Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/14—Monomers containing five or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2400/00—Characteristics for processes of polymerization
  • C08F2400/02—Control or adjustment of polymerization parameters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2420/00—Metallocene catalysts
  • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor

Definitions

• the present invention relates to a cyclic olefin copolymer and a method for producing a cyclic olefin copolymer.
• Cyclic olefin polymers and cyclic olefin copolymers have low hygroscopicity and high transparency. Therefore, COPs and COCs are used in various applications, including the field of optical materials such as optical disk substrates, optical films, and optical fibers.
• a typical COC is a copolymer of cyclic olefin and ethylene. The glass transition temperature (Tg) of such a copolymer can be changed by changing the copolymer composition of the cyclic olefin and ethylene.
• a copolymer of cyclic olefin and ethylene can be produced as a copolymer having a glass transition temperature higher than that of COP, and a Tg of over 200°C, which is difficult with COP, can be achieved. It is possible. However, such copolymers have a hard and brittle character. Therefore, such copolymers have problems of low mechanical strength and poor handling and workability.
• the copolymerization of a cyclic olefin and a specific ⁇ -olefin is significantly different from the copolymerization of a cyclic olefin and ethylene.
• copolymerizing a cyclic olefin and a specific ⁇ -olefin under conditions where a high molecular weight product can be obtained by copolymerizing a cyclic olefin with ethylene it has been difficult to obtain a high molecular weight copolymer. This is because a chain transfer reaction caused by the specific ⁇ -olefin occurs in the copolymerization of the cyclic olefin and the specific ⁇ -olefin. Therefore, copolymers of cyclic olefins and specific ⁇ -olefins have been considered unsuitable for molding materials (see, for example, Non-Patent Document 1).
• the present invention has been made in view of the above circumstances, and is a copolymer of a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms, which is a cyclic polymer having excellent tensile strength and breaking strain.
• An object of the present invention is to provide an olefin copolymer and a method for producing a cyclic olefin copolymer capable of satisfactorily producing the cyclic olefin copolymer.
• the present inventors found that in a copolymer of a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms, the amount of structural units derived from the ⁇ -olefin is 10 mol% of the total structural units. At least 50 mol% or less, and the average value of the relaxation time corresponding to each hydrogen of the cyclic olefin copolymer is 4.5 to 5.5 msec in the relaxation time T 1 ⁇ of the hydrogen nucleus obtained by solid-state NMR measurement of the cyclic olefin copolymer. and the difference between the maximum value and the minimum value of the relaxation time is in the range of 1.0 to 3.0 msec. . More specifically, the present invention provides the following.
• a cyclic olefin copolymer that is an addition-type polymer of a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms, The ratio of the number of moles of structural units derived from the ⁇ -olefin to the number of moles of all structural units is 10 mol% or more and 50 mol% or less,
• the average value of the relaxation time corresponding to each hydrogen of the cyclic olefin copolymer is in the range of 4.5 to 5.5 msec, and the maximum and minimum relaxation times
• the average relaxation time is in the range of 4.7 to 5.5 msec, and the difference between the maximum and minimum relaxation times is in the range of 1.5 to 2.5, in (I) The cyclic olefin copolymer described.
• R 1 to R 3 are each 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 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
• R 6 to R 13 each independently represent a hydrogen atom or 1 or more carbon atoms an alkyl group of 12 or less, an aryl group of 6 or more and 12 or less carbon atoms, or a silyl group optionally having a monovalent hydrocarbon group of 1 or more and 12 or less carbon atoms as a substituent.
• R 1 to R 3 are each 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 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
• R 6 to R 13 each independently represent a hydrogen atom or 1 or more carbon atoms an alkyl group of 12 or less, an aryl group of 6 or more and 12 or less carbon atoms, or a silyl group optionally having a monovalent hydrocarbon group of 1 or more and 12 or less carbon atoms as a substituent.
• a cyclic olefin copolymer which is a copolymer of a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms and is excellent in tensile strength and breaking strain, and the cyclic olefin copolymer It is possible to provide a method for producing a cyclic olefin copolymer capable of producing a polymer satisfactorily.
• a cyclic olefin copolymer is an addition type polymer of a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms.
