WO2001079312A1 - Copolymeres fonctionnels de styrene et leur procede de production - Google Patents
Copolymeres fonctionnels de styrene et leur procede de production Download PDFInfo
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- WO2001079312A1 WO2001079312A1 PCT/JP2001/003302 JP0103302W WO0179312A1 WO 2001079312 A1 WO2001079312 A1 WO 2001079312A1 JP 0103302 W JP0103302 W JP 0103302W WO 0179312 A1 WO0179312 A1 WO 0179312A1
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- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
Definitions
- the present invention relates to a method for producing a functional group-containing styrene copolymer and a functional group-containing styrene copolymer. More preferably, the present invention provides a method for efficiently producing a styrene-based copolymer having a syndiotactic structure containing a functional group, particularly an X-ethylene random copolymer, and a method of bonding with various adhesives.
- the present invention relates to a styrene random copolymer having a syndiotactic structure containing a functional group, which has improved properties such as properties and compatibility with various rubbers. Background art
- styrene-based polymers produced by radical polymerization methods are molded into various shapes by various molding methods.
- household electrical appliances, office equipment, household goods, packaging containers, toys, furniture, synthetics Although widely used as paper and other industrial materials, its three-dimensional structure has an atagistic structure, and has the disadvantage of poor heat and chemical resistance.
- the research group of the present inventors has succeeded in developing a styrene-based polymer having a high syndiotactic structure so far as solving the disadvantage of the styrene-based polymer having an atactic structure.
- a styrene-based copolymer having a syndiotactic structure which is obtained by copolymerizing a styrene-based monomer with another monomer.
- An example For example, a syndiotactic copolymer of styrene and a substituted styrene (Japanese Patent Application Laid-Open No.
- the present invention provides a method for efficiently producing a styrene-based copolymer having a functional group-containing syndiotactic structure, in particular, a styrene-based random copolymer under such a circumstance, and an adhesive property with various adhesives.
- a styrene-based random copolymer having a functional group-containing syndiotactic structure with improved physical properties.
- the inventors of the present invention have conducted intensive studies to achieve the above object, and after treating a functional group-containing vinyl compound with a metal compound and masking the functional group, this was used as a specific polymerization catalyst.
- styrene-based copolymer having a functional group-containing syndiotactic structure particularly a styrene-based random random copolymer
- the styrene random copolymer having a functional group-containing syndiotactic structure having a specific repeating unit is extremely useful for improving physical properties such as adhesion to various adhesives and compatibility with various rubbers. I found something. Takaaki Moto has been completed based on this knowledge.
- a metal compound is allowed to act on a functional group-containing vinyl compound to mask the functional group, and then the resulting compound is treated with (A) a transition metal compound, (B) an oxygen-containing compound and / or the transition metal.
- a functional group characterized by being copolymerized with a styrene compound in the presence of a compound capable of reacting with a compound to form an ionizable complex and optionally a (C) polymerization catalyst containing an organometallic compound It is intended to provide a method for producing a styrene-based copolymer having a syndiotactic structure, particularly a method for producing a styrene-based random copolymer.
- the present invention also provides (a) a compound represented by the general formula ( ⁇ ):
- R 8 is a hydrogen atom, a halogen atom or a C, substituents containing S n or S i, t is an integer of from 1 to 5, when R 8 is plural, each R 8 is also the same as each other May be different.
- D is —OR 1 , —COR 1 , —C 02 R 1 , —CN, one NR 1 R 2 , —SR 1 or one PR 1 R 2 , and R 1 and R 2 are Each is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylsilyl group having 3 to 20 carbon atoms, and R and are linear chains having 1 to 20 carbon atoms.
- each D may be the same or different, n is an integer of 1 to 5, m is an integer of 0 to 4, provided that n + m ⁇ 5.) It contains a repeating unit derived from a functional group-containing vinyl compound represented by the formula: and (b) the content of the unit is 0.01 to 50 mol%, and (a) The present invention also provides a styrene-based random copolymer having a syndiotactic structure containing a functional group, in which the stereoregularity of the polymer containing units and (b) units is a syndiotactic structure. .
- a styrene-based copolymer having a functional group-containing syndiotactic structure can be obtained. It is also possible to produce block copolymers and graft copolymers. it can. For example, if the method of the present invention is applied to the two-stage polymerization method described in JP-A-5-320281, a styrene block copolymer can be produced. If the method of the present invention is applied to the method described in Japanese Patent Application Laid-Open No. 3-240909, styrene-based blocks, random or alternating copolymers can be obtained.
- a functional group-containing vinyl compound and a styrene compound are used as the raw material monomers in the production method of the present invention.
- Examples of the functional group-containing vinyl compound include compounds represented by general formula (I)
- X represents a functional group maskable by a metal compound
- R ° represents a hydrocarbon group
- each X may be the same or different.
- N is an integer of 1 to 5
- m is an integer of 0 to 4, where n + m ⁇ 5.
- R 1 and R 2 each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 3 to 20 carbon atoms. Represents a rualkylsilyl group. When R 1 and R 2 are present in the same group, they may be the same or different.
- a linear or branched alkyl group is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Examples include an isobutyl group, a tert-butyl group, an n-hexyl group, and an n-decyl group.
- Examples of such functional group-containing styrenic compounds include: 0-hydroxystyrene, ⁇ -hydroxystyrene, -m-hydroxystyrene, such as hydroxystyrene; 0-methoxystyrene; p — methoxystyrene, m — methoxystyrene, 0 — ethoxystyrene, p — ethoxystyrene, m — ethoxystyrene, 4 — methoxy-3 — methylstyrene, p — propoxystyrene, p — phenoxystyrene, p—t—butoxystyrene, p—trityloxystyrene, ⁇ _trimethylsiloxystyrene, p—t-butyldimethylsiloxystyrene, p—triisopropylpropylsiloxys
- 4 vinylphenyl Alcohols such as ethanol; 2—amino styrene, 3—amino styrene, 4—amino styrene , 3, 4-diaminostyrene, 4-vinylbenzylamine, 2-
- Lecaptostyrene and alkylthiostyrenes Lecaptostyrene and alkylthiostyrenes; p-styryldiphenylphosphine, 3,5-dimethyl-4-hydroxystyrene, 3,5-getyl 4-hydroxystyrene, 3,5-dipropyl-4-hydroxy styrene, 3, 5 - diisopropyl Sopuro pills 4 - arsenide Dorokishisuchire emissions, 3, 5 - Sita one Sha Li-butyl 4 - hydroxycarboxylic styrene, 3, 5 - Sita - Shah Li-butyl 4 Ichia Mi Nosuchiren, 3, 5 - Dibutyl butyl 4-carboxystyrene and the like.
- Et al is, as the preferred correct functional group-containing styrene compounds, wherein the X in one general formula (I), - (CR 3 R 4) - as a group represented by D, and - Zeta (QR 5 R 6 R 7 ) What is a group represented by Q can be mentioned.
- D is—0 R 1 , —C 0 R 1 , —C 0 R 1 , one CN, —NR 1 R 2 , —SR or —PR substituents comprising 1 R 2
- R 3 and R 4 are each an alkyl group of indicated number 1-2 0 carbon atoms, an alkylsilyl group ⁇ rie group or a C 3 to C 2 0 of 6-2 0 carbon atoms
- R 1 and R 2 are the same as above, and p represents an integer of 1 to 10.
- each CR 3 R 4 may be the same or different.
- R 3 and R 4 may be the same or different.
- R 5 ⁇ R 7 are carbon atoms respectively 1
- the two — QR 5 R 6 R 7 may be the same or different.
