WO2015198990A1 - 反応射出成形用配合液およびその製造方法 - Google Patents
反応射出成形用配合液およびその製造方法 Download PDFInfo
- Publication number
- WO2015198990A1 WO2015198990A1 PCT/JP2015/067755 JP2015067755W WO2015198990A1 WO 2015198990 A1 WO2015198990 A1 WO 2015198990A1 JP 2015067755 W JP2015067755 W JP 2015067755W WO 2015198990 A1 WO2015198990 A1 WO 2015198990A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reaction injection
- liquid
- injection molding
- norbornene
- mixing
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
- B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
-
- 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
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/78—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2045/00—Use of polymers of unsaturated cyclic compounds having no unsaturated aliphatic groups in a side-chain, e.g. coumarone-indene resins or derivatives thereof, as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2120/00—Compositions for reaction injection moulding processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
Definitions
- the present invention relates to a reaction injection molding compounded liquid containing a norbornene-based monomer, a method for producing the same, a method for producing a reaction injection molded article using the reaction injection molding compounded liquid, and a reaction injection molded article obtained thereby.
- reaction injection molding in which a reaction liquid containing a norbornene-based monomer and a metathesis polymerization catalyst is injected into a mold and subjected to bulk ring-opening polymerization to produce a resin molded body (reaction injection molded body) made of a norbornene-based resin.
- a method called a method (RIM method) is known.
- Patent Document 1 discloses molding by a bulk ring-opening polymerization of a norbornene-based monomer-containing reaction injection molding compound containing a specific elastomer by the RIM method, regardless of the shape or size of the mold.
- a technique for obtaining a resin molded body with less sink marks on the body surface is disclosed.
- Patent Document 2 discloses that a novel metathesis polymerizable monomer containing a specific amount of exo-dicyclopentadiene is subjected to bulk ring-opening polymerization by the RIM method so that the monomer residual ratio is low and a sufficiently cured cross-linked polymer is obtained.
- a method for producing a resin molded body for obtaining a combined molded product is disclosed.
- Patent Document 2 describes that the storage stability can be improved by adding an ether compound to a reactive solution used in the production of a resin molded body.
- the present inventor examined the inventions disclosed in Patent Documents 1 and 2 with the aim of developing a technology for improving the quality of a resin molded body obtained by the RIM method. If used, the time required for gelation of the reactive liquid mixture obtained by mixing the compounded liquid (hereinafter sometimes referred to as “gel time”) becomes too short, resulting in poor filling of the mold or release. At this time, it became clear that resin residue may be generated on the mold surface, and the quality of the resulting resin molded product may be significantly reduced.
- an object of the present invention is to provide a reaction injection molding compound liquid excellent in storage stability, a production method thereof, and a reaction injection molded article having high quality and excellent strength using the reaction injection molding compound liquid. It is an object to provide a method and a reaction injection molded article obtained thereby.
- the inventor of the present invention has studied by paying attention to the blending components used in preparing the reaction injection molding liquid and the mixing order thereof. As a result, by using a predetermined ether compound and mixing the norbornene-based monomer and the catalyst activator in the presence of the compound, a desired reaction injection molding compound liquid can be obtained, and the above-described problems can be solved.
- the headline and the present invention were completed.
- a reaction injection molding liquid for polymerizing a norbornene monomer under a metathesis polymerization catalyst having tungsten as a central metal comprises a norbornene monomer, an activator for the catalyst, and a formula (1):
- R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- R 5 and R 6 each independently represent 1 to Represents an alkyl group of 6. However, when R 5 and R 6 are methyl groups, at least one of R 1 to R 4 is an alkyl group having 1 to 6 carbon atoms.
- An ether compound represented by A liquid mixture for reaction injection molding obtained by mixing the norbornene-based monomer and the activator in the presence of at least the ether compound [2] A method for producing the reaction injection molding compound liquid according to [1], A method for producing a compounded liquid for reaction injection molding, comprising the step of mixing the norbornene-based monomer and the activator in the presence of at least the ether compound; [3] A step of performing reaction injection molding by bulk polymerization of a reactive liquid mixture obtained by mixing the liquid mixture for reaction injection molding according to [1] and a metathesis polymerization catalyst having tungsten as a central metal in
- reaction injection molding compound liquid having excellent storage stability and a reaction injection molded article having high quality and excellent strength.
- Compound liquid for reaction injection molding comprises (a) a norbornene monomer, (b) an activator, and (c) an ether compound represented by formula (1) described later. contains.
- a reaction injection molded body can be obtained by subjecting the reactive liquid mixture obtained by mixing the compounding liquid for reaction injection molding and a metathesis polymerization catalyst having tungsten as a central metal to bulk polymerization in a mold.
- norbornene-based monomer (a) has the formula (2)
- the norbornene-based monomer (a) include a norbornene-based monomer having no ring condensed with a norbornene ring in the molecule, and a polycyclic norbornene-based monomer having three or more rings.
- the norbornene-based monomer (a) can be used alone or in combination of two or more.
- norbornene-based monomer having no ring condensed with the norbornene ring in the molecule include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5 -Norbornenes having an unsubstituted or alkyl group such as cyclohexyl norbornene and 5-cyclopentyl norbornene; Alkenyl groups such as 5-ethylidene norbornene, 5-vinyl norbornene, 5-propenyl norbornene, 5-cyclohexenyl norbornene and 5-cyclopentenyl norbornene Norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5 Methoxycarbonylnorbornene,
- the polycyclic norbornene monomer having 3 or more rings is a norbornene monomer having in its molecule a norbornene ring and one or more rings condensed with the norbornene ring.
- Specific examples thereof include monomers represented by the following formula (3) or formula (4).
- R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a silicon atom, oxygen And R 8 and R 9 are bonded to each other to form a ring.
- R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a silicon atom, oxygen And R 11 and R 12 or R 13 and R 14 may be bonded to each other to form a ring, and m is 1 or 2.
- Examples of the monomer represented by the formula (3) include dicyclopentadiene, methyldicyclopentadiene, tricyclo [5.2.1.0 2,6 ] dec-8-ene, and tetracyclo [9.2.1.0. 2,10 . 0 3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0 2 , 11 . 0 4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene) and the like.
- Dicyclopentadiene has two stereoisomers, endo-dicyclopentadiene [Formula (5)] and exo-dicyclopentadiene [Formula (6)].
- the simple term dicyclopentadiene refers to endo-dicyclopentadiene.
- the main component of dicyclopentadiene currently available industrially is endo-dicyclopentadiene, and the content of exo-dicyclopentadiene is about 0 to 2% by mass.
- Examples of the monomer represented by the formula (4) include tricyclopentadiene and tetracyclododecene in which m is 1, and hexacycloheptadecenes in which m is 2.
- tetracyclododecenes include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene.
- Tetracyclododecenes having a substituted or alkyl group 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetra Tetracyclododecenes having a double bond outside the ring such as cyclododecene and 8-cyclopentenyltetracyclododecene; tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxy Carbonyltetracyclododecene, 8-methyl-8 Methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclod
- a tetracyclododecene having a substituent containing a halogen atom such as 8-chlorotetracyclododecene
- a tetracyclododecene having a substituent containing a silicon atom such as 8-trimethoxysilyltetracyclododecene
- hexacycloheptadecenes include hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene and the like.
