Cyclic olefin copolymer, solution, film, and method for producing cyclic olefin copolymer
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- DAICEL CORP
- Filing Date
- 2024-09-20
- Publication Date
- 2026-06-05
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Abstract
Description
[Technical Field]
[0001] The present invention relates to cyclic olefin copolymers, solutions, films, and methods for producing cyclic olefin copolymers. [Background technology]
[0002] Cyclic olefin copolymers are resins that possess high transparency and other properties, and are used in a wide range of fields, including optical materials.
[0003] On the other hand, attempts are being made to impart even better properties to cyclic olefin copolymers. For example, Patent Document 1 proposes improving the durability against bending by combining multiple cyclic olefin copolymers whose glass transition temperatures are within a predetermined range. [Prior art documents] [Patent Documents]
[0004] [Patent Document 1] Japanese Patent Publication No. 2023-112594 [Overview of the Initiative] [Problems that the invention aims to solve]
[0005] On the other hand, cyclic olefin copolymers with multiple glass transition temperatures tend to have poor toughness, and this tendency can become particularly pronounced as the glass transition temperature increases.
[0006] This invention has been made in view of the above circumstances, and aims to provide a cyclic olefin copolymer, a solution, a film, and a method for producing a cyclic olefin copolymer, which have multiple glass transition temperatures and good toughness. [Means for solving the problem]
[0007] The inventors of the present invention have discovered that the above problems can be solved by adjusting the number-average molecular weight and the proportion of its constituent monomers in a cyclic olefin copolymer having multiple glass transition temperatures, and have completed the present invention. More specifically, the present invention provides the following.
[0008] <1> A cyclic olefin copolymer which is an addition polymer of norbornene monomer and α-olefin having 3 to 20 carbon atoms, The ratio of the number of moles of structural units derived from the α-olefin to the total number of moles of structural units in the cyclic olefin copolymer is 10 to 90 mol%, The number-average molecular weight of the cyclic olefin copolymer is between 200,000 and 500,000. The cyclic olefin copolymer has two or more glass transition temperatures within the range of 0 to 350°C, as determined by viscoelasticity measurement. Cyclic olefin copolymer.
[0009] <2> The α-olefin has 4 to 8 carbon atoms. <1> A cyclic olefin copolymer as described above.
[0010] <3> The cyclic olefin copolymer has at least one glass transition temperature measured by viscoelasticity in the range of 130 to 350°C. <1> or <2> A cyclic olefin copolymer as described above.
[0011] <4> <1> ~ <3> A solution comprising a cyclic olefin copolymer as described in any of the above, and a solvent.
[0012] <5> <4> A film made from the solution described above.
[0013] <6> <1> ~ <3> A method for producing the cyclic olefin copolymer as described in any of the following: The method includes addition polymerization of the norbornene monomer and the α-olefin in the presence of a titanocene catalyst represented by the following formula (1) and a co-catalyst, The co-catalyst comprises a borate compound and a hindered phenol. The total amount of norbornene monomer and α-olefin per 1 part by mass of titanocene catalyst is 1200 to 1600 parts by mass. Manufacturing method. [ka] (In formula (1), R 1 ~R 3 Each of these is independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 4 and R 5 Each of these is independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom, and R 6 ~R 13 Each of these is a silyl group that may independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent. [Effects of the Invention]
[0014] The present invention provides a cyclic olefin copolymer having multiple glass transition temperatures and good toughness, a solution, a film, and a method for producing a cyclic olefin copolymer. [Modes for carrying out the invention]
[0015] The following describes cyclic olefin copolymers, solutions, films, and methods for producing cyclic olefin copolymers. However, the cyclic olefin copolymers, solutions, films, and methods for producing cyclic olefin copolymers are not limited to the specific embodiments described below, and may be modified as appropriate, provided that the desired effects are not impaired.
[0016] <Cyclic olefin copolymer> Cyclic olefin copolymers satisfy the following requirements. It is an addition polymer of norbornene monomer and α-olefin with 3 to 20 carbon atoms. The ratio of the number of moles of structural units derived from α-olefins to the total number of moles of structural units in a cyclic olefin copolymer is 10 to 90 mol%. The number-average molecular weight of the cyclic olefin copolymer is between 200,000 and 500,000. The cyclic olefin copolymer has two or more glass transition temperatures within the range of 0 to 350°C, as measured by viscoelasticity.
[0017] Conventionally, cyclic olefin copolymers with multiple glass transition temperatures have been prone to poor toughness. This tendency was particularly pronounced when they had high glass transition temperatures. However, cyclic olefin copolymers that meet the above requirements can exhibit consistently good toughness despite having multiple glass transition temperatures. The reason for this is not entirely clear, but it is speculated that one contributing factor is the formation of a robust molecular structure due to the high number-average molecular weight, which improves strength.
[0018] In the specification of this application, "toughness" can be evaluated by specifying the number of bending cycles in a bending endurance test (MIT test) in accordance with JIS P 8115. A higher number of folding cycles indicates greater toughness of the cyclic olefin copolymer (or its molded product).
[0019] The composition of cyclic olefin copolymers is described in detail below.
[0020] (1) Addition polymer Cyclic olefin copolymers are addition polymers of monomers containing norbornene monomers and α-olefins having 3 to 20 carbon atoms. The ratio of moles of structural units derived from α-olefins to moles of total structural units in these addition polymers is 10 to 90 mol%.
