CN106232641B - Process for producing cyclic olefin copolymer - Google Patents
Process for producing cyclic olefin copolymer Download PDFInfo
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- CN106232641B CN106232641B CN201580021148.6A CN201580021148A CN106232641B CN 106232641 B CN106232641 B CN 106232641B CN 201580021148 A CN201580021148 A CN 201580021148A CN 106232641 B CN106232641 B CN 106232641B
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
- C08F4/6428—Component covered by group C08F4/64 with an organo-aluminium compound with an aluminoxane, i.e. a compound containing an Al-O-Al- group
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
Abstract
The invention provides a method for producing a copolymer, which can obtain a cyclic olefin copolymer having a molecular weight that is suitable for general molding and processing and is excellent in mechanical properties with a small amount of a catalyst. A method of making a copolymer, the method comprising: a polymerization step of polymerizing at least a cyclic olefin monomer (A) derived from norbornene and an alpha-olefin monomer (B) derived from an alpha-olefin of C4 to C12 in the presence of a titanocene catalyst to obtain a copolymer, wherein the amount of the copolymer obtained in the polymerization step is 1000g or more based on 1g of the titanocene catalyst, and the number-average molecular weight of the copolymer is 20000 or more and 200000 or less.
Description
Technical Field
The present invention relates to a method for producing a cyclic olefin copolymer.
Background
Cyclic olefin polymers and cyclic olefin copolymers (also referred to as "COP" and "COC", respectively) have low hygroscopicity and high transparency, and are used in various applications represented by the fields of optical materials such as optical disk substrates, optical films, and optical fibers. As a representative COC, a copolymer of cyclic olefin and ethylene, the glass transition temperature of which can be changed by the copolymerization composition of cyclic olefin and ethylene, can be produced, and thus a copolymer having a glass transition temperature (Tg) higher than COP can be produced, and although a Tg of more than 200 ℃ which is difficult to realize COP can be realized, it has a hard and brittle property, and thus has a problem of low mechanical strength and poor workability and processability.
In addition, although there are various polymers having high Tg, they have polar groups, so that there are limits to hygroscopicity and dielectric characteristics. Therefore, a polymer having a high Tg, which has no polar group, is formed of an olefin skeleton, and is excellent in optical properties, dielectric properties, and mechanical strength, has been desired.
As one of methods for improving the mechanical strength of a COC having a high Tg, there is a method of copolymerizing a cyclic olefin and an α -olefin other than ethylene (hereinafter referred to as a "specific α -olefin"). Various studies have been made on the copolymerization of cyclic olefins with specific α -olefins.
The copolymerization of cyclic olefins with specific alpha-olefins is significantly different from the copolymerization of cyclic olefins with ethylene. Under the condition that a high molecular weight product is obtained by copolymerization of a cyclic olefin and ethylene, in the copolymerization of a cyclic olefin and a specific α -olefin, a chain transfer reaction by the specific α -olefin occurs, and thus it has been difficult to obtain a high molecular weight product. Therefore, a copolymer of a cyclic olefin and a specific α -olefin is not suitable for a molding material (for example, see non-patent document 1).
Patent document 1 describes that a high molecular weight product composed of a cyclic olefin and a specific α -olefin can be obtained by a specific Ti-based catalyst, that the Tg is 245 to 262 ℃, that the moisture absorption is low, and that a film having excellent physical properties with a linear expansion coefficient of less than 80ppm can be obtained. However, the polymerization method disclosed in patent document 1 has the following problems because a large amount of catalyst and co-catalyst is used: resource saving is difficult to achieve, the cost required to obtain the copolymer is expensive, and the catalyst and cocatalyst remain and the transparency of the film is impaired. Patent document 1 describes that 92 to 164g of a copolymer can be obtained per 1g of a catalyst.
