperature and moldability. DETAILED DESCRIPTION

[0079] The above contents of the present invention are further described in detail below by means of specific implementation methods in the form of examples, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies implemented based on the above contents of the present invention belong to the scope of the present invention. Unless otherwise specified, conventional technical operations are used in the following examples. The following embodiments of the present invention are described in detail.

[0080] The present invention will be described in further detail below with reference to Examples and Comparative Examples. The present invention is not limited to these Examples. The "parts" and "%" in the following are by weight unless otherwise specified.

[0081] The measurement of various physical properties was carried out according to the following methods.

[0082] (1) Weight average molecular weight

[0083] The weight average molecular weight (Mw) of the hydrogenated cyclic olefin ring-opening polymer was measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, and was determined as a standard polystyrene-equivalent value.

[0084] As standard polystyrene, standard polystyrene manufactured by Agilent Technologies (Mw=602, 1390, 3920, 8050, 13800, 22700, 58800, 71300, 109000, 280000) was used.

[0085] The measurement was performed using three columns (manufactured by Agilent Technologies, PL1E10-3120EPA, PL1510-1520, and PL1510-5100) connected in series at a flow rate of 1.0 mL / min, a sample injection volume of 100 μL, and a column temperature of 40°C.

[0086] (2) Glass transition temperature (Tg)

[0087] The glass transition temperature of the hydrogenated cyclic olefin ring-opening polymer was measured using a differential scanning calorimeter (DSC-3 manufactured by Mettler) under the condition of a temperature increase rate of 10° C. / min in accordance with ASTM E794-2001.

[0088] (3) Proportion of syndiotactic diads

[0089] The ratio of the syndiotactic diads of the structural units of the formula I in the hydrogenated cyclic olefin ring-opening polymer is determined using deuterated o-dichlorobenzene as a solvent. 13 It was determined by calculating the intensity ratio of the signal derived from the syndiotactic dyad and the signal derived from the isotactic dyad in the C-NMR spectrum.

[0090] (4) Melt flow rate (MFR)

[0091] The melt flow rate of the resin composition containing the hydrogenated cyclic olefin ring-opening polymer was measured under the conditions of a temperature of 280° C. and a load of 2.16 kg.

[0092] (5) Linear transmittance measurement

[0093] The pellets of the resin composition containing the hydrogenated cyclic olefin ring-opening polymer were put into an injection molding machine (manufactured by Thermo Fisher Scientific, minijet-pro) and injection molded under the conditions of resin temperature 280°C, mold temperature (Tg-15)°C, and injection pressure 100 MPa to produce a resin plate of 80 mm long × 10 mm wide × 4 mm thick.

[0094] Next, the resin plate was made into a test piece, and its light transmittance and linear transmittance were measured using a photometer.

[0095] (6) Yellowing performance test

[0096] First, the test piece was placed in an oven and heated at 125° C. for 1000 hours.

[0097] Next, the yellowness (YI: Yellow index) of the test piece is measured using a colorimeter according to ASTM E313, with the blank as air. The value of the yellowness YI of air only is subtracted from the obtained yellowness YI as the yellowness difference (ΔYI) of the test piece. The smaller the ΔYI, the less yellowing at high temperature and the better the heat yellowing resistance.

[0098] (7) Comparison of structural unit ratio and feed quality

[0099] By ring-opening polymerization of cyclic olefins 13 C-NMR spectrum measurement, the characteristic peaks of different monomers in the carbon spectrum are integrated separately, the proportion of different monomer structural units is determined, and compared with the feed amount.

[0100] Example 1

[0101] In a polymerization reactor whose interior had been dried and purged with nitrogen, 10 parts of 1,4-methylene-1,4,4a,5,10,10a-hexahydroanthracene, 30 parts of 5-cyclohexyl-2-norbornene, 30 parts of dicyclopentadiene, 30 parts of ethyltetracyclo[6.2.1.1 3,6 .0 2,7 ] dodeca-4-ene, 600 parts of deoxygenated toluene, 1.21 parts of a molecular weight regulator (1-hexene), 0.98 parts of an n-hexane solution of diethylaluminum ethoxide (concentration: 19%), and 11.7 parts of a toluene solution of (phenylimide)tungsten tetrachloride·tetrahydrofuran (concentration: 2.0%).