[0021] As a result of the inventors' research, it was found that when preparing addition polymers having multiple glass transition temperatures, a high number-average molecular weight can be easily achieved by adjusting the amount of catalyst, for example, as described later, and as a result, high toughness can also be achieved. Particularly, in the case of an addition polymer having a high glass transition temperature, although it may be prone to poor toughness, the cyclic olefin copolymer that satisfies the above requirements can solve such problems.
[0022] In addition, the above cyclic olefin copolymer includes copolymers containing structural units derived from monomers other than the above monomers. That is, the cyclic olefin copolymer may have structural units other than those derived from norbornene monomers and structural units derived from α-olefins having 3 to 20 carbon atoms. However, from the viewpoint of stably realizing high toughness, it is preferable that the cyclic olefin copolymer consists only of structural units derived from norbornene monomers and structural units derived from α-olefins having 3 to 20 carbon atoms.
[0023] (1-1) Norbornene monomer Norbornene (CAS registration number: 498-66-8, chemical formula: C7H 10 ) is one kind of cyclic olefin monomer. In addition, the norbornene monomer also includes substituted norbornene which is norbornene having a substituent. The norbornene monomer may be one kind alone or a combination of two or more kinds.
[0024] The substituted norbornene is not particularly limited. Examples of the substituent of the substituted norbornene include a halogen atom, a monovalent or divalent hydrocarbon group. Specific examples of the substituted norbornene include the compound represented by the following formula (I).
[0025]
Chemical formula
[0026] In formula (I), R a1 ~R a12 may be the same or different from each other, and is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. R a9 and R a10, R a11 and R a12 These may integrate to form a divalent hydrocarbon group. R a9 or R a10 And, R a11 or R a12 These elements may be joined together to form a ring. n is 0 or a positive integer. If n is 2 or greater, R a5 ~R a8 These elements may be identical or different within each repeating unit. However, if n is 0, R a1 ~R a4 and R a9 ~R a12 At least one of them is not a hydrogen atom.
[0027] R a1 ~R a8 Specific examples include, for instance, hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; and alkyl groups having 1 to 20 carbon atoms. a1 ~R a8 It may consist entirely of different atoms or groups. a1 ~R a8 Some or all of these may be the same atom or group.
[0028] R a9 ~R a12 Specific examples include, for instance, hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; alkyl groups having 1 to 20 carbon atoms; cycloalkyl groups such as cyclohexyl groups; substituted or unsubstituted aromatic hydrocarbon groups such as phenyl, tolyl, ethylphenyl, isopropylphenyl, naphthyl, and anthryl groups; and aralkyl groups such as benzyl and phenethyl groups. a9 ~R a12 It may consist entirely of different atoms or groups. a9 ~R a12 Some or all of these may be the same atom or group.
[0029] R a9and R a10 , or R a11 and R a12 Specific examples of divalent hydrocarbon groups that can be formed by the integration of these include alkylidene groups such as ethylidene, propyridene, and isopropylidene.
[0030] R a9 or R a10 And, R a11 or R a12 When these elements bond to each other to form a ring, the resulting ring may be monocyclic or polycyclic. The resulting ring may be polycyclic with bridges. The resulting ring may have double bonds. The resulting ring may have substituents such as methyl groups.
[0031] Specific examples of substituted norbornenes represented by formula (I) include 5-methyl-bicyclo[2.2.1]hepta-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hepta-2-ene, 5-ethyl-bicyclo[2.2.1]hepta-2-ene, 5-butyl-bicyclo[2.2.1]hepta-2-ene, 5-ethylidene-bicyclo[2.2.1]hepta-2-ene, and 5-hexyl-bi Bicyclic olefins such as cyclo[2.2.1]hepta-2-ene, 5-octyl-bicyclo[2.2.1]hepta-2-ene, 5-octadecyl-bicyclo[2.2.1]hepta-2-ene, 5-methylidene-bicyclo[2.2.1]hepta-2-ene, 5-vinyl-bicyclo[2.2.1]hepta-2-ene, and 5-propenyl-bicyclo[2.2.1]hepta-2-ene; Tricyclo[4.3.0.1 2,5 Deca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 2,5 Deca-3-en; Tricyclo[4.4.0.1 2,5 ]Undeca-3,7-diene or tricyclo[4.4.0.1 2,5 ] Tricyclo[4.4.0.1 2,5]undeca-3-ene; 5-cyclopentyl-bicyclo[2.2.1]hepta-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hepta-2-ene, 5-cyclohexenylbicyclo[2.2.1]hepta-2-ene, 5-phenyl-bicyclo[2.2.1]hepta-2-ene, and other tricyclic olefins; Tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene (also simply called tetracyclododecene), 8-methyltetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-methylidenetetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-vinyltetracyclo[4,4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene and other tetracyclic olefins; 8-Cyclopentyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene; Tetracyclo[7.4.1 3,6 .0 1,9 .0 2,7 ]Tetradeca-4,9,11,13-tetraene (also known as 1,4-methano-1,4,4a,9a-tetrahydrofluorene), tetracyclo[8.4.1 4,7 .01,10 .0 3,8 Pentadeca-5,10,12,14-tetraene (also known as 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene); Pentacyclo[6.6.1.1 3,6 .0 2,7 .0 9,14 -4-hexadecene, Pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 -4-pentadecene, Pentacyclo[7.4.0.0 2,7 .1 3,6 .1 10,13 -4-pentadecene; Heptacyclo[8.7.0.1 2,9 .1 4,7 .1 11,17 .0 3,8 .0 12,16 -5-eicosene, Heptacyclo[8.7.0.1 2,9 .0 3,8 .1 4,7 .0 12,17 .1 13,l6 -14-eicosene; Polycyclic cyclic olefins such as tetramers of cyclopentadiene can be mentioned.