Patent document 2 discloses a film having excellent punching properties, but Tg is less than 170 ℃. In addition, in patent document 2, since a large amount of catalyst and co-catalyst is used, there are the following problems: resource saving is difficult to achieve, the cost required to obtain the copolymer is expensive, and transparency and thermal stability of the film are impaired. In patent document 2, it is described that 127-275g of a copolymer can be obtained per 1g of a catalyst.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-298999
Patent document 2: japanese patent No. 5017222
Non-patent document
Non-patent document 1: jung, H.Y., et al, Polyhedron, 2005, Vol.24, p.1269-1273
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a copolymer, which can produce a cyclic olefin copolymer having a molecular weight suitable for general molding and processing, and having excellent mechanical properties with a small amount of catalyst.
Means for solving the problems
The inventors of the present invention found that: the present inventors have completed the present invention by finding that a cyclic olefin copolymer having a molecular weight which is excellent in mechanical properties and suitable for general molding can be obtained by using a small amount of a titanocene catalyst. More specifically, the present invention provides the following technical solutions.
(1) A method of making a copolymer, the method comprising: a polymerization step of polymerizing at least a cyclic olefin monomer (A) derived from norbornene and an alpha-olefin monomer (B) derived from an alpha-olefin of C4 to C12 in the presence of a titanocene catalyst to obtain a copolymer, wherein the amount of the copolymer obtained in the polymerization step is 1000g or more based on 1g of the titanocene catalyst, and the number-average molecular weight of the copolymer is 20000 or more and 200000 or less.
(2) The production process according to (1), wherein the polymerization step is carried out in the presence of the titanocene catalyst, a cocatalyst comprising alkylaluminoxane and a chain transfer agent.
(3) The production process according to (2), wherein the chain transfer agent is an aluminum alkyl.
(4) The production method according to (3), wherein the aluminum alkyl is trimethylaluminum.
(5) The production method according to any one of (1) to (4), wherein the glass transition temperature (Tg) of the copolymer is 170 ℃ or higher.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a process for producing a copolymer, which can produce a cyclic olefin copolymer having a molecular weight suitable for general molding and excellent in mechanical properties with a small amount of a catalyst. In particular, the effect of the present invention can be further improved by controlling the amount of the chain transfer agent. In the present invention, since the amount of the catalyst used is small, the amount of the co-catalyst can be reduced. Therefore, it is possible to increase the amount of the cyclic olefin copolymer per 1 batch with a smaller amount of the catalyst and the cocatalyst inexpensively while maintaining the molecular weight range, and thus resource saving can also be achieved. Further, since the amount of the catalyst and the cocatalyst remaining in the obtained copolymer is small, the transparency and mechanical properties of a molded article such as a film obtained from the copolymer can be easily improved.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments.
The method for producing the copolymer of the present invention comprises: a polymerization step of polymerizing at least a cyclic olefin monomer (A) derived from norbornene and an alpha-olefin monomer (B) derived from an alpha-olefin of C4 to C12 in the presence of a titanocene catalyst to obtain a copolymer, wherein the amount of the copolymer obtained in the polymerization step is 1000g or more based on 1g of the titanocene catalyst, and the number-average molecular weight of the copolymer is 20000 or more and 200000 or less. According to the method for producing a copolymer of the present invention, a larger amount of a high molecular weight cyclic olefin copolymer can be obtained in 1 lot while maintaining the molecular weight range even with a smaller amount of a catalyst. In particular, in the method for producing a copolymer of the present invention, from the viewpoint of the amount of the catalyst used and the amount and number average molecular weight of the copolymer obtained, it is preferable that the polymerization step is carried out in the presence of a titanocene catalyst, a cocatalyst comprising alkylaluminoxane and a chain transfer agent.
[ copolymer ]
The copolymer obtained by the method for producing a copolymer of the present invention comprises: structural units derived from a cyclic olefin monomer (A) derived from norbornene and structural units derived from an alpha-olefin monomer (B) derived from an alpha-olefin of C4 to C12.
The amount of the copolymer obtained in the polymerization step included in the production method is 1000g or more, preferably 2000g or more, based on 1g of the titanocene catalyst used in the polymerization step.
