Patent Application
20210139622
The present invention relates to a 4-methyl-1-pentene polymer having specific physical properties, and a resin composition and a molded article comprising the same.
4-Methyl-1-pentene-α-olefin copolymers with 4-methyl-1-pentene as a main constitutional monomer are excellent in heat resistance, mold release properties, and chemical resistance and therefore widely used for various applications. For example, films made of the copolymers are used in FPC mold releasing films, films for composite material molding, mold releasing films, etc. by exploiting features such as favorable mold release properties, or used in experimental instruments and mandrels for rubber hose production, etc. by exploiting features such as chemical resistance, water resistance, and transparency.
On the other hand, molded articles made of resin compositions comprising a conventional 4-methyl-1-pentene polymer may need to be improved from the viewpoint of shape retention under a load at a high temperature, i.e., from the viewpoint of heat resistance (see, for example, Patent Literature 1). Since these molded articles contain a given level of low-molecular-weight components derived from the polymer, the molded articles need to be improved from the viewpoint of stain resistance and may be unable to be used for applications that require high purity (see, for example, Patent Literature 2).
Patent Literature 3 discloses a 4-methyl-1-pentene polymer having high stereoregularity and a high heat of fusion. Patent Literature 4 discloses a molded article improved in shape retaining properties at a high temperature and stain resistance by exploiting the characteristics of the polymer.
As mentioned above, the 4-methyl-1-pentene polymer and the molded article described in Patent Literatures 3 and 4 have high stereoregularity and a high heat of fusion and possess features excellent in heat resistance. On the other hand, from the viewpoint of molding, it is necessary, particularly, for large molding apparatuses, to render a set temperature much higher than a melting point in order to sufficiently melt resins. This may be responsible for dirt on molding dies, discoloration of molded products, or molded product surface stain. The studies of the present inventors have revealed that there is also a demand for a 4-methyl-1-pentene polymer that can be fused in a small amount of heat and can be molded in a small amount of heat.
4-Methyl-1-pentene polymers obtained by polymerization in a titanium catalyst system as described in Comparative Examples of Patent Literatures 3 and 4 exhibit lower stereoregularity and a lower heat of fusion than those of polymers described in Examples of Patent Literatures 3 and 4. However, it has turned out that the amount of low-molecular-weight components (oligomers) is large due to low molecular weight control, and this may be responsible for dirt on molding dies, discoloration of molded products, or molded product surface stain; thus there is a demand for improvement in the stain resistance of this polymer.
A molded article obtained from the 4-methyl-1-pentene polymer described in Patent Literatures 3 and 4 possesses features excellent in heat resistance, etc. However, the studies of the present inventors have suggested that there is a room for improvement in terms of neck-in during film formation or drawdown during blow molding, and improvement in melt tension is effective for such improvement in moldability.
An object of the present invention is to solve the problems of the conventional techniques. Specifically, an object of the present invention is to decrease a heat of fusion and improve fusibility without largely impairing the characteristics, such as high heat resistance, of the 4-methyl-1-pentene polymer, to thereby facilitate low-temperature molding at an apparatus temperature near the melting point, additionally to improve the melt tension of the polymer and thereby improve moldability, and to improve stain resistance.
The present inventors have conducted diligent studies to attain the object. As a result, the present inventors have completed the present invention by finding that the object can be attained by a 4-methyl-1-pentene polymer having a specific composition and having specific characteristics.
The present invention relates to the following [1] to [6]:
(i) the following expression (1) holds:
ΔHm<0.5×Tm−76 Expression (1)
wherein the heat of fusion is defined as ΔHm J/g, and the melting point is defined as Tm° C.; and
(ii) the melting point falls within the range of 180 to 260° C.
The present invention can provide a 4-methyl-1-pentene polymer and a resin composition which have a low heat of fusion, excellent fusibility, furthermore a high melt tension and excellent stain resistance without largely impairing the characteristics, such as high heat resistance, of the 4-methyl-1-pentene polymer.
Hereinafter, the 4-methyl-1-pentene polymer (X) (hereinafter, also simply referred to as the polymer (X)) according to the present invention, a resin composition comprising the polymer (X), and a molded article comprising the polymer (X) or the resin composition will be specifically described.