[0032] Among these, for example, alkyl-substituted norbornenes such as bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups, and alkylidene-substituted norbornenes such as bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups are preferred. 5-Ethylidene-bicyclo[2.2.1]hept-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidene norbornene) is particularly preferred.
[0033] (1-2) α-olefin The α-olefin is an α-olefin having 3 to 20 carbon atoms. The α-olefin may be a single kind or a combination of two or more kinds. From the viewpoint of easily obtaining the desired effect, it is preferably a single kind.
[0034] The α-olefin may be either an unsubstituted α-olefin or an α-olefin having a substituent (such as a halogen atom). From the viewpoint of easily obtaining the desired effect, an unsubstituted α-olefin is preferred.
[0035] The number of carbon atoms in the α-olefin is 3 to 20, preferably 4 to 12, more preferably 4 to 10, even more preferably 4 to 8, and most preferably 6 to 8.
[0036] Examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, and 1-dodecene. Among these, 1-hexene, 1-octene, and 1-decene are preferred. Of these, 1-hexene and 1-octene are more preferred, and 1-octene is particularly preferred, from the viewpoint of easily obtaining the desired effect.
[0037] (1-3) Ratio of constituent monomers In a cyclic olefin copolymer, the ratio of moles of structural units derived from α-olefins to moles of total structural units is preferably 10 to 90 mol%, more preferably 10 to 70 mol%, even more preferably 10 to 50 mol%, even more preferably 20 to 40 mol%, and most preferably 20 to 30 mol%. By ensuring that the ratio of constituent monomers satisfies the above requirements, a cyclic olefin copolymer having the glass transition temperature described later can be easily obtained.
[0038] In cyclic olefin copolymers, the ratio of moles of structural units derived from norbornene monomers to moles of total structural units is not particularly limited, but is preferably 10 to 90 mol%, more preferably 30 to 90 mol%, and even more preferably 50 to 90 mol%.
[0039] The ratio of moles of structural units derived from α-olefins or norbornene monomers to the total number of moles of structural units is: 13 It is calculated by measuring the 1C-NMR spectrum.
[0040] (2) Number-average molecular weight and weight-average molecular weight The number-average molecular weight of the cyclic olefin copolymer is more than 200,000 to 500,000, preferably 210,000 to 470,000, more preferably 220,000 to 450,000, even more preferably 230,000 to 430,000, and even more preferably 240,000 to 400,000.
[0041] The weight-average molecular weight of the cyclic olefin copolymer is not particularly limited, but is preferably 300,000 to 750,000, more preferably 350,000 to 600,000, and even more preferably 400,000 to 550,000.
[0042] The number-average molecular weight and weight-average molecular weight are determined as polystyrene-equivalent values measured by gel permeation chromatography (GPC), respectively.
[0043] (3) Glass transition temperature The cyclic olefin copolymer has two or more glass transition temperatures (also called "Tg") within the range of 0 to 350°C, preferably 130 to 350°C, and more preferably at least one within the range of 200 to 300°C.
[0044] In a preferred embodiment of the present invention, the cyclic olefin copolymer may have two or more glass transition temperatures in the range of 0 to 350°C and one glass transition temperature below 0°C.
[0045] Conventionally, it has been known that in cyclic olefin copolymers having multiple glass transition temperatures, the toughness tends to decrease as the glass transition temperature increases. However, as described above, it was found that by adjusting the number-average molecular weight and the proportion of its constituent monomers, good toughness can be achieved even at high glass transition temperatures. Therefore, in cyclic olefin copolymers that satisfy the above requirements, good toughness can be achieved even in the following embodiments, for example. The cyclic olefin copolymer has at least one (e.g., one or two) glass transition temperatures, preferably between 130 and 350°C. The cyclic olefin copolymer has at least one (e.g., one or two) glass transition temperatures, preferably between 200 and 300°C. The cyclic olefin copolymer has one glass transition temperature preferably between 130 and 350°C, and one glass transition temperature preferably between 0 and less than 130°C. The cyclic olefin copolymer preferably has one glass transition temperature between 130 and 350°C, preferably one between 0 and less than 130°C, and preferably one between -50 and less than 0°C. The cyclic olefin copolymer has one glass transition temperature preferably between 130 and 350°C, preferably between 40 and 100°C, and preferably between -50 and -10°C.
[0046] In the specification and claims of this application, "(the glass transition temperature of the cyclic olefin copolymer)" means a value determined by viscoelastic measurement. Specifically, as shown in the examples, the glass transition temperature is measured by observing the viscoelastic behavior of a 50 μm thick film obtained from a cyclic olefin copolymer at -100 to 300°C using a solid rheometer. The temperature at the top of the peak in the tan δ chart obtained by this measurement is defined as the glass transition temperature.
[0047] (4) Uses of cyclic olefin copolymers Cyclic olefin copolymers can be used for any application. For example, by incorporating the aforementioned cyclic olefin copolymer into the raw materials, either in place of or together with conventional cyclic olefin copolymers, good toughness can be imparted to the resulting resin molded product.