• the ratio of the number of moles of structural units derived from ⁇ -olefin to the number of moles of all structural units is 10 mol % or more and 50 mol % or less.
• the average relaxation time corresponding to each hydrogen of the cyclic olefin copolymer is in the range of 4.5 to 5.5 msec,
• the difference between the maximum and minimum relaxation times is in the range of 1.0 to 3.0 msec.
• the above cyclic olefin copolymer is excellent in tensile strength and breaking strain.
• the cyclic olefin copolymer preferably has a value of 25 MPa as measured by a tensile test performed using a No. 2 dumbbell test piece having a thickness of 50 ⁇ m at 23° C. by a method in accordance with ISO 527-3. Above, more preferably 30 MPa or more, still more preferably 40 MPa or more tensile strength.
• the cyclic olefin copolymer preferably exhibits a breaking strain of 3.5% or more, more preferably 5% or more, as measured by a tensile test according to the above method.
• the cyclic olefin copolymer preferably exhibits a tensile modulus of 1000 MPa or more, more preferably 1100 MPa or more, and still more preferably 1500 MPa or more as a measured value by a tensile test according to the above method.
• the ratio of the number of moles of structural units derived from ⁇ -olefin to the number of moles of all structural units is 10 mol% or more and 50 mol% or less, preferably 15 mol% or more and 45 mol% or less. , more preferably 20 mol % or more and 40 mol % or less, more preferably 20 mol % or more and 35 mol % or less, and particularly preferably 20 mol % or more and 30 mol % or less.
• the molar ratio of structural units derived from ⁇ -olefin is too high, it is difficult to obtain a cyclic olefin copolymer with high tensile strength and tensile elastic modulus. If the molar ratio of structural units derived from ⁇ -olefin is too high, it is difficult to obtain a cyclic olefin copolymer having a high glass transition temperature and excellent heat resistance.
• the molar ratio of structural units derived from ⁇ -olefin can be calculated by measuring 13 C-NMR spectrum.
• the cyclic olefin copolymer contains other structural units other than structural units derived from cyclic olefin monomers and structural units derived from ⁇ -olefins having 3 to 20 carbon atoms, as long as the object of the present invention is not impaired. may contain.
• As other structural units a structural unit derived from a compound having a carbon-carbon unsaturated double bond, which is copolymerizable with a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms, is adopted. obtain.
• Structural units derived from ethylene are typically preferred as other structural units.
• the total of the ratio of the number of moles of the structural units derived from the cyclic olefin monomer and the ratio of the number of moles of the structural units derived from the ⁇ -olefin to the number of moles of all structural units is 80 moles. % or more, more preferably 90 mol % or more, even more preferably 95 mol % or more, most preferably 100 mol %.
• the mechanical strength of a copolymer correlates with the molecular mobility of each copolymerized component. For example, at temperatures below Tg, components with low molecular mobility are considered to exhibit high tensile strength, and components with high molecular mobility are considered to exhibit high breaking strain. From this, it can be said that it is necessary to control the mobility of the copolymer in order to obtain a material having excellent tensile strength and breaking strain.
• the molecular mobility of the cyclic olefin copolymer can be evaluated by T 1 ⁇ relaxation time (msec) of the hydrogen nucleus obtained by solid-state NMR measurement.
• each hydrogen of the cyclic olefin copolymer is in the range of 4.5 to 5.5 msec, and the difference between the maximum and minimum relaxation times is in the range of 1.0 to 3.0 msec. , and it was found that it is easy to obtain a cyclic olefin copolymer excellent in breaking strain.
• the average relaxation time corresponding to each hydrogen in the cyclic olefin copolymer is in the range of 4.7 to 5.5 msec, and the difference between the maximum and minimum relaxation times is in the range of 1.5 to 2.5 msec. It is preferable to have
• the T 1 ⁇ relaxation time of the hydrogen nucleus of the cyclic olefin copolymer can be measured by the solid-state NMR relaxation time measurement method described below.
