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
• • 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
  • 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
• • 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 liquid formulation for reaction injection molding containing a norbornene-based monomer, a manufacturing method thereof, a method for manufacturing a reaction injection-molded article using the liquid formation for reaction injection molding, and a reaction injection-molded article obtained thereby.
• reaction injection molding method including injecting a liquid reaction mixture containing a norbornene-based monomer and a metathesis polymerization catalyst in a mold, and carrying out a bulk ring-opening polymerization of the liquid reaction mixture to manufacture a resin molded article (reaction injection-molded article) made of a norbornene-based resin has been known.
• Patent Publication 1 discloses a technique including carrying out a bulk ring-opening polymerization of a norbornene-based monomer-containing liquid formulation for reaction injection molding containing a specified elastomer according to RIM method, thereby giving a resin molded article with reduced sink marks on the surface of the molded article irrespective of shapes, sizes and the like of the mold.
• Patent Publication 2 discloses a method for manufacturing a resin molded article including carrying out a bulk ring-opening polymerization of a novel metathesis polymerizable monomer containing a specified amount of an exo-dicyclopentadiene according to RIM method, thereby giving a sufficiently cured cross-linked polymer molded article having a low residual ratio of monomer. Also, Patent Publication 2 describes that if an ether compound is added to a reactive solution used in the manufacture of a resin molded article, storage stability can be improved.
• an object of the present invention is to provide a liquid formulation for reaction injection molding having excellent storage stability, a manufacturing method thereof, a method for manufacturing a reaction injection-molded article having high quality and also excellent strength using the liquid formulation for reaction injection molding, and a reaction injection-molded article obtained thereby.
• the present inventor has remarked on the formulation components during the preparation of the liquid formulation for reaction injection molding, and further in the mixing order thereof, and studied. As a result, he has found that the above problems can be solved by obtaining a desired liquid formulation for reaction injection molding by using a given ether compound, and mixing a norbornene-based monomer with an activator of a catalyst in the presence of the above compound, and the present invention has been perfected thereby.
• the gist of the present invention relates to:
• each of R 1 , R 2 , R 1 and R 4 independently stands for a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; each of R 5 and R 6 independently stands for an alkyl group having from 1 to 6 carbon atoms, with proviso that when R 5 and R 6 are a methyl group, at least one of R 1 to R 4 is an alkyl group having from 1 to 6 carbon atoms,
• reaction injection-molded article including the step of subjecting a reactive liquid mixture obtained by mixing a liquid formulation for reaction injection molding as defined in the above [1], with a metathesis polymerization catalyst including tungsten as a center metal to bulk polymerization in a mold, thereby carrying out reaction injection molding; and
• a liquid formulation for reaction injection molding having excellent storage stability, and a reaction injection-molded article having high quality and also excellent strength can be provided.
• the liquid formulation for reaction injection molding of the present invention contains (a) a norbornene-based monomer, (b) an activator, and (c) an ether compound represented by formula (1) given later.
• a reaction injection-molded article can be obtained by subjecting a reactive liquid mixture obtained by mixing a liquid formulation for reaction injection molding, with a metathesis polymerization catalyst including tungsten as a center metal to a bulk polymerization in a mold.
• the norbornene-based monomer is a compound having a norbornene structure represented by formula (2):
• the norbornene-based monomer (a) includes norbornene-based monomers that do not have a ring that condenses with a norbornene ring in the molecule; tricyclic or higher polycyclic norbornene-based monomers; and the like.
• the norbornene-based monomer (a) can be used alone or in a mixture of two or more kinds.