[0048] In one embodiment of the present invention, the cyclic olefin copolymer may be formed into a film by any molding method (such as melt extrusion or vacuum pressing). The present invention also includes molded articles obtained by such methods.
[0049] (5) Solution One aspect of the present invention comprises a solution comprising a cyclic olefin copolymer and a solvent.
[0050] The solution can be prepared by combining the aforementioned cyclic olefin copolymer with any solvent. The method for producing the solution is not particularly limited. Typically, the solution is obtained by uniformly dissolving or dispersing each component of the solution in the desired type and amount. If the cyclic olefin copolymer is poorly soluble in the solvent, the solvent containing the cyclic olefin copolymer may be heated as needed.
[0051] Such solutions can be used for a variety of purposes, including the following: • Raw materials for the film (described later) • Raw materials for paints Varnish used for covering metal wiring, etc. Spinning for the production of cyclic olefin copolymer fibers
[0052] The solvent in the solution is not particularly limited as long as it can dissolve the cyclic olefin copolymer. Examples include aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, p-menthane, and decahydronaphthalene; aromatic hydrocarbon solvents such as toluene and xylene; and halogenated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride. Of these, cyclohexane, methylcyclohexane, dimethylcyclohexane, p-menthane, toluene, and xylene are preferred. The solvent can be used alone or in combination of two or more.
[0053] The amount of solvent used in a solution can be appropriately determined considering the intended use of the solution and the concentration of components other than the solvent. Typically, the amount of solvent used is preferably such that the concentration of non-solvent components in the solution is 1.0 to 50.0% by mass, and more preferably 5.0 to 40.0% by mass. If the concentrations of components other than the solvent in the solution are within the above range, it is easy to form a film with the desired thickness.
[0054] Any component other than the solvent in the solution can be used, as long as it does not hinder the objective of the present invention. Examples of such components include known additives and solvent-soluble resins (other than cyclic olefin copolymers).
[0055] The additives are not particularly limited, but examples include fillers, strengtheners, surface treatment agents, antioxidants, UV absorbers, flame retardants, colorants, and adhesion enhancers. As fillers and reinforcing agents, particulate fillers, flake-shaped fillers, and whiskers (tiny short fibers) are preferred from the standpoint of film-forming properties of the solution. Specific examples of fillers and reinforcing agents include silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium dioxide, mica, aluminum borate, potassium titanate, barium sulfate, boron nitride, forsterite, zinc oxide, magnesium oxide, and calcium carbonate. Furthermore, hollow particles such as hollow silica, glass balloons, and various hollow resin particles can be used as fillers to improve dielectric properties in the high-frequency range. The fillers and reinforcing agents may be surface-treated with a surface treatment agent having polymerizable unsaturated bonds. Examples of polymerizable unsaturated bonds include vinyl groups, allyl groups, methricle groups, styryl groups, acryloyl groups, methacryloyl groups, and maleimide groups. Examples of surface treatment agents include silane coupling agents having polymerizable unsaturated bonds.
[0056] While there are no particular limitations on the solvent-soluble resin, relatively low-polarity polymers are preferred from the viewpoint of not impairing the effects of the present invention. Examples of relatively low-polarity polymers include aliphatic polyimide resins, polyphenylene ether resins, and modified polyphenylene ether resins.
[0057] If the solution contains the additives described above, the ratio of the mass of the other additives to the total mass of the cyclic olefin copolymer can be adjusted as appropriate depending on the desired effect.
[0058] (6) Film One aspect of the present invention includes a film made from the aforementioned solution as a raw material. Such films can be manufactured by removing the solvent from a solution applied to a substrate or the like using a solution-based film-forming method, and can be referred to as cast films.
[0059] The method for manufacturing cast film is not particularly limited. For example, cast film can be manufactured by the following method. First, the solution is applied to a support made of a resin film, metal foil, or the like. The application method is not particularly limited. For example, known application methods such as dip coating, roll coating, curtain coating, die coating, slit coating, microgravure coating, comma coating, and spin coating can be used. The thickness of the cast film can be adjusted by adjusting the amount of solution applied. Therefore, the amount applied is determined appropriately considering the intended use of the cast film. Next, a cast film is obtained by removing the solvent from the coated film on the support, which is made of solution. The method for removing the solvent may be heating the coated film, placing the coated film in a reduced-pressure atmosphere, or a combination of heating the coated film and placing the coated film in a reduced-pressure atmosphere.
[0060] The film obtained in this manner possesses excellent toughness and superior folding resistance. Therefore, the above film is suitably used, for example, in optical applications, medical applications, packaging applications, electrical and electronic component applications, and the like.
[0061] <Process for Producing Cyclic Olefin Copolymer> The above-mentioned cyclic olefin copolymer can be stably produced, for example, by a production method that satisfies the following requirements. However, the method for producing the above-mentioned cyclic olefin copolymer is not limited to the method described below. ·It includes subjecting a norbornene monomer and an α-olefin to addition polymerization in the presence of a metallocene catalyst represented by formula (1) described later and a cocatalyst. ·The cocatalyst includes a borate compound and a hindered phenol. ·The total amount of the norbornene monomer and the α-olefin relative to 1 part by mass of the metallocene catalyst is 1200 to 1600 parts by mass.