In the 4-methyl-1-pentene polymer (X) of the present invention, a content of a constitutional unit derived from 4-methyl-1-pentene is 90 to 100% by mol with respect to all constitutional units contained in the polymer (X); a content of a constitutional unit derived from at least one olefin (hereinafter, also referred to as a comonomer) selected from ethylene and an α-olefin, other than 4-methyl-1-pentene, having 3 to 20 carbon atoms is 0 to 10% by mol; and the polymer (X) satisfies requirements (a) to (f) given below. The requirements thus specified mean that when the 4-methyl-1-pentene polymer (X) is a blend of a plurality of 4-methyl-1-pentene polymers, the blend satisfies the requirements (a) to (f).
Examples of the 4-methyl-1-pentene polymer (X) include homopolymers of 4-methyl-1-pentene (i.e., polymers in which the content of the constitutional unit derived from 4-methyl-1-pentene is 100% by mol) and copolymers of 4-methyl-1-pentene and other olefins.
In this context, the content of the constitutional unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (X) is preferably 92 to 100% by mol, more preferably 95 to 100% by mol, with respect to all constitutional units contained in the polymer (X), and the total content of the constitutional unit derived from at least one olefin selected from ethylene and an α-olefin having 3 to 20 carbon atoms (except for 4-methyl-1-pentene) is preferably 0 to 8% by mol, more preferably 0 to 5% by mol, from the viewpoint of transparency and heat resistance.
When the 4-methyl-1-pentene polymer (X) is a copolymer, specific examples of the ethylene and the α-olefin having 3 to 20 carbon atoms to be copolymerized with 4-methyl-1-pentene include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Among them, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferred. These α-olefins may be used alone or in combination of two or more thereof.
In the present invention, the amounts of the constitutional unit derived from 4-methyl-1-pentene and the constitutional unit derived from at least one olefin selected from ethylene and an α-olefin having 3 to 20 carbon atoms (except for 4-methyl-1-pentene) in the 4-methyl-1-pentene polymer (X) can be adjusted by the amounts of 4-methyl-1-pentene and at least one olefin selected from ethylene and an α-olefin having 3 to 20 carbon atoms (except for 4-methyl-1-pentene) to be added during polymerization reaction.
Hereinafter, each requirement to be satisfied by the 4-methyl-1-pentene polymer (X) will be described.
A meso diad fraction (m) measured by 13C-NMR falls within the range of 70.0% or more to less than 98.0%, preferably within the range of 80.0% or more to less than 98.0%, more preferably within the range of 90.0% or more to less than 98.0%, further preferably within the range of 95.0% or more to less than 98.0%.
When the meso diad fraction (m) of the 4-methyl-1-pentene polymer (X) is equal to or higher than the lower limit value described above, a molded article comprising the 4-methyl-1-pentene polymer (X) possesses sufficient performance such as heat resistance and rigidity.
In the present invention, the meso diad fraction (m) of the 4-methyl-1-pentene polymer (X) can be adjusted by the type of a catalyst for olefin polymerization mentioned later.
A ratio of weight-average molecular weight Mw to number-average molecular weight Mn (Mw/Mn) measured by gel permeation chromatography (GPC) falls within the range of 3.6 to 30, preferably within the range of 3.6 to 25, more preferably 3.8 to 25, further preferably 4.0 to 25, especially preferably 4.0 to 15. When the ratio (Mw/Mn) falls within the range described above, a molded article such as a film comprising the 4-methyl-1-pentene polymer (X) is excellent in tenacity, decreases internal cracks responsible for whitening, and is excellent in the elongation of the film. Also, the ratio (Mw/Mn) that falls within the range described above suggests that the 4-methyl-1-pentene polymer (X) contains a considerable amount of a polymer having a large molecular weight. A method for adjusting the ratio (Mw/Mn) of the 4-methyl-1-pentene polymer (X) to the range described above is specifically mentioned later.
A melt flow rate (MFR) of the 4-methyl-1-pentene polymer (X) measured under conditions of 260° C. and a 5 kg load in conformity to ASTM D1238 is 0.1 to 500 g/10 min, preferably 1 to 300 g/10 min, more preferably 2 to 100 g/10 min, further preferably 5 to 80 g/10 min.
The MFR of the 4-methyl-1-pentene polymer (X) that falls within the range described above is preferred from the viewpoint of resin flowability during molded article production.
In the present invention, a method for adjusting the MFR of the 4-methyl-1-pentene polymer (X) includes, for example, a method of adjusting the amount of hydrogen within a reactor during polymerization reaction, or blending plural types of polymers differing in MFR during or after polymerization.