- R 5 to R 7 may be the same or different from each other.
- Examples of such a styrene-containing compound having a functional group include, for example, 111- (4-vinylphenyl) 1-1,1-dimethyl- Methyl-methyl ether.
- one of these functional group-containing styrene compounds may be used alone, or two or more thereof may be used in combination.
- the styrene compound to be copolymerized with the functional group-containing styrene compound may be, for example, a compound represented by the general formula (IV)
- R 8 is a hydrogen atom, a halogen atom or a C, substituents containing S n or S i, t is an integer of from 1 to 5, when R 8 is plural, each R 8 is also the same as each other It may be different.
- styrene-based compound represented by the above general formula (IV) examples include styrene, ⁇ -methylstyrene, m-methylstyrene, 0-methylstyrene, 2,4-dimethylstyrene, 2,5 —Alkylstyrenes such as dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, p-t-butylstyrene; p-divinylbenzene, m-divinylbenzene, Polyvinylbenzenes such as vinylbenzene; ⁇ -chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluor
- P Nodogenated styrene such as fluorostyrene And the like; m-phenylstyrene, ⁇ -phenylstyrene and the like.
- one of these styrene compounds may be used alone, or two or more thereof may be used in combination.
- the use ratio of the styrene-based compound having the functional group and the styrene-based compound represented by the general formula (IV) is not particularly limited, but is usually 0.01% by mole. : 99.9 to 50: 50, preferably 0.5: 99.5 to 30: 70, more preferably 1: 99 to 20: Selected in the range of 80.
- a metal compound is first allowed to act on the vinyl compound having the functional group to mask the functional group.
- M is a metal selected from Groups 1 to 8 and 11 to 14 of the periodic table
- A is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number.
- An aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, r represents the valence of metal M, and when A is plural, A may be the same or different.
- M include Li, Na, KBe, Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, and Hf. , V, Nb, Ta, Cr, Mo, Mn, Fe, Ru, Cu, Zn, Cd, Hg, Al, Ga, Sn, and Pb. it can.
- L i, N a, K, M g, T i, Z r, H f, C u .Z n, C d, H g, A l, G a, S n and P b are preferred.
- a 1 is particularly preferred.
- an alkyl group-containing aluminum compound is preferable, and a trialkylaluminum and a dialkylaluminum compound are particularly preferable.
- this alkyl group-containing aluminum compound include trimethylaluminum, triethylaluminum. Tri-n-propylaluminum, triisopropylaluminum, trin-butylaluminum, and tri-n-butylaluminum.
- Trialkylaluminum and dimethyl such as lysobutylaluminum and tri-t-butylaluminum Lunoremi aluminum chloride, getylaluminum chloride, g-n-propylaluminum chloride, diisopropylaluminum chloride, g-n-butylaluminum chloride, diisobutylaluminum chloride, g-t —Dialkylaluminum halides such as butylaluminum chloride, dialkylaluminum alkoxides such as dimethylaluminum methoxide and dimethylaluminum methoxide, dimethylaluminum hydride, getylaluminum hydride, and diisobutylaluminum hydride And dialkyl aluminum hydrides such as hydrides.
- these metal compounds may be used alone or in a combination of two or more.
- transition metal complex (A) used in the present invention various ones can be used, and transition metal compounds of Groups 4 to 6 or Groups 8 to 10 of the periodic table are preferably used.
- transition metal compounds of Groups 4 to 6 of the periodic table those represented by the following general formulas (VI) to (IX) can be preferably mentioned.
- transition metal compound of the formula (I) a compound represented by the following general formula (X) can be mentioned as a preferable example.
- Q 1 is two conjugated five-membered ring ligand (C 5 H 5 - a - b R s b) ⁇ Beauty (C 5 H 5 - a - c R 10 c) binding group for cross-linking are shown
- Q 2 is conjugated five-membered ring ligand showing a bonding group which crosslinks the (C 5 H s - d R - a) a Z 1 group.
- R s , R 10 , R 11 and R 12 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group. And when there are a plurality of groups, they may be the same or different from each other, or may be bonded to each other to form a ring structure.
- a is 0, 1 or 2.
- e represents an integer of 0 to 5.
- M 1 represents a periodic table 4-6 transition metal of Groups
- M 2 represents a circumferential Kiritsuhyo 8-1 0 transition metals.
- L 1 and L 2 each represent a ligand having a coordination bond
- X 1 , Y 1 , Z 1 , W 1 and U 1 are ligands having a covalent bond or an ion bond, respectively. Is represented.
- L 1 , L 2 , X 1 , Y 1 , W 1 and U 1 may be bonded to each other to form a ring structure.
- Q 1 and Q 2 in the above general formulas (VI) and (VII) include (1) a methylene group, an ethylene group, an isopropylene group, a methylphenylmethylene group, a diphenylmethylene group, and a cyclohexane.
- sienic Which alkylene group having 1 to 4 carbon atoms, cycloalkylene group or lower alkyl or phenyl substituent thereof, (2) silylene group, dimethylsilylene group, methylphenylsilylene group, diphenylsilylene group; Group, disilylene group, tetramethyldisilylene group or other silylene group, oligosilylene group or its lower-chain lower alkyl or phenyl substituent, (3) containing germanium, phosphorus, nitrogen, boron, or aluminum.
- Hydrocarbon groups [lower alkyl groups, phenyl groups, hydrocarbyloxy groups (preferably lower alkoxy groups), etc.], specifically, (CH 3 ) 2 Ge groups, (C 6 H 5 ) 2 Ge groups , (CH 3 ) P, (C 6 H 5 ) P, (C 4 H s ) N, (C 6 H 5) N, (CH 3 ) B, (C 4 H 9) B , and the like (C s H 5) B group, (C 8 H s) A 1 group, (CH a 0) A 1 group .
- an alkylene group and a silylene group are preferred.
- (C 5 H 5 - a - b R 8 b), (C 5 H 5 - a - c R 10 c) and (C 5 H 5 _ a - d R xl d -) is conjugated five-membered cyclic distribution Ligands, R 9 , R 1 .
- R 11 represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, respectively. Or 2.
- the hydrocarbon group those having 1 to 20 carbon atoms are preferable, and those having 1 to 12 carbon atoms are particularly preferable.
- This hydrocarbon group may be bonded as a monovalent group to a cyclopentagenenyl group which is a conjugated 5-membered ring group, and when there are a plurality of these, two of them are bonded to each other. To form a ring structure together with part of the cyclopentenyl group.
- conjugated five-membered ring ligand are substituted or unsubstituted.
- These are cyclopentagenenyl, indenyl and fluorenyl groups.
- the halogen atom includes chlorine, bromine, iodine and fluorine atoms, and the alkoxy group preferably has 1 to 12 carbon atoms.
- Examples of the silicon-containing hydrocarbon group include one Si (R 13 ) (R , 4 ) (R 15 ) (R 13 , R 14 and R 15 are a hydrocarbon group having 1 to 24 carbon atoms).
- a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group and a boron-containing hydrocarbon group include P- (R 18 ) (R 17 ), N (R 16 ) (R 17 ) and R 16 ) (R 17 ) (R 16 and R 17 are a hydrocarbon group having 1 to 18 carbon atoms).
- R 9 b) and (C 5 H 5-a-c R 10 c) may be the same or different.
- M 1 represents a transition metal element of Groups 4 to 6 of the periodic table, and specific examples thereof include titanium, zirconium, hafnium, niobium, molybutene, tungsten, and the like. Among them, titanium, zirconium and hafnium are preferred, and titanium is particularly preferred.