- Hexacycloheptadecenes having a substituted or alkyl group 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexa Hexacycloheptadecenes having a double bond outside the ring such as cycloheptadecene, 12-cyclopentenylhexacycloheptadecene, etc .; Heterocyclic rings such as 12-phenylhexacycloheptadecene Sacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene,
- norbornene-based monomers tricyclic or higher polycyclic norbornene-based monomers are preferable from the viewpoint of obtaining resin molded products that are easily available, excellent in reactivity, and excellent in heat resistance.
- a cyclic or pentacyclic norbornene-based monomer is more preferable.
- a crosslinkable norbornene monomer having two or more reactive double bonds such as a symmetric cyclopentadiene trimer
- a norbornene-based monomer that provides a ring-opening polymer having a heavy bond and another norbornene-based monomer (a norbornene-based monomer that provides a ring-opening polymer having no crosslinkable double bond).
- the use ratio of the crosslinkable norbornene monomer is preferably 2 to 30% by mass in the total norbornene monomer (a).
- a monomer that can be ring-opening copolymerized with a norbornene-based monomer may be used as long as the object of the present invention is not impaired.
- examples of such a monomer include monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclododecene.
- the proportion of such a monomer used is preferably 10 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass of the norbornene monomer (a).
- activator (b) is also called a cocatalyst and is added for the purpose of increasing the polymerization activity of the metathesis polymerization catalyst. It is.
- the activator (b) is not particularly limited as long as it enhances the polymerization activity of the metathesis polymerization catalyst having tungsten as a central metal mixed with the compounded liquid of the present invention.
- Examples of the activator (b) include organometallic compounds of metals in Groups 11 to 14 of the periodic table.
- alkylaluminum compounds such as triethylaluminum, triisobutylaluminum, trimethylaluminum, tributylaluminum, trihexylaluminum, and trioctylaluminum; ethylaluminum dichloride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, isobutyl
- alkylaluminum halide compounds such as aluminum dichloride and dioctylaluminum iodide
- alkylaluminum alkoxide compounds such as diethylaluminum ethoxide
- organotin compounds such as tetrabutyltin
- organozinc compounds such as diethylzinc.
- an alkylaluminum compound and an alkylaluminum halide compound are preferable, and more specifically, triethylaluminum, trioctylaluminum, diethylaluminum chloride, and dioctylaluminum iodide are more preferable.
- An activator (b) can be used individually by 1 type or in mixture of 2 or more types.
- the amount of the activator (b) used is not particularly limited, but from the viewpoint of increasing the polymerization activity of the metathesis polymerization catalyst and improving the reaction efficiency, the activator (b) may be blended in a predetermined ratio with respect to the norbornene monomer (a). preferable. That is, the molar ratio (norbornene monomer (a) / activator (b)) is preferably 100/1 to 2000/1, more preferably 150/1 to 1500/1, and further 200/1 to 1200/1. preferable.
- the compounding liquid for reaction injection molding of the present invention may be further referred to as an ether compound represented by the following formula (1) (hereinafter referred to as “ether compound (c)”). .).
- ether compound (c) is used as an activity regulator for the metathesis polymerization catalyst.
- R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- R 5 and R 6 each independently represents an alkyl group having 1 to 6 carbon atoms. However, when R 5 and R 6 are methyl groups, at least one of R 1 to R 4 is an alkyl group having 1 to 6 carbon atoms.
- alkyl group having 1 to 6 carbon atoms examples include methyl group, ethyl group, isopropyl group, n-propyl group, isobutyl group, sec-butyl group, t-butyl group, n-butyl group, n-pentyl group, and n -Hexyl group and the like.
- Specific examples of the ether compound (c) include a compound group represented by the following formula.
- the ether compound (c) is represented by the following formula (1-1) from the viewpoint of suppressing the resin residue on the mold surface at the time of mold release and improving the strength of the reaction injection molded article.
- R 1 and R 2 represent the same meaning as described above, provided that R 1 and / or R 2 is an alkyl group having 1 to 6 carbon atoms.
- a compound represented by formula (1-1) is preferred, wherein R 1 and R 2 are both alkyl groups having 1 to 3 carbon atoms in formula (1-1). Is more preferable, and a compound (dipropylene glycol dimethyl ether) in which R 1 and R 2 are both methyl groups in the formula (1-1) is particularly preferable.
- the asymmetric carbon atom may exist in the ether compound represented by Formula (1), the configuration is not particularly limited.
- the ether compound (c) can be produced by any known method. Moreover, what is marketed as an ether compound (c) can also be used as it is or refine
- the ether compound (c) is added to the activator (b) in the compounding liquid for reaction injection molding of the present invention. It is preferable to mix
- the gel time when the compounding liquid for reaction injection molding of the present invention is mixed with a metathesis polymerization catalyst having tungsten as a central metal depends on the type, amount, mold temperature, etc. of the norbornene-based monomer used, but there is no surface appearance defect. In order to obtain a molded body, 2 seconds or more are preferable. The above ratio is advantageous for securing the gel time.
- components (d) include polymerization accelerators, elastomers, fillers, reinforcing materials, antioxidants, heat stabilizers, light stabilizers, UV absorbers, pigments, colorants, foaming agents, antistatic agents, difficulty Examples thereof include a flame retardant, a lubricant, a softener, a tackifier, a plasticizer, a release agent, a deodorant, a fragrance, a dicyclopentadiene-based thermal polymerization resin, and hydrogenated products thereof.
- a polymerization accelerator is added in order to improve the polymerization conversion rate of a monomer.
- a chlorine atom-containing compound is preferable, and an organic chlorine compound and a chlorinated silicon compound are more preferable.
- Specific examples include 2-chlorobenzotrichloride, 2,4-dichlorobenzotrichloride, hexachloro-p-xylene, 2,4-dichloro-trichlorotoluene, and silicon tetrachloride.
- the amount added is preferably an amount that is usually 10 mass ppm to 10 mass% in the whole reactive mixture.
- Elastomers include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), ethylene-propylene.
- SBR styrene-butadiene copolymer
- SBS styrene-butadiene-styrene block copolymer
- SIS styrene-isoprene-styrene copolymer
- ethylene-propylene examples thereof include a copolymer, an ethylene-propylene-diene terpolymer (EPDM), an ethylene-vinyl acetate copolymer (EVA), and a hydride thereof.
- EPDM ethylene-propylene-diene terpolymer
- EVA
- Elastomer is added to give fluidity to the blended liquid and to obtain a molded product with less sink marks.
- the elastomer an elastomer having a shear rate coefficient of 1.30 to 1.60 is preferable.
- the shear rate coefficient is a numerical value obtained by the method described in Patent Document 1.
- the blending amount is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the norbornene monomer.