• the tricyclic or higher polycyclic norbornene-based monomer refers to a norbornene-based monomer including a norbornene ring and one or more rings condensed with the norbornene ring in the molecule. Specific examples thereof include a monomer represented by formula (3) given below:
• each of R 7 , R 8 , R 9 , and R 10 is independently a hydrogen atom; a halogen atom; a hydrocarbon group having from 1 to 20 carbon atoms which may have a substituent; or a substituent including a silicon atom, an oxygen atom, or a nitrogen atom, wherein R 1 and R 9 are together bonded to each other to form a ring; or
• each of R 11 , R 12 , R 13 , and R 14 is independently a hydrogen atom a halogen atom; a hydrocarbon group having from 1 to 20 carbon atoms which may have a substituent; a substituent including a silicon atom, an oxygen atom, or a nitrogen atom, wherein 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.
• the monomer represented by formula (3) includes, for example, dicyclopentadiene, methyldicyclopentadiene, tricyclo[5.2.1.0 2,6 ]deca-8-ene, 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-methan-1,4,4a,9,9a,10-hexahydroanthracene), and the like.
• dicyclopentadienes There are two kinds of steric isomers for the dicyclopentadienes: endo-dicyclopentadiene [formula (5)] and exo-dicyclopentadiene [formula (6)]. Simply calling a dicyclopentadiene would refer to endo-dicyclopentadiene.
• the monomer represented by formula (4) includes tricyclopentadiene, and tetracyclododecenes, wherein m is 1; and hexacycloheptadecenes, wherein m is 2.
• tetracyclododecenes include tetracyclododecenes which are unsubstituted or have an alkyl group, such as tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene; tetracyclododecenes which have a double bond outside the ring, such as 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyletracyclododecene, and 8-cyclopentenyltetra
• tetracyclododecenes which have a substituent including an oxygen atom, such as 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, and tetracyclododecene-8,9-dicarboxylic acid anhydride; tetracyclododecenes which have a substituent including a nitrogen atom, such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic acid imide; tetracyclododecenes which have a substituent including a halogen atom, such as 8-chlorotetra
• hexacycloheptadecenes include hexacycloheptadecenes which are unsubstituted or have an alkyl group, such as hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene; hexacycloheptadecenes which have a double bond outside the ring, such as 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, and 12-
• norbornene-based monomers can be used alone or in a combination of two or more kinds.
• the tricyclic or higher polycyclic norbornene-based monomers are preferred, and tricyclic, tetracyclic, or pentacyclic norbornene-based monomers are more preferred, from the viewpoint of being readily available, having excellent reactivity and obtaining a resin molded article having excellent heat resistance.
• a cross-linkable norbornene-based monomer having two or more reactive double bonds such as a norbornene-based monomer that gives a ring-opening polymer having a cross-reactive double bond
• a norbornene-based monomer that gives a ring-opening polymer having a cross-reactive double bond such as a symmetric cyclopentadiene trimer
• another norbornene-based monomer a norbornene-based monomer that gives a ring-opening polymer without a cross-reactive double bond
• a proportion of the cross-linkable norbornene-based monomer used is from 2 to 30% by mass of the entire norbornene-based monomers (a).
• a monomer which is ring-opening copolymerizable with the norbornene-based monomer may be used within the range that would not impair the object of the present invention.
• the monomer as mentioned above includes monocyclic cycloolefins, such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, cyclododecene, and the like.
• a proportion of the monomer mentioned above used is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the norbornene-based monomer (a).
• activator (b) is also called a co-catalyst, which is added for the purpose of enhancing polymerization activity of the metathesis polymerization catalyst.
• the activator (b) is not particularly limited, so long as the polymerization activity of the metathesis polymerization catalyst including tungsten as a center metal which is mixed with the liquid formulation of the present invention is enhanced.
• the activator (b) includes, for example, organometal compounds of metals of Groups 11 to 14 of the Periodic Table.
• alkylaluminum compounds such as triethylaluminum, triisobutylaluminum, trimethylaluminum, tributylaluminum, trihexylaluminum, and trioctylaluminum
