Cycloolefin polymer hydride, resin composition, resin molded article, and pharmaceutical packaging material

Abstract

The invention relates to the field of medicine packaging, in particular to cycloolefin polymer hydride, a resin composition, a resin forming body and a medicine packaging material. The cycloolefin polymer hydride provided by the invention has high moisture resistance and grease resistance under a specific content ratio of a repeating unit with a monocyclic structure and a repeating unit containing a bridged ring structure, and has good flowability in the process of further melting and forming the polymer hydride into a resin forming body. And moreover, the metal residual quantity is low, the glass transition temperature is relatively high, and the method is very suitable for being applied to preparation of medicine packaging materials. In the test of the invention, the glass transition temperature of the cycloolefin polymer hydride provided by the invention is up to 139 DEG C, the melt index is up to 4.4 g / 10 min, the moisture resistance is up to 1.6 (g / m < 2 > 24 h) / 100 [mu] m, and the oil resistance is grade A.

Description

Technical Field

[0001] The invention relates to the field of pharmaceutical packaging, in particular to a cycloolefin polymer hydrogenate, a resin composition, a resin molding and a pharmaceutical packaging material. Background Art

[0002] In recent years, polymers obtained by ring-opening or addition polymerization of cyclic olefins have attracted attention as materials for optical elements and medical containers. For example, patent CN114787232B discloses a ring-opening copolymer composed of a norbornene compound, a monocyclic cyclic olefin structural unit, and a branched structural unit. The content of the branched structural unit is 0.005 to 0.08 mol% relative to all repeating structural units in the copolymer. By ring-opening copolymerization, a cyclic olefin polymer hydrogenate with good wear resistance and good fluidity can be obtained.

[0003] Patent CN106687500B discloses a tetracyclododecene repeating unit having a content of 55% by weight or more and 85% by weight or less relative to all repeating units, and the repeating units from other norbornene monomers have a content of 15% by weight or more and 45% by weight or less relative to all repeating units, and the repeating units from 3-ring norbornene monomers and / or 4-ring norbornene monomers contain 95% or more of repeating units relative to all repeating units, and the repeating units of the 3-ring norbornene monomers and / or 4-ring norbornene monomers contain repeating units from tetracyclododecene, and the proportion of the syndiotonic diads from the repeating units from tetracyclododecene is 65% or more, and the weight-average molecular weight Mw is 10000 to 40000. The cyclic olefin ring-opening polymer hydrogenated product provided by this patent has the characteristics of heat yellowing resistance, dimensional stability at high temperature and excellent moldability, and is applied to optical components.

[0004] Patent JP5126504B2 discloses a membrane composed of a hydrogenated alicyclic ring-opening polymer, wherein the hydrogenated alicyclic ring-opening polymer comprises 45-55 wt % of a structural unit (A) derived from a tricyclic [5.2.1.02,5] deca-3,7-diene compound, 45-55 wt % of a structural unit (A) derived from a tetracyclic [4.4.0.1 2，5 .1 7，10 ] 30-40 wt% of the structural unit (B) of a dodeca-3-ene compound, and an 8-substituted tetracyclic [4.4.0.1 2，5 .1 7，10] 10-20 wt% of the structural unit (C) of the dodeca-3-ene compound (wherein the total amount of the structural unit (A) + the structural unit (B) + the structural unit (C) is 100), and by adjusting the monomer ratio, a ring-opening polymer hydrogenate with good heat resistance and no substrate rupture is provided, which is used in a stretch film.

[0005] Patent CN117624555A discloses a cyclic olefin ring-opening hydrogenated copolymer, characterized in that, by mass percentage, all structural units of the cyclic olefin ring-opening hydrogenated copolymer are derived from 20-45% of structural units of dicyclopentadiene compounds, 30-55% of structural units of tetracyclododecene and its derivatives, and 5-25% of structural units of the compound of structural formula (1); the ratio of (endo, trans) forms of the compound of structural formula (1) is more than 70%; a resin with high heat resistance, excellent transparency and high yield toughness, and easy processing and molding is provided, which is used in pharmaceutical packaging.

[0006] In the above patents, good heat resistance and formability are achieved by adjusting the polymer ratio. However, in recent years, with the rapid development of the pharmaceutical industry, pharmaceutical packaging materials are in short supply. For pharmaceutical packaging materials, drug resistance is an indicator that cannot be ignored, and during long-term storage, the material will be affected by the environment and produce environmental stress cracking, which is not mentioned in the above patents. Summary of the invention

[0007] In view of this, the technical problem to be solved by the present invention is to provide a cycloolefin polymer hydrogenate, a resin composition, a resin molded body and a pharmaceutical packaging material. The cycloolefin polymer hydrogenate provided by the present invention has high moisture resistance and oil resistance, and good fluidity during the melt molding process, and is suitable for application in the preparation of pharmaceutical packaging materials.

[0008] The present invention provides a cycloolefin polymer hydrogenate having a structure of Formula 1;

[0009] Formula 1;

[0010] Wherein, p is an integer from 1 to 100; n and m are independently 0, 1, 2 or 3;

[0011] The R1 and R2 are independently H, halogen atoms other than fluorine atoms, C1~C 10 C1~C 10 heteroalkyl;

[0012] R3~R 10At least one of any two combinations of the above is connected to form a carbocyclic ring, a heterocyclic ring, a carbon atom bridge or a heteroatom bridge, and the remaining unconnected groups are independently H, a halogen atom other than a fluorine atom, a C1~C2 substituted with a halogen atom other than a fluorine atom, 10 C1~C 10 heteroalkyl;

[0013] The weight content of the repeating unit with a monocyclic structure relative to the total repeating units is 0.01% to 0.3%;

[0014] The content of repeating units containing bridge ring structures accounts for 30% to 40% of the weight content of all repeating units;

[0015] The remainder is repeating units of other structures.

[0016] In the hydrogenated cycloolefin polymer of the present invention, the total weight content of all repeating units is 100%, wherein the weight content of the repeating units with a monocyclic structure accounts for 0.01% to 0.3% of the total repeating units; the content of the repeating units containing a bridge ring structure accounts for 30% to 40% of the total repeating units; the remainder is repeating units of other structures. Preferably, the weight content of the repeating units with a monocyclic structure in Formula 1 accounts for 0.05% to 0.25% of the total repeating units, and the weight content of the repeating units containing a bridge ring structure in Formula 1 accounts for 30% to 35% of the total repeating units.

[0017] The inventors of the present application creatively discovered that for the polymer hydride of the structure shown in Formula 1, when the repeating units with a single ring structure and the repeating units containing a bridge ring structure are at a specific content ratio, the polymer hydride has high moisture resistance and grease resistance, and has good fluidity during the further melt molding process to become a resin molded body.