A cumulative weight fraction of amounts of eluates at 80° C. or lower measured in a cross fractionation chromatograph apparatus using an infrared spectrophotometer as a detector part is 5% by mass or less.
A low cumulative weight fraction of amounts of eluates at 80° C. or lower in the 4-methyl-1-pentene polymer (X) indicates that the amount of a low-molecular-weight polymer contained in the polymer (X) is small. When the cumulative weight fraction falls within the range described above, the efflux of a low-molecular-weight component serving as a contaminant component from a molded article obtained from a resin composition comprising the polymer can be suppressed, and the suppression of stain on a molding machine such as a die during molding, the suppression of discoloration of the resulting molded product, and the suppression of molded product surface stain or content stain can therefore be effectively performed.
In the present invention, the cumulative weight fraction can be adjusted by the type of a catalyst for olefin polymerization mentioned later.
A proportion of a polymer having a molecular weight of 1×106 or larger measured by gel permeation chromatography (GPC) is 15% by mass or more, preferably 16% by mass or more, more preferably 17% by mass or more, further preferably 18% by mass or more. The upper limit of the molecular weight is not particularly limited and also depends on MFR of the polymer (X), but is preferably 50% by mass or less, more preferably 40% by mass or less. When the molecular weight falls within the range described above, the 4-methyl-1-pentene polymer (X) is excellent in melt tension. Also, the proportion of a polymer having a molecular weight of 1×106 or larger that falls within the range described above suggests that a considerable amount of a component having a large molecular weight is contained therein. The proportion of a polymer having a molecular weight of 1×106 or larger in the 4-methyl-1-pentene polymer (X) can be adjusted to the range described above by allowing hydrogen to coexist in a reactor during polymerization reaction and increasing or decreasing the amount of the hydrogen.
A heat of fusion and a melting point of the 4-methyl-1-pentene polymer (X) measured by differential scanning calorimetry (DSC) satisfy the following requirements (i) and (ii):
(i) the following expression (1) holds:
ΔHm<0.5×Tm−76 Expression (1)
wherein the heat of fusion is defined as ΔHm J/g, and the melting point is defined as Tm° C.; and
(ii) the melting point falls within the range of 180 to 260° C.
The heat of fusion (ΔH mJ/g) measured by differential scanning calorimetry (DSC) (rate of temperature increase: 10° C./min) in the requirement (i) is preferably 5 to 80 J/g, more preferably 10 to 60 J/g. The melting point (Tm° C.) measured by differential scanning calorimetry (DSC) (rate of temperature increase: 10° C./min) in the requirement (ii) is preferably 180 to 250° C., more preferably 200 to 250° C., further preferably 210 to 245° C.
The requirement (i) indicates that the 4-methyl-1-pentene polymer (X) according to the present invention has a low heat of fusion with respect to the melting point. Specifically, the 4-methyl-1-pentene polymer that satisfies the requirement (i) is found to be excellent in fusibility while maintaining high heat resistance.
Disclosure related to this requirement (i) is made in Patent Literature 3, and similar disclosure is made in Patent Literature 4.
In the present invention, the heat of fusion of the 4-methyl-1-pentene polymer (X) can be adjusted to within the range specified above by using a catalyst for olefin polymerization mentioned later. The melting point can be adjusted by adjusting the proportion of the constitutional unit of 4-methyl-1-pentene in the requirement (a) while using the catalyst for olefin polymerization.
The 4-methyl-1-pentene polymer (X) satisfies the requirements (a) to (f) as mentioned above and preferably further satisfies the following requirement (g).
A melt tension at 260° C. is 15 mN or higher, more preferably 20 mN or higher. The upper limit is not particularly limited and is usually 100 mN or lower. The melt tension that falls within the range described above is preferred for moldability.
The 4-methyl-1-pentene polymer (X) can be obtained by the polymerization of 4-methyl-1-pentene or by the copolymerization of 4-methyl-1-pentene with at least one olefin selected from ethylene and an α-olefin having 3 to 20 carbon atoms (except for 4-methyl-1-pentene), in the presence of a catalyst for olefin polymerization mentioned later.
[1-1] Catalyst for Olefin Polymerization
The catalyst for olefin polymerization is preferably a catalyst comprising:
<Bridged Metallocene Compound (A)>
The bridged metallocene compound (A) is preferably a compound represented by the general formula [A1], more preferably a compound represented by the general formula [A2].