• alkylaluminum halide compounds such as ethylaluminum dichloride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminumsesqui chloride, isobutylaluminum dichloride, and dioctylaluminum iodide
• alkylaluminum alkoxide compounds such as diethylammonium ethoxide
• organotin compounds such as tetrabutyltin
• organozinc compounds such as diethylzinc; and the like.
• alkylaluminum compounds and the alkylaluminum halide compounds are preferred, and more specifically triethylaluminum, trioctylaluminum, diethylaluminum chloride, and dioctylaluminum iodide are more preferred.
• the activator (b) can be used alone or in a mixture of two or more kinds.
• the amount of the activator (b) used is not particularly limited, it is preferable that the activator is blended in a given proportion based on the above norbornene-based monomer (a), from the viewpoint of enhancing polymerization activity of the metathesis polymerization catalyst, and improving reaction efficiency.
• the norbornene-based monomer and the activator are in a molar ratio (norbornene-based monomer (a)/activator (b)) of preferably from 100/1 to 2,000/1, more preferably from 150/1 to 1,500/1, and even more preferably from 200/1 to 1,2000/1.
• the liquid formulation for reaction injection molding of the present invention further contains an ether compound represented by the following formula (1) (which may be hereinafter referred to as “ether compound (c)”).
• ether compound (c) is used as an activity modulator for the metathesis polymerization catalyst.
• each of R 1 , R 2 , R 3 and R 4 independently stands for a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; each of R 5 and R 6 independently stands for an alkyl group having from 1 to 6 carbon atoms, with proviso that when R 5 and R 6 are a methyl group, at least one of R 1 to R 4 is an alkyl group having from 1 to 6 carbon atoms.
• the alkyl group having from 1 to 6 carbon atoms includes a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group, and the like.
• ether compound (c) examples include a group of compounds represented by the following formulas.
• the ether compound (c) is preferably a compound represented by the following formula (1-1):
• R 1 and R 2 are as defined above, with proviso that R 1 and/or R 2 is an alkyl group having from 1 to 6 carbon atoms,
• an asymmetric carbon atom can be present in the ether compound represented by formula (1), and its steric configuration is not particularly limited.
• the ether compound (c) can be all produced in accordance with a known method.
• a commercially available product can be directly used, or can be purified as needed.
• the ether compound (c) can be used alone or in a mixture of two or more kinds.
• the ether compound (c) is blended in a given proportion based on the above activator (b) in the liquid formulation for reaction injection molding of the present invention, from the viewpoint of inhibition of residual resins on a surface of the mold upon mold release, and improvement in strength of the reaction injection-molded article.
• the ether compound and the activator are in a molar ratio (ether compound (c)/activator (b)) of preferably from 0.1/1 to 30/1, more preferably from 1/1 to 10/1, and even more preferably from 3/1 to 5/1.
• the gelation time when the liquid formulation for reaction injection molding of the present invention is mixed with a metathesis polymerization catalyst including tungsten as a center metal depends upon the kinds and amount of the norbornene-based monomer etc. used, and mold temperature, and the like, it is preferable that the gelation time is 2 seconds or longer in order to obtain a molded article free from failures in external appearances of the surface.
• the above ratio is advantageous in securing the gelation time.
• the liquid formulation for reaction injection molding of the present invention may be blended with other components (which may be hereinafter referred to as “other components (d)”) as desired, in order to more efficiently manufacture a resin molded article, or in order to improve or maintain the properties of the resin molded article.
• other components which may be hereinafter referred to as “other components (d)”
• components (d) include polymerization promoters, elastomers, fillers, reinforcing materials, antioxidants, thermal stabilizers, photo-stabilizers, ultraviolet absorbents, pigments, colorants, blowing agents, antistatic agents, flame retardants, lubricants, softening agents, tackifying agents, plasticizers, mold-releasing agents, deodorants, perfume, dicyclopentadiene-based heat-polymerization resin and hydrogenated compounds thereof, and the like.
• the polymerization promoter is added in order to improve a polymerization conversion rate of the monomers.