[0018] The p described in the present invention is an integer of 1 to 100, which means that the cycloolefin polymer hydrogenated compound described in the present invention has 1 to 100 repeating units. The n and m described in the present invention are independently 0, 1, 2 or 3, and the values ​​of n and m jointly determine the number of rings of a certain repeating unit in the cycloolefin polymer hydrogenated compound. For example, when n and m are both 0, it means that the repeating unit has only one five-membered ring, which has a structure of formula 1-a and is a repeating unit with a monocyclic structure. When n and m are both 1, the repeating unit has a structure of formula 1-b; when n and m are both 2, the repeating unit has a structure of formula 1-c; other cases are analogous and will not be repeated.

[0019] Formula 1-a

[0020] Formula 1-b; Formula 1-c;

[0021] The present invention R3~R 10 At least one of any two combinations of R3 to R4 is connected to form a carbocyclic ring, a heterocyclic ring, a carbon atom bridge or a heteroatom bridge. 10 They can be connected in any combination, for example, R3 and R4 are connected, R3 and R5 are connected, R3 and R7 are connected, R3 and R9 are connected, R5 and R6 are connected, R5 and R7 are connected, R5 and R9 are connected, R7 and R8 are connected, R7 and R9 are connected, R9 and R 10 The two are connected, etc. The present invention R3~R 10 In the embodiment, the combination of two groups located at the same C atom or adjacent C atoms is connected to the C atom where they are located to form a carbocyclic ring or a heterocyclic ring. For example, if R3 and R4 are connected, and R3 and R4 are located at the same C atom, then R3 and R4 are connected to the C atom where they are located to form a carbocyclic ring or a heterocyclic ring; if R3 and R5 are connected, and R3 and R5 are located at adjacent C atoms, then R3 and R5 are connected to the C atom where they are located to form a carbocyclic ring or a heterocyclic ring. 10 In the embodiment, any two combinations of C atoms located alternately are connected to the C atoms where they are located to form a carbon atom bridge or a heteroatom bridge. Non-limiting examples include: if R3 and R7 are connected, and R3 and R7 are located at the alternate C atoms, then R3 and R7 are connected to form a carbon atom bridge or a heteroatom bridge; if R3 and R9 are connected, and R3 and R9 are located at the alternate C atoms, then R3 and R9 are connected to form a carbon atom bridge or a heteroatom bridge.

[0022] The present invention R3~R 10 The groups that are not connected in pairs are independently H, halogen atoms other than fluorine atoms, C1~C 10 C1~C 10 Heteroalkyl, non-limiting examples include R3~R 10 If only R3 and R9 are connected, then R3 and R9 are connected to form a carbon atom bridge or a heteroatom bridge, and R4~R8 and R 10 are independently H, a halogen atom other than a fluorine atom, or a C1~C 10 C1~C 10 Heteroalkyl.

[0023] Preferably, one of R3 or R4 described in the present invention and R7 to R 10Two of the above R5 or R6 are connected to form a carbon atom bridge or a heteroatom bridge, or one of the above R5 or R6 is connected to the above R9 or R 10 Two of the above groups are connected to form a carbon atom bridge or a heteroatom bridge, and the remaining unconnected groups are independently H, halogen atoms other than fluorine atoms, C1~C 10 C1~C 10 Heteroalkyl.

[0024] In the present invention, there are said R3~R 10 The repeating units corresponding to the case where two of them are connected to form a carbon atom bridge or a heteroatom bridge belong to the repeating units containing a bridge ring structure. 10 If only R3 and R7 are connected, the corresponding repeating unit belongs to a repeating unit containing a bridge ring structure; 10 If only R3 and R9 are connected, the corresponding repeating unit belongs to a repeating unit containing a bridge ring structure; 10 If only R3 and R7 and R4 and R9 are connected, the corresponding repeating unit belongs to a repeating unit containing a bridge ring structure.

[0025] The monocyclic repeating unit of the present invention is the same as the above, and will not be described in detail. In certain embodiments of the present invention, the monocyclic repeating unit is derived from one or more monomers including bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, propenyl norbornene, 5-n-butyl norbornene, 5-methyl-6-ethyl norbornene, 1-methyl norbornene, and 5-methyl norbornene.

[0026] The repeating unit containing a bridged ring structure of the present invention is the same as described above. Preferably, the repeating unit containing a bridged ring structure of the present invention is a repeating unit of the structure shown in Formula 2:

[0027] Formula 2;

[0028] In Formula 2, n is 1, 2 or 3;

[0029] The R x is R3 or R4, the R y R9 or R 10 ;

[0030] The R5-R8 are independently H, halogen atoms other than fluorine atoms, C1-C 10 C1~C 10 heteroalkyl;

[0031] The S1 is a C1-C5 alkyl group, preferably a C1-C3 alkyl group.

[0032] In certain embodiments of the present invention, the repeating unit containing a bridged ring structure is derived from 8-methoxycarbonyl tetracyclic [4.4.0.1 2.5. 1 7.10 ]-3-dodecene, 8-ethoxycarbonyltetracyclo[4.4.0.1 2.5 .1 7.10 ]-3-dodecene, 8-n-propoxycarbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]-3-dodecene, 8-isopropoxycarbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]-3-dodecene, 8-n-butoxycarbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]-3-dodecene, 8-phenoxycarbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]-3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]-3-dodecene, 8-methyl-8-ethoxycarbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]-3-dodecene, 8-methyl-8-n-propoxycarbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]-3-dodecene, 8-methyl-8-isopropoxycarbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]-3-dodecene, 8-methyl-8-n-butoxycarbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]-3-dodecene, 8-methyl-8-(4-phenylphenoxy)carbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]-3-dodecene, 8-ethylenetetracyclo[4.4.0.1 2.5. 1 7.10 ]-3-dodecene, hexacyclo[6.6.1.1 3,6 .1 10,13 .0 2,7 .0 9,14 ] one or more monomers of heptadecene;

[0033] Excluding the repeating units with a monocyclic structure and the repeating units containing a bridge ring structure, the remaining repeating units are repeating units of the other structures. In certain embodiments of the present invention, the repeating units of the other structures are derived from the tricyclic [5.2.1.0 2,5 ]deca-3,7-diene, methyl dicyclopentadiene, dimethyl dicyclopentadiene, ethyl dicyclopentadiene, vinyl dicyclopentadiene, propenyl dicyclopentadiene, 7,8-benzotricyclo[4,3.0.1 2,5 ] one or more monomers of dec-3-ene.