- the filler is not particularly limited, but a fibrous filler having an aspect ratio of usually 5 to 100, preferably 10 to 50, and a particulate filler having an aspect ratio of usually 1 to 2, preferably 1 to 1.5.
- An inorganic filler made of The aspect ratio of the filler refers to the ratio between the average major axis diameter of the filler and the 50% volume cumulative diameter.
- the average major axis diameter is a number average major axis diameter calculated as an arithmetic average value obtained by measuring the major axis diameters of 100 fillers randomly selected from an optical micrograph.
- the 50% volume cumulative diameter is a value obtained by measuring the particle size distribution by the X-ray transmission method.
- the amount used is preferably 5 to 55 parts by mass, and more preferably 10 to 45 parts by mass with respect to 100 parts by mass of the total amount of the norbornene monomer and the metathesis polymerization catalyst. .
- the amount of the filler is too large, there is a possibility that the reactive liquid mixture settles in the tank or the pipe when it is injected into the mold or the injection nozzle is clogged.
- the amount of the filler is too small, the resulting molded article may have insufficient rigidity and dimensional stability.
- the method of adding the other component (d) can be appropriately selected depending on the type of additive.
- the compounding liquid for reaction injection molding of the present invention contains the above-described norbornene monomer (a), activator (b) and ether compound (c) as essential components.
- the reaction injection molding compounded liquid of the present invention may contain other component (d) as desired. Further, the reaction injection molding liquid of the present invention needs to be obtained by mixing the norbornene monomer (a) and the activator (b) in the presence of at least the ether compound (c). is there.
- Aspect A The aspect which mixes the liquid mixture containing an ether compound (c) and an activator (b), and a norbornene-type monomer (a).
- the norbornene monomer (a) may be mixed as a mixed liquid containing a part of the ether compound (c) to be used.
- (Other components (d) may optionally be included in the (a), (b), (c) and the mixed solution as long as the effects of the present invention are not impaired).
- Aspect B The aspect which mixes the liquid mixture containing an ether compound (c) and a norbornene-type monomer (a), and an activator (b).
- (Other components (d) may optionally be included in the (a), (b), (c) and the mixed solution as long as the effects of the present invention are not impaired).
- (Other components (d) may optionally be included in the (a), (b) and (c) as long as the effects of the present invention are not impaired).
- the embodiment A is preferable from the viewpoint of improving the storage stability of the reaction injection molding compounded liquid of the present invention.
- reaction injection molded body of the present invention comprises a reactive liquid mixture prepared by mixing the above-mentioned reaction injection molding compound liquid of the present invention and a metathesis polymerization catalyst having tungsten as a central metal. It is obtained by a method having a step of bulk polymerization and reaction injection molding.
- the resulting reactive liquid mixture can exhibit an appropriate gel time even after storage for a required period.
- the gel time depends on the type, amount, mold temperature and the like of the norbornene-based monomer used, but is preferably 2 seconds or more, more preferably 5 seconds to 6 minutes, and even more preferably 10 seconds to 5 minutes.
- the metathesis polymerization catalyst is not particularly limited as long as it is a catalyst having tungsten as a central metal and capable of ring-opening polymerization of a norbornene-based monomer.
- the metathesis polymerization catalyst can be used alone or in combination of two or more.
- the metathesis polymerization catalyst is a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a tungsten atom as a central atom.
- tungsten halides such as WCl 6 , WCl 5 , WCl 4 , WCl 2 , WBr 6 , WBr 4 , WBr 2 , WF 6 , WF 4 , WI 6 , WI 4 ; WOCl 4 , WOBr 4 , WOF 4 , WCl 4 2 (OC 6 H 5 ) 4 , tungsten oxyhalides such as W (OC 2 H 5 ) 2 Cl 3 ; metal oxides such as tungsten oxide; (CO) 5 WC (OCH 3 ) (CH 3 ), (CO ) 5 WC (OC 2 H 5 ) (CH 3 ), (CO) 5 WC (OC 2 H 5 ), W (OC 6 H 5 ) 6 , W (CO) 3.
- the amount of the metathesis polymerization catalyst used is 1 mol of norbornene monomers used in the reaction (total mol when two or more types of norbornene monomers are used) in consideration of the balance between maintaining appropriate reaction efficiency and economy. 0.01 mmol or more, preferably 0.1 mmol or more, more preferably 50 mmol or less, and even more preferably 20 mmol or less.
- the metathesis polymerization catalyst is preferably used in a predetermined ratio with respect to the activator (b) contained in the liquid mixture for reaction injection molding of the present invention from the viewpoint of maintaining a good polymerization reaction and production efficiency. That is, the metathesis polymerization catalyst is used in such an amount that the amount of the activator (b) is preferably 0.1 mol or more and 100 mol or less, more preferably 1 mol or more and 10 mol or less with respect to 1 mol of the metathesis polymerization catalyst. It is desirable.
- the metathesis polymerization catalyst is preferably used after being suspended in an inert solvent such as benzene, toluene and chlorobenzene and solubilized by adding a small amount of an alcohol compound and / or a phenol compound.
- an alcohol compound used here include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and t-butanol.
- the phenol compound used include t-butylphenol, t-octylphenol, nonylphenol, and dodecylphenol.
- Lewis base or chelating agent may be added to 1 mole of the metathesis polymerization catalyst.
- Lewis base and chelating agent include acetylacetone, acetoacetic acid alkyl ester, tetrahydrofuran, benzonitrile and the like.
- the RIM method in general, at least two compounded liquids of a mixed liquid A containing an activator and not containing a metathesis polymerization catalyst and a mixed liquid B containing a metathesis polymerization catalyst are mixed, and bulk polymerization of the resulting reactive mixed liquid is performed.
- a resin molded body is manufactured by simultaneously performing molding and molding.
- the reaction injection molded body manufacturing method of the present invention is usually preferably carried out by the RIM method.
- the compounding liquid for reaction injection molding of the present invention is suitably used as compounding liquid A.
- the compounding liquid B used together is not particularly limited as long as it contains a metathesis polymerization catalyst having tungsten as a central metal. From the viewpoint of improving the uniformity of the ionic liquid mixture, those comprising the norbornene monomer (a) and the metathesis polymerization catalyst are preferred. Further, the compounded liquid B may contain an ether compound (c) and other components (d). When the blending liquid B contains a norbornene monomer (a) or the like, the norbornene monomer (a) or the like of the blending liquid A and the norbornene monomer (a) or the like of the blending liquid B may be the same or different. good.
- a reaction comprising a compounded liquid A comprising the compounded liquid for reaction injection molding of the present invention, and a compounded liquid B containing a metathesis polymerization catalyst having a norbornene monomer (a) and tungsten as a central metal.
- a two-component liquid mixture for injection molding can also be provided.
- reaction injection molding (RIM) apparatus.
- the above-mentioned apparatus is prepared by separately preparing a compounding liquid A comprising the compounding liquid for reaction injection molding of the present invention and a compounding liquid B containing the above-described norbornene-based monomer (a) and a metathesis polymerization catalyst having tungsten as a central metal.
- the mixture A and the mixture B are mixed together, the obtained reactive mixture is poured into a mold, and bulk polymerization is performed in the mold, whereby a reaction injection molded body can be manufactured.