• a CP (cross-polarization) method of transferring the magnetization of hydrogen nuclei to carbon-13 nuclei after spin-locking the magnetization of hydrogen nuclei for a spin-lock time ⁇ was used. In this method, multiple points are measured while changing the spin-lock time ⁇ until the signal intensity is sufficiently attenuated, and the signal of carbon-13 nuclei after the time ⁇ is observed as a spectrum.
• the intensity I( ⁇ ) of each signal at the spectral chemical shift of 10 to 60 ppm is plotted against time ⁇ , and the hydrogen nucleus T 1 ⁇ relaxation time of each signal is obtained by the least squares method from the regression equation shown in Equation (1).
• the hydrogen nucleus T1 ⁇ relaxation time of each signal obtained by this method can be calculated, and the average value of each hydrogen nucleus T1 ⁇ relaxation time and the difference between the maximum value and the minimum value can be evaluated.
• the cyclic olefin copolymer preferably has two or more glass transition temperatures within the range of 0° C. to 300° C. by viscoelasticity measurement.
• the glass transition temperature can be measured by observing the viscoelastic behavior at ⁇ 100° C. to 300° C. with a solid rheometer using a film-like molded product with a thickness of 50 ⁇ m. Specifically, regarding the peaks in the tan ⁇ chart obtained by the above measurement, the peak top temperature is taken as the glass transition temperature.
• the cyclic olefin copolymer has at least one It preferably has a glass transition temperature.
• the breaking strain measured by the above tensile test is large, the cyclic olefin copolymer is in the range of less than 0 ° C., in the range of 0 ° C. to 100 ° C., and in the range of 160 ° C. to 300 ° C. and preferably each have at least one glass transition temperature.
• the range of 30°C to 80°C is preferred, and the range of 40°C to 70°C is more preferred.
• the cyclic olefin copolymer has one glass transition temperature in the range of 0° C. to 100° C. and one in the range of 160° C. to 300° C., or less than 0° C. and one glass transition temperature in the range of 0° C. to 100° C. and one in the range of 160° C. to 300° C., respectively.
• the molecular weight of the cyclic olefin copolymer is not particularly limited.
• the weight average molecular weight (Mw) of the cyclic olefin copolymer is preferably 5,000 or more and 200,000 or less, more preferably 10,000 or more and 100,000, as a polystyrene-equivalent value measured by gel permeation chromatography (GPC).
• the number average molecular weight (Mn) of the cyclic olefin copolymer is preferably 5,000 or more and 200,000 or less, more preferably 10,000 or more and 100,000 as a polystyrene-equivalent value measured by gel permeation chromatography (GPC).
• the dispersion ratio (Mw/Mn) is preferably 1.2 or more, more preferably 1.3 or more.
• the cyclic olefin monomer is not particularly limited as long as it does not impair the object of the present invention.
• norbornene and substituted norbornenes are preferably used as cyclic olefin monomers.
• norbornene is particularly preferred from the viewpoint of good balance of cost, polymerizability, and physical properties of the obtained cyclic olefin copolymer.
• a cyclic olefin monomer can be used individually by 1 type or in combination of 2 or more types.
• substituted norbornene is not particularly limited.
• Substituents possessed by substituted norbornene include, for example, halogen atoms and monovalent or divalent hydrocarbon groups.
• Specific examples of substituted norbornenes include compounds represented by the following formula (I).
• R a1 to R a12 which may be the same or different, are atoms or groups selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group.
• R a9 and R a10 and R a11 and R 12 may combine to form a divalent hydrocarbon group.
• R a9 or R a10 and R a11 or R a12 may combine with each other to form a ring.
• n is 0 or a positive integer. When n is 2 or more, R a5 to R a8 may be the same or different in each repeating unit. However, when n is 0, at least one of R a1 to R a4 and R a9 to R a12 is not a hydrogen atom.
• R a1 to R a8 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; and an alkyl group having 1 to 20 carbon atoms.
• R a1 to R a8 may all consist of different atoms or groups. Some or all of R a1 to R a8 may be the same atoms or groups.
• R a9 to R a12 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; substituted or unsubstituted aromatic hydrocarbon groups such as ethylphenyl group, isopropylphenyl group, naphthyl group and anthryl group; aralkyl groups such as benzyl group and phenethyl group; R a9 to R a12 may all consist of different atoms or groups. Some or all of R a9 to R a12 may be the same atoms or groups.