[0062] (1) Components Used in Addition Polymerization The addition polymerization is carried out using a raw material monomer containing a norbornene monomer and an α-olefin in the presence of a predetermined metallocene catalyst and a cocatalyst.
[0063] (1-1) Metallocene Catalyst As the metallocene catalyst, a metallocene compound represented by the following formula (1) is used.
[0064] [Chemical Formula]
[0065] (In formula (1), R 1 ~R 3 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R 4 and R 5 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom, and R 6 ~R 13Each of these is a silyl group that may independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent.
[0066] As a titanocene catalyst, the titanium complex "(t-BuNSiMe2Flu)TiMe2" represented by the following formula (2) is preferred from the viewpoint that copolymers satisfying the aforementioned predetermined requirements can be easily obtained.
[0067] [ka]
[0068] (In the formula, Me represents a methyl group, and t-Bu represents a tert-butyl group.)
[0069] The main technical feature of the method for producing cyclic olefin copolymers is that the amount of monomer used as raw material (total amount of norbornene monomer and α-olefin per 1 part by mass of titanocene catalyst) is 1200 to 1600 parts by mass. This amount of catalyst used is higher than conventional methods (i.e., the relative amount of catalyst used is less compared to conventional methods). In such cases, conventional knowledge predicts a decrease in reaction activity (yield). However, surprisingly, no such decrease is observed, and it is possible to achieve high molecular weight copolymerization.
[0070] The amount of titanocene catalyst in addition polymerization is not particularly limited as long as the addition polymerization reaction proceeds smoothly. For example, the amount of titanocene catalyst in addition polymerization may be 0.0030 to 0.0040 mmol.
[0071] The amount of monomer added (total amount of norbornene monomer and α-olefin per 1 part by mass of titanocene catalyst) is 1200 to 1600 parts by mass, preferably 1300 to 1500 parts by mass.
[0072] (1-2) Co-catalyst The co-catalyst comprises at least a borate compound and a hindered phenol. The co-catalyst is preferably composed of a borate compound and a hindered phenol.
[0073] (1-2-1) Borate Compounds As the borate compound, any compound used as a co-catalyst in the copolymerization of cyclic olefin monomers, etc., can be used.
[0074] Examples of borate compounds include triphenylmethylium tetrakis(pentafluorophenyl) borate, dimethylphenylammonium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, and N-methyldinormaldecylammonium tetrakis(pentafluorophenyl) borate. Of these, triphenylmethylium tetrakis(pentafluorophenyl)borate is preferred from the viewpoint of easily obtaining copolymers that satisfy the aforementioned specified requirements.
[0075] The amount of borate compound used is not particularly limited, as long as the addition polymerization reaction proceeds well and the desired cyclic olefin copolymer is obtained. For example, the amount of borate compound used is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total amount of norbornene monomer and α-olefin.
[0076] (1-2-2) Hindered phenol As the hindered phenol, any type used as a co-catalyst in the copolymerization of cyclic olefin monomers, etc., can be used.
[0077] In the specification and claims of this application, “hindered phenol” means phenols having a bulky substituent at at least one of the two adjacent positions of a phenolic hydroxyl group. In the specification of this application, "bulky substituent" includes alkyl groups other than methyl groups (isopropyl group, isobutyl group, sec-butyl group, and tert-butyl group, etc.), alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, substituted amino groups, alkylthio groups, and arylthio groups, etc.
[0078] Examples of hindered phenols include 2,6-di-tert-butyl-4-hydroxytoluene (BHT), 2,6-di-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-p-cresol, 3,3',5,5'-tetra-tert-butyl-4,4'-dihydroxybiphenyl, 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4',4”-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)2,4,6-trimethylbenzene. Of these, 2,6-di-tert-butyl-4-hydroxytoluene is preferred from the viewpoint of easily obtaining copolymers that satisfy the aforementioned predetermined requirements.
[0079] The amount of hindered phenol used is not particularly limited, as long as the addition polymerization reaction proceeds well and the desired cyclic olefin copolymer is obtained. For example, the amount of hindered phenol used is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total amount of norbornene monomer and α-olefin.
[0080] (2) Addition polymerization conditions Other addition polymerization conditions are not particularly limited, as long as the addition polymerization reaction proceeds well and the desired cyclic olefin copolymer is obtained.
[0081] During addition polymerization, the components to be used in the reaction (norbornene monomer, α-olefin, etc.) may be added to the reaction vessel simultaneously or separately.
[0082] Addition polymerization may be carried out in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the polymerization reaction. Preferred solvents include, for example, hydrocarbon solvents and halogenated hydrocarbon solvents. When a solvent is used, the amount used is not particularly limited and is set appropriately according to the amount of monomer, etc.
[0083] The temperature of addition polymerization is not particularly limited. The temperature of addition polymerization can be, for example, -20 to 200°C.
[0084] The duration of addition polymerization is not particularly limited. The addition polymerization time can be, for example, 0.25 to 2 hours.
[0085] The atmosphere in which the addition polymerization reaction takes place is not particularly limited, as long as the reaction is not inhibited. An inert gas atmosphere (such as nitrogen gas or helium gas) is preferred for the addition polymerization reaction to take place.
[0086] After the addition polymerization is complete, the cyclic olefin copolymer can be recovered from the reaction vessel according to a conventional method. [Examples]
[0087] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
[0088] <Preparation of cyclic olefin copolymers> The cyclic olefin copolymers according to the examples or comparative examples were prepared by the following method.