[0034] The weight average molecular weight of the cycloolefin polymer hydride of the present invention is 50000-100000. The glass transition temperature of the cycloolefin polymer hydride of the present invention is 130-140°C, preferably 135-140°C. The metal residue of the cycloolefin polymer hydride of the present invention is ≤1 ppm. In certain embodiments of the present invention, the metal ion content of the cycloolefin polymer hydride measured by inductively coupled plasma atomic emission spectrometry is less than 0.5 mass ppb.

[0035] The present invention also provides a method for preparing the cycloolefin polymer hydrogenate described in any of the above technical solutions, wherein the cycloolefin ring-opening polymer described in the present invention is prepared by ring-opening polymerization of a cycloolefin monomer composition using a ring-opening polymerization catalyst. That is, the cycloolefin monomer composition is polymerized by ring-opening metathesis polymerization in the presence of a metathesis polymerization catalyst. Specifically, the ring-opening polymerization is initiated by mixing the cycloolefin monomer composition and the metathesis polymerization catalyst.

[0036] More specifically, the method for preparing the cycloolefin polymer hydrogenate described in any of the above technical solutions comprises the following steps:

[0037] In the presence of a metathesis polymerization catalyst, at least one first monomer, at least one second monomer and at least one third monomer are reacted, and the reaction product is hydrogenated in the presence of a hydrogenation catalyst to obtain the cycloolefin polymer hydrogenate;

[0038] The first monomer is a monomer that obtains a repeating unit having a monocyclic structure after the reaction;

[0039] The second monomer is a monomer that obtains a repeating unit containing a bridged ring structure after the reaction;

[0040] The third monomer is a monomer that obtains repeating units of other structures after the reaction;

[0041] The repeating units with a monocyclic structure, the repeating units containing a bridge ring structure and the repeating units with other structures are the same as those described above and will not be described in detail.

[0042] The metathesis polymerization catalyst of the present invention is preferably a metathesis polymerization catalyst containing a transition metal compound catalyst component and a metal compound co-catalyst component. Wherein, the transition metal compound catalyst component includes a transition metal compound of the 3rd to 11th group of the periodic table; for example, transition metal halides, oxyhalides, alkoxy halides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes or hydride complexes of the 3rd to 11th groups of the periodic table and derivatives of each of the above transition metal compounds. The metal compound co-catalyst component includes metal compounds of the 1st to 2nd groups and the 12th to 14th groups of the periodic table, and the metal compound has at least one metal element-carbon bond or metal element-hydrogen bond. Specifically, the metal compound includes organic compounds containing Al, Sn, Li, Na, Mg, Zn, Cd, etc. In certain embodiments of the present invention, the metal compound includes at least one of an organic aluminum compound, an organic tin compound, an organic lithium compound, an organic sodium compound, an organic magnesium compound, an organic zinc compound, and an organic cadmium compound, preferably a compound of a Group 13 metal, and particularly preferably an organic aluminum compound; wherein the organic aluminum compound includes at least one of trimethylaluminum, triisobutylaluminum, diethylaluminum monochloride, methylaluminum trichloride, ethylaluminum dichloride, etc.; the organic tin compound includes at least one of tetramethyltin, diethyldimethyltin, tetrabutyltin, tetraphenyltin, etc.; the organic lithium compound includes n-butyllithium, etc.; the organic sodium compound includes n-pentylsodium, etc.; the organic magnesium compound includes methylmagnesium iodide, etc.; the organic zinc compound includes diethylzinc, etc.; the organic cadmium compound includes diethylcadmium, etc.

[0043] The mass ratio of the metathesis polymerization catalyst used in the present invention to the total monomers used is 1:(100-2000000), preferably 1:(1000-20000), more preferably 1:(5000-8000). If the amount of the catalyst is too large, it is difficult to remove the catalyst after the polymerization reaction, and the molecular weight distribution may become broad.

[0044] The reaction of the present invention is a ring-opening metathesis polymerization reaction, which can be carried out in the absence of a solvent, but is preferably carried out in a suitable solvent, specifically in a suitable organic solvent. As the organic solvent used, as long as the polymer and the hydride are dissolved or dispersed under the prescribed conditions and the polymerization reaction and the hydrogenation reaction are not affected, there is no particular restriction, but preferably a solvent commonly used in industry. As such an organic solvent, aliphatic hydrocarbons such as pentane, hexane, and heptane can be cited; alicyclic hydrocarbons such as cyclodecane, hexahydroindene cyclohexane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; dichloromethane, chloroform, 1,2-dichloroethane; halogenated aromatic hydrocarbons such as dichlorobenzene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; ethers such as ether and tetrahydrofuran; these organic solvents can be used alone or in combination of two or more. Preferably, the solvent is selected from one or more of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers. When the reaction of the present invention is carried out in an organic solvent, the concentration of all monomers is preferably 1 to 50 wt %, more preferably 2 to 45 wt %, and particularly preferably 3 to 40 wt %.

[0045] The preparation method of the present invention can also add a molecular weight regulator to the reaction system. By adding the molecular weight regulator, the molecular weight of the obtained ring-opening polymer containing an alicyclic structure can be adjusted. The amount of the molecular weight regulator added in the present invention is preferably sufficient to obtain a polymer with a desired molecular weight. The molar ratio of the molecular weight regulator used to the total monomers used is usually 1: (50-1000000), preferably 1: (100-5000), and more preferably 1: (300-3000). The present invention does not particularly limit the molecular weight regulator used, and conventionally known substances can be used. For example, at least one of α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; at least one of styrenes such as styrene and vinyl toluene; at least one of ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; at least one of halogen-containing vinyl compounds; at least one of oxygen-containing vinyl compounds such as glycidyl methacrylate; at least one of nitrogen-containing vinyl compounds such as acrylamide; at least one of non-conjugated dienes such as 1,4-pentadiene and 2,5-dimethyl-1,5-hexadiene, at least one of conjugated dienes such as 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, butadiene, 1,3-pentadiene and 1,3-hexadiene. Among them, the molecular weight regulator is preferably α-olefin because they are easy to control the molecular weight.

[0046] The present invention has no particular restrictions on the temperature and time of the reaction, but the reaction temperature is usually -20°C to 100°C, preferably 10°C to 80°C; the reaction time is 1 min to 100 h. If the temperature is too low, the reaction rate will decrease, and if the temperature is too high, side reactions may occur, making the molecular weight distribution wider. The present invention does not particularly limit the pressure conditions during the reaction. If the polymerization is carried out under pressure, the applied pressure is usually less than 1 MPa.

[0047] After the reaction of the present invention, the product obtained by the reaction is hydrogenated in the presence of a hydrogenation catalyst. The product obtained by the reaction can be separated by a common post-processing operation to obtain the target ring-opening polymer containing an alicyclic structure, and then the obtained ring-opening polymer containing an alicyclic structure is supplied to the next hydrogenation reaction step for hydrogenation in the presence of a hydrogenation catalyst; or a hydrogenation catalyst can be added to the product obtained by the reaction, and the ring-opening polymer containing an alicyclic structure is not separated and the hydrogenation reaction is continuously carried out. The common post-processing operation includes centrifugal separation, filtration and other treatments, so that the catalyst residue can be removed. In addition, adsorbents such as activated soil and alumina can also be added as needed.

[0048] The hydrogenation catalyst of the present invention can be a homogeneous catalyst or a heterogeneous catalyst. Wherein, the homogeneous catalyst is easy to disperse in the hydrogenation reaction liquid, so the addition amount of the catalyst can be suppressed. In addition, because even if it is not under high temperature and high pressure, it has sufficient activity, so it is not easy to cause the decomposition and gelation of cyclic olefin ring-opening polymers and their hydrides, but for polymers, the molecular weight is higher, and the hydrogenation difficulty is large, so generally use noble metal catalysts such as ruthenium and iridium, and the cost is large. On the other hand, because heterogeneous catalysts show particularly excellent activity under high temperature and high pressure, cyclic olefin ring-opening polymers can be hydrogenated in a short time. Therefore, from the viewpoint of time cost and the quality of the product, it is preferred to use heterogeneous catalysts.

[0049] The homogeneous catalyst of the present invention may be selected from one or more of the catalysts formed by the combination of transition metal compounds and alkyl metal compounds; in certain embodiments of the present invention, the homogeneous catalyst is selected from one or more of the combinations of Wilkinson coordination compound [tri(triphenylphosphine)rhodium chloride (I)], cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, dichlorodipentadienyl titanocene and n-butylaluminum, dichlorodipentadienyl zirconocene and sec-butyl lithium, tetrabutoxy titanate and dimethyl magnesium. The heterogeneous catalyst of the present invention may be selected from a heterogeneous catalyst in which one or more metals such as nickel (Ni), palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh) are loaded on a carrier. In particular, in the case where the impurity content in the obtained hydride is reduced, as a carrier, an adsorbent such as alumina, diatomaceous earth, activated carbon, etc. is preferably used.

[0050] The hydrogenation described in the present invention 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 usually used from the viewpoint of being easy to dissolve the generated hydride. As a hydrocarbon solvent, it can be selected from: one or more aromatic hydrocarbon solvents such as benzene, toluene and xylene; one or more aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; one or more alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, decalin and bicyclononane. These organic solvents can 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 that after adding a hydrogenation catalyst to the ring-opening polymerization reaction liquid, it can be supplied to the hydrogenation reaction.

[0051] The reaction conditions of the hydrogenation of the present invention can be appropriately selected according to the type of hydrogenation catalyst used. Specifically, the temperature of the hydrogenation is usually -20°C to 250°C, preferably -10°C to 220°C, and more preferably 0°C to 200°C. In order to control the hydrogenation rate, the time of hydrogenation can be appropriately selected, but it is usually in the range of 0.1 h to 50 h. The hydrogenation of the present invention is carried out at a pressure of 0.01 MPa to 10.0 MPa, preferably 0.05 MPa to 8.0 MPa, and more preferably 0.1 MPa to 6.0 MPa.

[0052] The present invention also provides a resin composition, which comprises an antioxidant and the cycloolefin polymer hydrogenate described in any of the above technical solutions. The antioxidant of the present invention is selected from at least one of antioxidant 1076, antioxidant 1010, antioxidant 168 and thioester antioxidants, preferably a combination of antioxidant 1010 and antioxidant 168. Based on the total amount of the cycloolefin polymer hydrogenate as 100 parts by weight, the content of the antioxidant is 0.1 to 1.5 parts by weight, preferably 0.2 to 0.4 parts by weight.

[0053] The present invention also provides a resin molded body, which is obtained from the hydrogenated cycloolefin polymer described in any of the above technical solutions; or, it is obtained from the resin composition described in any of the above technical solutions. Specifically, it is obtained by injection molding the hydrogenated cycloolefin polymer described in any of the above technical solutions; or, it is obtained by injection molding the resin composition described in any of the above technical solutions.

[0054] The present invention also provides a medical packaging material obtained from the resin molding described in any of the above technical solutions. The present invention also provides a medical product, which includes a substrate and a medical packaging material packaged on the substrate, wherein the medical packaging material is obtained from the resin molding described in any of the above technical solutions.

[0055] The present invention provides a cycloolefin polymer hydride, a resin composition, a resin molding and a pharmaceutical packaging material. The cycloolefin polymer hydride provided by the present invention has a structure of Formula 1. When the repeating units of the structure being a single ring and the repeating units containing a bridge ring structure are at a specific content ratio, the polymer hydride has high moisture resistance and grease resistance, and in the process of further melt molding it into a resin molding, it has good fluidity, and its metal residue is low and has a relatively high glass transition temperature, which is very suitable for application in the preparation of pharmaceutical packaging materials. In the experiment of the present invention, the glass transition temperature of the cycloolefin polymer hydride provided by the present invention is as high as 139°C, the melt index is as high as 4.4 g / 10min, and the moisture resistance is as high as 1.6 (g / m 2 •24 h) / 100 μm, and the oil resistance is Class A. DETAILED DESCRIPTION

[0056] The present invention discloses cycloolefin polymer hydrogenates, resin compositions, resin moldings and pharmaceutical packaging materials. Those skilled in the art can refer to the contents of this article and appropriately improve the process parameters to achieve the above. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in the present invention. The methods and applications of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the methods and applications of this article without departing from the content, spirit and scope of the present invention to achieve and apply the technology of the present invention.

[0057] Weight average molecular weight (Mw), number average molecular weight (Mn):

[0058] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer dissolved in tetrahydrofuran (THF) or trifluorotoluene (TFT) were determined using gel permeation chromatography (GPC) under the following conditions of use and the molecular weight was calibrated by polystyrene standards;

[0059] Detector: Agilent 1260 Infinity II, serially connected columns: PL1110-6300, column temperature 35°C, flow rate 1 mL / min, sample concentration: 3.0~9.0 mg / mL.

[0060] Glass transition temperature:

[0061] A Mettler DSC 3 manufactured by Mettler was used, with a heating rate of 20 K / min, a carrier gas of nitrogen at 50 mL / min, and a temperature rise range of 60°C to 220°C.

[0062] Melt Flow Rate (MFR):

[0063] The melt flow rate of the resin composition containing the hydrogenated cyclic olefin ring-opening polymer was measured in accordance with JIS K6719 under the conditions of a temperature of 280° C. and a load of 21.18 N (load of 2.16 kgf).

[0064] The proportion of the monocyclic structural units in the ring-opening polymer hydrogenation is determined by 13 C-NMR measurement (solvent: deuterated o-dichlorobenzene, measurement temperature: 135° C.) was used to calculate the monocyclic structure ratio. Specifically, in the obtained NMR spectrum, the monocyclic structure ratio was determined based on the intensity ratio of the signal intensity of 40.0 to 40.5 ppm derived from a monocyclic ring, the signal intensity of 43.0 to 43.5 ppm derived from a polycyclic ring, and the signal intensity of 40.0 to 40.5 ppm derived from a monocyclic ring.

[0065] Moisture resistance:

[0066] The thickness of the film of the present invention is not particularly limited, and may be, for example, greater than or equal to 1 μm or less than 10 mm. In addition, the film of the present invention preferably has a moisture permeability of less than 2.00 (g / m 2 ·24 h) / 100 μm).

[0067] Grease resistance:

[0068] Using an injection molding machine (manufactured by Fanuc, Roboshot α-100B, maximum mold clamping amount), the particles (medical resin material) obtained in the examples and comparative examples were heated to a resin temperature of 350°C and a mold temperature of 135°C. Under an injection pressure of 100 MPa, 10 test pieces of 100 mm long × 10 mm wide × 1 mm thick were prepared. Using simulated sebum (50% oleic acid, 40% isostearyl palmitate, 10% squalene) as a reagent, a bending strength test was performed based on ISO178 at a fulcrum distance of 30 mm and a crosshead speed of 5 mm / min. The appearance of the test piece was inspected and judged according to the following standards. Those with good results in the pseudo-sebum test have excellent oil resistance.

[0069] A: There are no cracks on the test piece.

[0070] B: A crack occurred at one location on the test piece.

[0071] C: Two or more cracks occurred on the test piece, or the test piece was broken.

[0072] The present invention will be further described below in conjunction with embodiments:

[0073] Example 1

[0074] The resin molded body is prepared according to the following steps:

[0075] In a flask purged with nitrogen, 0.05 parts of benzylidene (1,3-bis (2,4,6-trimethylphenyl) imidazolidin-2-yl) (tricyclohexylphosphine) ruthenium dichloride as a polymerization catalyst, 400 parts of toluene as a solvent, 0.01 parts of methylvinyl norbornene as a cyclic olefin monomer, 69.99 parts of dicyclopentadiene (end body content 99 mass % or more), and 0.1 tetracyclo[4.4.0] 2,5. 1 7,10 ] 30 parts of dodec-3-ene and 0.02 parts of 1-hexene as a chain transfer agent, the reaction solution was stirred at 70°C for 2 hours to carry out ring-opening polymerization, the conversion rate of monomer to polymer was 100%, and the mass average molecular weight (Mw) of the obtained ring-opening polymer (1) was 34000, and the molecular weight distribution (Mw / Mn) was 1.90.

[0076] 300 parts of the obtained polymerization reaction solution of the ring-opening polymer (1) were transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of alumina-supported palladium (wet basis, 10% Pd / Al2O3, wetted with ca. 55% Water, produced by Adamas) was added as a hydrogenation catalyst. The hydrogenation reaction was carried out at 150°C and a hydrogen pressure of 4.5 MPa for 5 hours; the reaction solution was filtered through diatomaceous earth to remove the catalyst.

[0077] To the hydrogenation reaction solution, 0.3 parts by mass of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) / tris[2,4-di-tert-butylphenyl]phosphite=1:1 was added as an antioxidant relative to 100 parts of the polymer hydrogenate, and metal impurities were removed by filtration using a filter (pore size 0.5 to 1 μm) and a metal fiber filter (pore size 0.4 μm).

[0078] The obtained filtrate was placed in a cylindrical concentrating dryer to remove volatile components such as solvent cyclohexane at a temperature of 290°C and a pressure of less than 1 kPa, and then extruded into strips in a molten state from a directly connected mold, cooled with water, and then cut with a granulator to obtain pellets (medical resin material). The above-mentioned measurements and evaluations were carried out using the pellets. The results are shown in Table 1.

[0079] Example 2

[0080] The resin molded body is prepared according to the following steps:

[0081] In a flask purged with nitrogen, 0.05 parts of benzylidene (1,3-bis (2,4,6-trimethylphenyl) imidazolidin-2-yl) (tricyclohexylphosphine) ruthenium dichloride as a polymerization catalyst, 400 parts of toluene as a solvent, 0.3 parts of 1-methylnorbornene as a cyclic olefin monomer, 59.7 parts of methyldicyclopentadiene (end body content 99% by mass or more), 8-methoxycarbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]40 parts of 3-dodecene and 0.02 parts of 1-hexene as a chain transfer agent were added, and the reaction solution was stirred at 70°C for 2 hours to carry out ring-opening polymerization. The conversion rate of monomer to polymer was 100%. The mass average molecular weight (Mw) of the obtained ring-opening polymer (1) was 34500, and the molecular weight distribution (Mw / Mn) was 1.95.

[0082] 300 parts of the obtained polymerization reaction solution of the ring-opening polymer (1) were transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of alumina-supported palladium (wet basis, 10% Pd / Al2O3, wetted with ca. 55% Water, produced by Adamas) was added as a hydrogenation catalyst. The hydrogenation reaction was carried out at 150°C and a hydrogen pressure of 4.5 MPa for 5 hours; the reaction solution was filtered through diatomaceous earth to remove the catalyst.

[0083] To the hydrogenation reaction solution, 0.3 parts by mass of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) / tris[2,4-di-tert-butylphenyl]phosphite=1:1 was added as an antioxidant relative to 100 parts of the polymer hydrogenate, and metal impurities were removed by filtration using a filter (pore size 0.5 to 1 μm) and a metal fiber filter (pore size 0.4 μm).

[0084] The obtained filtrate was placed in a cylindrical concentrating dryer to remove volatile components such as solvent cyclohexane at a temperature of 290°C and a pressure of less than 1 kPa, and then extruded into strips in a molten state from a directly connected mold, cooled with water, and then cut with a granulator to obtain pellets (medical resin material). The above-mentioned measurements and evaluations were carried out using the pellets. The results are shown in Table 1.