- Z 1 is a ligand having a covalent bond, specifically, oxygen (—0—), sulfur (—S—), an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, Number 1 to 20, preferably 1 to 12 thioalkoxy group, carbon atom 1 to 40, preferably 1 to 18 nitrogen-containing hydrocarbon group, carbon number 1 to 40, preferably 1 To 18-containing phosphorus-containing hydrocarbon groups.
- X 1 and Y 1 are each a covalent ligand, specifically, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, and a carbon atom having 1 carbon atom.
- ⁇ 20 preferably 1-10 Alkoxy group, amino group, C 1 to C 20, preferably C 1 to C 12 phosphorus-containing hydrocarbon group (for example, diphenylphosphine group) or C 1 to C 20, preferably Is a silicon-containing hydrocarbon group having 1 to 12 carbon atoms (for example, trimethylsilyl group, etc.), a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a boron compound containing halogen compound (for example,
- B (C 6 H 5) 4 , BF) shows a.
- a halogen atom and a hydrocarbon group are preferred.
- X 1 and Y 1 may be the same or different.
- X 1 and Y 1 may be bonded to each other to form a ring structure.
- M 1 is a transition metal belonging to Groups 4 to 6 of the periodic table as described above, and X 1 and Y 1 are the same as above.
- W 1 is the same as X 1 and Y 1 . That is, W 1 is a covalent ligand, and specifically, is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms.
- X 1 , ⁇ 1 and W 1 may be the same or different.
- X 1 , ⁇ 1 and W 1 may be bonded to each other to form a ring structure.
- ⁇ 1 is the same as above in the Periodic Tables 4 to 6
- X 1 , ⁇ 1 and W 1 are the same as above.
- U 1 is the same as X 1 , ⁇ 1 and W 1 .
- Sand U 1 is a covalent ligand, specifically, a hydrogen atom, a halogen atom, a carbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, and a carbon atom having 1 carbon atom.
- amino groups 1 to 20 carbon atoms, preferably 1 to 12 phosphorus-containing hydrocarbon groups (for example, diphenylphosphine groups).
- a carbon atom having 1 to 20 carbon atoms preferably 1 to 12 carbon atoms.
- Indicates a hydrocarbon group or a halogen-containing boron compound for example, B (C 6 H 5 ) 4 , BF 4 ). Of these, halogen atoms and hydrocarbon groups are preferred.
- X 1. Y 1 , W 1, and U 1 may be the same or different from each other. Note that X 1 , Y 1 , and U 1 are bonded to each other to form a ring structure. Is also good.
- a transition metal compound having one conjugated five-membered ring ligand of 5 is particularly preferably used in the production of a styrene-based polymer having a syndiotactic structure. .
- transition metal compound represented by the general formula (VIII) include the following compounds.
- transition metal compounds in which the (C 5 H 5 -e R 12 e ) group in the above general formula (VIII) is represented by the following general formulas (XI) to (XVII) are preferable.
- A represents an element belonging to Group 13, 14, 15, or 16, and A may be the same or different from each other.
- R is a hydrogen atom; a halogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and a 6 to 3 carbon atoms.
- a represents 0, 1 or 2
- n and m each represent an integer of 1 or more.
- Specific examples of the (C 5 H 5 -e R 12 e ) group include the following.
- Cyclopentagenenyl group Methylcyclopentagenenyl group, 1,2-Dimethylcyclopentagenenyl group, 1,3—Dimethylenocyclopentagenenyl group, 1,2,3—Trimethylcyclopentagenenyl group, 1,3,4-Trimethylcyclopentagenenyl group , A tetrapentacyclyl pentagenenyl group, a pentamethiccyclopenta pentageninole group, an ethylcyclopentagenenyl group, a 1,2-diethylcyclopentadienyl group, a 1,3-a-ethylcyclopentadienyl group, a 1,2,3-triethylcyclopentagenenyl 1,3,4—trietinolecyclopentagenenyl group, tetraethynolecyclopentagenenyl group, pentaethy
- Examples include a hydrofluorenyl group.
- transition metal compound represented by the general formula (VIII) is shown below.
- Cyclopentagenenyl titanium trichloride cyclopentagenyl titanium trimethyl, cyclopentagenenyl titanium Trimethoxide, cyclopentagenyltitanium tribenzyl, methylcyclopentagenyltitanium trichloride, methylcyclopentagenyltitanium trimethyl, methylcyclopentane trititanium trimethoxide , Methylcyclopentagenyltitanium tribenzyl, dimethylcyclopentagenyltitanium trichloride, dimethylcyclopentagenyltitanium trimethyl, dimethylcyclopentapentanenyltitanium trimethoxide, dimethylcyclopentapentaenyl Tritium tribenzyl, trimethylcyclopentagenyl titanium trichloride, trimethylcyclopentagenyltitanium trimethyl, trimethylsilicone Penta genyl titanium trimethoxide, trimethyl cyclopentadiene retinitanium tribenzy
- titanium compounds are preferred.
- ⁇ (C) Specific examples of the general formula (IX) are shown below. Tetramethyltitanium, Tetrabenziltitanium, Tetraethyltitanium. Tetraphenyltitanium, Tetrame.
- M 2 is shows the periodic table 8-1 0 transition metal of group, in particular iron, cobalt Bok, nickel, palladium, platinum And two of them. Radium is preferred.
- L 1 and L 2 each represent a ligand having a coordination bond
- X 1 and Y 1 each represent a ligand having a covalent bond or an ionic bond.
- X 1 and Y 1 as described above, specifically, a hydrogen atom, a halogen atom, and a
- 20 preferably 1 to 10 hydrocarbon groups, 1 to 20 carbon atoms, preferably 110 alkoxy groups, amino groups, 120 carbon atoms, preferably 1 to 1 carbon atoms
- a phosphorus-containing hydrocarbon group eg, diphenylphosphine group
- L 1 L 2 include triphenylphosphine; acetonitrinole; benzonitrile; 12-bisdiphenylphosphinoethane; 13-bisdiphenylphosphinoprone; 1 1 '— bisdiphenylphosphinophenic acid; cyclooctagen; pyridine; bistrimethylsilyl Luminobis trimethylsilyliminophosphorane and the like can be mentioned.
- the above-mentioned 1 , L 2 , X 1 and Y 1 may be bonded to each other to form a ring structure.
- transition metal compounds of Groups 8 to 10 of the periodic table represented by the general formula (X) those having a dimine compound as a ligand are preferable, and such compounds are preferable.
- R 18 and R 21 are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic group having a hydrocarbon group on a ring having 7 to 20 carbon atoms
- R 19 and R 2fl independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
- R 19 and R 2 ° may be bonded to each other to form a ring
- X and Y each independently represent Represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
- M 2 represents a transition metal belonging to Groups 8 to 10 of the periodic table.
- a linear or branched carbon group having 1 to 20 carbon atoms is branched.
- Alkyl groups or cycloalkyl groups having 3 to 20 carbon atoms such as methyl, ethyl, ⁇ -propyl, isopropyl Pill, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclo Examples include a hexyl group and a cyclooctyl group.
- An appropriate substitution difference such as a lower alkyl group may be introduced on the ring of the cycloalkyl group. Also the total carbon number?
- the aromatic group having a hydrocarbon group on a ring of from 20 to 20 include a linear, branched or cyclic group having 1 to 10 carbon atoms on an aromatic ring such as a phenyl group or a naphthyl group. And a group into which one or more alkyl groups have been introduced.
- R 18 and R 21 an aromatic group having a hydrocarbon group on the ring is preferable, and a 2,6-diisopropylphenyl group is particularly preferable.
- R 18 and R 21 may be the same or different.