[0102] All the reactants were kept at 50°C and stirred for 200 minutes, and then 4 parts of isopropanol were added to terminate the polymerization reaction. The polymerization reaction solution was measured by gas chromatography, showing that the conversion rate of monomer to polymer was 100%. The structural unit and the feed ratio were compared in reverse by nuclear magnetic resonance carbon spectrum, and the structural unit ratio was consistent with the feed mass comparison.

[0103] Next, 500 parts of the obtained polymerization reaction solution were transferred to an autoclave equipped with a stirrer, and 5 parts of a diatomaceous earth-supported nickel catalyst (manufactured by Gansu Zhongke Pharmaceutical Source Co., Ltd., with a nickel loading of 55%) were added. After the autoclave was replaced with hydrogen, the reaction was allowed to proceed at 190° C. and a hydrogen pressure of 7 MPa for 6 hours.

[0104] The reaction solution was passed through a 300-mesh filter bed and pressure-filtered at a pressure of 0.25 MPa to remove the hydrogenation catalyst, thereby obtaining a colorless and transparent solution.

[0105] Next, the solution obtained by the above filtration is treated by vacuum rotary evaporation to remove the solvent and other volatile components from the solution. The rotary evaporation liquid is then poured into a mold directly connected to a concentrator, and the solid components contained in the solution are extruded in a molten state and cooled to obtain particles of norbornene-based hydrogenated ring-opening polymer. Various measurements and evaluations are then performed. The results are shown in Table 1.

[0106] Example 2

[0107] Into a polymerization reactor whose interior had been dried and purged with nitrogen, 40 parts of pentacyclopentadecadiene, 60 parts of methyl 5-norbornene-2-carboxylate, 740 parts of deoxygenated cyclohexane, 4.2 parts of a molecular weight regulator (1-octene), and 0.048 parts of bis(tricyclohexylphosphine)benzylideneruthenium (II) dichloride dissolved in 60 parts of cyclohexane were added.

[0108] Next, the entire reactant was maintained at 30° C. and stirred for 240 minutes, and then 4 parts of ethanol were added to terminate the polymerization reaction. The polymerization reaction solution was measured by gas chromatography, and the conversion rate of the monomer to the polymer was 100%.

[0109] Next, 300 parts of the obtained polymerization reaction solution were transferred to an autoclave equipped with a stirrer, and 5 parts of palladium carbon catalyst (Shaanxi Ruike, palladium loading 10%) were added. After the autoclave was replaced with hydrogen, the reaction was carried out at 200°C and 2 MPa of hydrogen pressure for 20 hours.

[0110] The reaction solution was filtered under pressure at a pressure of 0.25 MPa through a 300-mesh filter bed to remove the hydrogenation catalyst, thereby obtaining a colorless transparent solution.

[0111] Next, the solution obtained by the above filtration is treated by vacuum rotary evaporation to remove the solvent and other volatile components from the solution. The rotary evaporation liquid is then poured into a mold directly connected to a concentrator, and the solid components contained in the solution are extruded in a molten state and cooled to obtain particles of norbornene hydrogenated ring-opening polymer. Various measurements and evaluations are then performed. The structural unit ratio is consistent with the feed mass comparison, and other results are shown in Table 1.

[0112] Example 3

[0113] Into a polymerization reactor whose interior had been dried and purged with nitrogen, 30 parts of benzonorbornene, 15 parts of 2-chloro-5-norbornene, 55 parts of tetracyclododecene, 785 parts of deoxygenated cyclohexane, 1.6 parts of a molecular weight regulator (1-hexene), and 0.05 parts of bis(1,3-diisopropylimidazolin-2-ylidene)benzylideneruthenium dichloride were added.

[0114] Next, the entire reactant was maintained at 50° C. and stirred for 200 minutes, and then 4 parts of isopropyl alcohol was added to terminate the polymerization reaction. The polymerization reaction solution was measured by gas chromatography, and the conversion rate of the monomer to the polymer was 100%.

[0115] Next, 300 parts of the obtained polymerization reaction solution were transferred to an autoclave equipped with a stirrer, and 5 parts of diatomaceous earth-supported nickel catalyst (manufactured by Gansu Zhongke Pharmaceutical Source Co., Ltd., nickel loading 55%) were added. After the autoclave was replaced with hydrogen, the reaction was allowed to proceed at 160° C. and 4 MPa of hydrogen pressure for 10 hours.