• a chlorine atom-containing compound is preferred, and an organic chlorine compounds and silicon chloride compounds are more preferred.
• Specific examples include 2-chlorobenzotrichloride, 2,4-dichlorobenzotrichloride, hexachloro-p-xylene, 2,4-dichloro-trichlorotoluene, and silicon tetrachloride, and the like.
• the amount thereof would be usually from 10 mass ppm to 10% by mass of the overall reactive liquid mixture.
• the elastomer includes natural rubbers, polybutadiene, polyisoprene, styrene-butadiene copolymers (SBR), styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene copolymers (SIS), ethylene-propylene copolymers, ethylene-propylene-diene terpolymers (EPDM), ethylene-vinyl acetate copolymers (EVA) and hydrogenated products thereof, and the like.
• SBR styrene-butadiene copolymers
• SBS styrene-butadiene-styrene block copolymers
• SIS styrene-isoprene-styrene copolymers
• EPDM ethylene-propylene-diene terpolymers
• EVA ethylene-vinyl acetate copo
• the elastomer is added in order to give fluidity to the liquid formulation, thereby giving a molded article with reduced sink marks.
• an elastomer having a shear rate coefficient of from 1.30 to 1.60 is preferred.
• the shear rate coefficient is a numerical value obtained by a method described in Patent Publication 1 mentioned above.
• its blending amount is preferably from 0.5 to 20 parts by mass, and more preferably from 2 to 10 parts by mass, based on 100 parts by mass of the norbornene-based monomers.
• the filler is not particularly limited, and a fibrous filler having an aspect ratio of usually from 5 to 100, and preferably from 10 to 50, and an inorganic filler made of a particulate filler having an aspect ratio of usually from 1 to 2, and preferably from 1 to 1.5 are preferred.
• the aspect ratio of the filler refers to a ratio of the average length diameter to a 50% volume cumulative diameter of the filler.
• the average length diameter as used herein is a number-average length diameter obtained by measuring length diameters of 100 fillers randomly selected with an optical photomicrograph, and calculating an arithmetic means thereof.
• the 50% volume cumulative diameter is a value obtained by measuring the particle size distribution according to X-ray permeation method.
• the amount of the filler used is preferably from 5 to 55 parts by mass, and more preferably from 10 to 45 parts by mass, based on 100 parts by mass of a total amount of the norbornene-based monomer and the metathesis polymerization catalyst.
• the amount of the filler is exceedingly large, there are some risks that the reactive liquid mixture precipitates in the tank or the pipe when injected into a mold, or the injection nozzles are clogged.
• the amount of the filler is too small, there are some cases where rigidity or dimensional stability of the molded articles obtained is insufficient.
• the method for adding the other component (d) can be appropriately selected depending upon the kinds of the additives and the like.
• the liquid formulation for reaction injection molding of the present invention contains a norbornene-based monomer (a), an activator (b), and an ether compound (c) as mentioned above as essential components.
• the liquid formulation for reaction injection molding of the present invention may contain other component (d) as desired.
• it is needed that the liquid formulation for reaction injection molding of the present invention is obtained by mixing a norbornene-based monomer (a) and an activator (b) in the presence of at least an ether compound (c).
• a liquid formulation is prepared through the steps of mixing only two components of a norbornene-based monomer (a) and an activator (b)
• the norbornene-based monomer (a) used is at least a part of all the norbornene-based monomer (a) used
• the gelation time of a reactive liquid mixture obtained from the liquid formulation becomes too short, so that filling failure to a mold, or residual resin on a mold surface upon mold release is caused, thereby lowering the quality of the molded article obtained.
• Examples of specific embodiments of mixing a norbornene-based monomer (a) and an activator (b) in the presence of at least an ether compound (c) include the following:
• a norbornene-based monomer (a) may be mixed as a liquid mixture containing a pan of an ether compound (c) used.
• ((a), (b), (c), and the liquid mixture may each optionally contain other component (d) within the range that would not impair the effects of the present invention.)
• an activator (b) may be mixed as a liquid mixture containing a part of an ether compound (c) used.
• ((a), (b), (c), and the liquid mixture may each optionally contain other component (d) within the range that would not impair the effects of the present invention.)
• ((a), (b), and (c) may each optionally contain other component (d) within the range that would not impair the effects of the present invention.
• Embodiment A is preferred, from the viewpoint of improving storage stability of the liquid formulation for reaction injection molding of the present invention.
• the reaction injection-molded article of the present invention is obtained by a method including the step of subjecting a reactive liquid mixture prepared by mixing a liquid formulation for reaction injection molding of the present invention mentioned above and a metathesis polymerization catalyst including tungsten as a center metal to bulk polymerization in a mold, thereby carrying out reaction injection molding.
• the liquid formulation for reaction injection molding of the present invention By using the liquid formulation for reaction injection molding of the present invention, even after storage for a needed time, a reactive liquid mixture obtained is capable of showing a proper gelation time.
• the gelation time depends upon the kinds and amounts of the norbornene-based monomer or the like used, mold temperatures, and the like, the gelation time is preferably 2 seconds or more, more preferably from 5 seconds to 6 minutes, and even more preferably from 10 seconds to 5 minutes.
• the metathesis polymerization catalyst is not particularly limited, so long as the catalyst includes tungsten as a center metal, and is capable of allowing ring-opening polymerization of a norbornene-based monomer.
• the metathesis polymerization catalyst can be used alone or in a mixture of two or more kinds.
• the metathesis polymerization catalyst is a complex including a tungsten atom as a center atom, and plural ions, atoms, polyatomic ions and/or compounds are bonded thereto.
• the metathesis polymerization catalyst includes, for example, tungsten halides such as WCl 6 , WCl 5 , WCl 4 , WCl 2 , WBr 5 , WBr 4 , WBr 2 , WF 6 , WF 4 , WI 6 , and WI 4 ; tungsten oxyhalides such as WOCl 4 , WOBr 4 , WOF 4 , WCl 2 (OC 6 H 5 ) 4 , and W(OC 2 H 5 ) 2 Cl 3 ; metal oxides such as tungsten oxide; organotungsten compounds such as (CO) 5 WC(OCH 3 )(CH 3 ), (CO) 5 WC(OC 2 H 5 )(CH 3 ), (CO) 5 WC(OC 2 H 5 ), W(
• the tungsten halides and the tungsten oxyhalides are preferred, and more specifically WCl 6 and WOCl 4 are more preferred.
• the amount of the metathesis polymerization catalyst used is preferably 0.01 mmol or more, and more preferably 0.1 mmol or more, and preferably 50 mmol or less, and more preferably 20 mmol or less, based on one mol of the norbornene-based monomer to be used in the reaction (or a total mol when two or more kinds of the norbornene-based monomers are used), when taking the balance between maintenance of appropriate reaction efficiency and economic advantages into consideration.
• the metathesis polymerization catalyst is used in a given ratio to the activator (b) contained in the liquid formulation for reaction injection molding of the present invention, from the viewpoint of favorably keeping polymerization reaction and production efficiency. Specifically, it is desired that the metathesis polymerization catalyst is used so that the activator (b) would be in an amount of preferably 0.1 mol or more and 100 mol or less, and more preferably 1 mol or more and 10 mol or less, based on one mol of the metathesis polymerization catalyst.
• a metathesis polymerization catalyst is used after previously suspending in an inert solvent such as benzene, toluene and chlorobenzene, and adding a small amount of an alcoholic compound and/or a phenolic compound to solubilize.
• the alcoholic compound to be used herein includes ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, and the like.
• the phenolic compound to be used includes t-butylphenol, t-octylphenol, nonylphenol, dodecylphenol, and the like.
• a Lewis base or a chelating agent may be added and used in an amount of from about 1 to about 5 mol, based on one mol of the metathesis polymerization catalyst.
• the Lewis base and the chelating agent include acetyl acetone, alkyl acetoacetates, tetrahydrofuran, and benzonitrile, and the like.
• a resin molded article is manufactured by mixing at least two liquid formulations of a liquid formulation A that contains an activator but does not contain a metathesis polymerization catalyst, and a liquid formulation B containing a metathesis polymerization catalyst, and subjecting a reactive liquid mixture obtained to bulk polymerization and molding concurrently.
• the method for manufacturing a reaction injection-molded article of the present invention is preferably carried out according to an RIM method.
• the liquid formulation for reaction injection molding of the present invention is suitably used as a liquid formulation A.
• a liquid formulation B which is used together therewith is not particularly limited, so long as the liquid formulation contains a metathesis polymerization catalyst including tungsten as a center metal, and it is preferable that the liquid formulation contains a norbornene-based monomer (a) mentioned above and a metathesis polymerization catalyst mentioned above, from the viewpoint of improving homogeneity of a reactive liquid mixture obtained.
• a liquid formulation B may contain each of an ether compound (c) and other components (d).
• a norbornene-based monomer (a) and the like of a liquid formulation A and a norbornene-based monomer (a) and the like of a liquid formulation B may be identical or different from each other.
• a two-liquid-type liquid formulation for reaction injection molding composed of a liquid formulation A composed of a liquid formulation for reaction injection molding of the present invention and a liquid formulation B containing a norbornene-based monomer (a) and a metathesis polymerization catalyst including tungsten as a center metal can also be provided.
• a reaction injection-molded article can be manufactured by individually preparing a liquid formulation A composed of a liquid formulation for reaction injection molding of the present invention, and a liquid formulation B containing a norbornene-based monomer (a) and a metathesis polymerization catalyst including tungsten as a center atom mentioned above, mixing the liquid formulation A and the liquid formulation B within the above apparatus, injecting a reactive liquid mixture obtained into a mold, and subjecting the reactive liquid mixture to bulk polymerization.
• RIM reaction injection molding
• a liquid formulation C composed of a norbornene-based monomer (a) or the like may be further used as desired.
• the liquid formulation A, the liquid formulation B, and the liquid formulation C or the like which are used in the method for manufacturing a reaction injection-molded article of the present invention may be collectively referred to as a reaction stock solution.
• the mixing of a liquid formulation A, a liquid formulation B or the like mentioned above can be carried out by supplying each of them individually to an apparatus for reaction injection molding, and instantaneously mixing in a collision mixing apparatus (mixing head).
• a collision mixing apparatus mixing head
• a dynamic mixer or a low-pressure injection machine such as a static mixer can be used in place of the collision mixing apparatus.
• the temperature of the reaction stock solution before supplying to an apparatus for reaction injection molding is preferably from 10° to 60° C.
• the viscosity of the reaction stock solution is, for example, preferably from 5 to 3,000 mPa ⁇ s or so, and more preferably from 50 to 1,000 mPa ⁇ s or so, at 30° C.
• the mold used in the reaction injection molding is not particularly limited, and usually a mold formed by a core mold and a cavity mold is used.
• the material of the mold is not particularly limited, and includes metals such as steel, aluminum, zinc alloys, nickel, copper, and chromium, and resins and the like.
• these molds may be manufactured by any of methods such as casting, forging, metallizing, and electroforming, or those that are plated may be also used.
• the structure of the mold may be determined by considering the pressure upon injecting a reactive liquid mixture into a mold.
• the mold clamping pressure of the mold is preferably a gauge pressure of from 0.1 to 9.8 MPa or so.
• a mold temperature T1 (° C.) of the mold at a design surface is set higher than a mold temperature T2 (° C.) at a side opposing to the design surface.
• a temperature difference T1 ⁇ T2 is preferably 5° C. or more, and more preferably 10° C. or more, and the upper limit is preferably 60° C. or less.
• a temperature T1 is preferably 110° C. or lower, and more preferably 95° C. or lower, and the lower limit is preferably 50° C. or higher.
• a temperature T2 is preferably 70° C. or lower, and more preferably 60° C. or lower, and the lower limit is preferably 30° C. or higher.
• a method for adjusting a mold temperature includes, for example, a method of adjusting a mold temperature with a heater, a temperature-adjustment method with a heating medium such as temperature-controlled water or oil, circulated in a pipe embedded in the internal of a mold, and the like.
• an in-mold coating method including injecting a coating agent into a space formed by the molded article and a mold from an a coating agent injection inlet separately provided in the mold, to form a coating agent layer on a surface of the molded article may be subsequently carried out as desired.
• a mold After the termination of bulk polymerization (or when in-mold coating method is carried out, after the in-mold coating method), a mold is subjected to mold opening to demold, whereby a reaction injection-molded article can be obtained.
• the reaction injection-molded article of the present invention is obtained according to “the method for manufacturing a reaction injection-molded article” of the present invention, mentioned above.
• the reaction injection-molded article of the present invention can be manufactured efficiently on an industrial manufacturing scale by using a liquid formulation for reaction injection molding of the present invention.
• the reaction injection-molded article can be directly immediately used, or a plating and/or painting may be provided in accordance with a known method as desired, in order to improve or maintain the properties of a molded article.
• the reaction injection-molded article of the present invention can be suitably used in automobile applications such as bumpers and air deflectors; construction and industrial machinery applications such as wheel loaders and power shovels; recreational applications such as golf carts and arcade game machines; medical applications such as medical instruments; industrial applications such as large-scaled panels and chairs; house facility applications such as shower pans and washbowls; and the like.
• a 50 mL container containing a stirring bar and subjected to nitrogen replacement was maintained at 30° C.
• 10 mL of a liquid formulation (B) at 30° C. which was previously nitrogen-replaced was injected, and the contents were stirred with a magnetic stirrer at a rotational speed of 1,000 rpm.
• 10 mL of a liquid formulation (A) at 30° C. which was previously nitrogen-replaced was injected to the above container, and stirred for 5 seconds, to mix with the liquid formulation (B).
• the liquid formulation (A) and the liquid formulation (B) were reacted to start the polymerization.
• a liquid formulation (A) and a liquid formulation (B) were mixed to obtain a reactive liquid mixture, and the reactive liquid mixture was injected into a plate-like mold having sizes of 297 mm ⁇ 210 mm ⁇ 0.1 mm, and allowed to heat-cure, and its flow length was measured.
• heat curing was carried out by setting a mold temperature to 80° C.
• the flexural strength of a molded article was measured under the condition of a measurement temperature of 23° C., as prescribed in JIS K7171.
• the flexural modulus of a molded article was measured under the condition of a testing speed of 2 mm/minute, as prescribed in JIS K7171.
• the manufacture of a molded article was repeated 10 times, and the mold was then cooled, and the mold surfaces were observed at 10 locations of the optional areas 10 mm ⁇ 10 mm by expanding 10 times with an optical microscope, and the residual resin on the mold surface was evaluated in accordance with the following evaluation criteria.
• Residual resins are found in one or more and 2 or less areas.
• DPG Dipropylene glycol dimethyl ether
• TEAL triethylaluminum
• DPG and TEAL were mixed so as to have a molar ratio of 4.5:1, to prepare a liquid mixture 2.
• DPG and TEAL were mixed so as to have a molar ratio of 6:1, to prepare a liquid mixture 3.
• DPG and dicyclopentadiene (DCPD) were mixed, and TEAL was added to the mixture obtained and mixed, to prepare a liquid mixture 4.
• a molar ratio of DPG, DCPD, and TEAL was 1:5:1.
• DCPD and TEAL were mixed so as to have a molar ratio of 5:1, to prepare a liquid mixture 5.
• a liquid formulation (A) The amount 4.1 parts of an ethylene-propylene copolymer [propylene units: 89%, ethylene units: 11%] was added to a mixture of norbornene-based monomers composed of 90 parts of DCPD and 10 parts of tricyclopentadiene (TCPD). Next, 0.6 parts of a liquid mixture 1 were added thereto, to give a liquid formulation (A).
• a TEAL concentration was 22 mmol/kg
• a molar ratio of the norbornene-based monomers to TEAL (norbornene-based monomers:TEAL) was 340:1.
• tungsten hexachloride as a metathesis polymerization catalyst, 1 part of t-butanol, 14 parts of dodecylphenol, and 9 parts of acetyl acetone were mixed in toluene, to prepare a metathesis polymerization catalyst solution having a tungsten concentration of 11%.
• the liquid formulation (A) and the liquid formulation (B) prepared above was used after storage at 50° C. for 16 hours under nitrogen atmosphere, and the gelation time was measured in accordance with the method mentioned above, to evaluate filling ability into a mold.
• the results are shown in Table 1.
• Example 1 The same procedures as in Example 1 were carried out except that a liquid mixture 2, 3, or 4 was used in place of the liquid mixture 1, to prepare a liquid formulation (A) and a liquid formulation (B), and the gelation time was measured to evaluate filling property to a mold. The results are shown in Table 1.
• Example 1 The same procedures as in Example 1 were carried out except that DPG was added to the above norbornene-based monomer and mixed, and that a liquid mixture 5 was used in place of the liquid mixture 1, to prepare a liquid formulation (A) and a liquid formulation (B), and the gelation time was measured to evaluate filling property to a mold.
• a molar ratio of DPG to TEAL was 1:1. The results are shown in Table 1.
• liquid formulations (A) and (B) were stored at 50° C. for 16 hours under nitrogen atmosphere, and the changes during storage were accelerated and used (acceleration test).
• a mold for reaction injection molding made of two aluminum plates capable of forming a cavity of length 245 mm ⁇ width 210 mm ⁇ thickness 3 mm in an internal thereof was furnished, and one of the molds was heated with a heater to 90° C. to adjust a temperature difference between a core mold and a cavity mold to 40° C.
• this mold for reaction injection molding has a structure of having an injection pore for a liquid formulation for reaction injection molding on one side of the aluminum plates.
• a liquid formulation (A) and a liquid formulation (B) obtained in each of Examples 1 to 4 and Comparative Example 1 were each heated to 30° C., and the liquid formulations were injected to a mold for reaction injection molding from an injection pore, while mixing the contents in a proportion of a mixing ratio of 1:1 (mass ratio) with a static mixer.
• Bulk polymerization was carried out in the mold for 120 seconds, and the mold was subjected to mold opening to demold, thereby giving each of molded articles made of a polymerization-cured norbornene-based resin.
• the manufacture of molded articles was carried out 10 times. All the norbornene-based resins obtained had a specific gravity of 1.04, and a glass transition temperature (Tg) measured according to the DSC method of 145° C.
• Example 5 to 8 the molded articles having excellent flexural strength and flexural modulus, and excellent demoldability were obtained.
• Comparative Example 2 it can be seen in Comparative Example 2 that a mixing failure of the reactive liquid mixture is caused due to a very short gelation time (shorter than 2 seconds), and the metathesis polymerization catalyst is not sufficiently activated, so that the polymerization activity is assumed to be lowered, whereby physical properties of the molded articles such as flexural strength, flexural modulus, and the evaluation of residual resin on surface of the mold are markedly lowered.
• Example 6 a molded article of Example 6 in which a liquid formulation (A) prepared by mixing an ether compound (DPG) and an activator (TEAL) in a molar ratio of 4.5:1 is used is preferred.
• A liquid formulation prepared by mixing an ether compound (DPG) and an activator (TEAL) in a molar ratio of 4.5:1 is used is preferred.
• the liquid formulation for reaction injection molding of the present invention can be suitably used in the field of manufacture of reaction injection-molded articles. Further, the reaction injection-molded article of the present invention has excellent mechanical properties and finishing of surface of the manufactured articles, so that the reaction injection-molded article can be suitably used in applications of automobile parts, parts of housing facilities, and the like.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
• Injection Moulding Of Plastics Or The Like (AREA)

Applications Claiming Priority (3)

Related Parent Applications (1)

Related Child Applications (1)

Publications (1)

Family

ID=54938074

Family Applications (2)

Family Applications After (1)

Country Status (9)

Cited By (2)

Families Citing this family (2)

Citations (2)

Family Cites Families (16)

• 2015
  • 2015-06-19 CA CA2951820A patent/CA2951820C/en active Active
  • 2015-06-19 KR KR1020177000186A patent/KR102361537B1/ko active IP Right Grant
  • 2015-06-19 MX MX2016016688A patent/MX2016016688A/es unknown
  • 2015-06-19 WO PCT/JP2015/067755 patent/WO2015198990A1/ja active Application Filing
  • 2015-06-19 US US15/319,059 patent/US20170114160A1/en not_active Abandoned
  • 2015-06-19 EP EP15812526.0A patent/EP3162831A4/en active Pending
  • 2015-06-19 CN CN201580033258.4A patent/CN106471036B/zh active Active
  • 2015-06-19 RU RU2017102308A patent/RU2689981C2/ru active
  • 2015-06-19 JP JP2016529546A patent/JP6577466B2/ja active Active
• 2019
  • 2019-12-27 US US16/728,549 patent/US11066497B2/en active Active

Patent Citations (2)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events