- Examples of the hydrocarbon group having 1 to 20 carbon atoms in R 19 and R 2 ° include, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, and a carbon group having 3 to 2 carbon atoms. 0 cycloalkyl group, 6 to 20 carbon atom aryl group, carbon number? To 20 aralkyl groups.
- a linear or branched alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms those having 1 to 20 carbon atoms out of R 18 and R 21 can be used.
- the same as those exemplified in the description of the aliphatic hydrocarbon group can be given.
- Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a silyl group, a naphthyl group, and a methylnaphthyl group. Examples include a benzyl group and a phenyl group.
- R 19 and R 2 ° may be the same or different. Further, they may combine with each other to form a ring.
- hydrocarbon group having 1 to 20 carbon atoms in X and Y The hydrocarbon group having 1 to 20 carbon atoms at R 19 and R 2 ° is as described above.
- X and Y a methyl group is particularly preferable.
- X and Y may be the same or different.
- Examples of the complex compound represented by the general formula (XVIII) include a compound represented by the following formula.
- transition metal compound represented by the general formula ( ⁇ ) include dibromobistriphenylphosphine nickel, dichlorobistriphenylphosphine nickel, dibromodiacetonitrile nickel, dibromodibenzonitrino nickel, dibromo 1 2 — Bisdiphenylphosphinoethane Nickel, Dibromo (13 — Bisdiphenylphosphinopro) Nickel, Dibromo (11 ′ —Diphenylbisphosphinophene) Nickel, Dimethylbisdiphenylphosphine Nickel, Dimethyl (12) — Bisdiphenylphosphinoethane) Nickel, methyl (12—Bisdiphenylphosphinoethane) Nickel tetrafluoroborate, (2—Diphenylphosphino-1- 1—Phenylethyleneoxy) ) Phenylpyridin nickel, dichlorobistriphenylphosphine.
- a cation-like complex such as tetrafluoroborate tetralate is preferably used.
- one of the complex compounds may be used, or two or more of them may be used in combination.
- (A) reacts with an oxygen-containing compound and / or (a) transition metal compound Among these, compounds that can form an ionic complex are preferred. (Ii) Oxygen-containing compounds.
- R 22 to R 28 each represent an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups. Groups, various pentyl groups: various hexyl groups, various heptyl groups, various octyl groups.
- R 22 to R 26 may be the same or different, and R 27 and R 28 may be the same or different.
- Y 2 to Y 6 each represent a Group 13 element of the Periodic Table, specifically ⁇ , A 1, G a, In and T 1, of which ⁇ and A 1 are preferred It is.
- Y 2 to Y 4 may be the same or different, and ⁇ 5 and ⁇ 8 may be the same or different.
- a to d are 0 to (A + b) and (c + d) are each 1 or more. a to d are preferably in the range of 1 to 20 respectively, and in particular,
- a range of 1 to 5 is preferred.
- Alkyl aluminoxane is preferable as the oxygen-containing compound used as such a catalyst component.
- Specific preferred examples include methylaluminoxane and isobutylaluminoxane.
- Examples of the compound capable of reacting with the transition metal compound to form an ionic complex include a coordination complex compound comprising an anion having a plurality of groups bonded to a metal and a cation, or a Lewis acid.
- a coordination complex compound comprising an anion having a plurality of groups bonded to a metal and a cation, or a Lewis acid.
- a compound represented by the following general formula (XXI) or (XXII) is preferably used. can do.
- L 4 is described below M 5, R 28 R 39 M 6 or R 31 3 C, L 3 5 Lewis base, M 3 and M respectively Periodic Table metal selected from group-1 group 5, M metals 5 selected from group 1 and group 8 to group 1 group 2 of the periodic table, M 6 is a metal selected groups 8 to 1 0 group or al of the periodic table, X 2 to X n are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, Arylalkyl group, substituted alkyl group, organic metalloid group or halogen atom Indicates a child.
- R 2 S and R 3 ° each represent a cyclopentagenenyl group, a substituted cyclopenta.tagenyl group, an indenyl group or a fluorenyl group, and R 31 represents an alkyl group.
- m is the valence of M 3 and M 4 and is an integer of 1 to 7
- n is an integer of 2 to 8
- g is the valence of L 3 -H and L 4 and is an integer of 1 to 7
- h is an integer of 1 or more
- I h X g (n-m).
- M 3 and M 4 B A 1, S i, P, A s, S b each atom such as, in the specific example of M 4 A g, C u, N a,
- Each atom such as L i and specific examples of M 5 include each atom such as Fe, Co, and Ni.
- X 2 ⁇ ⁇ for example, Jimechirua Mi cyano group as a Jiarukirua Mi amino group, such as Jechirua Mi amino group, an alkoxy group and to main butoxy group, e butoxy group, .eta.
- Bed Alkoxy groups such as phenyl, 2,6-dimethylphenoxy, naphthyloxy, and other alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, and ⁇ -propyl.
- a plurality of groups and Anion bound to a metal specifically, B (C 6 F 5 A - , B (C 6 HF 4) 4 ", B (C ⁇ ⁇ 2 F 3) 4 ⁇ , B (C 6 H 3 F 2 ) 4- , B (C 6 H 4 F) r, B (C ⁇ CF 3 F 4) 4-, B (C 8 H 5 ), PF, P (C 6 F 5 ) 6 1, A 1 (C 6 HF 4 ) 4 _, etc.
- the metal cations are C p 2 Fe +, (M e C p) 2 Fe +, (t B u C p) 2 F e + , (M e 2 C p) 2 F e + , (M e 3 C p) 2 F e + , (M e 4 C p) 2 F e +, (M e 5 C p) 2 F e +, a g +, N a +, L i + and the like, also as the other cation, pyridinium Jiniu ⁇ , 2., 4 - dinitrate Russia - N, N-GETS Thianilinium, diphenylammonium, p-dichloroaniline, 2,5—dichloroaniline, p—dinitroN, N-dimethylanilinium, quinolium, N, N —Jim Chillaniline, N, N— Nitrogen-containing compounds such as getylanilinium, triphenylcarbenyl, tri (4-
- the following compounds can be used particularly preferably.
- the compound represented by the general formula (XXI) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraborate, trimethylammonium tetrabutylborate, and tetrakisammonium (Pentafluorophenyl) triethylammonium borate, tetrakis (pentafluor.
- the compounds of the general formula (XXI I) include, for example, tetraphenyl borate ferrocene, tetrax (pentafluorophenyl) borate dimethyl ferrosenium, and tetrakis (pentafluorophenyl) borate Furosenium, tetrax (pentafluorophenyl) decamethyl thiocyanate, botanic acid tetrakis (pentafluorophenyl) acetyl folate mouth mouth, tetrakis (pentafluorophenyl) holmifluorosenium borate, tetrakis ( Pennofluorophenyl) cyanoborate borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate, trityl tetrabutyl borate, trityl tetraetra
- an organometallic compound in the catalyst used in the method of the present invention, (C) an organometallic compound can be used, if necessary, together with the components (A) and (B).
- the organometallic compound as the component (C) is a compound represented by the following general formula ( ⁇ ).
- R 32 is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, Represents an aryloxy group having 6 to 30 carbon atoms, a thioalkoxy group having 6 to 30 carbon atoms, a thioaryloxy group, an amino group, an amide group, or a carboxyl group having 6 to 30 carbon atoms; each R 32 may be independently identical or different from each other, respectively. the R 32 in, respectively it binds optionally may form a ring structure.
- X is 1 4
- Y represents an element of Group 16;
- Z represents a metal element of Groups 2 to 13.