- a blending liquid C composed of a norbornene-based monomer (a) may be further used as desired.
- the blended liquid A, the blended liquid B, the blended liquid C, and the like used in the method for producing a reaction injection molded body of the present invention may be collectively referred to as a reaction stock solution.
- the mixing of the compounding liquid A and the compounding liquid B can be usually performed by supplying them separately to a reaction injection molding apparatus and instantaneously mixing them in a collision mixing apparatus (mixing head).
- a low-pressure injector such as a dynamic mixer or a static mixer can be used instead of the collision mixing device.
- the temperature of the reaction stock solution before being supplied to the reaction injection molding apparatus is preferably 10 to 60 ° C., and the viscosity of the reaction stock solution is preferably about 5 to 3,000 mPa ⁇ s at 30 ° C., for example 50 to 1, About 000 mPa ⁇ s is more preferable.
- mold used for reaction injection molding
- mold is used.
- the material of the mold is not particularly limited, and examples thereof include metals such as steel, aluminum, zinc alloy, nickel, copper, and chromium, and resins. These dies may be manufactured by any method such as casting, forging, thermal spraying, electroforming, or may be plated.
- the mold structure may be determined in consideration of the pressure when the reactive liquid mixture is injected into the mold.
- the mold clamping pressure is preferably about 0.1 to 9.8 MPa in terms of gauge pressure.
- the mold temperature T1 Is preferably set higher than the mold temperature T2 (° C.) of the mold corresponding to the design surface.
- T1-T2 is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and the upper limit is preferably 60 ° C. or lower.
- T1 is preferably 110 ° C. or lower, more preferably 95 ° C. or lower, and the lower limit is preferably 50 ° C. or higher.
- T2 is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, and the lower limit is preferably 30 ° C. or higher.
- Examples of the method of adjusting the mold temperature include a method of adjusting with a heater; a method of adjusting the temperature with a heat medium such as temperature-controlled water or oil that is circulated in a pipe embedded in the mold.
- a mold is separately provided in a space formed by the molded body and the mold. You may implement the in-mold coating method which inject
- the reaction injection molded body After completion of the bulk polymerization (after the in-mold coating method is performed), the reaction injection molded body can be obtained by opening the mold and removing the mold.
- reaction injection molded product of the present invention is obtained by the above-described "method for producing a reaction injection molded product" of the present invention.
- the reaction injection molded article of the present invention can be efficiently produced on an industrial production scale using the reaction injection molding compounded liquid of the present invention.
- reaction injection molded article of the present invention can be used immediately as it is, but may be plated and / or painted according to a known method if desired in order to improve or maintain the characteristics of the molded article.
- the reaction injection molded article of the present invention is used in automobiles such as bumpers and air deflectors; construction and industrial machinery applications such as wheel loaders and power shovels; leisure applications such as golf carts and game machines; medical applications such as medical equipment; It can be suitably used for industrial applications such as showers and chairs; residential equipment applications such as shower pans and wash bowls.
- the increase in viscosity of the mixed solution accompanying polymerization was measured with a B-type viscometer installed in the container.
- the time from the start of mixing of the blended liquid (A) and the blended liquid (B) until the viscosity of the mixed liquid showed 1000 mPa ⁇ s was defined as “gel time”.
- Mixture 1 was prepared by mixing so that the molar ratio of dipropylene glycol dimethyl ether (DPG) and triethylaluminum (TEAL) was 1: 1.
- DPG dipropylene glycol dimethyl ether
- TEAL triethylaluminum
- Mixture 2 was prepared by mixing so that the molar ratio of DPG to TEAL was 4.5: 1.
- Mixture 3 was prepared by mixing so that the molar ratio of DPG to TEAL was 6: 1.
- Mixture 5 was prepared by mixing so that the molar ratio of DCPD and TEAL was 5: 1.
- Example 1 [Combination liquid (A)] To a mixture of norbornene monomers consisting of 90 parts of DCPD and 10 parts of tricyclopentadiene (TCPD), 4.1 parts of an ethylene-propylene copolymer (propylene unit 89%, ethylene unit 11%) was added. 0.6 part was added and the liquid mixture (A) was obtained. In the compounded liquid (A), the TEAL concentration was 22 mmol / kg, and the molar ratio of norbornene monomer to TEAL (norbornene monomer: TEAL) was 340: 1.
- Combination liquid (B) As a metathesis polymerization catalyst, 17 parts of tungsten hexachloride (WCl 6 ), 1 part of t-butanol, 14 parts of dodecylphenol, and 9 parts of acetylacetone were mixed in toluene to prepare a metathesis polymerization catalyst solution having a tungsten concentration of 11%. Next, 4.1 parts of the ethylene-propylene copolymer was dissolved in the mixture of norbornene monomers. To this solution, 1.7 parts of the metathesis polymerization catalyst solution was further added to obtain a blended liquid (B). In the compounded liquid (B), the tungsten concentration was 7.6 mmol / kg.
- Examples 2, 3, 4 A mixed liquid (A) and a mixed liquid (B) were prepared in the same manner as in Example 1 except that the mixed liquids 2, 3, and 4 were used instead of the mixed liquid 1, respectively, the gel time was measured, and the mold was measured. The filling property was evaluated. The results are shown in Table 1.
- Comparative Example 1 DPG is added to and mixed with the norbornene-based monomer mixture, and mixed liquid (A) and mixed liquid (B) are prepared in the same manner as in Example 1 except that mixed liquid 5 is used instead of mixed liquid 1. Then, the gel time was measured and the filling property into the mold was evaluated. In the blended liquid (A), the molar ratio of DPG and TEAL was 1: 1. The results are shown in Table 1.
- Example 1 using the compounding liquid (A) prepared by mixing a norbornene monomer (mixture of DCPD and TCPD) and an activator (TEAL) in the presence of an ether compound (DPG).
- TEAL ether compound
- the gel time of the reactive liquid mixture obtained by mixing the compounded liquids (A) and (B) is 4 seconds or more and is filled in the entire mold (297 mm). It turns out that the molded object without a problem was able to be obtained.
- Examples 5 to 8 and Comparative Example 2 Inside, a reaction injection mold made of two aluminum plates capable of forming a cavity of length 245 mm ⁇ width 210 mm ⁇ thickness 3 mm is prepared, and one mold is heated to 90 ° C. with a heater, The temperature difference between the mold and the female mold was adjusted to 40 ° C.
- the reaction injection molding die has a structure in which one aluminum plate has injection holes for the reaction injection molding compound liquid.
- the blended liquid (A) and blended liquid (B) obtained in Examples 1 to 4 and Comparative Example 1 were each heated to 30 ° C., and the mixing ratio While mixing with a static mixer at a ratio of 1: 1 (mass ratio), the mixture was injected into the reaction injection mold from the injection hole. Bulk polymerization was performed in the mold for 120 seconds, and the mold was opened and demolded to obtain molded bodies made of polymerization-cured norbornene resin. In each example and comparative example, the molded article was produced 10 times. All of the obtained norbornene resins had a specific gravity of 1.04 and a glass transition temperature (Tg) measured by DSC method of 145 ° C.