[0085] Example 3

[0086] The resin molded body is prepared according to the following steps:

[0087] In a flask purged with nitrogen, 0.05 parts of benzylidene (1,3-bis (2,4,6-trimethylphenyl) imidazolidin-2-yl) (tricyclohexylphosphine) ruthenium dichloride as a polymerization catalyst, 400 parts of cyclohexane as a solvent, 0.02 parts of 5-n-butylnorbornene as a cyclic olefin monomer, 64.98 parts of methyldicyclopentadiene (end body content 99% by mass or more), 8-methyl-8-(4-phenylphenoxy) carbonyltetracyclo[4.4.0.1] 2.5. 1 7.10 ]35 parts of -3-dodecene and 0.02 parts of 1-hexene as a chain transfer agent, the reaction solution was stirred at 70°C for 2 hours to carry out ring-opening polymerization, the conversion rate of monomer to polymer was 100%, and the mass average molecular weight (Mw) of the obtained ring-opening polymer (1) was 33200, and the molecular weight distribution (Mw / Mn) was 1.85.

[0088] 300 parts of the obtained polymerization reaction solution of the ring-opening polymer (1) were transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of alumina-supported palladium (wet basis, 10% Pd / Al2O3, wetted with ca. 55% Water, produced by Adamas) was added as a hydrogenation catalyst. The hydrogenation reaction was carried out at 150°C and a hydrogen pressure of 4.5 MPa for 5 hours; the reaction solution was filtered through diatomaceous earth to remove the catalyst.

[0089] To the hydrogenation reaction solution, 0.3 parts by mass of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) / tris[2,4-di-tert-butylphenyl]phosphite=1:1 was added as an antioxidant relative to 100 parts of the polymer hydrogenate, and metal impurities were removed by filtration using a filter (pore size 0.5 to 1 μm) and a metal fiber filter (pore size 0.4 μm).

[0090] The obtained filtrate was placed in a cylindrical concentrating dryer to remove volatile components such as solvent cyclohexane at a temperature of 290°C and a pressure of less than 1 kPa, and then extruded into strips in a molten state from a directly connected mold, cooled with water, and then cut with a granulator to obtain pellets (medical resin material). The above-mentioned measurements and evaluations were carried out using the pellets. The results are shown in Table 1.

[0091] Example 4

[0092] The resin molded body is prepared according to the following steps:

[0093] In a flask purged with nitrogen, 0.05 parts of benzylidene (1,3-bis (2,4,6-trimethylphenyl) imidazolidin-2-yl) (tricyclohexylphosphine) ruthenium dichloride as a polymerization catalyst, 400 parts of cyclohexane as a solvent, 0.25 parts of propenyl norbornene as a cyclic olefin monomer, and 0.10 parts of 7,8-benzotricyclo[4,3-dihydro-1-nitropropene] were added. 2,5 ] 69.75 parts of dec-3-ene, 8-methyl-8-(4-phenylphenoxy)carbonyltetracyclic [4.4.0.1 2.5. 1 7.10 ]30 parts of -3-dodecene and 0.02 parts of 1-hexene as a chain transfer agent, the reaction solution was stirred at 70°C for 2 hours to carry out ring-opening polymerization, the conversion rate of monomer to polymer was 100%, and the mass average molecular weight (Mw) of the obtained ring-opening polymer (1) was 34200, and the molecular weight distribution (Mw / Mn) was 1.94.

[0094] 300 parts of the obtained polymerization reaction solution of the ring-opening polymer (1) were transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of alumina-supported palladium (wet basis, 10% Pd / Al2O3, wetted with ca. 55% Water, produced by Adamas) was added as a hydrogenation catalyst. The hydrogenation reaction was carried out at 150°C and a hydrogen pressure of 4.5 MPa for 5 hours; the reaction solution was filtered through diatomaceous earth to remove the catalyst.

[0095] To the hydrogenation reaction solution, 0.3 parts by mass of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) / tris[2,4-di-tert-butylphenyl]phosphite=1:1 was added as an antioxidant relative to 100 parts of the polymer hydrogenate, and metal impurities were removed by filtration using a filter (pore size 0.5 to 1 μm) and a metal fiber filter (pore size 0.4 μm).

[0096] The obtained filtrate was placed in a cylindrical concentrating dryer to remove volatile components such as solvent cyclohexane at a temperature of 290°C and a pressure of less than 1 kPa, and then extruded into strips in a molten state from a directly connected mold, cooled with water, and then cut with a granulator to obtain pellets (medical resin material). The above-mentioned measurements and evaluations were carried out using the pellets. The results are shown in Table 1.

[0097] Example 5

[0098] The resin molded body is prepared according to the following steps:

[0099] In a flask purged with nitrogen, 0.05 parts of benzylidene (1,3-bis (2,4,6-trimethylphenyl) imidazolidin-2-yl) (tricyclohexylphosphine) ruthenium dichloride as a polymerization catalyst, 400 parts of cyclohexane as a solvent, 0.2 parts of 5-methyl-6-ethylnorbornene as a cyclic olefin monomer, and 0.1 parts of 7,8-benzotricyclo[4,3-dihydro-1-nitropropene] were added. 2,5 ] 67.8 parts of dec-3-ene, 8-methyl-8-(4-phenylphenoxy)carbonyltetracyclic [4.4.0.1 2.5. 1 7.10 ]32 parts of -3-dodecene and 0.02 parts of 1-hexene as a chain transfer agent, the reaction solution was stirred at 70°C for 2 hours to carry out ring-opening polymerization, the conversion rate of monomer to polymer was 100%, and the mass average molecular weight (Mw) of the obtained ring-opening polymer (1) was 34800, and the molecular weight distribution (Mw / Mn) was 1.92.

[0100] 300 parts of the obtained polymerization reaction solution of the ring-opening polymer (1) were transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of alumina-supported palladium (wet basis, 10% Pd / Al2O3, wetted with ca. 55% Water, produced by Adamas) was added as a hydrogenation catalyst. The hydrogenation reaction was carried out at 150°C and a hydrogen pressure of 4.5 MPa for 5 hours; the reaction solution was filtered through diatomaceous earth to remove the catalyst.

[0101] To the hydrogenation reaction solution, 0.3 parts by mass of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) / tris[2,4-di-tert-butylphenyl]phosphite=1:1 was added as an antioxidant to 100 parts of the polymer hydrogenate, and metal impurities were removed by filtration using a filter (pore size 0.5 to 1 μm) and a metal fiber filter (pore size 0.4 μm).

[0102] The obtained filtrate was placed in a cylindrical concentrating dryer to remove volatile components such as solvent cyclohexane at a temperature of 290°C and a pressure of less than 1 kPa, and then extruded into strips in a molten state from a directly connected mold, cooled with water, and then cut with a granulator to obtain pellets (medical resin material). The above-mentioned measurements and evaluations were carried out using the pellets. The results are shown in Table 1.

[0103] Example 6

[0104] The resin molded body is prepared according to the following steps:

[0105] In a flask purged with nitrogen, 0.05 parts of benzylidene (1,3-bis (2,4,6-trimethylphenyl) imidazolidin-2-yl) (tricyclohexylphosphine) ruthenium dichloride as a polymerization catalyst, 400 parts of cyclohexane as a solvent, 0.15 parts of norbornene as a cyclic olefin monomer, and 0.15 parts of 7,8-benzotricyclo[4,3.0.1 2,5 ] 65.85 parts of dec-3-ene, tetracyclo[4.4.0.1 2.5. 1 7.10 ]34 parts of -3-dodecene and 0.02 parts of 1-hexene as a chain transfer agent, the reaction solution was stirred at 70°C for 2 hours to carry out ring-opening polymerization, the conversion rate of monomer to polymer was 100%, and the mass average molecular weight (Mw) of the obtained ring-opening polymer (1) was 33900, and the molecular weight distribution (Mw / Mn) was 1.91.

[0106] 300 parts of the polymerization reaction solution of the obtained ring-opening polymer (1) were transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of alumina-supported palladium (wet basis, 10% Pd / Al2O3, wetted with ca. 55% Water, produced by Adamas) was added as a hydrogenation catalyst. The hydrogenation reaction was carried out at 150°C and a hydrogen pressure of 4.5 MPa for 5 hours; the reaction solution was filtered through diatomaceous earth to remove the catalyst.

[0107] To the hydrogenation reaction solution, 0.3 parts by mass of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) / tris[2,4-di-tert-butylphenyl]phosphite=1:1 was added as an antioxidant to 100 parts of the polymer hydrogenate, and metal impurities were removed by filtration using a filter (pore size 0.5 to 1 μm) and a metal fiber filter (pore size 0.4 μm).

[0108] The obtained filtrate was placed in a cylindrical concentrating dryer to remove volatile components such as solvent cyclohexane at a temperature of 290°C and a pressure of less than 1 kPa, and then extruded into strips in a molten state from a directly connected mold, cooled with water, and then cut with a granulator to obtain pellets (medical resin material). The above-mentioned measurements and evaluations were carried out using the pellets. The results are shown in Table 1.

[0109] Comparative Example 1

[0110] The resin molded body is prepared according to the following steps:

[0111] In a flask purged with nitrogen, 0.05 parts of benzylidene (1,3-bis (2,4,6-trimethylphenyl) imidazolidin-2-yl) (tricyclohexylphosphine) ruthenium dichloride as a polymerization catalyst, 400 parts of cyclohexane as a solvent, and 7,8-benzotricyclo[4,3.0.12,5 ] 66 parts of dec-3-ene, tetracyclo[4.4.0.1 2.5. 1 7.10 ]34 parts of -3-dodecene and 0.02 parts of 1-hexene as a chain transfer agent, the reaction solution was stirred at 70°C for 2 hours to carry out ring-opening polymerization, the conversion rate of monomer to polymer was 100%, and the mass average molecular weight (Mw) of the obtained ring-opening polymer (1) was 33950, and the molecular weight distribution (Mw / Mn) was 1.93.

[0112] 300 parts of the obtained polymerization reaction solution of the ring-opening polymer (1) were transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of alumina-supported palladium (wet basis, 10% Pd / Al2O3, wetted with ca. 55% Water, produced by Adamas) was added as a hydrogenation catalyst. The hydrogenation reaction was carried out at 150°C and a hydrogen pressure of 4.5 MPa for 5 hours; the reaction solution was filtered through diatomaceous earth to remove the catalyst.

[0113] To the hydrogenation reaction solution, 0.3 parts by mass of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) / tris[2,4-di-tert-butylphenyl]phosphite=1:1 was added as an antioxidant relative to 100 parts of the polymer hydrogenate, and metal impurities were removed by filtration using a filter (pore size 0.5 to 1 μm) and a metal fiber filter (pore size 0.4 μm).

[0114] The obtained filtrate was placed in a cylindrical concentrating dryer to remove volatile components such as solvent cyclohexane at a temperature of 290°C and a pressure of less than 1 kPa, and then extruded into strips in a molten state from a directly connected die, cooled with water, and then cut with a granulator to obtain pellets (medical resin material). The above-mentioned measurements and evaluations were carried out using the pellets. The results are shown in Table 1.

[0115] Comparative Example 2

[0116] The resin molded body is prepared according to the following steps:

[0117] In a flask purged with nitrogen, 0.05 parts of benzylidene (1,3-bis (2,4,6-trimethylphenyl) imidazolidin-2-yl) (tricyclohexylphosphine) ruthenium dichloride as a polymerization catalyst, 400 parts of cyclohexane as a solvent, 0.5 parts of norbornene as a cyclic olefin monomer, and 0.1 parts of 7,8-benzotricyclo[4,3.0.1 2,5 ] dec-3-ene 49.5 parts, tetracyclo[4.4.0.1 2.5. 1 7.10]50 parts of 3-dodecene and 0.02 parts of 1-hexene as a chain transfer agent, the reaction solution was stirred at 70°C for 2 hours to carry out ring-opening polymerization, the conversion rate of monomer to polymer was 100%, and the mass average molecular weight (Mw) of the obtained ring-opening polymer (1) was 33983, and the molecular weight distribution (Mw / Mn) was 1.91.

[0118] 300 parts of the obtained polymerization reaction solution of the ring-opening polymer (1) were transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of alumina-supported palladium (wet basis, 10% Pd / Al2O3, wetted with ca. 55% Water, produced by Adamas) was added as a hydrogenation catalyst. The hydrogenation reaction was carried out at 150°C and a hydrogen pressure of 4.5 MPa for 5 hours; the reaction solution was filtered through diatomaceous earth to remove the catalyst.

[0119] To the hydrogenation reaction solution, 0.3 parts by mass of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) / tris[2,4-di-tert-butylphenyl]phosphite=1:1 was added as an antioxidant relative to 100 parts of the polymer hydrogenate, and metal impurities were removed by filtration using a filter (pore size 0.5 to 1 μm) and a metal fiber filter (pore size 0.4 μm).

[0120] The obtained filtrate was placed in a cylindrical concentrating dryer to remove volatile components such as solvent cyclohexane at a temperature of 290°C and a pressure of less than 1 kPa, and then extruded into strips in a molten state from a directly connected mold, cooled with water, and then cut with a granulator to obtain pellets (medical resin material). The above-mentioned measurements and evaluations were carried out using the pellets. The results are shown in Table 1.

[0121] Comparative Example 3

[0122] The resin molded body is prepared according to the following steps:

[0123] In a flask purged with nitrogen, 0.05 parts of benzylidene (1,3-bis (2,4,6-trimethylphenyl) imidazolidin-2-yl) (tricyclohexylphosphine) ruthenium dichloride as a polymerization catalyst, 400 parts of cyclohexane as a solvent, 0.25 parts of norbornene as a cyclic olefin monomer, 74.75 parts of dicyclopentadiene, and 8-methoxycarbonyltetracyclo[4.4.0.1 2.5. 1 7.10 ]25 parts of 3-dodecene and 0.02 parts of 1-hexene as a chain transfer agent, the reaction solution was stirred at 70°C for 2 hours to carry out ring-opening polymerization, the conversion rate of monomer to polymer was 100%, and the mass average molecular weight (Mw) of the obtained ring-opening polymer (1) was 34900, and the molecular weight distribution (Mw / Mn) was 1.95.

[0124] 300 parts of the obtained polymerization reaction solution of the ring-opening polymer (1) were transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of alumina-supported palladium (wet basis, 10% Pd / Al2O3, wetted with ca. 55% Water, produced by Adamas) was added as a hydrogenation catalyst. The hydrogenation reaction was carried out at 150°C and a hydrogen pressure of 4.5 MPa for 5 hours; the reaction solution was filtered through diatomaceous earth to remove the catalyst.

[0125] To the hydrogenation reaction solution, 0.3 parts by mass of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) / tris[2,4-di-tert-butylphenyl]phosphite=1:1 was added as an antioxidant relative to 100 parts of the polymer hydrogenate, and metal impurities were removed by filtration using a filter (pore size 0.5 to 1 μm) and a metal fiber filter (pore size 0.4 μm).

[0126] The obtained filtrate was placed in a cylindrical concentrating dryer to remove volatile components such as solvent cyclohexane at a temperature of 290°C and a pressure of less than 1 kPa, and then extruded into strips in a molten state from a directly connected mold, cooled with water, and then cut with a granulator to obtain pellets (medical resin material). The above-mentioned measurements and evaluations were carried out using the pellets. The results are shown in Table 1.

[0127] Table 1

[0128]

[0129] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A cycloolefin polymer hydrogenate, characterized in that: It has the structure of Formula 1; Formula 1; Wherein, p is an integer of 1 to 100; n and m are independently 0, 1, 2 or 3; The R1 and R2 are independently H, halogen atoms other than fluorine atoms, C1~C 10 C1~C 10 heteroalkyl; R3~R 10 At least one of any two combinations of the above is connected to form a carbocyclic ring, a heterocyclic ring, a carbon atom bridge or a heteroatom bridge, and the remaining unconnected groups are independently H, a halogen atom other than a fluorine atom, a C1~C2 substituted with a halogen atom other than a fluorine atom, 10 C1~C 10 heteroalkyl; The weight content of the repeating unit with a monocyclic structure relative to the total repeating units is 0.01% to 0.3%; The content of repeating units containing bridge ring structures accounts for 30% to 40% of the weight content of all repeating units; The remainder is repeating units of other structures.

2. The cycloolefin polymer hydrogenate according to claim 1, characterized in that The weight content of the repeating unit with a monocyclic structure relative to the total repeating units is 0.015% to 0.25%; The content of the repeating unit containing the bridge ring structure accounts for 30% to 35% by weight of the total repeating units.

3. The cycloolefin polymer according to claim 1, characterized in that The weight average molecular weight of the hydrogenated cycloolefin polymer is 50,000-100,000.

4. The hydrogenated cycloolefin polymer according to claim 1, characterized in that The repeating unit containing a bridged ring structure is a repeating unit of the structure shown in Formula 2: Formula 2; In Formula 2, n is 1, 2 or 3; The R x is said R3 or said R4, said R y is the R9 or the R 10 ; The R5-R8 are independently H, halogen atoms other than fluorine atoms, C1-C 10 C1~C 10 heteroalkyl; The S1 is a C1~C5 alkyl group.

5. The hydrogenated cycloolefin polymer according to claim 1, characterized in that The monocyclic repeating unit is derived from one or more monomers including bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, propenyl norbornene, 5-n-butyl norbornene, 5-methyl-6-ethyl norbornene, 1-methyl norbornene, and 5-methyl norbornene; The repeating unit containing a bridged ring structure is derived from 8-methoxycarbonyl tetracyclic [4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, 8-ethoxycarbonyltetracyclo[4.4.0.1 2.5 .1 7.10 ]-3-dodecene, 8-n-propoxycarbonyltetracyclo[4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, 8-isopropoxycarbonyltetracyclo[4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, 8-n-butoxycarbonyltetracyclo[4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, 8-phenoxycarbonyltetracyclo[4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, 8-methyl-8-ethoxycarbonyltetracyclo[4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, 8-methyl-8-n-propoxycarbonyltetracyclo[4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, 8-methyl-8-isopropoxycarbonyltetracyclo[4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, 8-methyl-8-n-butoxycarbonyltetracyclo[4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, 8-methyl-8-(4-phenylphenoxy)carbonyltetracyclo[4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, 8-ethylenetetracyclo[4.4.0.1 2.

5. 1 7.10 ]-3-dodecene, hexacyclo[ 6.6.1.1 3,6 .1 10,13 .0 2,7 .0 9,14 ] one or more monomers of heptadecene; The repeating units of the other structures are derived from the tricyclic [5.2.1.0 2,5 ]deca-3,7-diene, methyl dicyclopentadiene, dimethyl dicyclopentadiene, ethyl dicyclopentadiene, vinyl dicyclopentadiene, propenyl dicyclopentadiene, 7,8-benzotricyclo[4,3.0.1 2,5 ] one or more monomers of dec-3-ene.

6. A resin composition, characterized in that The invention comprises an antioxidant and the cycloolefin polymer hydrogenate according to any one of claims 1 to 5.

7. The resin composition according to claim 6, characterized in that The antioxidant is selected from at least one of hindered phenol, hindered amine, phosphite and thioester antioxidants.

8. The resin composition according to claim 6, characterized in that Based on 100 parts by weight of the total amount of the cycloolefin polymer hydrogenate, the content of the antioxidant is 0.1 to 1.5 parts by weight.

9. A resin molded article, characterized in that: It is obtained from the hydrogenated cycloolefin polymer described in any one of claims 1 to 5; or it is obtained from the resin composition described in any one of claims 6 to 8.

10. A pharmaceutical packaging material, characterized in that: This is obtained from the resin molded article according to claim 9.

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