In the formula [A1], M is a transition metal atom of group 4 of the periodic table, for example, a titanium atom, a zirconium atom or a hafnium atom; Q is selected in the same or different combination from a halogen atom, a hydrocarbon group, a neutral conjugated or unconjugated diene having 10 or less carbon atoms, an anion ligand, and a neutral ligand capable of being coordinated as a lone electron pair; j is an integer of 1 to 4; RA and RB may be the same as or different from each other and each are a mononuclear or polynuclear hydrocarbon residue capable of forming a sandwich structure together with M; Y is a carbon atom or a silicon atom; and RC and RD may be the same as or different from each other and are each selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group or may be bonded to each other to form a ring.
In the formula [A2], R1 is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group; R2 to R10 may be the same as or different from each other and are each selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group; each of R2 to R10 may be bonded to another substituent to form a ring; M is a transition metal atom of group 4 of the periodic table; Q is selected in the same or different combination from a halogen atom, a hydrocarbon group, a neutral conjugated or unconjugated diene having 10 or less carbon atoms, an anion ligand and a neutral ligand capable of being coordinated as a lone electron pair; and j is an integer of 1 to 4.
<Compound (B)>
The catalyst for olefin polymerization preferably contains at least one compound (B) selected from
Specific examples of the compound (B) and a support (C) and an organic compound component (D) mentioned later are as disclosed in Patent Literatures 3 and 4 or International Publication No. WO 2014-123212. Examples disclosed in International Publication No. WO 2010-055652, International Publication No. WO 2011-142400, International Publication No. WO 2013-146337, and Japanese Patent Laid-Open No. 2015-74645 are further applicable to the support (C).
<Support (C)>
The catalyst for olefin polymerization more preferably further contains a support (C).
Examples of the support (C) include inorganic or organic compounds which are solids in the form of granules or fine particles. The transition metal compound (A) is preferably used in a form supported by the support (C).
<Organic Compound Component (D)>
The catalyst for olefin polymerization of the present invention may further contain (D) an organic compound component, if necessary. The organic compound component (D) is used, if necessary, for the purpose of improving polymerization performance and the physical properties of a product polymer. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers and sulfonates.
<Methods for Adjusting Ratio (Mw/Mn)>
The ratio (Mw/Mn) of the 4-methyl-1-pentene polymer (X) can be adjusted by blending a plurality of polymers differing in molecular weight during or after polymerization in a single-stage or multiple-stage (e.g., two-stage) polymerization method.
Alternatively, (Mw/Mn) may be adjusted to an arbitrary value by adding hydrogen in divided portions “at the initial stage of polymerization” and “during polymer production” even in single-stage polymerization. More specifically, the ratio (Mw/Mn) of the polymer to be finally obtained can be adjusted by adding a small amount of hydrogen at the initial stage of polymerization to produce a high-molecular-weight polymer and feeding a larger amount of hydrogen at a polymerization stage advanced to some extent to produce a relatively low-molecular-weight polymer.
The resin composition comprising the 4-methyl-1-pentene polymer (X) according to the present invention comprises the 4-methyl-1-pentene polymer (X) as an essential constituent and additionally comprises various components according to the purpose of the molded article according to the present invention.
The resin composition comprising the 4-methyl-1-pentene polymer (X) can optionally contain an additional resin or polymer, an additive for resins, etc., without inhibiting the effect of the present invention, according to its purpose.
A thermoplastic resin (E) given below can be widely used as the additional resin or polymer to be added. The amount of the resin or the polymer added is preferably 0.1 to 30% by mass with respect to the total mass of the resin composition.
The thermoplastic resin (E) is not particularly limited as long as the thermoplastic resin (E) is different from the 4-methyl-1-pentene polymer (X) according to the present invention. Examples thereof include the following resins:
thermoplastic polyolefin resins, for example, low-density, medium-density, or high-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-3-methyl-1-pentene, poly-3-methyl-1-butene, ethylene-α-olefin copolymers, propylene-α-olefin copolymers, 1-butene-α-olefin copolymers, 4-methyl-1-pentene-α-olefin copolymers, cyclic olefin copolymers, chlorinated polyolefin, and modified polyolefin resins prepared by modifying these olefin resins;
thermoplastic polyamide resins, for example, aliphatic polyamides (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, and nylon 612);
thermoplastic polyester resins, for example, polyethylene terephthalate, polybutylene terephthalate, and polyester elastomers;
thermoplastic vinyl aromatic resins, for example, polystyrene, ABS resin, AS resin, and styrene elastomers (styrene-butadiene-styrene block polymers, styrene-isoprene-styrene block polymers, styrene-isobutylene-styrene block polymers, and hydrogenated products thereof);
thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; ethylene-vinyl acetate copolymers; ethylene-methacrylic acid-acrylate copolymers; ionomers; ethylene-vinyl alcohol copolymers; polyvinyl alcohol; fluorinated resins; polycarbonate; polyacetal; polyphenylene oxide; polyphenylene sulfide; polyimide; polyarylate; polysulfone; polyethersulfone; rosin resins; terpene resins; petroleum resins; and
copolymer rubbers, for example, ethylene-α-olefin-diene copolymers, propylene-α-olefin-diene copolymers, 1-butene-α-olefin-diene copolymers, polybutadiene rubber, polyisoprene rubber, neoprene rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, natural rubber, and silicone rubber.