- Tg glass transition temperature
- reaction injection molding compounded liquid of the present invention can be suitably used in the field of production of reaction injection molded articles. Furthermore, since the reaction injection molded article of the present invention is excellent in mechanical properties and product finish, it can be suitably used for applications such as automobile parts and housing equipment members.
Abstract
Description
例えば、特許文献1には、RIM法により、特定のエラストマーを含有するノルボルネン系モノマー含有反応射出成形用配合液を塊状開環重合させることで、金型の形状や大きさ等によらず、成形体表面にヒケの少ない樹脂成形体を得る技術が開示されている。
また、特許文献2には、RIM法により、特定量のエキソ-ジシクロペンタジエンを含有する新規なメタセシス重合性モノマーを塊状開環重合させることで、モノマー残留率が低く、十分に硬化した架橋重合体成形物を得る樹脂成形体の製造方法が開示されている。また、特許文献2には、樹脂成形体の製造に用いる反応性溶液にエーテル化合物を加えると保存安定性が向上しうることが記載されている。
〔1〕 タングステンを中心金属とするメタセシス重合触媒下でノルボルネン系モノマーを重合させる反応射出成形用配合液であって、
前記配合液は、ノルボルネン系モノマー、前記触媒の活性化剤、および式(1):
で表されるエーテル化合物を含み、
前記ノルボルネン系モノマーと前記活性化剤とを、少なくとも前記エーテル化合物の存在下で混合して得られる、反応射出成形用配合液、
〔2〕 前記〔1〕に記載の反応射出成形用配合液の製造方法であって、
前記ノルボルネン系モノマーと前記活性化剤とを、少なくとも前記エーテル化合物の存在下で混合する工程を含む、反応射出成形用配合液の製造方法、
〔3〕 前記〔1〕に記載の反応射出成形用配合液とタングステンを中心金属とするメタセシス重合触媒とを混合してなる反応性混合液を型内で塊状重合させ、反応射出成形を行う工程を有する、反応射出成形体の製造方法、並びに
〔4〕 前記〔3〕に記載の製造方法により得られる反応射出成形体
に関する。
本発明の反応射出成形用配合液は、(a)ノルボルネン系モノマー、(b)活性化剤、及び(c)後述の式(1)で表されるエーテル化合物を含有する。
当該反応射出成形用配合液と、タングステンを中心金属とするメタセシス重合触媒とを混合した反応性混合液を、型内で塊状重合させることにより、反応射出成形体を得ることができる。
本発明に用いるノルボルネン系モノマー(以下、「ノルボルネン系モノマー(a)」ということがある。)は、式(2)
ノルボルネン系モノマー(a)としては、分子内にノルボルネン環と縮合する環を有しないノルボルネン系モノマー、及び3環以上の多環式ノルボルネン系モノマー等が挙げられる。ノルボルネン系モノマー(a)は、1種単独で、あるいは2種以上を混合して用いることができる。
これらのノルボルネン系モノマーは1種単独で、あるいは2種以上を組み合わせて用いることができる。
本発明において活性化剤(以下、「活性化剤(b)」ということがある。)は、共触媒ともよばれ、メタセシス重合触媒の重合活性を高める目的で添加されるものである。
活性化剤(b)は、本発明の配合液と混合されるタングステンを中心金属としたメタセシス重合触媒の重合活性を高めるものであれば特に限定されない。活性化剤(b)としては、例えば、周期表第11~14族の金属の有機金属化合物等が挙げられる。具体的には、トリエチルアルミニウム、トリイソブチルアルミニウム、トリメチルアルミニウム、トリブチルアルミニウム、トリヘキシルアルミニウム、及びトリオクチルアルミニウム等のアルキルアルミニウム化合物;エチルアルミニウムジクロリド、ジエチルアルミニウムクロリド、ジイソブチルアルミニウムクロリド、エチルアルミニウムセスキクロリド、イソブチルアルミニウムジクロリド、及びジオクチルアルミニウムアイオダイド等のアルキルアルミニウムハライド化合物;ジエチルアルミニウムエトキシド等のアルキルアルミニウムアルコキシド化合物;テトラブチル錫等の有機スズ化合物;ジエチル亜鉛等の有機亜鉛化合物等が挙げられる。
これらの中でも、アルキルアルミニウム化合物及びアルキルアルミニウムハライド化合物が好ましく、さらに具体的にはトリエチルアルミニウム、トリオクチルアルミニウム、ジエチルアルミニウムクロリド、及びジオクチルアルミニウムアイオダイドがより好ましい。活性化剤(b)は、1種単独で、あるいは2種以上を混合して用いることができる。
本発明の反応射出成形用配合液は、さらに下記式(1)で表されるエーテル化合物(以下、「エーテル化合物(c)」ということがある。)を含有する。エーテル化合物(c)は、メタセシス重合触媒の活性調節剤として用いられる。
エーテル化合物(c)の具体例としては、下記式で表される化合物群が挙げられる。
で表される化合物が好ましく、式(1-1)で表される化合物であって、式(1-1)中、R1及びR2がいずれも炭素数1~3のアルキル基である化合物がより好ましく、式(1-1)で表される化合物であって、式(1-1)中、R1及びR2がいずれもメチル基である化合物(ジプロピレングリコールジメチルエーテル)が特に好ましい。
なお、式(1)で表されるエーテル化合物には不斉炭素原子が存在し得るが、その立体配置は特に限定されない。
本発明の反応射出成形用配合液を、タングステンを中心金属とするメタセシス重合触媒と混合した際のゲルタイムは、用いるノルボルネン系モノマー等の種類、量、型温度等によるが、表面の外観不良がない成形体を得るには、2秒以上が好ましい。上記比率は当該ゲルタイムの確保に有利である。
本発明の反応射出成形用配合液には、樹脂成形体をより効率よく製造するために、あるいは、樹脂成形体の特性の改良や維持のために、所望によりその他の成分(以下、「その他の成分(d)」ということがある。)を配合してもよい。
その他の成分(d)としては、重合促進剤、エラストマー、充填剤、補強材、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、顔料、着色剤、発泡剤、帯電防止剤、難燃剤、滑剤、軟化剤、粘着付与剤、可塑剤、離型剤、防臭剤、香料、ジシクロペンタジエン系熱重合樹脂及びその水添物等が挙げられる。
重合促進剤を用いる場合、その添加量は、反応性混合液全体中、通常10質量ppmから10質量%となる量が好ましい。
その他の成分(d)の添加方法は、添加剤の種類等により適宜選定することができる。
ノルボルネン系モノマー(a)と活性化剤(b)とを、少なくともエーテル化合物(c)の存在下で混合する具体的態様の例としては、下記が挙げられる。
エーテル化合物(c)と活性化剤(b)を含む混合液と、ノルボルネン系モノマー(a)とを混合する態様。なお、本態様においてノルボルネン系モノマー(a)は、用いるエーテル化合物(c)の一部を含む混合液として混合してもよい。(当該(a)、(b)、(c)及び混合液には、本発明の効果を損なわない範囲で、それぞれ、その他の成分(d)が任意に含まれていても良い。)
エーテル化合物(c)とノルボルネン系モノマー(a)を含む混合液と、活性化剤(b)とを混合する態様。なお、本態様において活性化剤(b)は、用いるエーテル化合物(c)の一部を含む混合液として混合してもよい。(当該(a)、(b)、(c)及び混合液には、本発明の効果を損なわない範囲で、それぞれ、その他の成分(d)が任意に含まれていても良い。)
ノルボルネン系モノマー(a)、前記活性化剤(b)、及び前記エーテル化合物(c)を同時に混合する工程。(当該(a)、(b)及び(c)には、本発明の効果を損なわない範囲で、それぞれ、その他の成分(d)が任意に含まれていても良い。)
本発明の反応射出成形体は、上記本発明の反応射出成形用配合液とタングステンを中心金属とするメタセシス重合触媒とを混合した反応性混合液を、型内で塊状重合させ、反応射出成形を行う工程を有する方法により得られる。
これらの中でも、タングステンハロゲン化物及びタングステンオキシハロゲン化物が好ましく、より具体的にはWCl6及びWOCl4がより好ましい。
反応射出成形装置に供給する前の反応原液の温度は、好ましくは10~60℃であり、反応原液の粘度は、例えば30℃において、5~3,000mPa・s程度が好ましく、50~1,000mPa・s程度がより好ましい。
型の材質は、特に限定されず、スチール、アルミニウム、亜鉛合金、ニッケル、銅、クロム等の金属及び樹脂等が挙げられる。また、これらの型は、鋳造、鍛造、溶射、電鋳等のいずれの方法で製造されたものでもよく、また、メッキされたものであってもよい。
本発明の反応射出成形体は、上述した、本発明の「反応射出成形体の製造方法」によって得られるものである。本発明の反応射出成形体は、本発明の反応射出成形用配合液を用い、工業的生産規模で効率よく製造することができる。
撹拌子を入れて窒素置換した50mLの容器を30℃下に維持した。当該容器に、予め窒素置換した30℃の配合液(B)10mLを注入し、マグネチックスターラーを用いて回転数1000rpmで撹拌した。次いで、予め窒素置換した30℃の配合液(A)10mLを上記容器に注入し、5秒間撹拌して配合液(B)と混合した。当該混合により、配合液(A)と配合液(B)とが反応して重合が開始される。重合に伴う混合液の粘度上昇を上記容器に設置したB型粘度計により測定した。配合液(A)と配合液(B)の混合開始時点から混合液の粘度が1000mPa・sを示すまでの時間を“ゲルタイム”とした。
配合液(A)と配合液(B)とを混合して反応性混合液を得、297mm×210mm×0.1mmのサイズを有する板状金型中に注入し、加熱硬化させて、その流動長を計測した。なお、加熱硬化は、金型温度を80℃として行った。
成形体の曲げ強度は、JIS K7171に準拠して、測定温度23℃の条件にて測定した。
成形体の曲げ弾性率は、JIS K7171に準拠し、試験速度2mm/分の条件にて測定した。
成形体の製造を10回繰り返した後、金型を冷却し、金型表面に関して任意の10mm×10mmの領域10ヵ所につき、光学顕微鏡で10倍に拡大して観察し、以下の評価基準で金型表面における樹脂残りを評価した。
〔評価基準〕
優:全ての領域で樹脂残りがない。
良:1ヶ所以上2ヶ所以下の領域で樹脂残りがある。
可:3ヶ所以上5ヶ所以下の領域で樹脂残りがある。
不可:6ヶ所以上の領域で樹脂残りがある。
ジプロピレングリコールジメチルエーテル(DPG)とトリエチルアルミニウム(TEAL)のモル比が1:1となるように混合して混合液1を調製した。
DPGとTEALのモル比が4.5:1となるように混合して混合液2を調製した。
DPGとTEALのモル比が6:1となるように混合して混合液3を調製した。
DPGとジシクロペンタジエン(DCPD)とを混合した後、得られた混合物にTEALを添加して混合し、混合液4を調製した。なお、DPG、DCPDおよびTEALのモル比は1:5:1とした。
DCPDとTEALのモル比が5:1となるように混合して混合液5を調製した。
〔配合液(A)〕
DCPD90部とトリシクロペンタジエン(TCPD)10部とからなるノルボルネン系モノマーの混合物に、エチレン-プロピレンコポリマー〔プロピレン単位89%、エチレン単位11%〕4.1部を添加し、次いで、混合液1を0.6部添加し、配合液(A)を得た。配合液(A)中、TEAL濃度は22mmol/kg、ノルボルネン系モノマーとTEALとのモル比(ノルボルネン系モノマー:TEAL)は340:1となった。
メタセシス重合触媒として六塩化タングステン(WCl6)17部、t-ブタノール1部、ドデシルフェノール14部、およびアセチルアセトン9部をトルエン中で混合し、タングステン濃度として11%のメタセシス重合触媒溶液を調製した。
次いで、前記ノルボルネン系モノマーの混合物に、前記エチレン-プロピレンコポリマー4.1部を溶解させた。この溶液に、更に、前記メタセシス重合触媒溶液を1.7部添加し、配合液(B)を得た。配合液(B)中、タングステン濃度は7.6mmol/kgとなった。
それぞれ、混合液1の代わりに混合液2、3、4を用いたこと以外は実施例1と同様にして配合液(A)と配合液(B)を調製し、ゲルタイムを測定し、金型への充填性を評価した。結果を表1に示す。
前記ノルボルネン系モノマーの混合物にDPGを添加して混合し、混合液1の代わりに混合液5を用いたこと以外は実施例1と同様にして配合液(A)と配合液(B)を調製し、ゲルタイムを測定し、金型への充填性を評価した。なお、配合液(A)中、DPGとTEALのモル比は1:1とした。結果を表1に示す。
表1より、ノルボルネン系モノマー(DCPDとTCPDの混合物)と活性化剤(TEAL)とを、エーテル化合物(DPG)の存在下で混合することにより調製した配合液(A)を用いた実施例1~4では、配合液(A)と(B)を混合して得られた反応性混合液のゲルタイムは4秒以上であり、型内全体(297mm)に充填されており、いずれも形状品質に問題のない成形体を得ることができたことが分かる。
これに対し、エーテル化合物(DPG)の非存在下で、ノルボルネン系モノマーの一部(DCPD)と活性化剤(TEAL)の2成分のみを予め混合することにより調製した配合液(A)を用いた比較例1の場合、得られた反応性混合液のゲルタイムは非常に短いもの(2秒未満)となり、ゲルタイムが非常に短いことに伴って、流動長が短くなり、充填性が顕著に悪化し、所望の形状品質の成形体が得られなかったことが分かる。
内部に、縦245mm×横210mm×厚さ3mmのキャビティを形成しうる2枚のアルミニウム板からなる反応射出成形用金型を用意し、一方の金型をヒータで90℃に加温し、雄型と雌型の温度差が40℃となるように調整した。なお、この反応射出成形用金型は、一方のアルミニウム板に反応射出成形用配合液の注入孔を有する構造となっている。
これに対し、比較例2では、ゲルタイムが非常に短い(2秒未満)ことで、反応性混合液の混合不良が生じ、メタセシス重合触媒が充分に活性化されなかったため、重合活性が低下したと推定され、曲げ強度、曲げ弾性率及び金型表面における樹脂残りの評価といった成形品の物性も顕著に低下したことが分かる。
実施例5~8の中では、エーテル化合物(DPG)と活性化剤(TEAL)とのモル比が4.5:1で調製された配合液(A)を用いた実施例6の成形体が好適であったことが分かる。
Claims (11)
- タングステンを中心金属とするメタセシス重合触媒下でノルボルネン系モノマーを重合させる反応射出成形用配合液であって、
前記配合液は、ノルボルネン系モノマー、前記触媒の活性化剤、および式(1):
で表されるエーテル化合物を含み、
前記ノルボルネン系モノマーと前記活性化剤とを、少なくとも前記エーテル化合物の存在下で混合して得られる、反応射出成形用配合液。 - 前記混合を、前記エーテル化合物と前記活性化剤を含む混合液と、ノルボルネン系モノマーとを混合することにより行う、請求項1記載の反応射出成形用配合液。
- 前記混合を、前記エーテル化合物と前記ノルボルネン系モノマーを含む混合液と、前記活性化剤とを混合することにより行う、請求項1記載の反応射出成形用配合液。
- 前記混合を、前記ノルボルネン系モノマー、前記活性化剤および前記エーテル化合物を同時に混合することにより行う、請求項1記載の反応射出成形用配合液。
- 前記エーテル化合物と前記活性化剤との配合割合がモル比(エーテル化合物/活性化剤)で0.1/1~30/1である、請求項1~4いずれか記載の反応射出成形用配合液。
- 前記式(1)で表されるエーテル化合物がジプロピレングリコールジメチルエーテルである、請求項1~5いずれか記載の反応射出成形用配合液。
- タングステンを中心金属とするメタセシス重合触媒と混合した際のゲルタイムが2秒以上である、請求項1~6いずれか記載の反応射出成形用配合液。
- 請求項1~7いずれか記載の反応射出成形用配合液の製造方法であって、
前記ノルボルネン系モノマーと前記活性化剤とを、少なくとも前記エーテル化合物の存在下で混合する工程を含む、反応射出成形用配合液の製造方法。 - 請求項1~7いずれか記載の反応射出成形用配合液とタングステンを中心金属とするメタセシス重合触媒とを混合してなる反応性混合液を型内で塊状重合させ、反応射出成形を行う工程を有する、反応射出成形体の製造方法。
- 前記反応性混合液を、請求項1~7いずれか記載の反応射出成形用配合液と、ノルボルネン系モノマーおよび前記タングステンを中心金属とするメタセシス重合触媒を含む配合液とを混合して調製する、請求項9記載の反応射出成形体の製造方法。
- 請求項9または10記載の製造方法により得られる反応射出成形体。
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/319,059 US20170114160A1 (en) | 2014-06-27 | 2015-06-19 | Liquid formulation for reaction injection molding and manufacturing method thereof |
MX2016016688A MX2016016688A (es) | 2014-06-27 | 2015-06-19 | Formulacion liquida para el moldeo por inyeccion-reaccion y metodo de manufactura de la misma. |
EP15812526.0A EP3162831A4 (en) | 2014-06-27 | 2015-06-19 | Liquid formulation for reaction injection molding and manufacturing method thereof |
KR1020177000186A KR102361537B1 (ko) | 2014-06-27 | 2015-06-19 | 반응 사출 성형용 배합액 및 그 제조 방법 |
JP2016529546A JP6577466B2 (ja) | 2014-06-27 | 2015-06-19 | 反応射出成形用配合液およびその製造方法 |
CA2951820A CA2951820C (en) | 2014-06-27 | 2015-06-19 | Liquid formulation for reaction injection molding and manufacturing method thereof |
RU2017102308A RU2689981C2 (ru) | 2014-06-27 | 2015-06-19 | Жидкостная рецептура, предназначенная для реакционно-литьевого формования, и способ ее изготовления |
CN201580033258.4A CN106471036B (zh) | 2014-06-27 | 2015-06-19 | 反应注射成型用配合液及其制造方法 |
US16/728,549 US11066497B2 (en) | 2014-06-27 | 2019-12-27 | Liquid formulation for reaction injection molding and manufacturing method thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-132008 | 2014-06-27 | ||
JP2014132008 | 2014-06-27 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/319,059 A-371-Of-International US20170114160A1 (en) | 2014-06-27 | 2015-06-19 | Liquid formulation for reaction injection molding and manufacturing method thereof |
US16/728,549 Continuation US11066497B2 (en) | 2014-06-27 | 2019-12-27 | Liquid formulation for reaction injection molding and manufacturing method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015198990A1 true WO2015198990A1 (ja) | 2015-12-30 |
Family
ID=54938074
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/067755 WO2015198990A1 (ja) | 2014-06-27 | 2015-06-19 | 反応射出成形用配合液およびその製造方法 |
Country Status (9)
Country | Link |
---|---|
US (2) | US20170114160A1 (ja) |
EP (1) | EP3162831A4 (ja) |
JP (1) | JP6577466B2 (ja) |
KR (1) | KR102361537B1 (ja) |
CN (1) | CN106471036B (ja) |
CA (1) | CA2951820C (ja) |
MX (1) | MX2016016688A (ja) |
RU (1) | RU2689981C2 (ja) |
WO (1) | WO2015198990A1 (ja) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11597797B2 (en) * | 2012-12-27 | 2023-03-07 | Rimtec Corporation | Liquid blend for reaction injection molding, method for producing reaction injection molded body, and reaction injection molded body |
WO2017179318A1 (ja) * | 2016-04-11 | 2017-10-19 | ポリマテック・ジャパン株式会社 | 熱伝導性シート |
KR102200327B1 (ko) * | 2019-04-30 | 2021-01-08 | 한국화학연구원 | Rim 성형용 폴리디사이클로펜타디엔 및 그의 제조방법 |
CN112812232B (zh) * | 2021-02-10 | 2022-07-26 | 上海东杰汽车装饰件有限公司 | 聚三环戊二烯ptcpd高分子材料及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003025364A (ja) * | 2001-07-16 | 2003-01-29 | Nippon Petrochemicals Co Ltd | メタセシス重合性モノマーの重合による架橋重合体成形物の製造方法 |
JP2005153265A (ja) * | 2003-11-25 | 2005-06-16 | Hitachi Housetec Co Ltd | 高分子成形品の製造方法及びその方法により得られた高分子成形品 |
WO2014103830A1 (ja) * | 2012-12-27 | 2014-07-03 | Rimtec株式会社 | 反応射出成形用配合液、反応射出成形体の製造方法および反応射出成形体 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0287762A3 (en) * | 1987-02-16 | 1991-01-23 | Hercules Incorporated | Methathesis polymerized copolymer |
EP0329063A3 (en) * | 1988-02-15 | 1990-07-25 | Hercules Incorporated | Process for producing a colored molded article of metathesis polymerized polymer |
JPH03284699A (ja) * | 1990-02-09 | 1991-12-16 | Kazuhisa Sugimura | 新規蛋白質、そのdnaおよび該蛋白質の製造方法 |
JPH04279628A (ja) | 1991-03-07 | 1992-10-05 | Nippon Zeon Co Ltd | ノルボルネン系ポリマーの製造方法 |
US5268232A (en) | 1991-10-15 | 1993-12-07 | Hercules Incorporated | Dicyclopentadiene polymers with heat-resistant dimensional integrity and high Tg |
JP3284699B2 (ja) * | 1993-09-30 | 2002-05-20 | 日本ゼオン株式会社 | ノルボルネン系樹脂成形品製造用反応原液及びノルボルネン系樹脂成形品の製造方法 |
EP0815155B1 (en) | 1996-01-18 | 2002-08-07 | Teijin-Metton Kabushiki Kaisha | Metathesis polymerization catalyst solution and system for preparing cross-linked polymers |
JP2002121266A (ja) * | 2000-10-12 | 2002-04-23 | Sekisui Chem Co Ltd | ノルボルネン系モノマーの重合方法 |
JP4781568B2 (ja) | 2001-07-16 | 2011-09-28 | Jx日鉱日石エネルギー株式会社 | メタセシス重合性モノマーの反応性溶液並びに架橋重合体成形物およびその製造方法 |
JP2008163105A (ja) | 2006-12-27 | 2008-07-17 | Rimtec Kk | 配合液、反応射出成形体の製造方法及び反応射出成形体 |
JP2009221402A (ja) | 2008-03-18 | 2009-10-01 | Nippon Zeon Co Ltd | ノルボルネン系単量体の開環重合触媒系、並びに開環重合体及び開環重合体水素化物の製造方法 |
JP2010254980A (ja) | 2009-03-31 | 2010-11-11 | Jsr Corp | 環状オレフィン系開環重合体の製造方法 |