[0116] The reaction solution was filtered under pressure at a pressure of 0.25 MPa through a 300-mesh filter bed to remove the hydrogenation catalyst, thereby obtaining a colorless transparent solution.

[0117] Next, the solution obtained by the above filtration is treated by vacuum rotary evaporation to remove the solvent and other volatile components from the solution. The rotary evaporation liquid is then poured into a mold directly connected to a concentrator, and the solid components contained in the solution are extruded in a molten state and cooled to obtain particles of norbornene hydrogenated ring-opening polymer. Various measurements and evaluations are then performed. The structural unit ratio is consistent with the feed mass comparison, and other results are shown in Table 1.

[0118] Example 4

[0119] Into a polymerization reactor whose interior had been dried and purged with nitrogen, were added 27 parts of 1,4-methylene-1,4,4a,9a-tetrahydrofluorene, 33 parts of tetracyclododec-9-ene-4,5-dicarboxylic anhydride, 40 parts of dicyclopentadiene, 400 parts of deoxygenated cyclohexane, 1.21 parts of a molecular weight regulator (1-butene), 0.98 parts of an n-hexane solution of ethoxydiethylaluminum (concentration: 19%), and 11.7 parts of a toluene solution of (phenylimide)tungsten tetrachloride·tetrahydrofuran (concentration: 2.0%).

[0120] The entire reaction product was maintained at 50° C. and stirred for 200 minutes, and then 4 parts of isopropanol were added to terminate the polymerization reaction. The polymerization reaction solution was measured by gas chromatography, which showed that the conversion rate of the monomer to the polymer was 100%.

[0121] Next, 300 parts of the obtained polymerization reaction solution were transferred to an autoclave equipped with a stirrer, and 5 parts of diatomaceous earth-supported nickel catalyst (manufactured by Gansu Zhongke Pharmaceutical Source Co., Ltd., nickel loading 55%) were added. After the autoclave was replaced with hydrogen, the reaction was allowed to proceed at 190° C. and 6 MPa of hydrogen pressure for 4 hours.

[0122] The reaction solution was filtered under pressure at a pressure of 0.25 MPa through a 300-mesh filter bed to remove the hydrogenation catalyst, thereby obtaining a colorless transparent solution.

[0123] Next, the solution obtained by the above filtration is treated by vacuum rotary evaporation to remove the solvent and other volatile components from the solution. The rotary evaporation liquid is then poured into a mold directly connected to a concentrator, and the solid components contained in the solution are extruded in a molten state and cooled to obtain particles of norbornene hydrogenated ring-opening polymer. Various measurements and evaluations are then performed. The structural unit ratio is consistent with the feed mass comparison, and other results are shown in Table 1.

[0124] Table 1

[0125]

[0126] Example 5

[0127] Into a polymerization reactor whose interior had been dried and purged with nitrogen, a monomer mixture consisting of 20 parts of 1,4-methylene-1,4,4a,9a-tetrahydrofluorene (ICP), 50 parts of dicyclopentadiene (DCPD), and 30 parts of tetracyclododecene (TCD), 785 parts of deoxygenated cyclohexane, 1.21 parts of a molecular weight regulator (1-hexene), 0.98 parts of an n-hexane solution of ethoxydiethylaluminum (concentration: 19%), and 11.7 parts of a toluene solution of (phenylimide)tungsten tetrachloride·tetrahydrofuran (concentration: 2.0%) were added.

[0128] Next, the entire reactant was maintained at 50° C. and stirred for 200 minutes, and then 4 parts of isopropyl alcohol was added to terminate the polymerization reaction. The polymerization reaction solution was measured by gas chromatography, and the conversion rate of the monomer to the polymer was 100%.

[0129] Next, 300 parts of the obtained polymerization reaction solution were transferred to an autoclave equipped with a stirrer, and 5 parts of diatomaceous earth-supported nickel catalyst (manufactured by Gansu Zhongke Pharmaceutical Source Co., Ltd., nickel loading 55%) were added. After the autoclave was replaced with hydrogen, the reaction was carried out at 190° C. and 7 MPa of hydrogen pressure for 6 hours.

[0130] The reaction solution was filtered under pressure at a pressure of 0.25 MPa through a 300-mesh filter bed to remove the hydrogenation catalyst, thereby obtaining a colorless transparent solution.