- R 33 represents a hydrocarbon group;
- m represents a metal element of Z A valence is an integer, and
- n is an integer from 1 to (m-1).
- R32 is an alkyl group having 2 or more carbon atoms.
- R 32 is all phenyl
- X is carbon
- Y is oxygen
- Z is aluminum
- n 1
- R 33 is an isobutyl group.
- the component (C) can be produced by any method as long as it has a structure represented by the above general formula.
- R 32 ) 3 wherein all of three R 32 are hydrocarbon groups having 1 or more carbon atoms, (3) all of three R 32 in (R 28 ) 3 have 6 to 30 carbon atoms
- An aromatic hydrocarbon group preferably a phenyl group
- R 33 is an alkyl group having 2 or more carbon atoms are preferably used, and specifically, those in which all R 32 are phenyl groups and R 33 is an isobutyl group are preferred. . That is, the reaction product of triphenylmethyl alcohol and triisobutylaluminum is most I can give it a favor.
- the reaction temperature is between 180 ° C and 300 ° C, preferably —10 ° C and 50 ° C, and the reaction time is between 0.1 minutes and 50 hours, preferably between 0.1 minutes and 3 hours. It is.
- the solvent used in the reaction is not limited, but the solvent used in the polymerization is preferably used.
- the compound (C 1) or the like (C 2) shown below as the component (C) may be directly used in the case of catalyst synthesis or polymerization. May be thrown. That is, in this case, as the catalyst component, (A) the transition metal compound, (B) a compound capable of reacting with the oxygen-containing compound and / or the transition metal compound to form an ionizable complex, (C 1), ( C 2), and an alkylating agent used as needed.
- (C 1) is at least one selected from compounds represented by the general formula (R 32 ) 3 —C—OR 32 , R 32 —C 0 —R 32 or R 32 —CO—0 R 32 And (C 2) — is a compound represented by the general formula Z (R 33 ) m .
- R 32 is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, Represents an aryloxy group having 6 to 30 carbon atoms, a thioalkoxy group having 1 to 30 carbon atoms, a thioallyloxy group having 6 to 30 carbon atoms, an amino group, an amide group, or a carboxyl group.
- each R 32 may be the same or different from each other.
- Each R 32 may be bonded as needed to form a ring structure.
- Z represents a Group 2 to Group 13 metal element
- m represents an integer of the valence of the metal element Z
- R 33 represents a hydrocarbon group.
- (C 1) includes at least one selected from alcohols, ethers, aldehydes, ketones, carboxylic acids, and carboxylic esters, preferably alcohols.
- (C 2) include an aluminum compound.
- those (R 32) 3 of the three R 32 in one at least is a aromatic hydrocarbon group having 6 to 3 0 carbon atoms
- (2) (R 32 ) all three R 32 in the 3 1 or more carbon atoms of a hydrocarbon group der shall, (3) (R 32) 3 all aromatic 6-3 0 carbon atoms for R 32 in 3 hydrocarbon group, things like properly a phenyl group
- R 33 is used properly preferred are those wherein alkyl group having 2 or more carbon atoms, more specifically, as the (C 1), Application Benefits Phenylmethyl alcohol may be mentioned, and (C 2) may most preferably be triisobutylaluminum.
- an alkylating agent can be used if necessary.
- alkylating agents There are various alkylating agents.
- R 34 and R 35 each represent an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and X represents a hydrogen atom or a halogen atom. Also, m is 0 ⁇ m ⁇ 3, preferably 2 or 3, most preferably 3, and n is On, preferably 0 or 1.
- alkyl group-containing aluminum compounds particularly trialkyl aluminum dialkyl aluminum compounds
- Trialkylaluminum dimethylaluminum chloride, getylaluminum chloride, di-n-propylaluminum chloride, diisopole, pillaluminum chloride, di-n-butylaluminum chloride , Diisobutylaluminum chloride, dialkylaluminum alcohol such as dit-butylaluminum chloride, dimethylaluminum methoxide, dimethylaluminum ethoxide, etc.
- dialkyl magnesium dimethylmagnesium, dimethylmagnesium, dialkylmagnesium dimethylmagnesium, dimethylmagnesium, etc. give dialkyl zinc such as zinc be able to.
- the catalyst can be prepared by the following method.
- each component is not particularly limited, and the components can be contacted in the following order.
- the order of contact with the alkylating agent does not matter. That is, the component (A) may be used after being brought into contact with an alkylating agent, the component (B) may be used after being brought into contact with an alkylating agent, and the component (C) may have the general formula (X XIII )) May be used after contacting the organometallic compound represented by the above with the alkylating agent. Further, an alkylating agent of the components (A), (B), and (C) is brought into contact with the component in advance, and then the organometallic compound represented by the general formula (XXIII) of the component (C) is added. The contact method may be used.
- the molar ratio of the component (A) to the component (B) is usually 1 mole of the component (A), and the component (B) is more powerful.
- the molar ratio of aluminum atoms is selected from the range of 1 to 100,000, preferably from 10 to: L, 000.
- the component (B) reacts with the transition metal compound.
- the mole ratio of the boron atom is usually 0.5 to 10, preferably 1 mole of the component (A) and 1 mole of the component (B) when the component (B) is a boron compound. Is selected in the range of 0.8 to 5.
- the organometallic compound represented by the general formula (XXIII) of the component (C) is used in an amount of 1 mole of the component (A) and, when the component (C) is an aluminum compound, an aluminum atom.
- the molar ratio is selected from the range of 0.5 to 1000, preferably 1 to 100.
- the alkylating agent is an aluminum compound with respect to 1 mole of the component (A)
- the molar ratio of the aluminum atom is 0 to 1 mol.
- the molar ratio of the component (C1): component (C2) 1: 0.1 to 10 is preferable. Or 1: 0.5 to 2, more preferably 1: 0.8 to 1.2.
- the component (C 2) is used in an amount of 0.5 to 1 mole of the component (A) with respect to 1 mole of the component (A) when the component (C 2) is an aluminum compound.
- 1, 000 preferably in the range of 1 to 100.
- the amount of the alkylating agent is the same as described above.
- the contact of the catalyst components can be carried out in an inert gas such as nitrogen at a temperature lower than the polymerization temperature, but may be carried out within a temperature range of -30 to 200 ° C. No.
- the above-mentioned metal compound is allowed to act on the functional group-containing vinyl compound to mask the functional group.
- the functional group-containing vinyl compound and the metal compound may be brought into contact with each other, and there are no particular restrictions on the order of addition, the presence or absence of a solvent, the contact temperature and the contact time, and other conditions under which they act.
- As the proportion of the metal compound and the functional group-containing vinyl compounds, to the functional group-containing vinyl compound to 1 mole as long amount is 1 mole or more metal compounds, so that the favored by rather a 1-1 0 9 mole Is chosen.
- a treating solution containing a metal compound may be used as it is, or a masked functional group may be used from the treating solution.
- the vinyl compound contained may be isolated and used.
- a functional group-containing vinyl compound with a metal compound is considered to cause the metal compound to interact with the functional group and form a vinyl compound containing the metal compound.
- This interaction involves the following three reactions: (1) the reaction of active hydrogen, such as a carboxyl group, a hydroxyl group, or an amino group, with a substituent of a metal compound; (2) the formyl group, a carbonyl group, Reaction of a metal compound or the like with a substituent of a metal compound, (3) coordination of a metal compound to an ether group or a tertiary amino group, and the like are possible, but are not necessarily limited thereto.
- the above reactions (1) to (.3) can be confirmed by measuring a proton nuclear magnetic resonance spectrum (_NMR).
- _NMR proton nuclear magnetic resonance spectrum
- the peak of the active hydrogen derived from the vinyl compound disappears due to the action of the metal compound.
- the functional group-containing vinyl compound masked with the metal compound can be confirmed by observing it with another chemical shift value. It is copolymerized with a styrenic compound in the presence of a catalyst.
- the prepolymerization can be carried out by bringing a small amount of styrene into contact with the catalyst, for example, but the method is not particularly limited and can be carried out by a known method. There is no particular limitation on the styrene used for the prepolymerization, and those described above can be used.
- the pre-polymerization temperature is usually from ⁇ 20 ° C. to 200 ° C., preferably from ⁇ 10 ° C. to 130 ° C. In the pre-polymerization, inert solvents, aliphatic hydrocarbons, aromatic hydrocarbons, monomers and the like can be used as the solvent.
- the method of copolymerizing the styrene compound and the functional group-containing vinyl compound is not particularly limited, and may be any method such as a slurry polymerization method, a solution polymerization method, a gas phase polymerization method, a bulk polymerization method, and a suspension polymerization method.
- the polymerization method can be adopted.
- a method of putting the components of the catalyst and the monomers in a completely arbitrary order into the polymerization site may be used.
- Preferred forms include the compounds represented by the general formula (XXI II) among the above components (C), or components other than the components (C 1) and (C 2), that is, the components (A),
- the alkylating agent of the component (B) and the component (C) is preliminarily mixed, while the monomer and the compound represented by the general formula ( ⁇ ⁇ ) of the component (C) or the monomer and ( C1) component and (C2) component are separately mixed, After that, a method of performing polymerization by mixing these two immediately before polymerization can be mentioned.
- the solvent may be benzene, toluene, xylene, n-hexane, n-heptane, cyclohexane, methylene chloride, chloroform, 1,2- Examples include hydrocarbons such as dichloroethane and black benzene, and halogenated hydrocarbons. These may be used alone or in combination of two or more. Further, the monomers used for polymerization may be used depending on the type.
- the pressure is usually selected from the range of normal pressure to 2000 kg kgm G.
- the reaction temperature is usually in the range of 150 to 250 ° C.
- Methods for controlling the molecular weight of the polymer include the type and amount of each catalyst component, the selection of the polymerization temperature, and the introduction of hydrogen.
- the metal compound masking the functional group can be eliminated, and the functional group can be regenerated. Thereby, a desired random copolymer is obtained.
- the elimination reaction of this metal compound is represented by the following reaction formulas (4) and (5).
- an aqueous solution in an aqueous solution, it includes aqueous solutions containing water and acid or base, as the acid, for example HC 1, HB r, HN 03 , and H 2 S 0 4, H a P 0 4,
- the acid for example, HC 1, HB r, HN 03 , and H 2 S 0 4, H a P 0 4,
- the ⁇ group for example, ammonia, sodium hydroxide, sodium methoxide and the like can be used.
- alcohols having 1 to 10 carbon atoms such as methanol, ethanol, isoprono, ethanol, and t-butanol, are preferred.
- the temperature is usually between ⁇ 100 and 300 ° C., preferably between 0 and 300 ° C. ° C, and the pressure is usually in the range of normal pressure to 200 MPa.G.
- a copolymer of a functional group-containing vinyl compound and a styrene-based compound, wherein the repeating unit derived from the styrene-based compound has a syndiotactic structure The copolymer can be produced efficiently.
- the styrenic random copolymer having a functional group-containing syndiotactic structure of the present invention has the following general formula (a):
- D is - OR 1, - COR 1, - C 02 R 1, one CN, - NR 1 R 2, - SR 1 or - substituent containing a PR 1 R, R 1 and R 2 are each A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylsilyl group having 3 to 20 carbon atoms, and R 'is a linear or branched having 1 to 20 carbon atoms
- each D may be the same or different, n is an integer of 1 to 5, m is an integer of 0 to 4, provided that n + m ⁇ 5.
- the syndiotactic structure is mainly a stereochemical structure, that is, a phenyl group or a substituted phenyl group, which is a side chain to a main chain formed from carbon-carbon bonds, is alternately formed. It has a three-dimensional structure located in the opposite direction. It is quantified by nuclear magnetic resonance ( 13C NMR) using isotope carbon. Tacticity measured by 13 C-NMR method is based on the ratio of the presence of a plurality of consecutive structural units, such as diat, diat, triad, and total of five.
- the styrene-based copolymer having a syndiotactic structure referred to in the present invention is usually 75% by weight in the chain of the styrene-based repeating units.
- the content of the unit (b) is selected in the range of 0.01 to 50 mol%.
- the content is less than 0.01% by weight, the effect of improving the physical properties such as the adhesiveness of the copolymer is not sufficiently exhibited, while when it exceeds 50 mol%, the heat resistance of the copolymer decreases.
- the preferred content of this (b) unit is in the range of 0: 5 to 30 mol%, especially in the range of 1 to 20 mol%. Is preferred.
- the styrenic random copolymer having a functional group-containing syndiotactic structure of the present invention has excellent physical properties such as adhesiveness to various adhesives and compatibility with various rubbers. It is suitably used as a body in various applications.
- the styrene random copolymer having a functional group-containing syndiotactic structure of the present invention can be efficiently produced by using the above-mentioned production method of the present invention.
- Various molded articles can be obtained by molding the styrene-based copolymer of the present invention, but the styrene-based copolymer is generally used as long as the object of the present invention is not hindered.
- Thermoplastic resin, rubber Add rubber-like elastic material, antioxidant, inorganic filler, cross-linking agent, cross-linking aid, nucleating agent, plasticizer, compatibilizer, coloring agent, antistatic agent, etc. to use as a composition be able to.
- thermoplastic resin examples include styrene-based polymers such as polystyrene having an atactic structure, polystyrene having an isotactic structure, AS resin and ABS resin, and polyethylene terephthalate.
- Polyethers such as polyester, polycarbonate, polyphenylene ether, polysulfone, and polyethersulfone; condensation polymers such as polyamide, polyphenylene sulfide (PPS), and polyoxymethylene; polyacrylic acid; Acrylic polymers such as polyacrylic acid esters and polymethylmethacrylate, polyethylene, polypropylene, polybutene, poly4-methylpentene-1, ethylene-propylene copolymer, etc.
- a variety of rubbery elastic bodies can be used.
- natural rubber polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acryl rubber, urethane Rubber, silicone rubber, ebichlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP) ), Styrene-isoprene-styrene Styrene block copolymer (SIS), hydrogenated st
- EPR ethylene propylene diene rubber
- EPDM ethylene propylene diene rubber
- ABS butadiene-acrylonitrile propylene-styrene-core-shell rubber
- MCS methyl methacrylate
- BSS Methyl methacrylate styrene-core shell rubber
- MAS Methyl methacrylate styrene-core shell rubber
- MABS alkyl acrylate-butadiene acrylic acid
- Core-shell type granules such as siloxane core core rubber (AABS), butadiene-styrene-core-shell rubber (SBR), siloxane-containing core-shell rubber such as methyl methacrylate, butyl acrylate and siloxane.
- SBR SBR
- SBS SEB
- SEBS SEBS
- SER SEP.SIS
- SEPS core shell rubber
- rubber modified from these, and the like are particularly preferably used.
- modified rubbery elastomer examples include styrene-butyl acrylate copolymer rubber, styrene-butadiene block copolymer (SBR), and hydrogenated styrene-butadiene block copolymer.
- SEB styrene-butadiene-styrene block copolymer
- SEBS hydrogenated styrene-butadiene-styrene block copolymer
- SEBS styrene-isoprene block copolymer
- SIR hydrogenated Styrene-isoprene block copolymer
- SEP hydrogenated Styrene-isoprene block copolymer
- Styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene copolymer Modifications of polar copolymers such as random copolymers, styrene-ethylene-propylene random copolymers, styrene-ethylene-butylene random copolymers, ethylene propylene rubber (EPR), and ethylene propylene rubber (EPDM) Rubber modified by an agent.
- polar copolymers such as random copolymers, styrene-ethylene-propylene random copolymers, styrene-ethylene-butylene random copolymers, ethylene propylene rubber (EPR), and ethylene propylene rubber (EPDM) Rubber modified by an agent.
- rubbers obtained by modifying SEB, SEBS, SEP, SEPS, EPR, and EPDM are preferably used.
- Specific examples include maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, maleic anhydride-modified EPR, maleic anhydride-modified EPDM, epoxy-modified SEBS, and epoxy-modified SEPS.
- These rubber-like elastic bodies may be used alone or in combination of two or more.
- antioxidants such as tris (2,4-di-t-butylphenyl) phosphite and tris (mono- and di-nonylphenyl) phosphites.
- a phosphorus antioxidant such as phosphite diphosphite and a phenolic antioxidant are preferred.
- the general formula for diphosphite is
- R36-0-P C .: P-0-R37
- R 3 6 and R 3 7 each independently represent an alkyl group having a carbon number of 1-2 0, an a cycloalkyl group or ⁇ Li Ichiru group having a carbon number of 6 to 2 0 carbon atoms 3-2 0 )
- phosphorus compound represented by the above general formula examples include distearylpentaerythritol diphosphite; dioctyl penyl erythritol diphosphite; diphenylpentaerythritol diphosphite.
- phenolic antioxidants can be used, and specific examples thereof include 2,6-di-t-butyl_4-methyl phenol; 2,6 —Diphenylenol 4 —Methoxy phenol; 2,2′—Methylene bis (6—t—butyl-4.—Methyl phenol); 2,2′—Methylene bis (6—t—Butyl 4-methyl phenol) 2,2'-Methylenebis [4-methyl-6- ( ⁇ -methylcyclohexyl) phenol]; 1,1—Bis (5-t-butyl-4-hydroxy-1--2-methyl phenyl) 2,2'-Methylenebis (4-methylhexylphenol); 2,2'-Methylenebis (4-methyl-16-nonylphenol); 1,1, 3 — tris — (5 — t — butyl — 4 — hydroxy 2,2-Methylphenyl) butane; 2,2-Bis (5—t—Ptinole 4—Hydroxy-2—Methylpheny
- an amine antioxidant, a sulfur antioxidant and the like can be used alone or in combination.
- the above antioxidant is usually used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the styrene-based copolymer of the present invention. If the compounding ratio of the antioxidant is less than 0.001 part by weight, the molecular weight is significantly reduced, while if it exceeds 1 part by weight, the mechanical strength is affected. Not preferred.
- the inorganic filler may be in the form of fibrous or granular or powder.
- fibrous inorganic filler include glass fiber, carbon fiber, and alumina fiber.
- talc, carbon black, graphite, titanium dioxide, silica, myriki, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate are examples of granular and powdery inorganic fillers.
- the molded article made of the styrenic copolymer of the present invention has a particular shape.
- the material is not limited, and may be, for example, a sheet, a film, a fiber, a nonwoven fabric, a container, an injection molded product, or a blow molded product.
- the following method can be mentioned as a preferable method. That is, first, the styrene-based copolymer or a composition to which the above-mentioned various components are added as necessary is preformed to obtain a preformed body (film, sheet, or container) for heat treatment. In this molding, it is only necessary to extrude the above-mentioned molding material which has been heated and melted to obtain a predetermined shape. Can be molded.
- the extruder used here may be either a single-screw extruder or a twin-screw extruder, or may be one with or without a vent.
- Extrusion conditions are not particularly limited and may be appropriately selected depending on various situations.
- the temperature at the time of melting is selected in a range of 50 ° C. higher than the melting point of the molding material to the decomposition temperature, and shearing is performed.
- the stress and 5 xl 0 7 Jz NZ cm 2 or less it is possible to obtain a small heat treatment for the preform of surface roughness.
- the obtained preformed body for heat treatment is cooled and solidified.
- various refrigerants such as gas, liquid, and metal can be used.
- a metal roll or the like is used to form the preform for heat treatment by sheet molding, it is possible to prevent thickness unevenness and ripples by using a method such as air knife, air chamber, touch roll, or electrostatic application. It is effective for
- the temperature for cooling and solidification is usually in the range of 0 ° C to 30 ° C higher than the glass transition temperature of the preform for heat treatment, preferably in the range of ⁇ 0 ° C lower than the glass transition temperature to the glass transition temperature or lower. Temperature range.
- the cooling rate is not particularly limited, It is appropriately selected in the range of 200 to 3 ° CZ seconds, preferably in the range of 200 to 10 seconds.
- the preform for heat treatment may be of various shapes, but is usually formed of a sheet, film, container (tube, tray, etc.) having a thickness of 5 mm or less, preferably 3 mm or less. It is. If the thickness of the preform for heat treatment before heat treatment is more than 5 mm, crystallization may occur inside the preform for heat treatment at the time of molding, and the preform may become cloudy.
- the crystallinity of the preform for heat treatment is not more than 20%, preferably not more than 15%. Here, if the crystallinity of the preform for heat treatment exceeds 20%, the transparency of the styrene-based copolymer molded article after heat treatment is not sufficient.
- the molded article may be prepared, for example, by heating the preformed article for thermal treatment comprising the styrenic union of the present invention at a temperature of 140 to 180 ° C, preferably 150 to 170 ° C. It can be obtained by performing a heat treatment.
- the heat treatment temperature is lower than 140 ° C., the heat resistance may not be sufficient and the film may become cloudy, and if it exceeds 180 ° C., the transparency may be insufficient.
- the time for this heat treatment is usually 1 second to 30 minutes, preferably 1 second to 10 minutes.
- the heating rate at this time is desirably set to a predetermined heat treatment temperature by rapidly raising the temperature of the preform for heat treatment, and from that point of view, 30 ° C or more, preferably 50 ° CZ More than a minute. If the heating rate is lower than 30 V / min, heat treatment is performed at a temperature lower than the predetermined heat treatment temperature, and the transparency of the styrene-based copolymer molded article may be impaired. Further, the heating method of the heat treatment is not particularly limited, but for example, it may be brought into contact with a heat medium such as a gas, a liquid, or a metal at 120 to 200 ° C.
- a heat medium such as a gas, a liquid, or a metal at 120 to 200 ° C.
- the styrene-based copolymer molded body that has been heat-treated under the above conditions may be heat-treated again if necessary.
- the heat treatment conditions at this time were glass rolling. It is appropriate that the temperature is higher than the transfer temperature, lower than the melting point, and the heat treatment time is 1 second or longer.
- the styrene-based copolymer molded article that has been heat-treated again cannot improve the crystallinity, but can increase the heat distortion temperature without impairing the transparency.
- the melting point and adhesiveness of the copolymer obtained in each example were determined according to the following methods.
- the sample is held at 50 ° C for 1 minute using “DSC 7” manufactured by Parkin Elmer, and then heated to 300 ° C in 20 minutes. Then, after holding at 300 ° C for 5 minutes, cool down to 50 ° C in 20 ° CZ minutes ⁇ After holding at 50 ° C for 1 minute, 20 ° CZ to 300 ° C To raise the temperature.