Examples of the polypropylene include isotactic polypropylene and syndiotactic polypropylene. The isotactic polypropylene may be homopolypropylene, may be a propylene-C2-20 α-olefin (except for propylene) random copolymer, or may be a propylene block copolymer.
The poly-4-methyl-1-pentene and the 4-methyl-1-pentene-α-olefin copolymer are polymers different from the 4-methyl-1-pentene polymer (X) and are a homopolymer of 4-methyl-1-pentene or a 4-methyl-1-pentene-α-olefin random copolymer. For the 4-methyl-1-pentene-α-olefin random copolymer, examples of the α-olefin to be copolymerized with 4-methyl-1-pentene include α-olefins having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. These can be used alone or in combination of two or more thereof. The melt flow rate (MFR; ASTM D1238, 260° C., a 5.0 kg load) is preferably 0.1 to 200 g/10 min, more preferably 1 to 150 g/10 min. A commercially available product may be used as the poly-4-methyl-1-pentene. Examples thereof include TPX (brand name) manufactured by Mitsui Chemicals, Inc. Poly-4-methyl-1-pentene from any of other manufacturers can also be preferably used as long as the requirements described above are satisfied.
Low-density polyethylene, medium-density polyethylene, high-density polyethylene, or high-pressure low-density polyethylene produced by a conventional approach known in the art can be used as the polyethylene.
Examples of the polybutene can include homopolymers of 1-butene and copolymers of 1-butene and olefins except for 1-butene. Examples of the olefin to be copolymerized with polybutene include the α-olefins listed as the α-olefin to be copolymerized with 4-methyl-1-pentene. These olefins are used alone or as a mixture of two or more thereof. Examples of the copolymer include 1-butene-ethylene random copolymers, 1-butene-propylene random copolymers, 1-butene-methylpentene copolymers, 1-butene-methylbutene copolymers, and 1-butene-propylene-ethylene copolymers. In such a copolymer, the content of a constitutional unit derived from 1-butene is preferably 50% by mol or more, more preferably 70% by mol or more, particularly preferably 85% or more, from the viewpoint of heat resistance.
The modified polyolefin resin can be obtained by graft-modifying the polyolefin resin mentioned above with an ethylenic unsaturated bond-containing monomer using an organic peroxide. Examples of the type of the functional group carried by the modified polyolefin include a halogen atom, a carboxyl group, an acid anhydride group, an epoxy group, a hydroxy group, an amino group, an amide group, an imide group, an ester group, an alkoxysilane group, an acid halide group and a nitrile group.
Examples of the rosin resin include natural rosin, polymerized rosin, modified rosin prepared by modification with maleic acid, fumaric acid, (meth)acrylic acid, or the like, and rosin derivatives. Examples of this rosin derivative include esterified products of the natural rosin, the polymerized rosin or the modified rosin described above, phenol-modified products thereof and their esterified products. Further examples thereof can also include hydrogenated products thereof.
Examples of the terpene resin include resins consisting of α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, or terpene aldehyde and also include aromatic modified terpene resins prepared by polymerizing an aromatic monomer such as styrene with α-pinene, β-pinene, limonene, dipentene, or the like. Further examples thereof can also include hydrogenated products thereof.
Examples of the petroleum resin include aliphatic petroleum resins with a C5 fraction of tar naphtha as a main raw material, aromatic petroleum resins with a C9 fraction thereof as a main raw material and copolymerized petroleum resins thereof. Specific examples thereof include C5 petroleum resin (resin prepared by polymerizing a C5 fraction of cracked naphtha), C9 petroleum resin (resin prepared by polymerizing a C9 fraction of cracked naphtha), and C5-C9 copolymerized petroleum resin (resin prepared by copolymerizing C5 and C9 fractions of cracked naphtha). Further examples thereof also include coumarone indene resins containing styrenes, indenes, coumarone, and dicyclopentadiene, etc. of tar naphtha fractions, alkylphenol resins typified by condensates of p-tertiary butylphenol and acetylene, and xylene resins prepared by reacting o-xylene, p-xylene or m-xylene with formalin.