[0089] The terms used in this examination have the following meanings. • "Nb": 2-Norbornen • "Oct": 1 - Octen • "Hex": 1 - Hexene • "BHT": 2,6-di-tert-butyl-4-hydroxytoluene (equivalent to hindered phenol). • "Charge amount": Total amount of monomer charged per 1 part by mass of catalyst • "Copolymer (g) / Catalyst (g)": Amount of the obtained cyclic olefin copolymer relative to the amount of catalyst. • "α-olefin ratio": The ratio of the number of moles of structural units derived from 1-octene or 1-hexene to the total number of moles of structural units in the obtained cyclic olefin copolymer (the type of α-olefin used is indicated in parentheses in the table). ·“Mw”: Weight average molecular weight ·“Mn”: Number average molecular weight • "Tg": Glass transition temperature • "CC1": 6.5% by mass (as Al atom content) MMAO-3A toluene solution ([ (CH3) 0.7 (iso-C4H9) 0.3 AlO] n A solution of methylisobutylaluminoxane, represented by [formula], manufactured by Tosoh Finechem Co., Ltd., containing 6 mol% trimethylaluminum relative to total Al. • "CC2": 9.0% by mass (as Al atom content) TMAO-211 toluene solution (methylaluminoxane solution, manufactured by Tosoh Finechem Co., Ltd., containing 26 mol% trimethylaluminum relative to total Al).
[0090] In all of these test examples, the titanium complex "(t-BuNSiMe2Flu)TiMe2" represented by the following formula (2) was used as the titanocene catalyst.
[0091] [ka]
[0092] (In the formula, Me represents a methyl group, and t-Bu represents a tert-butyl group.)
[0093] (1) Example 1 2-norbornene and 1-octene were used in the proportions shown in Table 1, in amounts such that the total amount of 2-norbornene and 1-octene was 17.28 mmol. In a 50 mL Schlenk flask, which had been purged with a nitrogen atmosphere, the total amounts of 2-norbornene and 1-octene, along with 0.0032 mmol of tri-t-butyl and 0.0064 mmol of 2,6-di-tert-butyl-4-hydroxytoluene were added. The resulting mixture was diluted with decalin until the contents of the flask reached a volume of 18.6 mL. Next, the contents of the flask were cooled to 0°C. After cooling, a toluene solution containing 0.032 mmol / mL of titanocene catalyst was added to the reaction mixture so that the amount of titanocene catalyst was 0.0032 mmol. Next, a toluene solution of the borate compound with a concentration of 0.008 mmol / L was added to the reaction mixture so that the amount of borate compound was 0.0032 mmol. Triphenylmethylium tetrakis(pentafluorophenyl)borate was used as the borate compound. After initiating addition polymerization by adding the titanocene catalyst and borate compound, the addition polymerization reaction was continued at 0°C for 30 minutes while stirring the reaction mixture with a magnetic stirrer. After 30 minutes of reaction, a small amount of 2-propanol was added to the reaction mixture to stop the addition polymerization reaction. Hydrochloric acid was added to the reaction mixture and stirred for 10 minutes, after which the organic layer was washed with deionized water. Washing with deionized water was repeated until the aqueous layer became neutral, and then the washed organic layer was collected. The recovered organic layer was added dropwise to a large amount of acetone, and the resulting cyclic olefin copolymer was precipitated. After recovering the precipitated copolymer by filtration, the copolymer was washed at least twice with methanol and acetone. The washed copolymer was dried under reduced pressure at 110°C for 16 hours or more, and the dried product was recovered as the cyclic olefin copolymer according to Example 1.
[0094] (2) Example 2 The synthesis was carried out in the same procedure as in Example 1, except that the total amount of monomer charged to the catalyst was 1780 parts by mass, and the cyclic olefin copolymer according to Example 2 was obtained.
[0095] (3) Example 3 The cyclic olefin copolymer according to Example 3 was obtained by synthesizing it using the same procedure as in Example 1, except that decalin was replaced with toluene.
[0096] (4) Examples 4-6 The cyclic olefin polymers according to Examples 4-6 were synthesized using the same procedure as in Example 1, except that the type of α-olefin and / or the ratio of the starting monomers were changed as shown in the table.