• divalent hydrocarbon group that can be formed by combining R a9 and R a10 or R a11 and R a12 are alkylidene groups such as ethylidene group, propylidene group, and isopropylidene group. etc.
• the ring formed may be monocyclic or polycyclic.
• the rings formed may be polycyclic with bridges.
• the ring formed may have a double bond.
• the formed ring may have a substituent such as a methyl group.
• substituted norbornenes represented by formula (I) include 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept-2 -ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1 ]hept-2-ene, 5-hexyl-bicyclo[2.2.1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[2 .2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5-propenyl - bicyclic cyclic olefins such as bicyclo[2.2.1]hept-2-en
• alkyl-substituted norbornenes such as bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups
• bicyclo[2.2.1]hept-2-ene Preferred are alkylidene-substituted norbornenes substituted with one or more alkylidene groups such as.
• 5-ethylidene-bicyclo[2.2.1]hept-2-ene commonly name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene
• 5-ethylidene-bicyclo[2.2.1]hept-2-ene common name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene
• the ⁇ -olefin is an ⁇ -olefin having 3 to 20 carbon atoms.
• ⁇ -olefins not only unsubstituted ⁇ -olefins but also substituted ⁇ -olefins having substituents such as halogen atoms can be used.
• the number of carbon atoms in the ⁇ -olefin is 3 or more and 20 or less, preferably 4 or more and 12 or less, and more preferably 6 or more and 10 or less.
• ⁇ -olefins having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3- to ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1- xene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and the like. Among these, 1-hexene, 1-octene and 1-decene are preferred.
• cyclic olefin copolymers are mixed with various additives, if necessary, and then formed into films, sheets, etc., and then widely used in various applications such as packaging applications and optical applications.
• additives that can be added to the cyclic olefin copolymer include antioxidants, weather stabilizers, ultraviolet absorbers, antibacterial agents, flame retardants, colorants, and the like. These additives are added to the cyclic olefin copolymer in an amount that takes into consideration the general amount used according to the type.
• a method for producing a cyclic olefin copolymer includes addition polymerization of a cyclic olefin monomer and an ⁇ -olefin in the presence of a titanocene catalyst represented by the following formula (1) and a co-catalyst. Promoters include borate compounds and hindered phenols.
• the cyclic olefin monomer and the ⁇ -olefin are separately added to the reaction system in which the addition polymerization is carried out in two or more portions.
• R 1 to R 3 are each 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 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
• R 6 to R 13 each independently represent a hydrogen atom or 1 or more carbon atoms an alkyl group of 12 or less, an aryl group of 6 or more and 12 or less carbon atoms, or a silyl group optionally having a monovalent hydrocarbon group of 1 or more and 12 or less carbon atoms as a substituent.
• a cyclic olefin copolymer that satisfies the structural requirements described in any one of (I) to (III) above can be provided.
• This method below is also referred to as "first manufacturing method”.
• the following production method is also preferable as the production method of the cyclic olefin copolymer.
• a cyclic olefin copolymer that satisfies the structural requirements described in (I) or (II) above can be provided.
• this method includes addition polymerization of a cyclic olefin monomer and an ⁇ -olefin in the presence of a titanocene catalyst represented by formula (1) and a cocatalyst. Promoters include borate compounds and hindered phenols.
• the addition polymerization is carried out at a temperature within the range of 10°C or higher and 60°C or lower.
• the titanocene catalyst represented by Formula (1) is the same as the titanocene catalyst described above for the first production method.
• this method is also referred to as "second manufacturing method”.
• a monomer containing the aforementioned cyclic olefin monomer and an ⁇ -olefin is used.
• the type of cyclic olefin monomer, the type of ⁇ -olefin, and the copolymerization ratio thereof are as described for the cyclic olefin copolymer.
• the cyclic olefin monomer and the ⁇ -olefin are separately added to the reaction system in which the addition polymerization is carried out in two or more steps.
• the average relaxation time corresponding to each hydrogen of the cyclic olefin copolymer in the relaxation time T 1 ⁇ of the hydrogen nucleus by solid-state NMR measurement is in the range of 4.5 to 5.5 msec, and the difference between the maximum and minimum relaxation times is in the range of 1.0 to 3.0 msec.
• the number of divisions is not particularly limited.
• the number of divisions is, for example, preferably 2 or more and 5 or less, more preferably 2 or 3, and even more preferably 2.
• the amount of cyclic olefin monomer or ⁇ -olefin added per time is TA / N ⁇ 0.5 or more TA, where TA is the mass of the entire addition amount and N is the number of divisions. /N ⁇ 1.5 or less is preferable, TA/N ⁇ 0.7 or more and TA/N ⁇ 1.3 or less is more preferable, and TA/N ⁇ 0.9 or more and TA/N ⁇ 1.1 or less is more preferable.
• the amount of the cyclic olefin monomer or ⁇ -olefin added per time is preferably 25% by mass or more and 75% by mass or less, and 35% by mass or more, based on the total mass of the added amount. 65% by mass or more is more preferable, and 45% by mass or more and 55% by mass or less is even more preferable.
• At least one of the cyclic olefin monomer and the alpha-olefin is added to the reaction vessel at or before the initiation of the addition polymerization, if split addition is used. Second and subsequent additions of cyclic olefin monomers or ⁇ -olefins are then made at arbitrary times after initiation of the addition polymerization.
• the time between each addition is preferably 3 minutes or more and 20 minutes or less, more preferably 5 minutes or more and 15 minutes or less.
• the timing of adding the cyclic olefin monomer and the timing of adding the ⁇ -olefin may be the same or different. Further, the number of divided additions of the cyclic olefin monomer and the divided number of additions of the ⁇ -olefin may be different.
• R 1 to R 3 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.
• alkyl groups such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopentyl group and cyclohexyl group; phenyl group and biphenyl group; , a phenyl group or biphenyl group having the above alkyl group as a substituent, a naphthyl group, and an aryl group such as a naphthyl group having the above alkyl group as a substituent.
• 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.
• Halogen atoms such as bromine and iodine atoms; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl groups , these alkyl groups having the above halogen atoms as substituents; phenyl groups, biphenyl groups, naphthyl groups, and these aryl groups having the above halogen atoms or alkyl groups as substituents.
• R 6 to R 13 each independently represents 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. is a silyl group optionally having as a substituent.
• alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group and octyl group. , a cyclopentyl group, a cyclohexyl group, and the like.
• aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, and those aryl groups having the alkyl group as a substituent.
• silyl group having a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and t-butyl group.
• a pentyl group a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, and the like, having 1 to 12 carbon atoms as a substituent.
• titanocene catalyst represented by the general formula (1) examples include (isopropylamido)dimethyl-9-fluorenylsilanetitaniumdimethyl, (isobutylamido)dimethyl-9-fluorenylsilanetitaniumdimethyl, (t-butylamide) ) dimethyl-9-fluorenylsilanetitanium dimethyl, (isopropylamido)dimethyl-9-fluorenylsilanetitanium dichloride, (isobutylamido)dimethyl-9-(3,6-dimethylfluorenyl)silanetitanium dichloride, ( t-butylamido)dimethyl-9-fluorenylsilanetitanium dichloride, (isopropylamido)dimethyl-9-(3,6-dimethylfluorenyl)silanetitanium dichloride, (isobutylamido)dimethyldi
• (t-butylamido)dimethyl-9-fluorenylsilanetitanium dimethyl (t-BuNSiMe 2 Flu)TiMe 2 ).
• (t-BuNSiMe 2 Flu)TiMe 2 is a titanium complex represented by the following formula (2), and can be easily synthesized, for example, based on the description in "Macromolecules, Vol. can be done.
• Me represents a methyl group
• t-Bu represents a tert-butyl group
• the amount of the titanocene catalyst used is not particularly limited as long as the addition polymerization reaction proceeds well.
• the amount of the titanocene catalyst used is preferably 0.001 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 5 parts by mass or less, relative to the total amount of 100 parts by mass of the cyclic olefin monomer and the ⁇ -olefin. 0.1 parts by mass or more and 1 part by mass or less is more preferable.
• Addition polymerization of a monomer containing a cyclic olefin monomer and an ⁇ -olefin is carried out in the coexistence of the titanocene catalyst and co-catalyst.
• Promoters include borate compounds and hindered phenols.
• a cyclic olefin copolymer having both excellent breaking strain and excellent toughness can be obtained by carrying out addition polymerization in the presence of the titanocene catalyst and co-catalyst so as to satisfy the above-mentioned predetermined conditions.
• borate compound any borate compound conventionally used as a cocatalyst in the homopolymerization or copolymerization of cyclic olefin monomers can be used without particular limitation.
• Preferred specific examples of borate compounds include triphenylmethylium tetrakis(pentafluorophenyl)borate, dimethylphenylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, and N- Methyl di-normal decyl ammonium tetrakis(pentafluorophenyl) borate and the like can be mentioned.
• the hindered phenol any hindered phenol that has been conventionally used as a co-catalyst in the homopolymerization or copolymerization of cyclic olefin monomers can be used without particular limitation.
• the hindered phenol is a phenol having a bulky substituent at at least one of the two adjacent positions of the phenolic hydroxyl group.
• bulky substituents include alkyl groups other than methyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, substituted amino groups, alkylthio groups, and arylthio groups. be done.
• Specific examples of alkyl groups other than methyl groups include isopropyl, isobutyl, sec-butyl, and tert-butyl groups.
• 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-trimethylbenzen
• the hindered phenol can increase the yield of the cyclic olefin copolymer by reacting with the alkylaluminum compound in the polymerization system.
• the cocatalyst further comprises an alkylaluminum compound.
• alkylaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum and tri-n-octylaluminum; dimethylaluminum chloride; dialkylaluminum halides such as diisobutylaluminum chloride; dialkylaluminum hydrides such as diisobutylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminum methoxide.
• trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum and tri-n-octylaluminum
• the amount of the borate compound used is not particularly limited as long as the addition polymerization reaction proceeds well and a cyclic olefin copolymer having desired properties can be obtained.
• the amount of the borate compound used is preferably 0.01 parts by mass or more and 100 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, relative to the total amount of 100 parts by mass of the cyclic olefin monomer and the ⁇ -olefin. 1 part by mass or more and 5 parts by mass or less is more preferable.
• the amount of the hindered phenol used is not particularly limited as long as the addition polymerization reaction proceeds well and a cyclic olefin copolymer with desired properties is obtained.
• the amount of the hindered phenol used is preferably 0.001 parts by mass or more and 100 parts by mass or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total amount of the cyclic olefin monomer and the ⁇ -olefin. , more preferably 0.1 parts by mass or more and 1 part by mass or less.
• the amount of the alkylaluminum compound used is not particularly limited as long as the addition polymerization reaction proceeds well and a cyclic olefin copolymer having desired properties can be obtained.
• the amount of the alkylaluminum compound used is preferably 0.001 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass as the total amount of the cyclic olefin monomer and the ⁇ -olefin. , more preferably 0.1 parts by mass or more and 1 part by mass or less.
• 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, and hydrocarbon solvents are preferred because they are excellent in handleability, thermal stability, and chemical stability.
• preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene, chloroform, Halogenated hydrocarbon solvents such as methylene chloride, dichloromethane, dichloroethane, and chlorobenzene are included.
• hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene, chloroform
• Halogenated hydrocarbon solvents such as
• the solvent may be charged into the polymerization vessel as a solvent alone, or may be charged into the polymerization vessel in the form of a monomer solution, a catalyst solution, or a cocatalyst solution.
• the amount used is not particularly limited.
• the amount of the solvent used is preferably 100 parts by mass or more and 100000 parts by mass or less, more preferably 500 parts by mass or more and 10000 parts by mass or less, and 1000 parts by mass or more and 5000 parts by mass, based on the total amount of 100 parts by mass of the cyclic olefin monomer and the ⁇ -olefin. Part by mass or less is more preferable.
• the addition polymerization temperature is not particularly limited.
• the addition polymerization temperature is, for example, preferably -20°C or higher and 200°C or lower, more preferably -10°C or higher and 10°C or lower, and even more preferably -5°C or higher and 5°C or lower.
• the addition polymerization time is not particularly limited.
• the addition polymerization time is, for example, preferably 5 minutes or more and 30 minutes or less, more preferably 8 minutes or more and 20 minutes or less, and even more preferably 10 minutes or more and 15 minutes or less.
• the atmosphere in which the above addition polymerization reaction is carried out is not particularly limited, but an inert gas atmosphere is preferred. Nitrogen gas or helium gas can be used as the inert gas.
• the cyclic olefin copolymer is recovered from the reaction vessel in accordance with a conventional method.
• the second production method is the same as the first production method, except that the method of charging the cyclic olefin monomer and the ⁇ -olefin is not particularly limited, and that the addition polymerization is performed at a temperature within the range of 10 ° C. or higher and 60 ° C. or lower. It is the same as the manufacturing method.
• the method of charging the cyclic olefin monomer and the ⁇ -olefin in the second production method may be the same as in the first production method. Since the charging operation is simple, the method for charging the cyclic olefin monomer and the ⁇ -olefin in the second production method is to batch the cyclic olefin monomer and the ⁇ -olefin at or before the start of the addition polymerization reaction. is preferably charged into the reaction vessel.
• Examples 1 to 4 In Examples 1 to 4, 2-norbornene (Nb) and 1-octene (Oct) were added in the ratios shown in Table 1, respectively, and the total amount of 2-norbornene and 1-octene was 118.8 mmol. board. In a 500 mL eggplant-shaped flask replaced with a nitrogen atmosphere, half of 2-norbornene and 1-octene, 0.198 mmol of tri-n-octylaluminum, and 2,6-di-tert-butyl-4- 0.396 mmol of hydroxytoluene was added. Toluene was then used to dilute the contents of the flask to a volume of 258 mL.
• the contents of the flask were then cooled to 0°C. After cooling, a toluene solution of a titanocene catalyst with a concentration of 0.04 mmol/L was added to the reaction solution so that the amount of the titanocene catalyst was 0.22 mmol.
• the titanocene catalyst the compound represented by the above formula (2) was used.
• a toluene solution of a borate compound with a concentration of 0.008 mmol/L was added to the reaction solution so that the amount of the borate compound was 0.22 mmol.
• Triphenylmethylium tetrakis(pentafluorophenyl)borate was used as the borate compound.
• the molar ratio of structural units derived from ⁇ -olefin (1-octene) was specified by the following method.
• About 50 mg of the obtained cyclic olefin copolymer was dissolved in 0.6 mL of chloroform-d, and using a BRUKER AVANCE III 400+ cryoprobe, 300 K, 90° pulse, repetition time of 30 seconds, and integration of 1000 times.
• a 13 C-NMR spectrum was measured. From the obtained spectrum, the ⁇ -olefin ratio was calculated based on the following formula in accordance with the method described in Macromolecules 2010, 43, 4527-4531.
• Ratio of ⁇ -olefin (mol%) [integral value of ⁇ -olefin-derived carbon / (integral value of ⁇ -olefin-derived carbon + integral value of carbon derived from cyclic olefin monomer)] ⁇ 100
• a No. 2 dumbbell test piece cut out from the film obtained by the following method was used as a measurement sample.
• the tensile test conforms to ISO527-3, using a tensile tester (manufactured by A&D Co., Ltd., Tensilon Universal Material Testing Machine RTM-100), a temperature of 23 ° C., a distance between chucks of 50 mm, and a tensile speed of 50 mm / min. was performed under the conditions of
• Solid-state NMR measurement was performed by the following method.
• a resin piece of 2.1 mm ⁇ punched out from a film obtained by the following method was used as a measurement sample.
• a sample tube made of zirconia with a diameter of 3.2 mm was filled with the measurement sample.
• the 1 H relaxation time T 1 ⁇ of each signal was measured by the CP/MAS Spinlock method at a sample rotation speed of 15 kHz and a measurement temperature of -50 ° C. asked.
• the CH signal of adamantane was measured at 29.5 ppm.
• Films used as samples in glass transition temperature measurements, tensile tests, and solid-state NMR measurements were prepared by the following method.
• a 50 ⁇ m deep mold was made using Kapton® film with a size of 10 cm ⁇ 10 cm ⁇ 50 ⁇ m.
• the cyclic olefin copolymer filled in the mold was pressed under the conditions of pressure of 15 MPa, temperature of 320 to 340 ° C., and time of 15 minutes. The polymer was vacuum pressed. After pressing, the pressed cyclic olefin copolymer was rapidly cooled by sandwiching it between room temperature metal plates. After cooling, the metal plate was removed to obtain a cyclic olefin copolymer film having a thickness of about 50 ⁇ m.
• Examples 5 to 8 Before starting the addition polymerization reaction, the total amount of norbornene and 1-octene was charged at once, the reaction temperature was changed to 25 ° C., and the reaction time was changed to 10 minutes. A cyclic olefin copolymer was obtained in the same manner. The charging ratio of norbornene and 1-octene is as shown in Table 1. Regarding the obtained cyclic olefin copolymer, the molecular weight was measured by gel permeation chromatography in the same manner as in Example 1, the Oct ratio in the resin was measured, and the hydrogen nucleus relaxation time T 1 ⁇ was measured by solid-state NMR measurement by the method described above.
• Example 1 A cyclic olefin copolymer was obtained in the same manner as in Example 5, except that the reaction temperature was changed to 0°C.
• the charging ratio of norbornene and 1-octene is as shown in Table 1.
• the molecular weight was measured by gel permeation chromatography in the same manner as in Example 1, the Oct ratio in the resin was measured, and the hydrogen nucleus relaxation time T 1 ⁇ was measured by solid-state NMR measurement by the method described above.
• CC1 Methylisobutylaluminoxane represented by 6.5 mass % (as Al atom content) MMAO-3A toluene solution ([(CH 3 ) 0.7 (iso-C 4 H 9 ) 0.3 AlO] n solution, manufactured by Tosoh Finechem Co., Ltd., containing 6 mol% trimethylaluminum relative to the total Al)
• CC2 9.0% by mass (as Al atom content) TMAO-211 toluene solution (solution of methylaluminoxane, manufactured by Tosoh Finechem Co., Ltd., containing 26 mol% trimethylaluminum relative to total Al)
• Example 5 except that only 0.22 mmol of triphenylmethylium tetrakis(pentafluorophenyl)borate was used as a cocatalyst, the reaction temperature was changed to 25° C., and the reaction temperature was changed to 2 hours.
• a cyclic olefin copolymer was obtained in the same manner.
• the charging ratio of norbornene and 1-octene is as shown in Table 1.
• the molecular weight was measured by gel permeation chromatography in the same manner as in Example 1, the Oct ratio in the resin was measured, and the hydrogen nucleus relaxation time T 1 ⁇ was measured by solid-state NMR measurement by the method described above.
• the ratio of the number of moles of structural units derived from ⁇ -olefins to the number of moles of all structural units is 10 mol% or more and 50 mol% or less, and the number of hydrogen nuclei is determined by solid-state NMR measurement.
• the average relaxation time corresponding to each hydrogen of the cyclic olefin copolymer is in the range of 4.5 to 5.5 msec, and the difference between the maximum and minimum relaxation times is 1.0 to In the range of 3.0 msec, the cyclic olefin copolymers of the examples maintain a high tensile strength, while the cyclic olefin copolymers of the comparative examples have the same charge ratio of norbornene and 1-octene. It can be seen that the breaking strain is superior to that of

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Crystallography & Structural Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=87552539

Family Applications (1)

Country Status (6)

Cited By (1)

Citations (2)

Family Cites Families (7)

• 2023
  • 2023-02-02 DE DE112023000805.1T patent/DE112023000805T5/de active Pending
  • 2023-02-02 US US18/730,260 patent/US20250129192A1/en active Pending
  • 2023-02-02 KR KR1020247027576A patent/KR102905437B1/ko active Active
  • 2023-02-02 JP JP2023535610A patent/JP7383853B1/ja active Active
  • 2023-02-02 CN CN202380019845.2A patent/CN118696070A/zh active Pending
  • 2023-02-02 WO PCT/JP2023/003405 patent/WO2023149506A1/ja not_active Ceased

Patent Citations (2)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events