One or more resin(s) selected from the group consisting of a rosin resin, a terpene resin and a petroleum resin is preferably a hydrogenated derivative because of excellent weather resistance and resistance to discoloration. The softening point of the resin in a ring-and-ball method preferably falls within the range of 40 to 180° C. The number-average molecular weight (Mn) of the resin measured by GPC preferably falls within the range of approximately 100 to 10,000. Commercially available products may be used as the rosin resin, the terpene resin and the petroleum resin.
The thermoplastic resin (E) is preferably low-density, medium-density, or high-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-3-methyl-1-pentene, poly-3-methyl-1-butene, an ethylene-α-olefin copolymer, a propylene-α-olefin copolymer, a 1-butene-α-olefin copolymer, a styrene elastomer, a vinyl acetate copolymer, an ethylene-methacrylic acid-acrylate copolymer, an ionomer, a fluorinated resin, a rosin resin, a terpene resin or a petroleum resin, more preferably polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly-1-butene, an ethylene-α-olefin copolymer, a propylene-α-olefin copolymer, a 1-butene-α-olefin copolymer, a vinyl acetate copolymer, a styrene elastomer, a rosin resin, a terpene resin or a petroleum resin from the viewpoint of improvement in heat resistance, improvement in cold resistance, and flexibility.
Examples of the thermoplastic resin (E) preferably include poly-3-methyl-1-pentene and poly-3-methyl-1-butene. These contribute to improvement in the rigidity of the resulting film, etc. by working as a nucleating agent of the 4-methyl-1-pentene polymer (X) of the present invention.
One of the thermoplastic resins described above may be used alone as the thermoplastic resin (E), or two or more thereof may be used in combination.
Examples of the additive for resins include nucleating agents, antiblocking agents, pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antimicrobial agents, surfactants, antistatic agents, weathering stabilizers, heat stabilizers, anti-slip agents, foaming agents, crystallization aids, anti-fogging agents, (transparent) nucleating agents, antiaging agents, hydrochloric acid absorbers, impact modifiers, cross-linking agents, co-cross-linking agents, cross-linking aids, pressure-sensitive adhesives, softening agents, and processing aids. These additives can be used alone or in appropriate combination of two or more thereof.
A nucleating agent known in the art can be used as the nucleating agent for further improving the moldability of the 4-methyl-1-pentene polymer (X), i.e., increasing the crystallization temperature and increasing the crystallization rate. Specific examples thereof include dibenzylidene sorbitol nucleating agents, phosphoric acid ester salt nucleating agents, rosin nucleating agents, benzoic acid metal salt nucleating agents, fluorinated polyethylene, sodium 2,2-methylenebis(4,6-di-t-butylphenyl)phosphate, pimelic acid and salts thereof, and 2,6-naphthalenedicarboxylic acid dicyclohexylamide. The amount of the nucleating agent added is not particularly limited and is preferably 0.1 to 1 parts by mass with respect to 100 parts by mass of the 4-methyl-1-pentene polymer (X). The nucleating agent can be appropriately added, for example, during polymerization, after polymerization, or during molding.
An antiblocking agent known in the art can be used as the antiblocking agent. Specific examples thereof can include fine silica powders, fine aluminum oxide powders, fine clay powders, powdery or liquid silicon resin, tetrafluoroethylene resin, and fine cross-linked resin powders, for example, cross-linked acrylic or methacrylic resin powders. Among them, a fine silica powder and a cross-linked acrylic or methacrylic resin powder are preferred.
Examples of the pigment include inorganic pigments (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azolake pigments, thioindigo pigments, phthalocyanine pigments and anthraquinone pigments). Examples of the dye include azo dyes, anthraquinone dyes, and triphenylmethane dyes. The amounts of the pigment and the dye added are not particularly limited, and the total amount thereof is usually 5% by mass or less, preferably 0.1 to 3% by mass, with respect to the total mass of the resin composition comprising the 4-methyl-1-pentene polymer.