JP5545078B2 (ja) | 2009-06-30 | 2014-07-09 | Jsr株式会社 | 環状オレフィン系開環共重合体 |
JP2011122117A (ja) | 2009-12-14 | 2011-06-23 | Nippon Zeon Co Ltd | シクロペンテン開環重合体の製造方法 |
RU2450028C2 (ru) * | 2010-06-07 | 2012-05-10 | Открытое акционерное общество "Нижнекамскнефтехим" | Способ приготовления двухкомпонентной системы на основе дициклопентадиена |
-
2015
- 2015-06-19 CA CA2951820A patent/CA2951820C/en active Active
- 2015-06-19 CN CN201580033258.4A patent/CN106471036B/zh active Active
- 2015-06-19 US US15/319,059 patent/US20170114160A1/en not_active Abandoned
- 2015-06-19 MX MX2016016688A patent/MX2016016688A/es unknown
- 2015-06-19 JP JP2016529546A patent/JP6577466B2/ja active Active
- 2015-06-19 KR KR1020177000186A patent/KR102361537B1/ko active IP Right Grant
- 2015-06-19 EP EP15812526.0A patent/EP3162831A4/en active Pending
- 2015-06-19 WO PCT/JP2015/067755 patent/WO2015198990A1/ja active Application Filing
- 2015-06-19 RU RU2017102308A patent/RU2689981C2/ru active
-
2019
- 2019-12-27 US US16/728,549 patent/US11066497B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003025364A (ja) * | 2001-07-16 | 2003-01-29 | Nippon Petrochemicals Co Ltd | メタセシス重合性モノマーの重合による架橋重合体成形物の製造方法 |
JP2005153265A (ja) * | 2003-11-25 | 2005-06-16 | Hitachi Housetec Co Ltd | 高分子成形品の製造方法及びその方法により得られた高分子成形品 |
WO2014103830A1 (ja) * | 2012-12-27 | 2014-07-03 | Rimtec株式会社 | 反応射出成形用配合液、反応射出成形体の製造方法および反応射出成形体 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3162831A4 * |
Also Published As
Publication number | Publication date |
---|---|
EP3162831A4 (en) | 2018-02-21 |
EP3162831A1 (en) | 2017-05-03 |
US11066497B2 (en) | 2021-07-20 |
KR102361537B1 (ko) | 2022-02-09 |
JP6577466B2 (ja) | 2019-09-18 |
RU2017102308A3 (ja) | 2018-10-04 |
RU2689981C2 (ru) | 2019-05-30 |
CA2951820C (en) | 2022-05-10 |
CA2951820A1 (en) | 2015-12-30 |
KR20170026450A (ko) | 2017-03-08 |
RU2017102308A (ru) | 2018-07-31 |
MX2016016688A (es) | 2017-07-11 |
US20170114160A1 (en) | 2017-04-27 |
JPWO2015198990A1 (ja) | 2017-04-20 |
CN106471036A (zh) | 2017-03-01 |
CN106471036B (zh) | 2018-11-13 |
US20200140582A1 (en) | 2020-05-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11066497B2 (en) | Liquid formulation for reaction injection molding and manufacturing method thereof | |
JP5681837B2 (ja) | 反応射出成形用配合液、反応射出成形体の製造方法および反応射出成形体 | |
JP5772600B2 (ja) | 表面被覆型補強材、反応射出成形用配合液、及び反応射出成形体 | |
JP5563748B2 (ja) | 反応射出成形用反応原液、反応射出成形方法及び反応射出成形体 | |
JP2008163105A (ja) | 配合液、反応射出成形体の製造方法及び反応射出成形体 | |
JPWO2007125787A1 (ja) | 表面に被覆膜を有する反応射出成形体及びその製造方法 | |
WO2015198992A1 (ja) | ゲル化促進剤 | |
US11597797B2 (en) | Liquid blend for reaction injection molding, method for producing reaction injection molded body, and reaction injection molded body | |
JP3767134B2 (ja) | 反応射出成形方法 | |
JP2009072958A (ja) | ノルボルネン系樹脂成形体および配合液 | |
JP2005271535A (ja) | 反応射出成形方法およびそれに用いる反応原液 | |
JP2007313395A (ja) | インモールドコーティング法及び被覆成形体 | |
JP2009263575A (ja) | 複合成形体 | |
JPH02223433A (ja) | メタセシス重合体成形物 | |
JP2007009043A (ja) | ノルボルネン系樹脂成形体およびその製造方法 | |
JP2007009063A (ja) | ノルボルネン系樹脂成形体およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15812526 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016529546 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2951820 Country of ref document: CA |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112016028156 Country of ref document: BR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15319059 Country of ref document: US Ref document number: MX/A/2016/016688 Country of ref document: MX |
|
REEP | Request for entry into the european phase |
Ref document number: 2015812526 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015812526 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20177000186 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2017102308 Country of ref document: RU Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 112016028156 Country of ref document: BR Kind code of ref document: A2 Effective date: 20161130 |