[0131] Next, the solution obtained by the above filtration is treated by vacuum rotary evaporation to remove cyclohexane and other volatile components as a solvent from the solution. The rotary evaporation liquid is then poured into a mold directly connected to a concentrator, and the solid components contained in the solution are extruded in a molten state and cooled to obtain particles of norbornene-based hydrogenated ring-opening polymers. Various measurements and evaluations are then performed. The structural unit ratio is consistent with the feed mass comparison, and other results are shown in Table 2.

[0132] Example 6

[0133] Into a glass reactor whose interior had been dried and purged with nitrogen, 30 parts of acenaphthene-norbornene (ANB), 25 parts of dicyclopentadiene (DCPD), 25 parts of tetracyclododecene (TCD), 20 parts of a monomer mixture of norbornene, 300 parts of deoxygenated cyclohexane, 0.8 parts of a molecular weight regulator (1-octene), and 0.05 parts of (1,3-diimidazole-2-ylidene)(tricyclohexylphosphine)benzylideneruthenium dichloride were added.

[0134] Next, all the reactants were kept at 60°C and stirred for 120 minutes, and then the obtained polymerization reaction solution was directly transferred to an autoclave equipped with a stirrer, and 0.4 parts of tris(triphenylphosphine)ruthenium carbonyl chloride was added. After the autoclave was replaced with hydrogen, the reaction was allowed to proceed at 130°C and a hydrogen pressure of 4 MPa for 20 hours.

[0135] After the reaction is completed, the solution obtained above is treated by vacuum rotary evaporation to remove cyclohexane and other volatile components as a solvent from the solution. The rotary evaporation liquid is then poured into a mold directly connected to a concentrator, and the solid components contained in the solution are extruded in a molten state and cooled to obtain particles of norbornene hydrogenated ring-opening polymers, and various measurements and evaluations are performed. The structural unit ratio is consistent with the feed mass comparison, and other results are shown in Table 2.

[0136] Example 7

[0137] Into a polymerization reactor whose interior had been dried and purged with nitrogen, a monomer mixture of 30 parts of 1,4-methylene-1,4,4a,9a-tetrahydrofluorene (ICP) and 70 parts of tetracyclododecene (TCD), 500 parts of deoxygenated cyclohexane, 0.8 parts of a molecular weight regulator (1-hexene), 0.05 parts of tungsten hexachloride and isobutylaluminum were added.

[0138] Next, the entire reaction solution was maintained at 40°C and stirred for 300 minutes, and then the obtained polymerization reaction solution was directly transferred to an autoclave equipped with a stirrer, and 0.2 parts of palladium trialuminum oxide catalyst was added. After the autoclave was replaced with hydrogen, the reaction was allowed to proceed at 200°C and 2 MPa of hydrogen pressure for 10 hours.

[0139] The reaction solution was filtered under pressure at a pressure of 0.25 MPa through a 300-mesh filter bed to remove the hydrogenation catalyst, thereby obtaining a colorless transparent solution.

[0140] Next, the solution obtained by the above filtration is treated by vacuum rotary evaporation, thereby removing cyclohexane as a solvent and other volatile components from the solution. The rotary evaporation liquid is then poured into a mold directly connected to a concentrator, and the solid components contained in the solution are extruded in a molten state and cooled to obtain particles of norbornene hydrogenated ring-opening polymer, and various measurements and evaluations are performed. The structural unit ratio is consistent with the feed mass comparison, and other results are shown in Table 2.

[0141] Comparative Example 1

[0142] The same procedure as in Example 5 was carried out except that the monomers used in Example 5 were changed to 3 parts of ICP, 50 parts of DCPD, and 47 parts of TCD to obtain pellets, and to carry out tests and evaluations.

[0143] Comparative Example 2

[0144] The same procedures as in Example 5 were followed except that the monomers used in Example 5 were changed to 70 parts of ICP, 10 parts of DCPD, and 20 parts of TCD to obtain pellets, and to conduct tests and evaluations.

[0145] Comparative Example 3

[0146] The hydrogenation conditions in Example 5 were changed to add 0.4 parts of tris(triphenylphosphine)ruthenium carbonyl chloride hydrogenate. After replacing the autoclave with hydrogen, the reaction was carried out at 50°C and 0.5 MPa of hydrogen pressure for 20 hours. The other conditions were the same as in Example 5 to obtain particles, and then tested and evaluated. The results are shown in Table 2.

[0147] Table 2

[0148]

[0149]

[0150] From Table 1 and Table 2, we can see that:

[0151] The heat yellowing resistance and linear transmittance of the hydrogenated cyclic olefin ring-opening polymers obtained in Examples 1 to 4 have good parallelism.

[0152] By comparing Example 5 with Comparative Example 1, it can be seen that when the content of monomer component A is too low, the material will have a certain degree of crystallinity, thereby affecting the transparency of the material. However, when the content of component A is too high (Comparative Example 2), the Tg of the material is significantly reduced, and the thermal stability is significantly reduced.

[0153] The degree of hydrogenation of the material in Comparative Example 3 is less than 99%, and the material undergoes obvious yellowing behavior under high temperature conditions, which greatly affects the optical properties of the material and cannot be used in the field of optical materials.

Claims

1. A cyclic olefin ring-opening polymer, characterized in that The ring-opening polymer comprises a structural unit (A) from formula I and a structural unit (B) from other norbornene-based monomers, wherein the content of the structural unit (A) accounts for 10% to 40% of all structural units; In Formula I, R1 to R4 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms; R5 to R 12 They independently represent a hydrogen atom, a hydrocarbon group having 1-10 carbon atoms, a polar group consisting of a halogen atom or / and an alkoxy group or / and a hydroxyl group or / and an ester group or / and a cyano group or / and an amide group or / and an imide group or / and a silyl group, a group having an aromatic or heterocyclic ring, or a group in which an aromatic or heterocyclic ring is combined with an alkylene group having 1-5 carbon atoms; m represents an integer of 0 to 2, and n represents an integer of 0 to 10.

2. A cyclic olefin ring-opening polymer according to claim 1, characterized in that: R6 and R9, R9 and R 11 , R 10 With R 12 , R 12 and R8 may bond to each other to form a carbocyclic ring or a heterocyclic ring, and the carbocyclic ring or the heterocyclic ring may be a monocyclic structure or a polycyclic structure or an aromatic ring.

3. A cyclic olefin ring-opening polymer according to claim 1, characterized in that: The proportion of the syndiotactic dyad from the structural unit composed of formula I in the ring-opening polymer structural unit to the total mass of the polymer is less than 30%.

4. A cyclic olefin ring-opening polymer according to claim 1, characterized in that: The formula I is selected from bicyclo-2-heptene derivatives (bicyclohept-2-ene derivatives), tricyclo-3-decene derivatives, tricyclo-3-undecene derivatives, tetracyclo-3-dodecene derivatives, pentacyclo-4-pentadecaene derivatives, pentacyclopentadecadiene derivatives, pentacyclo-3-pentadecaene derivatives, pentacyclo-4-hexadecene derivatives, pentacyclo-3-hexadecene derivatives, hexacyclo-4-heptadecene derivatives, heptacyclo-5-eicosene derivatives , heptacyclic-4-eicosene derivatives, heptacyclic-5-heneicosene derivatives, octacyclic-5-hexadecene derivatives, nonacyclic-5-pentadecene derivatives, nonacyclic-6-hexadecene derivatives, derivatives of cyclopentadiene-acenaphthene adducts, 1,4-methylene-1,4,4a,9a-tetrahydrofluorene derivatives, 1,4-methylene-1,4,4a,5,10,10a-hexahydroanthracene derivatives, and cycloolefin derivatives having 3 to 20 carbon atoms.

5. A cyclic olefin ring-opening polymer hydrogenate, characterized in that: The cyclic olefin ring-opening polymer is obtained by hydrogenating the cyclic olefin ring-opening polymer according to any one of claims 1 to 4, wherein the hydrogenation rate is greater than 99%.

6. A cyclic olefin ring-opening polymer hydrogenate according to claim 5, characterized in that: The weight average molecular weight Mn of the cyclic olefin ring-opening polymer hydrogenate is 1,000 to 500,000.

7. A cyclic olefin ring-opening polymer hydrogenate according to claim 5, characterized in that: The molecular weight distribution Mw / Mn of the hydrogenated cyclic olefin ring-opening polymer is 1-5.

8. The cyclic olefin ring-opening polymer hydrogenate according to claim 5, characterized in that: The glass transition temperature of the cyclic olefin ring-opening polymer hydrogenate is above 120°C.

9. A resin molded body, characterized in that: The resin composition is obtained by molding the hydrogenated cyclic olefin ring-opening polymer resin composition according to any one of claims 5 to 8.

10. An optical component, characterized in that: The resin molded article according to claim 9.

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