Examples of the filler include glass fiber, carbon fiber, silica fiber, metal (stainless, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicates (calcium silicate, talc, clay, etc.), metal oxides (iron oxide, titanium oxide, alumina, etc.), carbonates of metals (calcium sulfate, barium sulfate), various metal (magnesium, silicon, aluminum, titanium, copper, etc.) powders, mica, and glass flake. These fillers may be used alone or in combination of two or more thereof.
Examples of the lubricant include waxes (carnauba wax, etc.), higher fatty acids (stearic acid, etc.), higher alcohols (stearyl alcohol, etc.), and higher fatty acid amides (stearic acid amide, etc.).
Examples of the plasticizer include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (methyl acetyl ricinoleate, etc.), aliphatic dicarboxylic acid esters (adipic acid-propylene glycol polyester, etc.), aliphatic tricarboxylic acid esters (triethyl citrate, etc.), phosphoric acid triesters (triphenyl phosphate, etc.), epoxy fatty acid esters (epoxy butyl stearate, etc.), and petroleum resins.
Examples of the mold release agents include lower (C1 to C4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4 to C30) (hydrogenated castor oil, etc.), glycol esters of fatty acids, and liquid paraffin.
An antioxidant known in the art can be used as the antioxidant. Specific examples thereof include phenol antioxidants (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenol antioxidants (2,2′-methylenebis(4-methyl-6-t-butylphenol), etc.), phosphorus antioxidants (tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylene diphosphonate, etc.), sulfur antioxidants (dilauryl thiodipropionate, etc.), amine antioxidants (N,N-diisopropyl-p-phenylenediamine, etc.), and lactone antioxidants. Plural types thereof may be used in combination.
Examples of the flame retardant include organic flame retardants (nitrogen-containing flame retardants, sulfur-containing flame retardants, silicon-containing flame retardants, phosphorus-containing flame retardants, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.).
Examples of the ultraviolet absorber include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylic acid ultraviolet absorbers, and acrylate ultraviolet absorbers.
Examples of the antimicrobial agent include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenol, and organic iodine.
Examples of the surfactant can include nonionic, anionic, cationic and amphoteric surfactants. Examples of the nonionic surfactant include: polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; and polyhydric alcohol-type nonionic surfactants such as polyethylene oxide, fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and aliphatic amides of alkanolamines. Examples of the anionic surfactant include: sulfuric acid ester salts such as alkali metal salts of higher fatty acids; sulfonates such as alkylbenzenesulfonates, alkylsulfonates, and paraffin sulfonate; and phosphoric acid ester salts such as higher alcohol phosphoric acid ester salt. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric surfactant include: amino acid-type amphoteric surfactants such as higher alkylaminopropionates; and betaine-type amphoteric surfactants such as higher alkyl dimethyl betaine and higher alkyl dihydroxyethyl betaine.
Examples of the antistatic agent include the surfactants described above, fatty acid esters, and polymer-type antistatic agents. Examples of the fatty acid ester include esters of stearic acid and oleic acid. Examples of the polymer-type antistatic agent include polyether ester amide.
The amounts of these various additives (filler, lubricant, plasticizer, mold release agent, antioxidant, flame retardant, ultraviolet absorber, antimicrobial agent, surfactant, antistatic agent, etc.) added are not particularly limited and are each preferably 0.1 to 30% by mass with respect to the total mass of the resin composition comprising the 4-methyl-1-pentene polymer (X), without impairing the object of the present invention, according to a purpose.
The method for producing the resin composition comprising the 4-methyl-1-pentene polymer (X) according to the present invention is not particularly limited, and, for example, the 4-methyl-1-pentene polymer (X) and other components are mixed at the ratios of addition mentioned above and then melt-kneaded to obtain the resin composition.
The melt kneading is not particularly limited by its method and can be performed using a generally commercially available melt kneading apparatus such as an extruder.
For example, the cylinder temperature of a site where kneading is performed in a kneading machine is usually 220 to 320° C., preferably 250 to 300° C. If the cylinder temperature is lower than 220° C., kneading is insufficient due to insufficient melting so that the physical properties of the resin composition are less likely to be improved. On the other hand, if the temperature is higher than 320° C., the thermal decomposition of the 4-methyl-1-pentene polymer (X) may occur. The kneading time is usually 0.1 to 30 minutes, particularly preferably 0.5 to 5 minutes. If the kneading time is shorter than 0.1 minutes, sufficient melt kneading is not performed. If the kneading time exceeds 30 minutes, the thermal decomposition of the 4-methyl-1-pentene polymer (X) may occur.