[0097] (5) Comparative Examples 1-1 to 1-3 2-norbornene and 1-octene were used in the proportions shown in Table 2, in amounts such that the total amount of 2-norbornene and 1-octene was 118.8 mmol. In a 500 mL round-bottom flask, under a nitrogen atmosphere, half the amount of 2-norbornene and 1-octene, along with 0.198 mmol of tri-n-octylaluminum and 0.396 mmol of 2,6-di-tert-butyl-4-hydroxytoluene were added. The resulting mixture was diluted with decalin until the contents of the flask reached a volume of 258 mL. Next, the contents of the flask were cooled to 0°C. After cooling, a toluene solution containing 0.04 mmol / L of titanocene catalyst was added to the reaction mixture so that the amount of titanocene catalyst was 0.22 mmol. Next, a toluene solution containing 0.008 mmol / L of the borate compound was added to the reaction mixture so that the amount of the borate compound was 0.22 mmol. Triphenylmethylium tetrakis(pentafluorophenyl)borate was used as the borate compound. After adding the titanocene catalyst and borate compound to initiate addition polymerization, the reaction mixture was stirred with a magnetic stirrer and the addition polymerization reaction was continued at 0°C for 10 minutes. After 10 minutes of reaction, the remaining half of the monomers (2-norbornene and 1-octene), along with 0.022 mmol of tri-n-octylaluminum and 0.044 mmol of 2,6-di-tert-butyl-4-hydroxytoluene, were added to the round-bottom flasks. The addition polymerization reaction was then continued for 15 minutes. After a total reaction time of 25 minutes, a small amount of 2-propanol was added to the reaction mixture to stop the addition polymerization reaction. Hydrochloric acid was added to the reaction mixture and stirred for 10 minutes, after which the organic layer was washed with deionized water. Washing with deionized water was repeated until the aqueous layer became neutral, and then the washed organic layer was collected. The recovered organic layer was added dropwise to a large amount of acetone, and the resulting cyclic olefin copolymer was precipitated. After recovering the precipitated copolymer by filtration, the copolymer was washed at least twice with methanol and acetone. The washed copolymer was dried under reduced pressure at 110°C for 16 hours or more, and the dried product was recovered as the cyclic olefin copolymer according to Comparative Examples 1-1 to 1-3.
[0098] (6) Comparative Examples 2-1 to 2-3 2-norbornene and 1-octene were used in the proportions shown in Table 2, in amounts such that the total amount of 2-norbornene and 1-octene was 118.8 mmol. In a 500 mL round-bottom flask, under a nitrogen atmosphere, the total amounts of 2-norbornene and 1-octene, along with 0.198 mmol of tri-n-octylaluminum and 0.396 mmol of 2,6-di-tert-butyl-4-hydroxytoluene were added. The resulting mixture was diluted with decalin until the contents of the flask reached a volume of 258 mL. Next, the contents of the flask were cooled to 25°C. After cooling, a toluene solution containing 0.04 mmol / L of titanocene catalyst was added to the reaction mixture so that the amount of titanocene catalyst became 0.22 mmol. Next, a toluene solution containing 0.008 mmol / L of the borate compound was added to the reaction mixture so that the amount of the borate compound was 0.22 mmol. Triphenylmethylium tetrakis(pentafluorophenyl)borate was used as the borate compound. After initiating addition polymerization by adding the titanocene catalyst and borate compound, the addition polymerization reaction was carried out at 25°C for 15 minutes while stirring the reaction mixture with a magnetic stirrer. After 15 minutes of reaction, a small amount of 2-propanol was added to the reaction mixture to stop the addition polymerization reaction. Hydrochloric acid was added to the reaction mixture and stirred for 10 minutes, after which the organic layer was washed with deionized water. Washing with deionized water was repeated until the aqueous layer became neutral, and then the washed organic layer was collected. The recovered organic layer was added dropwise to a large amount of acetone, and the resulting cyclic olefin copolymer was precipitated. After recovering the precipitated copolymer by filtration, the copolymer was washed at least twice with methanol and acetone. The washed copolymer was dried under reduced pressure at 110°C for 16 hours or more, and the dried product was recovered as the cyclic olefin copolymer according to Comparative Examples 2-1 to 2-3.
[0099] (7) Comparative Examples 3-1 to 3-3 2-norbornene and 1-octene were used in the ratios shown in Table 2, in quantities such that the total amount of 2-norbornene and 1-octene was 118.8 mmol. 2-norbornene, 1-octene, 0.97 mmol of CC1, and 0.68 mmol of CC2 were added to a 500 mL round-bottom flask under a nitrogen atmosphere. Next, the contents of the flask were diluted with toluene to a volume of 258 mL. Next, the contents of the flask were heated to 40°C. After heating, a toluene solution containing 0.04 mmol / L of titanocene catalyst was added to the reaction mixture so that the amount of titanocene catalyst became 0.22 mmol. After adding the titanocene catalyst to initiate addition polymerization, the reaction was carried out at 40°C for 4 hours while stirring the reaction mixture with a magnetic stirrer. After 4 hours of reaction, a small amount of 2-propanol was added to the reaction solution to stop the addition polymerization reaction. Hydrochloric acid was added to the reaction mixture and stirred for 10 minutes, after which the organic layer was washed with deionized water. The washing with deionized water was repeated until the aqueous layer became neutral, and then the washed organic layer was collected. The recovered organic layer was added dropwise to a large amount of acetone to precipitate the resulting cyclic olefin copolymer. After recovering the precipitated copolymer by filtration, the copolymer was washed at least twice with methanol and acetone. The washed copolymer was dried under reduced pressure at 110°C for 16 hours or more, and the dried product was recovered as the cyclic olefin copolymer according to Comparative Examples 3-1 to 3-3.
[0100] (8) Evaluation The molecular weight, glass transition temperature, and toughness of each obtained copolymer were determined by the following method. The results are shown in Tables 1 and 2.
[0101] The glass transition temperature and toughness were evaluated using films of each copolymer prepared according to the method described below. A mold with a depth of 50 μm was fabricated using "Kapton® film" (size: 10 cm x 10 cm x 50 μm). Each copolymer was filled into a mold and vacuum pressed using a hot vacuum press. The vacuum pressing conditions were set to a pressure of 15 MPa, a temperature of 320-340°C, and a time of 15 minutes. After pressing was complete, each pressed copolymer was rapidly cooled by sandwiching it between metal plates at room temperature. After cooling, the metal plates were removed to obtain films of each copolymer (film thickness approximately 50 μm).