The number average molecular weight of the copolymer of the present invention is preferably 20000 or more and 200000 or less, more preferably 30000 or more and 150000 or less. When the number average molecular weight is 20000 or more, the glass transition temperature (Tg) of the resulting copolymer is not likely to be too low. When the number average molecular weight is 200000 or less, the viscosity of the resulting copolymer solution is not likely to be excessively high. In the present specification, the number average molecular weight refers to a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography.
The copolymer of the present invention has a glass transition temperature (Tg) of 170 ℃ or higher, preferably 200 ℃ or higher, more preferably 230 ℃ or higher, and particularly preferably 260 ℃ or higher. When the glass transition temperature is 170 ℃ or higher, the transparent film obtained from the copolymer has sufficient heat resistance, and therefore, can be suitably used as a substrate for ITO deposition, for example. In particular, when the glass transition temperature is 260 ℃ or higher, the transparent film obtained from the copolymer has more sufficient heat resistance, and therefore, for example, even when it comes into contact with a molten lead-free solder, deformation, cracking, melting, and the like are less likely to occur, and therefore, it can be suitably used as a member for a lead-free solder. The upper limit of the glass transition temperature of the copolymer is not particularly limited, but when the glass transition temperature is high, the structural unit derived from the α -olefin in the copolymer is small, and therefore the effect of improving the mechanical strength by copolymerization of the α -olefin tends to be reduced, and therefore the glass transition temperature is preferably 350 ℃ or less, more preferably 330 ℃ or less. In the present specification, the glass transition temperature is a value measured by a DSC method (method described in JIS K7121) at a temperature increase rate of 20 ℃/min.
[ titanocene catalyst ]
The titanocene catalyst is not particularly limited, and a known catalyst can be used. The titanocene catalyst can be used singly or in combination of more than 2.
Examples of the titanocene catalyst include: a substance represented by the following formula (1).
R1～R3Each independently is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Specific examples thereof include: alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopentyl, and cyclohexyl; an aryl group such as a phenyl group, a biphenyl group, a phenyl group or a biphenyl group having the above alkyl group as a substituent, a naphthyl group, or a naphthyl group having the above alkyl group as a substituent.
R4And R5Each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and specifically, there may be mentioned: fluorine atom, chlorine atomHalogen atoms such as bromine atom and iodine atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, alkyl groups thereof having the above-mentioned halogen atom as a substituent; phenyl group, biphenyl group, naphthyl group, aryl group thereof having the above halogen atom or alkyl group as a substituent.
R6～R13Each 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 silyl group which may have a 1-valent hydrocarbon group having 1 to 12 carbon atoms as a substituent. Specific examples of the alkyl group having 1 to 12 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl and the like. Specific examples of the aryl group having 6 to 12 carbon atoms include: phenyl, biphenyl, naphthyl, aryl groups thereof having the above alkyl group as a substituent, and the like. Specific examples of the silyl group having a 1-valent hydrocarbon group having 1 to 12 carbon atoms as a substituent include: a silyl group having, as a substituent, an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, etc.
Specific examples of the titanocene catalyst represented by the general formula (1) include: (isopropylamide) dimethyl-9-fluorenylsilanedimethyltitanium, (isobutylamide) dimethyl-9-fluorenylsilanedimethyltitanium, (tert-butylamide) dimethyl-9-fluorenylsilanedimethyltitanium, (isopropylamide) dimethyl-9-fluorenylsilanetiumdichloride, (isobutylamide) dimethyl-9- (3, 6-dimethylfluorenyl) silanetiumdichloride, (tert-butylamide) dimethyl-9-fluorenylsilanetiumdichloride, (isopropylamide) dimethyl-9- (3, 6-dimethylfluorenyl) silanetiumdichloride, (isobutylamide) dimethyl-9- (3, 6-dimethylfluorenyl) silanetiumdichloride, (tert-butylamide) dimethyl-9- (3, 6-dimethylfluorenyl) silanetitanium dimethyl, (isopropylamide) dimethyl-9- [3, 6-di (isopropyl) fluorenyl]Silane titanium dichloride, (isobutylamide) dimethyl-9- [3, 6-di (isopropyl) fluorenyl]Silane titanium dichloride,(tert-butylamide) dimethyl-9- [3, 6-di (isopropyl) fluorenyl]Silane dimethyl titanium, (isopropyl amide) dimethyl-9- [3, 6-di (tert-butyl) fluorenyl]Silane titanium dichloride, (isobutylamide) dimethyl-9- [3, 6-di (tert-butyl) fluorenyl]Silane titanium dichloride, (tert-butylamide) dimethyl-9- [3, 6-di (tert-butyl) fluorenyl]Silanetitanium dimethyl, (isopropylamide) dimethyl-9- [2, 7-di (tert-butyl) fluorenyl]Silane titanium dichloride, (isobutylamide) dimethyl-9- [2, 7-di (tert-butyl) fluorenyl]Silane titanium dichloride, (tert-butylamide) dimethyl-9- [2, 7-di (tert-butyl) fluorenyl]Silane dimethyl titanium, (isopropylamide) dimethyl-9- (2,3,6, 7-tetramethylfluorenyl) silane titanium dichloride, (isobutylamide) dimethyl-9- (2,3,6, 7-tetramethylfluorenyl) silane titanium dichloride, (tert-butylamide) dimethyl-9- (2,3,6, 7-tetramethylfluorenyl) silane dimethyl titanium and the like. (t-butylamide) dimethyl-9-fluorenylsilane dimethyl titanium ((t-BuNSiMe) is preferred2Flu)TiMe2)。(t-BuNSiMe2Flu)TiMe2The titanium complex represented by the following formula (2) can be easily synthesized, for example, according to the description of Macromolecules, volume 31, page 3184, 1998.
(wherein Me represents a methyl group and t-Bu represents a tert-butyl group.)
[ cocatalyst comprising alkylaluminoxane ]
The cocatalyst used in the present invention is composed of alkylaluminoxane. The above-mentioned cocatalysts may be used singly or in combination of 2 or more.
The alkylaluminoxane is not particularly limited, and examples thereof include: a compound represented by the following formula (3) or (4). The alkylaluminoxane represented by the following formula (3) or (4) is a product obtained by reacting trialkylaluminum with water.
(wherein R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 40, preferably 2 to 30.)
Examples of the alkylaluminoxane include: methylaluminoxane and modified methylaluminoxane obtained by substituting a part of the methyl group of methylaluminoxane with another alkyl group. The modified methylaluminoxane is preferably a modified methylaluminoxane having an alkyl group having 2 to 4 carbon atoms such as an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group as a substituted alkyl group, and particularly, a modified methylaluminoxane in which a part of a methyl group is substituted with an isobutyl group is more preferable. Specific examples of the alkylaluminoxane include: methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like, and among them, methylaluminoxane and methylisobutylaluminoxane are preferable.
The alkylaluminoxane can be produced by a known method. Further, as the alkylaluminoxane, a commercially available product can be used. Examples of commercially available alkylaluminoxanes include: MMAO-3A, TMAO-200 series, TMAO-340 series (both manufactured by Tosoh Finechem Corporation.), methylaluminoxane solution (manufactured by Albemarle Corporation), and the like.
[ chain transfer agent ]
The chain transfer agent used in the present invention is a compound having a chain transfer ability. The chain transfer agent may be used alone in 1 kind or in combination of 2 or more kinds.
The chain transfer agent is not particularly limited, and known compounds having a chain transfer ability can be used, and examples thereof include: an aluminum alkyl. Examples of the aluminum alkyl include: a compound represented by the following general formula (5).
(R10)zAlX3-z (5)
(in the formula, R10Is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and z is an integer of 1 to 3. )
Examples of the alkyl group having 1 to 15 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, and the like.
Specific examples of the aluminum alkyls include: trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, and tri-n-octylaluminum; dialkylaluminum halides such as dimethylaluminum chloride and diisobutylaluminum chloride; dialkylaluminum hydrides such as diisobutylaluminum hydride; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide.
As another Chain transfer agent, a Chain Shuttling agent (Chain Shuttling) known in polymerization using a metallocene catalyst may be used. Examples of chain shuttling agents include: the alkyl aluminum and the alkyl zinc. Examples of the zinc alkyl include: a compound represented by the following general formula (6).
(R11)zZnX2-y (6)
(in the formula, R11Is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and y is an integer of 0 to 2. )
Examples of the alkyl group having 1 to 15 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, and the like.
Specific examples of the zinc alkyl include: dialkylzinc such as dimethylzinc, diethylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc, di-sec-butylzinc aluminum, and di-n-octylzinc; alkyl zinc halides such as methyl zinc chloride and isobutyl zinc chloride; alkyl zinc hydrides such as isobutyl zinc hydride; zinc alkyl alkoxides such as zinc methyl methoxide; zinc halides such as zinc chloride.
The alkyl aluminum or alkyl zinc may be directly charged into the polymerization system, or may be charged in a state of being contained in the alkyl aluminoxane. Further, the alkyl aluminum may be a raw material remaining after the production, which is used in the production of the alkylaluminoxane. In addition, a combination of aluminum alkyl and zinc alkyl may be used.
[ Cyclic olefin monomer (A) ]
Examples of the cyclic olefin monomer (a) derived from norbornene include: norbornene and substituted norbornenes, preferably norbornene. The cyclic olefin monomer (A) can be used alone or in combination of 2 or more.
The substituted norbornene is not particularly limited, and examples of the substituent of the substituted norbornene include: halogen atom, 1-valent or 2-valent hydrocarbon group. Specific examples of the substituted norbornene include: a substance represented by the following general formula (I).
(in the formula, R1～R12May be the same or different from each other, and is selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group,
R9and R10、R11And R12Can be integrated to form a 2-valent hydrocarbon group,
R9or R10And R11Or R12May form a ring with each other.
In addition, n represents 0 or a positive integer,
when n is 2 or more, R5～R8The respective repeating units may be the same or different.
Wherein, when n is 0, R1～R4And R9～R12At least 1 of which is not a hydrogen atom. )
The substituted norbornene represented by the general formula (I) will be described. R in the general formula (I)1～R12May be the same or different and is selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.
As R1～R8Specific examples of (3) include: a hydrogen atom; halogen atoms such as fluorine, chlorine and bromine; alkyl groups having 1 to 20 carbon atoms, and the like, and they may be different from each other, may be partially different from each other, or may be the same as each other.
In addition, as R9～R12Specific examples of (3) include: a hydrogen atom; halogen atoms such as fluorine, chlorine and bromine; an alkyl group having 1 to 20 carbon atoms; cycloalkyl groups such as cyclohexyl; phenyl, tolylSubstituted or unsubstituted aromatic hydrocarbon groups such as ethyl phenyl, isopropyl phenyl, naphthyl, and anthryl; benzyl group, phenethyl group, and aralkyl group in which an aryl group is substituted with an alkyl group, and the like may be different from each other, may be partially different from each other, or may be the same as each other.
As R9And R10Or R11And R12Specific examples of the case where the 2-valent hydrocarbon group is formed by integration include: and alkylidene groups (alkylidene groups) such as ethylidene group (ethylidene group), propylidene group (propylidene group), and isopropylidene group (isopropylidene group).
R9Or R10And R11Or R12When they form a ring with each other, the formed ring may be monocyclic or polycyclic, may be bridged polycyclic, may be a ring having a double bond, or may be a ring formed by a combination of these rings. These rings may have a substituent such as a methyl group.
Specific examples of the substituted norbornene represented by the general formula (I) include: 5-methyl-bicyclo [2.2.1] hept-2-ene, 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, bicyclic cyclic olefins such as 5-octyl-bicyclo [2.2.1] hept-2-ene, 5-octadecyl-bicyclo [2.2.1] hept-2-ene, 5-methylene-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, and 5-propenyl-bicyclo [2.2.1] hept-2-ene;
tricyclic [4.3.0.1 ]2,5]Deca-3, 7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 ]2,5]Dec-3-ene; tricyclic [4.4.0.1 ]2,5]Undec-3, 7-dienes or tricyclo [4.4.0.12,5]Undec-3, 8-dienes or their partial hydrides (or adducts of cyclopentadiene and cyclohexene) i.e. tricyclo [4.4.0.12,5]Undec-3-ene; 5-cyclopentyl-bicyclo [2.2.1]Hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1]Hept-2-ene, 5-cyclohexenylbicyclo [2.2.1]Hept-2-ene, 5-phenyl-bicyclo [2.2.1]Tricyclic cyclic olefins such as hept-2-ene;
tetracyclic [4.4.0.12,5.17,10]Dodec-3-enes (also referred to as tetracyclododecenes), 8-methyltetracyclo [4.4.0.12,5.17,10]Dodec-3-ene, 8-ethyltetracyclo [4.4.0.12,5.17,10]Dodec-3-ene, 8-methylenetetracyclo [4.4.0.12,5.17,10]Dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.12,5.17,10]Dodec-3-ene, 8-vinyltetracyclo [4, 4.0.12,5.17,10]Dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.12,5.17,10]Tetracyclic cyclic olefins such as dodec-3-ene;
8-cyclopentyl-tetracyclo [ 4.4.0.1%2,5.17,10]Dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.12,5.17,10]Dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.12,5.17,10]Dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.12,5.17,10]Dodec-3-ene; tetracyclic [7.4.1 ]3,6.01,9.02,7]Tetradeca-4, 9,11, 13-tetraene (also known as 1, 4-methano-1, 4,4a,9 a-tetrahydrofluorene), tetracyclo [ 8.4.1%4,7.01,10.03,8]Pentadecane-5, 10,12, 14-tetraene (also known as 1, 4-methano-1, 4,4a,5,10,10 a-hexahydroanthracene); pentacyclic ring [6.6.1.13,6.02,7.09,14]-4-hexadecene, pentacyclic [6.5.1.1 ]3,6.02,7.09,13]-4-pentadecene, pentacyclic [7.4.0.0 ]2,7.13,6.110,13]-4-pentadecene; seven rings [8.7.0.12,9.14,7.111,17.03,8.012,16]-5-eicosene, heptacyclo [8.7.0.12,9.03,8.14,7.012,17.113,l6]-14-eicosene; polycyclic cyclic olefins such as tetramers of cyclopentadiene.
Of these, alkyl-substituted norbornenes (for example, bicyclo [2.2.1] hept-2-ene substituted with 1 or more alkyl groups), alkylidene-substituted norbornenes (for example, bicyclo [2.2.1] hept-2-ene substituted with 1 or more alkylidene groups), and particularly 5-ethylidene-bicyclo [2.2.1] hept-2-ene (common name: 5-ethylidene-2-norbornene or ethylidene norbornene for short) are preferable.
[ alpha-olefin monomer (B) ]
Examples of the α -olefin monomer (B) derived from a C4 to C12 α -olefin include: C4-C12 alpha-olefin, C4-C12 alpha-olefin having at least 1 substituent such as halogen atom, preferably C4-C12 alpha-olefin, more preferably C6-C10 alpha-olefin.
The C4 to C12 α -olefin is not particularly limited, and examples thereof include: 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-hexene, 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and the like. Among them, 1-hexene, 1-octene and 1-decene are preferable.
[ conditions of polymerization step ]
The conditions of the polymerization step are not particularly limited as long as the desired copolymer can be obtained, and known conditions can be used, and the polymerization temperature, polymerization pressure, polymerization time, and the like can be appropriately adjusted. The amounts of the respective components used are as follows.
The amount of the α -olefin monomer (B) added is preferably 1 part by mass or more and 500 parts by mass or less, more preferably 10 parts by mass or more and 300 parts by mass or less, with respect to 100 parts by mass of the cyclic olefin monomer (a).
The amount of the titanocene catalyst used is preferably 0.00001 part by mass or more and 0.1 part by mass or less, more preferably 0.0001 part by mass or more and 0.05 part by mass or less, per 100 parts by mass of the cyclic olefin monomer (a).
The amount of the alkylaluminoxane to be used is preferably 0.0001 part by mass or more and 5 parts by mass or less, more preferably 0.01 part by mass or more and 3 parts by mass or less based on Al, relative to 100 parts by mass of the cyclic olefin monomer (a).
The amount of the chain transfer agent to be used is preferably 0.0001 part by mass or more and 10 parts by mass or less, more preferably 0.01 part by mass or more and 5 parts by mass or less, per 100 parts by mass of the cyclic olefin monomer (a).
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" indicating amounts means "parts by mass".
[ preparation of copolymer ]
The respective monomers shown in table 1 and the co-catalyst shown in table 2 were added to a glass reactor which was dried and kept in a nitrogen atmosphere, and after the polymerization temperature was kept, the catalyst shown in table 2 was added. The catalyst and the cocatalyst were added to the reactor in a state of being dissolved in toluene, respectively. The polymerization was continued while stirring the inside of the reactor at the polymerization temperature and polymerization time shown in Table 3, and then 1 part by mass of 2-propanol was added to terminate the reaction. Then, the obtained polymerization reaction solution was poured into a large amount of hydrochloric acid-based methanol to completely precipitate a polymer, which was filtered off and washed, and then dried under reduced pressure at 60 ℃ for 1 day or more to obtain a copolymer. The quality of the resulting copolymer was measured ("yield" in Table 3). The ratio of the obtained copolymer to the amount of the catalyst used was calculated (in Table 3, "g (copolymer)/g (catalyst)").
The types of the catalyst and the co-catalyst used are as follows. Wherein t-Bu represents a tert-butyl group and Flu represents a fluorenyl group.
Catalyst A: (t-BuNSiMe)2Flu)TiMe2
Cocatalyst A: 6.5% by mass (in terms of Al atom content) of MMAO-3A toluene solution ([ (CH)3)0.7(iso-C4H9)0.3AlO]nA solution of methyl isobutyl aluminoxane shown, manufactured by Tosoh Finechem corporation, was described as containing 6 mol% of trimethylaluminum with respect to the total Al
And (3) a cocatalyst B: 9.0 mass% (in terms of Al atom content) of TMAO-211 toluene solution (a solution of methylaluminoxane, manufactured by Tosoh Finechem corporation, Note that 26 mol% of trimethylaluminum is contained with respect to the total Al)
A cocatalyst C: triisobutylaluminium
A cocatalyst D: dimethylanilinium tetrakis (pentafluorophenyl) borate
The number average molecular weight and Tg of each copolymer are shown in table 3.
The value of "part" in tables 1, 2 and 3 is a value relative to 100 parts of 2-norbornene. In addition, for the catalyst A and B in Table 2, "part" value is based on toluene solution.
[ Table 1]
[ Table 2]
[ Table 3]
As shown in Table 3, according to the present invention, the proportion of the obtained copolymer with respect to the amount of the catalyst used was high.
Claims (4)
1. A method of making a copolymer, the method comprising: a polymerization step of polymerizing at least a cyclic olefin monomer (A) derived from norbornene and an alpha-olefin monomer (B) derived from alpha-olefin having C4 to C12 in the presence of a titanocene catalyst to obtain a copolymer,
the amount of the copolymer obtained in the polymerization step is 1000g or more per 1g of the titanocene catalyst, the polymerization step is carried out in the presence of the titanocene catalyst, a cocatalyst comprising alkylaluminoxane, and a chain transfer agent, the titanocene catalyst is 0.00001 part by mass or more and 0.1 part by mass or less per 100 parts by mass of the cyclic olefin monomer (a), the amount of alkylaluminoxane used is 0.3618 parts by mass or more and 5 parts by mass or less based on Al, the chain transfer agent is 0.0001 parts by mass or more and 5 parts by mass or less, and the number average molecular weight of the copolymer is 20000 or more and 200000 or less;
the titanocene catalyst is shown by the following formula (1),
wherein R is1～R3Each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R4And R5Each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, R6～R13Each 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 silyl group optionally having a 1-valent hydrocarbon group having 1 to 12 carbon atoms as a substituent;
the chain transfer agent is aluminum alkyl.
2. The production process according to claim 1, wherein the alkylaluminum is introduced in a state of being contained in the alkylaluminoxane solution.
3. The production method according to claim 2, wherein the aluminum alkyl is trimethylaluminum.
4. The production method according to any one of claims 1 to 3, wherein the glass transition temperature (Tg) of the copolymer is 170 ℃ or higher.
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| JP2014-107144 | 2014-05-23 | ||
| PCT/JP2015/061986 WO2015178143A1 (en) | 2014-05-23 | 2015-04-20 | Method for producing cyclic olefin copolymer |
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| JP6491804B1 (en) * | 2017-08-01 | 2019-03-27 | ポリプラスチックス株式会社 | Copolymer and process for producing copolymer |
| JP7101063B2 (en) * | 2018-07-04 | 2022-07-14 | ポリプラスチックス株式会社 | A method for verifying the catalytic activity of a metallocene catalyst, a method for producing a catalyst composition for olefin monomer polymerization, and a method for producing a polymer. |
| CN114685715B (en) * | 2020-12-31 | 2024-05-03 | 江苏博睿光电股份有限公司 | Crosslinkable thermoplastic cycloolefin copolymer and preparation method and application thereof |
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| JP2000119328A (en) * | 1998-10-16 | 2000-04-25 | Teijin Ltd | Cyclic olefinic polymer with low content of catalyst residue, its use and production thereof |
| JP2000204120A (en) * | 1999-01-18 | 2000-07-25 | Mitsui Chemicals Inc | Production of norbornene-based polymer |
| JP2007119660A (en) * | 2005-10-31 | 2007-05-17 | Nippon Zeon Co Ltd | Cycloolefin addition copolymer, process for producing the same and molding material |
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| JP3181955B2 (en) * | 1991-11-11 | 2001-07-03 | 出光興産株式会社 | Method for producing cyclic olefin polymer |
| JPH08268927A (en) * | 1995-03-28 | 1996-10-15 | Tokuyama Corp | Purification of cyclic olefin and polymerization |
| JP5017222B2 (en) | 2007-09-25 | 2012-09-05 | 富士フイルム株式会社 | Cyclic olefin copolymer, film, polarizing plate and liquid crystal display device using the same |
| JP2009298999A (en) * | 2008-05-14 | 2009-12-24 | Kaneka Corp | Cyclic olefin addition copolymer, optical film and transparent conductive film for liquid crystal or el display element |
| KR20140011726A (en) * | 2012-07-19 | 2014-01-29 | (주)제이브이엠 | System for managing medicine and method for managing medicine of the same |
| KR101588368B1 (en) | 2013-03-11 | 2016-01-25 | 포리프라스틱 가부시키가이샤 | Norbornene-type polymer solution |
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| JP2000119328A (en) * | 1998-10-16 | 2000-04-25 | Teijin Ltd | Cyclic olefinic polymer with low content of catalyst residue, its use and production thereof |
| JP2000204120A (en) * | 1999-01-18 | 2000-07-25 | Mitsui Chemicals Inc | Production of norbornene-based polymer |
| JP2007119660A (en) * | 2005-10-31 | 2007-05-17 | Nippon Zeon Co Ltd | Cycloolefin addition copolymer, process for producing the same and molding material |
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| JP6685223B2 (en) | 2020-04-22 |
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