- the temperature of the endothermic peak in the second heating process in this operation was defined as the melting point.
- the evaluation of the adhesiveness is determined based on whether or not the cured adhesive layer can be pulled off from the sheet. That is, if the adhesive remains on the sheet surface or the adhesive layer does not peel off when the sheet is pulled, the adhesiveness is determined to be good (0). When the adhesive layer was completely separated from the surface of the substrate, it was judged that the adhesiveness was poor (X). Was.
- Example 1 3,4-di-tert-butyl 4-monoaminostyrene was replaced with (4-vinyl phenyl) -1,1,1-diphenyl methanol 9.04 g (3,1.6 mmol) instead of 3,4-di-tert-butyl 4-monoaminostyrene. Except for adding 7.4 g (31.6 millimoles), the same procedure as in Example 1 was performed to obtain 12 g of a polymer.
- Table 1 shows the properties of the obtained polymer and the content of one unit of the comonomer.
- Example 1 without using triisobutylaluminum,
- a toluene solution of (4-vinylvinyl) -1,1,1-diphenylmethanol at a concentration of 1 mol / liter was prepared, and a styrene and titanium mixed catalyst was added in the same manner as in Example 1 to carry out a polymerization reaction. At that time, only traces of polymer were obtained.
- the polymerization was stopped using methanol, and the obtained polymer was washed with methanol. After air drying the polymer, vacuum drying was performed at 200 ° C. for 2 hours. The amount of the obtained polymer was 20 g.
- Table 1 shows the properties of the obtained polymer and the content of one unit of the comonomer.
- Table 1 shows the properties of the obtained polymer and the content of the comonomer unit.
- Table 1 shows the properties of the obtained polymer.
- a random, block or graft copolymer particularly preferably a random copolymer, of a functional group-containing vinyl compound and a styrene compound, wherein the repeating unit derived from the styrene compound is used. It is possible to efficiently produce a functional group-containing styrenic copolymer having a syndiotactic structure.
- the styrenic random copolymer having a functional group-containing syndiotactic structure of the present invention is excellent in physical properties such as adhesiveness to various adhesives and compatibility with various rubbers. Therefore, it is suitably used for various purposes.
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- 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)
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/926,788 US6486272B1 (en) | 2000-04-19 | 2001-04-18 | Process for producing functional styrene copolymer |
EP01921867A EP1219649A4 (en) | 2000-04-19 | 2001-04-18 | METHOD FOR PRODUCING FUNCTIONAL STYROLCOPOLYMER AND FUNCTIONAL STYROLCOPOLYMER |
KR1020017015672A KR20020019065A (ko) | 2000-04-19 | 2001-04-18 | 작용기-함유 스티렌계 공중합체의 제조방법 및작용기-함유 스티렌계 공중합체 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000117942 | 2000-04-19 | ||
JP2000-117942 | 2000-04-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001079312A1 true WO2001079312A1 (fr) | 2001-10-25 |
Family
ID=18629177
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/003302 WO2001079312A1 (fr) | 2000-04-19 | 2001-04-18 | Copolymeres fonctionnels de styrene et leur procede de production |
Country Status (5)
Country | Link |
---|---|
US (1) | US6486272B1 (ja) |
EP (1) | EP1219649A4 (ja) |
KR (1) | KR20020019065A (ja) |
TW (1) | TW538054B (ja) |
WO (1) | WO2001079312A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007100076A (ja) * | 2005-09-06 | 2007-04-19 | Nippon Soda Co Ltd | 活性水素を含有するモノマーを用いた重合体の製造方法 |
JP2017526775A (ja) * | 2014-08-14 | 2017-09-14 | 中国科学院長春応用化学研究所 | 機能化高シンジオタクチックポリスチレン及びその製造方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5982277B2 (ja) * | 2012-12-21 | 2016-08-31 | 群栄化学工業株式会社 | 硬化性樹脂の製造方法 |
KR20150046996A (ko) * | 2013-10-23 | 2015-05-04 | 동우 화인켐 주식회사 | 접착제 조성물 및 이를 이용한 복합 편광판 |
CN105330779B (zh) * | 2014-08-14 | 2018-02-13 | 中国科学院长春应用化学研究所 | 一种苯乙烯与功能化苯乙烯的高间规共聚物及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0444210A1 (en) * | 1989-09-21 | 1991-09-04 | Idemitsu Kosan Company Limited | Arylstyrene polymer and copolymer and process for preparing the same |
EP0505972A2 (en) * | 1991-03-27 | 1992-09-30 | Idemitsu Kosan Company Limited | Process for producing styrenic copolymer |
EP0505997A2 (en) * | 1991-03-29 | 1992-09-30 | Idemitsu Kosan Company Limited | Process for producing styrenic polymer and copolymer |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5189125A (en) * | 1985-07-29 | 1993-02-23 | Idemitsu Kosan Co., Ltd. | Process for producing syndiotactic styrene copolymer |
US5153282A (en) * | 1987-06-08 | 1992-10-06 | Exxon Chemical Patents Inc. | Preparation of polyolefin incorporating functional groups from masked functional group-containing monomers |
WO1989003401A1 (en) * | 1987-10-08 | 1989-04-20 | Idemitsu Kosan Company Limited | Styrenic polymer and process for its production |
US5247020A (en) * | 1990-01-30 | 1993-09-21 | Idemitsu Kosan Co., Ltd. | Process for producing a styrene polymer composition |
JPH08314146A (ja) * | 1995-05-18 | 1996-11-29 | Konica Corp | シンジオタクチックポリスチレン支持体を用いたレリーフ像形成材料 |
EP0920463A1 (de) * | 1996-08-26 | 1999-06-09 | Basf Aktiengesellschaft | Sternpolymere und verfahren zu deren herstellung |
TW513446B (en) * | 1997-02-21 | 2002-12-11 | Idemitsu Petrochemical Co | Graft copolymer and styrene-based resin composition |
-
2001
- 2001-04-18 US US09/926,788 patent/US6486272B1/en not_active Expired - Fee Related
- 2001-04-18 WO PCT/JP2001/003302 patent/WO2001079312A1/ja not_active Application Discontinuation
- 2001-04-18 EP EP01921867A patent/EP1219649A4/en not_active Withdrawn
- 2001-04-18 KR KR1020017015672A patent/KR20020019065A/ko not_active Application Discontinuation
- 2001-04-19 TW TW090109393A patent/TW538054B/zh active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0444210A1 (en) * | 1989-09-21 | 1991-09-04 | Idemitsu Kosan Company Limited | Arylstyrene polymer and copolymer and process for preparing the same |
EP0505972A2 (en) * | 1991-03-27 | 1992-09-30 | Idemitsu Kosan Company Limited | Process for producing styrenic copolymer |
EP0505997A2 (en) * | 1991-03-29 | 1992-09-30 | Idemitsu Kosan Company Limited | Process for producing styrenic polymer and copolymer |
Non-Patent Citations (1)
Title |
---|
See also references of EP1219649A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007100076A (ja) * | 2005-09-06 | 2007-04-19 | Nippon Soda Co Ltd | 活性水素を含有するモノマーを用いた重合体の製造方法 |
JP2017526775A (ja) * | 2014-08-14 | 2017-09-14 | 中国科学院長春応用化学研究所 | 機能化高シンジオタクチックポリスチレン及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
US6486272B1 (en) | 2002-11-26 |
US20020173605A1 (en) | 2002-11-21 |
KR20020019065A (ko) | 2002-03-09 |
TW538054B (en) | 2003-06-21 |
EP1219649A4 (en) | 2003-07-23 |
EP1219649A1 (en) | 2002-07-03 |
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