[0102] (8-1)Molecular weight The number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured by gel permeation chromatography according to the following measurement conditions. Equipment: Malvern Viscotek TDA302 detector + pump autosampler system Detector: RI Solvent: Toluene Column: TSKgel GMHHR-M (300mm x 7.8mmφ) manufactured by Tosoh Corporation Flow rate: 1mL / min Temperature: 75℃ Sample concentration: 2.5 mg / mL Injection volume: 100μL Standard sample: Monodisperse polystyrene
[0103] (8-2) Glass transition temperature The glass transition temperature was measured by observing the viscoelastic behavior of films (50 μm thick) made from each copolymer using a solid-state rheometer from -100°C to 300°C. Specifically, the temperature at the top of the peak in the tan δ chart obtained from the aforementioned measurement was defined as the glass transition temperature.
[0104] (8-3) Toughness The toughness of each copolymer was evaluated by conducting a folding resistance test (MIT test) in accordance with JIS P 8115. Specifically, films made from each copolymer were used, and MIT tests were conducted using an MIT folding fatigue tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to measure the number of times the film could be folded before it broke (folding resistance). A higher number of folds indicates greater film toughness.
[0105] The details of the MIT exam requirements are as follows: Loading method: Spring load Load: 1kgf Bending angle: 135° Bending speed: 175 cpm
[0106] (8-4) Preparation of resin film (cast film) Each polymer (10g) from Examples 1-6 was dissolved in toluene (90g) to prepare a 10% by mass toluene solution. The resulting solution was applied to a PET film using a film applicator (SA202 Doctor Blade, manufactured by Tester Industries Co., Ltd., gap thickness 250μm), dried at 90°C for 8 minutes, and then further dried in a vacuum dryer at 100°C for 12 hours to obtain a cast film. The film thickness was set to 25μm. We confirmed that a good cast film could be formed with all of the polymers from Examples 1 to 6.
[0107] [Table 1]
[0108] [Table 2]
[0109] As shown in Examples 1 to 6, cyclic olefin copolymers satisfying the requirements of the present invention were obtained. These copolymers possessed high Tg and high toughness.
[0110] Copolymers having multiple Tg values, especially those with high Tg values (e.g., above 200°C) like the copolymer in "Example 1," have traditionally been known to have low toughness. However, in cyclic olefin copolymers that met the aforementioned requirements, it was surprisingly possible to achieve both high Tg and high toughness.
[0111] Furthermore, "Examples 1" through "Examples 6" involved high charge amounts (i.e., relatively less catalyst was used compared to "Comparative Example 1-1," etc.). In such cases, conventional knowledge would predict a decrease in reaction activity (yield). However, surprisingly, no such decrease was observed, and high molecular weight copolymerization was achieved.
[0112] In contrast, as shown in "Comparative Example 1-1" to "Comparative Example 1-3" and "Comparative Example 2-1" to "Comparative Example 2-3," these copolymers had low number-average molecular weights and could not be made high molecular weight. In particular, in "Comparative Example 1-1," both the number-average molecular weight and toughness were lower, even though the monomer used was the same as in "Example 1."
[0113] Furthermore, in "Comparative Example 3-2" and "Comparative Example 3-3," although the copolymer could be made to have a high molecular weight, its toughness was remarkably low.
Claims
1. A cyclic olefin copolymer which is an addition polymer of norbornene monomer and α-olefin having 3 to 20 carbon atoms, The ratio of the number of moles of structural units derived from the α-olefin to the total number of moles of structural units in the cyclic olefin copolymer is 10 to 90 mol%, The number-average molecular weight of the cyclic olefin copolymer is between 200,000 and 500,000. The cyclic olefin copolymer has at least one glass transition temperature measured by viscoelasticity within the range of less than 0°C, 0°C to less than 130°C, and 130°C to 350°C. Cyclic olefin copolymer.
2. The cyclic olefin copolymer according to Claim 1, wherein the cyclic olefin copolymer has at least one glass transition temperature determined by viscoelasticity measurement in the range of -50 to less than 0°C, in the range of 0°C to less than 130°C, and in the range of 130°C to 350°C.
3. The cyclic olefin copolymer according to Claim 1, wherein the cyclic olefin copolymer has at least one glass transition temperature determined by viscoelasticity measurement in the range of -50 to -10°C, in the range of 40 to 100°C, and in the range of 130 to 350°C.
4. The cyclic olefin copolymer according to claim 1, wherein the α-olefin has 4 to 8 carbon atoms.
5. A solution comprising a cyclic olefin copolymer according to any one of claims 1 to 4 and a solvent.
6. A film made from the solution described in claim 5.
7. A method for producing the cyclic olefin copolymer according to any one of claims 1 to 4, The method involves addition polymerization of the norbornene monomer and the α-olefin in the presence of a titanocene catalyst represented by the following formula (1) and a co-catalyst. The co-catalyst comprises a borate compound and a hindered phenol. The total amount of norbornene monomer and α-olefin per 1 part by mass of titanocene catalyst is 1200 to 1600 parts by mass. Manufacturing method. 【Chemistry 1】 (In formula (1), R １ ~R ３ Each of these is independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R ４ and R ５ Each of these is independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom, R ６ ~R １３ Each of these is a silyl group that may independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent.