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WO2005080467A1 - Polymere norbornene - Google Patents

Polymere norbornene Download PDF

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Publication number
WO2005080467A1
WO2005080467A1 PCT/JP2005/001965 JP2005001965W WO2005080467A1 WO 2005080467 A1 WO2005080467 A1 WO 2005080467A1 JP 2005001965 W JP2005001965 W JP 2005001965W WO 2005080467 A1 WO2005080467 A1 WO 2005080467A1
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Prior art keywords
norbornene
carbon
cyclic hydrocarbon
hydrocarbon structure
polymer
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English (en)
Japanese (ja)
Inventor
Yoshinori Miyagawa
Masaaki Komatsu
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Zeon Corp
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Zeon Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring

Definitions

  • the present invention relates to a norbornene-based polymer, and more particularly, to a norbornene-based polymer having excellent heat resistance and excellent balance between low birefringence and mechanical strength.
  • Norbornene polymers are excellent in optical properties such as transparency and low birefringence; weather resistance properties such as moisture resistance and heat resistance; and electrical properties such as low dielectric constant and low dielectric loss tangent. Used as a molding material in various fields! RU
  • norbornene-based polymers a norbornene-based monomer having an aromatic ring in a condensed polycyclic structure such as 1,4 methanol 1,4,4a, 9a-tetrahydrofluorene was subjected to ring-opening polymerization, and then obtained. Hydrogenation of the ring-opening polymer saturates the double bond in the main chain, and the hydrogenated norbornene-based ring-opened polymer converted to a saturated cyclohexane ring is compared with the conventional norbornene-based polymer. It is also known that they have a small birefringence and are excellent in oil and fat deterioration resistance.
  • the norbornene-based polymer having a cyclohexane ring in the condensed polycyclic structure constituting such a repeating unit has a glass transition temperature (Tg) of at most about 140 ° C and does not have sufficient heat resistance.
  • Tg glass transition temperature
  • Patent Document 1 discloses a cyclic hydrocarbon structure (I) derived from a norbornene ring constituting at least a part of a main chain, and one of the cyclic hydrocarbon structure (I).
  • C4 to C6 cyclic hydrocarbon structure (II) sharing at least one carbon bond (a), and at least one carbon other than the cyclic hydrocarbon structure ( ⁇ ) and the carbon-carbon bond (a) Contains a repeating unit derived from a norbornene monomer having a monocyclic or polycyclic hydrocarbon structure ( ⁇ ) sharing a carbon-carbon bond in a proportion of 20 to 100 mol% of all the repeating units
  • a norbornene polymer having a number average molecular weight of 1,000-1,000,0
  • the peak area on the high magnetic field side of the methylene peak derived from the methylene group in the cyclic hydrocarbon structure ( ⁇ ) in the C NMR ⁇ vector in the range of 00 and measured in the form of heavy metal (TMS standard) (A ), A peak area on the low magnetic field side (B), and a force equation BZ (A + B) ⁇ 0.3 are disclosed.
  • Patent document 1 International publication WO99Z09085 pamphlet
  • Optical products have been reduced in size and simplified in structure.
  • optical members such as lenses and prisms are exposed to high heat, and are also required to function as structures for maintaining the shape of optical products.
  • high mechanical strength is required.
  • the norbornene-based polymer described in Patent Document 1 sometimes has insufficient low birefringence and insufficient mechanical strength.
  • an object of the present invention is to provide a norbornene-based polymer which is excellent in heat deformation resistance and has a high balance between low birefringence and mechanical strength.
  • Patent Document 1 a norbornene-based monomer having a fused polycyclic structure containing a norbornene ring as described in Patent Document 1
  • the composition ratio of stereoisomers endo-exo isomers
  • the number-average molecular weight and the weight-average molecular weight of a norbornene-based polymer using a norbornene-based monomer containing 50 mol% or more of an endo-isomer are reduced. It has been found that it has an effect on thermal deformation resistance, low birefringence and mechanical strength.
  • the present inventors have further studied and found that a nonolevonolene-based polymer having a number average molecular weight in the range of 18,000 to 28,000 and a weight average molecular weight of 20,000 to 42,000 is heat-resistant deformable. With excellent birefringence and high mechanical strength. They found that they were lanced, and completed the present invention.
  • the cyclic hydrocarbon structure (I) derived from the norbornene ring constituting at least a part of the main chain, and the cyclic hydrocarbon structure (I) and one carbon-carbon bond (a) are formed.
  • a monomer mixture containing 20-100 mol% of the monomer (i) and another monomer copolymerizable with the norbornene-based monomer (i) (ii) 0-80 mol% Is a norbornene-based polymer obtained by polymerization or hydrogenation after polymerization, wherein ( ⁇ ) in the 13 C-NMR ⁇ vector measured in a double-mouthed form (TMS standard).
  • the norbornene-based polymer of the present invention is preferably a hydrogenated norbornene-based ring-opening polymer.
  • a molding material containing the norbornene-based polymer and a molded article obtained by molding the molding material.
  • the norbornene-based polymer of the present invention is excellent in heat deformation resistance, and has a high balance between low birefringence and mechanical strength.
  • FIG. 1 shows a part of a 13 C-NMR spectrum of a hydrogenated ring-opening polymer of 1,4 methanolic 1,4,4a, 9a-tetrahydrofluorene (MTF).
  • the norbornene-based polymer of the present invention contains the repeating unit derived from a norbornene-based monomer having the specific structure (I)-(III) at the specific ratio.
  • the structure referred to as “cyclic hydrocarbon structure ( ⁇ ) ”for convenience also includes a ring in which one or more carbon atoms of the ring are substituted with a nitrogen atom, an oxygen atom, or the like.
  • Such a polymer has a norbornene ring structure ( ⁇ ) and a C 4 -C 6 cyclic hydrocarbon structure ( ⁇ ) sharing one carbon-carbon bond (a) with the norbornene ring structure ( ⁇ ). And a monocyclic or polycyclic cyclic hydrocarbon structure ( ⁇ ) sharing at least one carbon-carbon bond other than the carbon-carbon bond (a) with the cyclic hydrocarbon structure ( ⁇ ).
  • Monomer or monomer containing 20-100 mol% of the monomer (i) and 0-80 mol% of another monomer copolymerizable with the norbornene monomer (i) (ii) It can be obtained by polymerizing a body mixture or by hydrogenating the obtained polymer as required.
  • the other monomer (ii) copolymerizable with the norbornene-based monomer (i) includes norbornene-based monomers such as tetracyclododecene, dicyclopentadiene, pentadichloropentadecene, and pentadichloropentadecadiene.
  • ⁇ -olefins such as ethylene, propylene, and 1-butene
  • cyclobutene 1-methylcyclopentene
  • norbornene-based monomers are particularly preferred because of their excellent heat resistance. Further, they share a norbornene ring constituting the main chain and one carbon-carbon bond with the norbornene ring. A tetracyclododecene monomer having a norbornane ring is most preferred.
  • the norbornene-based monomer (i) and the other monomer (ii) copolymerizable with the norbornene-based monomer (i) may have a substituent.
  • substituents include a hydrocarbon group, a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, a silyl group, or a polar group (a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group). Amide group, imide group or silyl group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the method for producing the norbornene-based polymer of the present invention include a ring-opening polymerization method and an addition polymerization method, and a ring-opening polymerization method is preferable.
  • a monomer component is subjected to ring-opening polymerization in a solvent or without a solvent using a ring-opening polymerization catalyst.
  • a catalyst system comprising a halide, nitrate, or acetylacetone compound of a metal such as ruthenium, rhodium, palladium, osmium, iridium, and platinum; and a reducing agent; Titanium, vanadium, zirconium, tungsten, and molybdenum forces
  • a catalyst system comprising a halide or acetylacetone compound of a selected metal and an organoaluminum compound as a promoter; or JP-A-7-179575, Am. Chem. Soc., 1986, 108, 733, J. Am. Chem.
  • a polar compound can be further added to the above-mentioned catalyst system to enhance polymerization activity and selectivity of ring-opening polymerization.
  • polar compounds include molecular oxygen, alcohols, ethers, peroxides, carboxylic acids, acid anhydrides, acid chlorides, esters, ketones, nitrogen-containing compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and others.
  • examples thereof include Lewis acids, and among them, isobutanol and diisopropyl ether are preferable.
  • These polar conjugates may be used alone or in combination of two or more, and the amount used is appropriately selected.
  • the ratio to the metal in the catalyst, that is, the polar compound Z metal Is usually in the range of 1.1 to 100,000, preferably 5 to 10,000.
  • the solvent is not particularly limited as long as it is inert to the polymerization reaction, but includes aromatic hydrocarbons such as benzene, toluene, and xylene; and aliphatic hydrocarbons such as n-pentane, hexane, and heptane. Hydrogens; alicyclic hydrocarbons such as cyclohexane; styrene dichloride, dichloronorethane, dichloronorethylene, tetrachloronorethane, chloronorbenzene, dichloronorbenzene
  • halogenated hydrocarbons such as trichlorobenzene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile, and benzo-tolyl;
  • the polymerization temperature is usually in the range of 50 ° C to 200 ° C, preferably 30 ° C to 180 ° C, more preferably -20 ° C to 150 ° C
  • the polymerization pressure is usually 0 ° C to 0 ° C to 150 ° C. —50 kgf / cm 2 , preferably 0-2 OkgfZcm 2
  • the polymerization time is appropriately selected depending on the polymerization conditions, but is usually in the range of 30 minutes to 20 hours, preferably in the range of 110 hours.
  • a chain transfer agent examples include, but are not limited to, ⁇ -olefins such as 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1 otaten, 1-dodecene, etc .; Xadiene and the like, and among them, 1-hexene, which is preferably an ⁇ -olefin, is more preferable.
  • ⁇ -olefins such as 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1 otaten, 1-dodecene, etc .
  • Xadiene and the like and among them, 1-hexene, which is preferably an ⁇ -olefin, is more preferable.
  • the weight average molecular weight and the number average molecular weight of the polymer can be adjusted.
  • the amount of a-olefin added is appropriately adjusted depending on the conditions of the polymerization catalyst type, the polymerization catalyst amount, the monomer type, the monomer amount, the ⁇ -olefin type, and the like. Both the molecular weight and the number average molecular weight decrease, and conversely, when the amount added is small, both the weight average molecular weight and the number average molecular weight increase.
  • the chain transfer agent As a method for adding the chain transfer agent, it is necessary to add the chain transfer agent with high precision to the reaction system in order to stably obtain a polymer having a molecular weight in a specific range in the present invention.
  • a chain transfer agent diluted in advance with a reaction solvent or the like or to weigh and add using a device having high measurement accuracy.
  • the weighing accuracy is determined to be the optimum molecular weight when the required amount of the chain transfer agent is usually 3% or less, preferably 2% or less, more preferably 1% or less. Is obtained.
  • the monomer component is dissolved in a solvent or without a solvent in the presence of a catalyst system comprising a titanium, zirconium, or vanadium compound and an organoaluminum compound, Usually, the polymerization is carried out at a polymerization temperature of 50-100 ° C and a polymerization pressure of 0-50 kgZcm 2 .
  • the norbornene-based polymer is preferably hydrogenated.
  • JP-A-58-43412, JP-A-60-26024, JP-A-64-24826, JP-A-1-138257, JP-A-7-41550 It is possible to use those described in gazettes and the like, and a homogeneous catalyst or a heterogeneous catalyst may be used.
  • the homogeneous catalyst is easy to disperse in the hydrogenation reaction liquid, so that the addition amount is small and the activity is high. Therefore, hydrogenation can be performed in a short time with a small amount of the catalyst.
  • a heterogeneous catalyst has high production efficiency when it is heated to high temperature and high pressure, and can be hydrogenated in a short time, and is easily removed.
  • a Wilkinson complex that is, chlorotris (triphenylphosphine) rhodium (I); a catalyst having a combination power of a transition metal compound and an alkyl metal compound, specifically, cobalt acetate Z triethyl
  • the combination include aluminum, nickel acetylacetonate Z triisobutylaluminum, titanocene dichloride Zn butyllithium, zirconocene dichloride Zsec butyllithium, tetrabutoxytitanate Z dimethylmagnesium, and the like.
  • Examples of the heterogeneous catalyst include those in which a hydrogenation catalyst metal such as Ni or Pd is supported on a carrier.
  • the hydrogenation catalyst metal to be supported includes activity, hydrogenation efficiency, or hydrogenation efficiency. It is preferable to use Ni from the viewpoint of the degree of isomerism. When a Pd catalyst is used, the progress of isomerization is promoted, and the softening point is lowered.
  • As the carrier it is preferable that the amount of impurities or the like is small, and in the case of L, it is preferable to use an adsorbent such as alumina and diatomaceous earth.
  • the hydrogenation reaction is usually performed in an organic solvent.
  • the organic solvent is not particularly limited as long as it is inert to the catalyst.
  • a hydrocarbon solvent is usually used because it is excellent in the solubility of the generated hydrogenated product.
  • hydrocarbon solvent examples include aromatic hydrocarbons such as benzene and toluene; n pentane , Hexane and other aliphatic hydrocarbons; cyclohexane, decalin, and other alicyclic hydrocarbons
  • cyclic aromatic hydrocarbons and alicyclic hydrocarbons are preferable.
  • organic solvents can be used alone or in combination of two or more.
  • the hydrogenation reaction can be carried out according to a conventional method.
  • the hydrogenation rate varies depending on the type of the hydrogenation catalyst and the reaction temperature.
  • the reaction temperature is usually 200 ° C. or lower, preferably 195 ° C. or lower, most preferably 190 ° C. or lower.
  • the reaction temperature is preferably in the range of 100-200 ° C, more preferably in the range of 130-195 ° C.
  • the hydrogen pressure is usually 0.1-100 kgf / cm 2 , preferably 0.5-60 kgf / cm 2 , and more preferably 1-150 kgf / cm 2 .
  • Removal of the catalyst after the completion of the hydrogenation reaction may be performed by a conventional method such as centrifugation or filtration.
  • a catalyst deactivator such as water or alcohol may be used, or an adsorbent such as activated clay alumina may be added.
  • transition metal In applications where it is not desirable for the remaining transition metal to be eluted, such as medical equipment, it is preferable that substantially no transition metal remains.
  • an adsorbent such as alumina having a specific pore volume and a specific surface area as disclosed in Japanese Patent No. 317411, etc., or to wash the resin solution with acidic water and pure water. .
  • the centrifugation method and filtration method are not particularly limited as long as the used catalyst can be removed.
  • Removal by filtration is preferred because it is simple and efficient.
  • pressure filtration or suction filtration may be used.
  • a filter aid such as diatomaceous earth and perlite. (Norbornene-based polymer)
  • the norbornene-based polymer of the present invention contains a repeating unit derived from the norbornene-based monomer (i) in a proportion of 20 to 100 mol% in all the repeating units of the polymer.
  • the ratio is, preferable to be 25 to 100 mol 0/0, preferably Ri to be 30- 100 mole 0/0. If the proportion of the repeating unit derived from the norbornene-based monomer (i) is too small, heat resistance is impaired and deformation at high temperatures is undesirably increased.
  • the proportion of the repeating unit derived from the norbornene-based monomer (i) depends on the proportion of the norbornene-based monomer (i) used for the polymerization, the other monomer (ii) used as necessary, and their polymerization conversion. It can be obtained from the dagger rate.
  • the repeating unit derived from a norbornene-based monomer is obtained by subjecting a norbornene-based monomer to ring-opening (co) polymerization or addition (co) polymerization, followed by hydrogenation to saturate unsaturated bonds.
  • a repeating unit obtained before or after the hydrogenation reaction by, for example, a modification reaction such as a graft reaction of an unsaturated monomer.
  • the norbornene-based polymer of the present invention reacts with the methylene group in the cyclic hydrocarbon structure (III) in the 13 C-NMR spectrum measured in a double-mouthed form (TMS (tetramethylsilane) group).
  • the peak area (A) on the high magnetic field side of the derived methylene peak and the peak area (B) on the low magnetic field side have a relationship of BZ (A + B) ⁇ 0.3. Above all, BZ (A + B) ⁇ 0.25 is preferable, and B / (A + B) ⁇ 0.2 is more preferable.
  • a BZ (A + B) value within this range is preferable in terms of heat resistance.
  • the methylene peak derived from the methylene group in the cyclic hydrocarbon structure (13) measured by 13 C-NMR has two peaks due to the difference in the steric structure of the repeating unit derived from the norbornene-based monomer (i). Split into This difference in steric structure is due to the endo-exo isomerism of the repeating unit derived from the norbornene-based monomer, and is ultimately due to the endo-exo isomerism of the norbornene-based monomer used.
  • a norbornene-based monomer having a condensed polycyclic structure having a monocyclic or polycyclic cyclic hydrocarbon structure having at least one carbon-carbon unsaturated bond in the ring (III) is polymerized, and When the carbon-carbon unsaturated bond in the ring is hydrogenated, it is present in the polymer before hydrogenation. However, a peak derived from a methylene group in the ring is newly generated in a state of splitting into two.
  • the norbornene-based polymer is a hydrogenated product of a single-ring-opened polymer of 1,4 methanol 1,4,4a, 9a-tetrahydrofluorene, 13 C-NMR measured in a double-mouthed form ⁇
  • the vector (TMS standard) chart is as shown in Fig. 1.
  • the arbitrary methylene peak in the cyclohexane ring in the repeating unit generated by the hydrogenated kafun has a high magnetic field side (A ) And the lower magnetic field side (B), and appear at 21-22 ppm and 22-22.5 ppm, respectively.
  • the area ratio between the peak area (A) on the high magnetic field side of the methylene peak and the peak area (B) on the low magnetic field side is calculated based on the data in FIG.
  • the peak position derived from the methylene group described above is a force appearing at a position different from that in Fig. 1.
  • Splitting on the magnetic field side The peak positions of the split two pairs can be easily identified because they appear as the split pairs forming the highest magnetic field in the range of the measurement region of the 13 C-NMR chart. Therefore, for all norbornene-based polymers, the above-mentioned area ratio can be obtained by calculating the data power of the integral curve.
  • the BZ (A + B) value can be adjusted by the composition ratio (a: b) of the endo-form (a) and the exo-form (b) of the norbornene-based monomer (i) used for the polymerization. .
  • an endo-form and an exo-form exist from the three-dimensional structures of two tertiary carbons bonded to the bridge structure of the norbornene ring and two tertiary carbons at the two 5-membered ring junctions.
  • Such stereoisomerism of the norbornene monomer is substantially maintained after polymerization and after hydrogenation.
  • hydrogenation is carried out under mild temperature conditions after ring-opening polymerization of MTF, slight isomerization occurs, but the three-dimensional structure of the obtained repeating unit reflects the three-dimensional structure of the MTF used. .
  • This endo-exo isomer has the above-mentioned 13 C—
  • composition ratio (a: b) of the endo-form (a) and the exo-form (b) of the norbornene-based monomer (i) used in the present invention is usually 50: 50-100: 0, preferably 70:30. - 100: 0, more preferably ⁇ or 80: 20- 100: 0 (molar 0/0).
  • the norbornene-based monomer (i) used in the present invention is obtained as a mixture of an endo-form (a) and an exo-form (b) by condensation of cyclopentadiene and a gen.
  • the composition ratio (a: b) of the end-form ( a ) and exo-form (b) of the obtained mixture is determined by the isomerization reaction in the presence of an acid catalyst, It can be adjusted by distillation purification, blending of mixtures having different composition ratios, and the like.
  • the norbornene-based polymer of the present invention has a number average molecular weight in the range of 18,000 to 28,000, and a weight average molecular weight in the range of 20,000 to 42,000.
  • the number average molecular weight force is preferably in the range of 19,000 to 28,000, more preferably in the range of 19,500 to 28,000, and particularly preferably in the range of 20,000 to 28,000. .
  • the weight average molecular weight is preferably in the range of 20,000 to 42,000, more preferably in the range of 20,000 to 40,000, and particularly preferably in the range of 20,000 to 35,000. .
  • the mechanical strength tends to increase as the number average molecular weight increases, but when the number average molecular weight is less than 18,000, the ratio of the decrease in mechanical strength to the decrease in the number average molecular weight is remarkable. If it exceeds 000, the ratio of increase in mechanical strength to increase in number average molecular weight becomes small.
  • the weight average molecular weight exceeds 42,000, the birefringence of the molded product due to the orientation during molding increases, and the retardation value at a scanning length of 32 mm and a measurement wavelength of 650 nm exceeds 220 nm.
  • the retardation value at a scanning length of 32 mm and a measurement wavelength of 650 nm exceeds 220 nm.
  • the retardation value exceeding 220 nm is used as the molding material for the F-lens of a laser beam printer, the blurring of the image becomes extremely large, which is a problem for use as a lens.
  • the birefringence tends to be smaller as the weight average molecular weight is smaller.
  • the weight average molecular weight is smaller than 000, it is difficult to maintain the above-mentioned range of the number average molecular weight. Therefore, when the number average molecular weight and the weight average molecular weight are within the above ranges, mechanical strength and low birefringence are highly balanced.
  • the number average molecular weight and the weight average molecular weight are values in terms of polyisoprene measured by gel permeation chromatography (GPC) using cyclohexane as a solvent.
  • the method for setting the number average molecular weight and the weight average molecular weight to the above ranges is not limited, but examples are as follows.
  • it can be adjusted by the aforementioned chain transfer agent.
  • the amount of the chain transfer agent to be added is appropriately adjusted according to various conditions such as the type of the polymerization catalyst, the amount of the polymerization catalyst, the type of the monomer, the amount of the monomer, and the amount of the chain transfer agent.
  • both the number average molecular weight and the number average molecular weight become small.
  • ratio of repetition units having a carbon-carbon double bond in the main chain structure of the norbornene-based polymer of the present invention 20 mol 0/0 - 0 mole 0/0 is the preferred tool 10 moles 0 / 0 - 0 mole 0/0 der Ru more preferably instrument 2 mol% - is particularly preferably 0 mol%.
  • the proportion of the repeating unit having a carbon-carbon double bond in the main chain structure be within this range.
  • the norbornene-based polymer is a ring-opening (co) polymer
  • a carbon-carbon double bond is formed in the main chain
  • the hydrogen-added polymer has a carbon-carbon double bond in the main chain structure.
  • the proportion of the repeating unit can be in the above range.
  • the repeating unit having a carbon-carbon unsaturated bond in the ring of the norbornene-based polymer of the present invention that is, the ratio of the unhydrogenated repeating unit is preferably 50 mol% to 0 mol%. 3 0 mole 0/0 - 0 mole 0/0 more preferred and is a fixture 10 mole 0/0 - 0 mole 0/0 and particularly preferably If it is /,. It is preferable from the viewpoint of heat resistance that the proportion of the unhydrogenated repeating unit falls within this range.
  • the glass transition temperature (Tg) of the norbornene-based polymer of the present invention is usually 145 ° C or higher, preferably 150 ° C or higher, more preferably 160 ° C or higher, since it is related to heat deformation resistance. is there. When high heat resistance is required, Tg can be adjusted to 165 ° C or higher.
  • the norbornene-based polymer of the present invention can be prepared, if necessary, by a method known in JP-A-3-95235 or the like, using a, j8-unsaturated carboxylic acid and Z or a derivative thereof, styrene-based hydrocarbon, It may be modified using an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group, or an unsaturated epoxy monomer. Denaturation is performed before or after the hydrogenation reaction.
  • the norbornene-based polymer of the present invention is excellent in heat deformability, and has a high balance between low birefringence and mechanical strength characteristics.
  • known additives may be used if necessary to impair the effects of the present invention.
  • the molding material can be contained in a range not to be controlled.
  • Known additives include antioxidants, light stabilizers, other polymer materials such as rubbery polymers and other thermoplastic resins, heat stabilizers, ultraviolet absorbers, and near infrared absorbers.
  • an antioxidant is preferred in order to improve the oxidation resistance and heat resistance at the time of molding. Agents are preferred.
  • antioxidants examples include a phenol-based antioxidant, a phosphorus-based antioxidant, and a zirconium-based antioxidant, and among them, the phenol-based antioxidant, particularly an alkyl-substituted phenol-based antioxidant. Is preferred ⁇ .
  • phenolic antioxidants include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) probionate, 2,2-methylenebis (4-methyl-6-tert-butylphenol), 1,3-tris (2-methyl-4-hydroxy-5 t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakismethylene Alkyl-substituted phenols such as 3- (3,, 5, -t-butyl-4, -hydroxyphenylpropionate) methane [ie pentaerythrityl-tetrakis 3- (3,5-d-t-butyl-4-hydroxyphenylpropionate)] 2t-butyl-6- (3t-butyl-2-hydroxy-5-methylbenzyl) 4-methylphenol acrylate, 2,4-zyt Mir
  • Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (nor-phenyl) phosphite, and tris (dino-phenyl).
  • Monophosphite compounds such as phosphite and tris (2,4-di-t-butylphenol) phosphite; 4,4′butylidene-bis (3-methyl-6-t-butylphenyl-tridecylphosphite) And the like.
  • the zirconium antioxidants include dilauryl 3,3,1-thiodipropionate and dimyristi. 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3,1-thiodipropionate and the like.
  • antioxidants may be used alone or in combination of two or more.
  • the added amount of the kneading agent is usually 0.01 to 2 parts by weight, preferably 0.02 to 1 part by weight, more preferably 0.05 to 0.5 part by weight, per 100 parts by weight of the norbornene-based polymer. Range of parts
  • examples of the light stabilizer include hindered amine light stabilizers (HALS) and benzoate light stabilizers. Among these, hindered amine light stabilizers are preferable.
  • HALS include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6 pentamethyl-4-piperidyl) sebacate, 1- [2- ⁇ 3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propio-roxy ⁇ ethyl] 4-1 ⁇ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propio-roxy ⁇ — 2, 2 , 6,6-Tetramethinolepidizidine, 8-benzinole 7,7,9,9-Tetramethinole 3-year-old cutinole 1,2,3 Triazaspiro [4,5] pandecane 2,4-dione, 4 Benzoyloxy 2,2,6,6-tetramethylbiperidine, dimethyl succinate 1- (2-hydroxyethyl) 4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly
  • These light stabilizers may be used alone or in combination of two or more.
  • the amount of the added kneading is usually 0.0001 to 5 parts by weight, preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the norbornene-based polymer. Range.
  • the rubbery polymer is a polymer having a glass transition temperature (Tg) of 40 ° C or lower, and includes a usual rubbery polymer and a thermoplastic elastomer.
  • Tg glass transition temperature
  • the viscosity of the rubbery polymer (ML, 100 ° C.) is appropriately selected depending on the purpose of use, and is usually 5-300.
  • the rubbery polymer examples include ethylene-a-olefin-based rubbery polymer; ethylene-a-one-year-old olefin-polyene copolymer rubber; ethylene methyl methacrylate, and ethylene-butyl acrylate Copolymer of ethylene and unsaturated carboxylic acid ester such as acrylate; copolymer of ethylene and fatty acid butyl such as ethylene acetate vinyl; ethyl acrylate, butyric acrylate, hexyl acrylate, acrylic acid 2 -Polymers of alkyl acrylates such as ethylhexyl and lauryl acrylate; random copolymers of polybutadiene, polyisoprene, styrene butadiene or styrene isoprene, acrylonitrile butadiene copolymer, butadiene isoprene copolymer, Gen-based rubbers such as butadiene
  • thermoplastic elastomer examples include styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-butadiene random copolymer, styrene-isoprene block copolymer, and hydrogenated styrene-isoprene block copolymer.
  • thermoplastic elastomers preferred are hydrogenated styrene butadiene block copolymer, hydrogenated styrene isoprene block copolymer, and the like.
  • JP-A-2-305814, JP-A-3-72512, JP-A-3-74409 and the like can be mentioned.
  • These rubbery polymers can be used alone or in combination of two or more.
  • the mixing ratio of the rubbery polymer is appropriately selected according to the purpose of use.
  • thermoplastic resins include low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, ethylene-ethyl acrylate copolymer, ethylene-butyl acetate copolymer, and polystyrene.
  • thermoplastic resins such as lensulfide, polyetherimide, polyester, polyamide, polyarylate, polysulfone, polyethersulfone and the like can be blended.
  • thermoplastic resins can be used alone or in combination of two or more, and the mixing ratio is appropriately selected within a range not to impair the object of the present invention.
  • the molding material is not particularly limited by its preparation method.
  • a method of obtaining a molding material by dissolving various additives in an appropriate solvent and adding the solution to a norbornene-based polymer solution, and then removing the solvent; and adding a norbornene-based polymer and, if necessary, an additive.
  • a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or a co-calender, or after this mixing, using a single-screw extruder, a twin-screw extruder, a kneader, or the like.
  • a method of melt-kneading and the like can be mentioned.
  • the molding material is preferably granulated or pulverized or pelletized from the viewpoint of moldability.
  • the molding material of the present invention can be formed into a molded body by using known molding means, for example, an injection molding method, a compression molding method, an extrusion molding method and the like.
  • the shape of the molded body can be appropriately selected depending on the application.
  • the molding conditions are not particularly limited! /, But the resin temperature during molding is t + 40 ° C-t +260, where the glass transition temperature of the norbornene-based polymer used is t ° C. Preferably in the range of ° C
  • T + 110 oC t + 190 oC is more preferable, t + 125 ° Ct + 150 oC
  • the ratio be in the range of 1 1 1 1 1.
  • the mold temperature is usually room temperature minus t + 15 ° C, preferably t-30 ° C-t +, where the glass transition temperature of the norbornene-based polymer to be used is t ° C. 10 ° C, yo
  • the molded article of the present invention can be subjected to an annealing treatment if desired. This gives The refractive index distribution of the molded article to be formed can be sharpened. In the annealing process, heat treatment is performed at 80-110 ° C for 5-24 hours after molding.
  • an inorganic compound such as a silane coupling agent, an acrylic resin, or a vinyl resin.
  • an inorganic compound such as a silane coupling agent, an acrylic resin, or a vinyl resin.
  • a hard coat layer having strength such as melamine resin, epoxy resin, fluorine resin, and silicone resin can be formed.
  • the heat resistance, optical properties, chemical resistance, abrasion resistance, water resistance, and the like of the molded article can be improved.
  • Examples of the method for forming the hard coat layer include known methods such as a thermosetting method, an ultraviolet curing method, a vacuum deposition method, a sputtering method, and an ion plating method.
  • the norbornene-based polymer of the present invention is excellent in heat deformation resistance, and has a high balance between low birefringence and mechanical strength. It is also excellent in impact resistance, solution stability, low water absorption, low moisture permeability, and chemical resistance, and thus is useful for various molded products.
  • medical equipment electrical insulating materials; equipment for processing electronic components; optical materials; electronic components such as windows for light-receiving elements; structural materials and building materials such as windows, mechanical components, and housings; Automobile equipment such as covers and instrument panels; speaker cones, vibration elements for speakers, electric equipment such as microwave oven containers; food containers such as bottles, returnable bottles, baby bottles; packaging materials such as wraps; It can be used for various applications such as helmets, seats and helmets.
  • camera lenses can be suitably used as an optical component.
  • camera lenses video camera lenses, finder lenses, pickup lenses for optical disks, f0 lenses for laser printers, eyeglass lenses, plastic lenses for medical examinations
  • It can be suitably used as a collimating lens, a projection lens for projection television, a projection lens for OHP, or a waveguide type lens such as a geodesic lens, a Fresnel lens, a lenticular lens or a grating lens.
  • the molecular weight was measured by gel permeation chromatography (GPC) at 40 ° C using cyclohexane as a solvent, and the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of standard polyisoprene were determined. .
  • the hydrogenation rate of the main chain and the cyclic hydrocarbon structure (III) in the norbornene-based polymer was calculated by measuring the NMR ⁇ vector.
  • the Tg of the norbornene polymer was measured by DSC.
  • the mechanical strength of the norbornene-based polymer was determined using a resin plate A (length 10 cm x width lcm x thickness lm m) using ASTM D790 [based on! / ⁇ , ⁇ / ⁇ ⁇ [3 ⁇ 4
  • the bending strength was measured using an Autograph A GS-10kND manufactured by Shimadzu Corporation under the conditions of a distance of 30. Omm, a pressure of 30 MPa, a method A, a temperature of 23 ° C, a humidity of 50%, and a molding time of 40 hours.
  • the birefringence of the norbornene polymer was measured with a birefringence meter (manufactured by Oji Scientific Instruments: KOBRA-CCDZX) using a resin plate B (length 60 mm x width 60 mm x thickness 2 mm).
  • the comparison was made by the value of the retardation at the measurement wavelength of 650 nm at the center. The smaller the value of the retardation, the better.
  • it exceeds 220 nm for example, when used as a molding material for an F0 lens of a laser beam printer, the image blur exceeds an allowable range, which poses a problem in use as a lens. Therefore, in Table 1, "A” is for the one with a retardation of 79 nm, "B” is for 80-220 nm, "C” is for 150-199 nm, and "D” is for those exceeding 220 nm.
  • Weight ratio 2Z1 1 / hexene 0.87 parts, diisopropyl ether 0.25 parts, isobutyl alcohol 0.18 parts, triisobutylaluminum 0.48 parts and hexachloride tungsten 0 in 400 parts of mixed solution 42 parts of a 77% by weight toluene solution were placed in a reaction vessel at room temperature and mixed. Then, at 45 ° C, 1,4 methanol 1,4,4a, 9a-200 parts of tetrahydrofluorene and 0.77% by weight of tungsten hexachloride were used. 25 parts by weight of a toluene solution were continuously added over 2 hours to carry out polymerization.
  • pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was added to the resulting solution as an antioxidant per 100 parts by weight of the polymer solid content. The parts by weight were dissolved in kauna.
  • the operating conditions of the concentration dryer were adjusted so that the pressure was 60 kPa, and the temperature of the polymer solution inside was 290 ° C.
  • the concentrated solution was continuously derived from the concentration dryer, and was supplied to the same dryer at a pressure of 1.5 MPa while maintaining the temperature at 290 ° C.
  • the operating conditions were a pressure of 1.5 kPa and a temperature of 290 ° C.
  • the polymer in the molten state is continuously drawn out from the concentration dryer, extrudes the die force in a class 100 clean room, water-cooled, cut with a pelletizer [OSP-2, Nagata Seisakusho], and becomes a norbornene polymer. Pellets were obtained.
  • This norbornene-based polymer was measured by 13 C-NMR spectrum.
  • the peak area ratio BZ (A + B) between the high magnetic field side (A) and the low magnetic field side (B) of the methylene peak derived from the cyclic hydrocarbon structure of a monocyclic or polycyclic hydrocarbon structure (in) sharing a bond is 0.17 o
  • a polyimide layer having an average thickness of 40 m is formed on the surface of a metal member (made of SUS) having a predetermined pattern shape by vacuum evaporation, and a Cr layer having a thickness of 10 m is further formed thereon as a protective layer.
  • a norbornene-based polymer was obtained in the same manner as in Example 1, except that the monomer was changed to 200 parts of 1,4-methano-1,4,4a, 4b, 5,8,8a, 9a-octahydro-19H-fluorene.
  • the peak area ratio BZ (A + B) of this norbornene polymer is 0.17, Mw is 31,800, Mn is 19,000, the hydrogen conversion of the main chain is 99.4%, and the cyclic hydrocarbon structure ( The conversion of part III) was 100%, and Tg was 160 ° C.
  • the peak area ratio BZ (A + B) of this norbornene polymer is 0.17, Mw is 31,900, Mn is 19,000, the hydrogen conversion of the main chain is 99.4%, and the cyclic hydrocarbon structure ( III) Part Has a hydrogen conversion of 100% and a Tg of 160 ° C.
  • a resin plate A4 and a resin plate B4 were prepared in the same manner as in Example 1 except that the resin temperature was set to 290 ° C using the norbornene-based polymer of Example 3, and the mechanical strength and birefringence were measured. It was measured. The results are shown in Table 1.
  • a norbornene-based polymer was obtained in the same manner as in Example 1 except that 0.57 parts of hexene was used.
  • the peak area ratio BZ (A + B) of this norbornene-based polymer was 0.17, Mw was 41,700, Mn was 21,000, the hydrogen conversion ratio of the main chain was 99.6%, and the cyclic carbonization was
  • the hydrogen conversion ratio of the hydrogen structure (III) portion was 100%, and Tg was 160 ° C.
  • a resin plate A6 and a resin plate B6 were prepared in the same manner as in Example 1 except that the resin temperature was changed to 290 ° C. using the norbornene-based polymer of Example 5, and the mechanical strength and birefringence were measured. It was measured. The results are shown in Table 1.
  • a norbornene-based polymer was obtained in the same manner as in Example 1 except that 1-hexene was changed to 0.99 parts.
  • the peak area ratio BZ (A + B) of this norbornene polymer is 0.17, Mw is 27,300, Mn is 19,000, the hydrogen conversion of the main chain is 99.7%, and the cyclic hydrocarbon structure ( The conversion of part III) was 100%, and Tg was 160 ° C.
  • a norbornene-based polymer was prepared in the same manner as in Example 1 except that 0.91 parts of hexene was used. Obtained.
  • the peak area ratio BZ (A + B) of this norbornene polymer is 0.17, Mw is 30,000, Mn is 17,700, the hydrogen transfer ratio of the main chain is 99.6%, and the cyclic hydrocarbon is The hydrogen conversion of the structure ( ⁇ ) was 100%, and Tg was 160 ° C.
  • a norbornene-based polymer was obtained in the same manner as in Example 1 except that the hydrogenation temperature was changed to 220 ° C.
  • the peak area ratio BZ (A + B) of this norbornene-based polymer was 0.41 and Mw was 31,800.
  • the Mn was 19,000
  • the hydrogen conversion in the main chain was 99.8%
  • the hydrogen conversion in the cyclic hydrocarbon structure (III) was 100%
  • the Tg was 140 ° C.
  • a norbornene-based polymer was obtained in the same manner as in Example 2 except that the hydrogenation temperature was changed to 220 ° C.
  • the peak area ratio BZ (A + B) of this norbornene-based polymer was 0.41, and Mw was 41,700.
  • the Mn was 21,000, the hydrogen conversion in the main chain was 99.7%, the hydrogen conversion in the cyclic hydrocarbon structure (III) was 100%, and the Tg was 140 ° C.
  • a norbornene-based polymer was obtained in the same manner as in Example 1, except that 0.53 parts of 1-hexene was used.
  • the peak area ratio BZ (A + B) of this norbornene-based polymer is 0.17, Mw is 42,300, Mn is 21,100, the hydrogen transfer ratio of the main chain is 99.5%, and the cyclic hydrocarbon is The hydrogen conversion of structure (III) was 100%, and Tg was 160 ° C. Further, in the same manner as in Example 1, a resin plate All and a resin plate Bl1 were prepared using the obtained norbornene-based polymer, and the mechanical strength and the birefringence were measured. Table 1 shows the results.
  • a norbornene-based polymer was obtained in the same manner as in Example 1, except that 0.5% of hexene was used.
  • the peak area ratio BZ (A + B) of this norbornene-based polymer is 0.17, Mw is 45,200, Mn is 24,700, the hydrogen transfer ratio of the main chain is 99.6%, and the cyclic hydrocarbon is Hydrogen conversion of the structure ( ⁇ ) was 100%, Tg was 160 ° C, mechanical strength was 117 MPa, and birefringence was 290 nm.
  • Table 1 shows the following.
  • a cyclic hydrocarbon structure (I) derived from a norbornene ring constituting at least a part of the main chain, and a ring of 4 or 6 carbon atoms sharing one carbon-carbon bond with the cyclic hydrocarbon structure (I). At least one carbon-carbon bond with the cyclic hydrocarbon structure ( ⁇ ) and the cyclic hydrocarbon structure ( ⁇ ).
  • a molded article molded from a molding material containing a norbornene-based polymer having a number average molecular weight of less than 19,000 has low mechanical strength (Comparative Examples 1 and 2).
  • the peak area ratio of the high-magnetic-field side (A) and low-magnetic-field side (B) of the methylene peak derived from the cyclic hydrocarbon structure ( ⁇ ) in the 13 C—NMR ⁇ vector falls within the range of BZ (A + B) ⁇ 0.3.
  • a molded product obtained by molding a molding material containing a sorbornene-based polymer has low mechanical strength (Comparative Examples 3 and 4).
  • a molded article obtained by molding a molding material containing a norbornene-based polymer having a weight average molecular weight of more than 42,000 is inferior in low birefringence (Comparative Examples 5 and 6).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

Un polymère norbornène de résistance excellente à la distorsion thermique et réalisant un équilibre amélioré entre la biréfringence basse et la résistance mécanique. Il est prévu un polymère norbornène comprenant des unités de répétition, les unités de répétition dérivées d'un monomère norbornène ayant une structure cyclique d'hydrocarbone (I) dérivée d'un anneau norbornène constituent au moins une partie de la chaîne principale, structure cyclique d'hydrocarbone C4-C6 (II) partageant un lien de carbone à carbone (a) avec la structure cyclique d'hydrocarbone (I) et la structure monocyclique ou polycyclique d'hydrocarbone (III) partageant au moins une liaison de carbone à carbone autre que la liaison de carbone à carbone (a) avec la structure cyclique d'hydrocarbone (II), dans une proportion de 20 á 100 mol% basée sur toutes les unités de répétition, dans lesquelles dans 13C-NMR, le rapport de la zone de boc sur un côté de champ magnétique élevé (A) à la zone de pic côté champ magnétique faible (B) par rapport aux pics de méthylène assignés à la structure cyclique d'hydrocarbone (III) satisfait la relation de B/(A+B) ≤ 0.3, et dont Mn et Mw sont compris entre 18,000 et 28,000 et 20,000 á 42,000, respectivement.
PCT/JP2005/001965 2004-02-19 2005-02-09 Polymere norbornene Ceased WO2005080467A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02255715A (ja) * 1989-02-28 1990-10-16 Shell Internatl Res Maatschappij Bv バルキーノルボルネン誘導体の重合及びその結果得られるポリマー
JPH06248164A (ja) * 1992-12-28 1994-09-06 Nippon Zeon Co Ltd 架橋性ノルボルネン系樹脂組成物、及びそれから成る成形品
JPH0741550A (ja) * 1993-07-30 1995-02-10 Nippon Zeon Co Ltd ノルボルネン系開環（共）重合体水素添加物、その製造方法、及びその用途
JPH0753680A (ja) * 1993-08-11 1995-02-28 Nippon Zeon Co Ltd 新規な樹脂、その水素添加物、それらの製造方法、及びそれらの用途
WO1999009085A1 (fr) * 1997-08-19 1999-02-25 Nippon Zeon Co., Ltd. Polymere de norbornene et son procede de preparation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02255715A (ja) * 1989-02-28 1990-10-16 Shell Internatl Res Maatschappij Bv バルキーノルボルネン誘導体の重合及びその結果得られるポリマー
JPH06248164A (ja) * 1992-12-28 1994-09-06 Nippon Zeon Co Ltd 架橋性ノルボルネン系樹脂組成物、及びそれから成る成形品
JPH0741550A (ja) * 1993-07-30 1995-02-10 Nippon Zeon Co Ltd ノルボルネン系開環（共）重合体水素添加物、その製造方法、及びその用途
JPH0753680A (ja) * 1993-08-11 1995-02-28 Nippon Zeon Co Ltd 新規な樹脂、その水素添加物、それらの製造方法、及びそれらの用途
WO1999009085A1 (fr) * 1997-08-19 1999-02-25 Nippon Zeon Co., Ltd. Polymere de norbornene et son procede de preparation

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