The resin composition is molded to obtain a molded article.
Various molding methods known in the art can be applied to the method for molding the resin composition. Examples thereof can include various molding methods such as injection molding, extrusion molding, injection stretch blow molding, blow molding, cast molding, calender molding, press molding, stamping molding, inflation molding, and roll molding. The resin composition can be processed into the molded article of interest, for example, a film, a sheet, a hollow molded article, an injection molded article, fiber, or the like by these molding methods. The molding conditions are similar to molding conditions for conventional 4-methyl-1-pentene polymers known in the art.
The shape of the molded article is not particularly limited. Examples thereof include tube, film, sheet, membrane, tape, plate, rod, fiber, and nonwoven fabric shapes.
Hereinafter, the film is a generic name for planar molded articles and also conceptually includes sheets, tapes, and the like.
The molded article of the present invention can be used for applications that may employ conventional 4-methyl-1-pentene polymers, without limitations.
Film elongation is required for characteristics in film formation. Applications of the film are not limited. Examples of the applications of the film include packaging materials for food, meat, processed fish, vegetables, fruits, fermented food, retort food, confectionery, medicines, flower bulbs, seeds, mushrooms, and the like, wrap films, cell culture bags, cell inspection films, heat-resistant vacuum molded containers, prepared food containers, lid materials for prepared food, baking cartons, and various mold releasing films.
Examples of the applications of the molded article according to the present invention will be listed below, but are not particularly limited thereto.
Examples of containers include: food containers and bottle containers, such as eating utensils, seasoning containers, kitchen goods, retort containers, freeze preservation containers, retort pouches, microwave oven heat-resistant containers, frozen food containers, chilled sweet cups, cups, nursing bottles, and beverage bottles; blood transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, transfusion bags, blood preservation bags, transfusion bottles, chemical containers, detergent containers, containers for fabric softeners, containers for bleaches, containers for shampoos, containers for rinses, cosmetics containers, perfume containers, toner containers, powder containers, containers for adhesives, containers for gasoline tanks, containers for kerosene, food containers, heat-resistant containers, medical containers, animal cages, and physicochemical experimental instruments.
Examples of packaging materials include food packaging materials, meat packaging materials, processed fish packaging materials, vegetable packaging materials, fruit packaging materials, fermented food packaging materials, confectionery packaging materials, oxygen absorber packaging materials, packaging materials for retort food, freshness keeping films, medicine packaging materials, cell culture bags, cell inspection films, flower bulb packaging materials, seed packaging materials, films for vegetable or mushroom cultivation, heat-resistant vacuum molded containers, prepared food containers, lid materials for prepared food, industrial wrap films, household wrap films, and baking cartons.
Examples of films other than those described above include: mold releasing films such as mold releasing films for flexible printed circuit boards, mold releasing films for ACM substrates, mold releasing films for rigid substrates, mold releasing films for rigid flexible printed circuit boards, mold releasing films for advanced composite materials, mold releasing films for carbon fiber composite material curing, mold releasing films for glass fiber composite material curing, mold releasing films for aramid fiber composite material curing, mold releasing films for nanocomposite material curing, mold releasing films for filler curing, mold releasing films for semiconductor encapsulation, mold releasing films for polarizing plates, mold releasing films for diffusion sheets, mold releasing films for prism sheets, mold releasing films for reflection sheets, cushion films for mold releasing films, mold releasing films for fuel cells, mold releasing films for various rubber sheets, mold releasing films for urethane curing, and mold releasing films for epoxy curing; solar cell encapsulating sheets, solar cell back sheets, plastic films for solar cells, battery separators, separators for lithium ion cells, electrolyte membranes for fuel cells, and pressure-sensitive adhesive or adhesive separators, light guide plates, and optical disks; base materials, pressure-sensitive adhesive materials, and separators for semiconductor process films such as dicing tapes, back grind tapes, die bonding films, two-layer FCCL, and films for film condensers; pressure-sensitive adhesive films, stress relaxation films, films for pellicles, and films for polarizing plates; protecting films such as protecting films for polarizing plates, protecting films for liquid crystal panels, protecting films for optical components, protecting films for lenses, protecting films for electric components or electric appliances, protecting films for mobile phones, protecting films for personal computers, protecting films for touch panels, window glass protecting films, films for bake coating, masking films, films for condensers, capacitor films, tab lead films, capacitor films for fuel cells, reflection films, diffusion films, laminates (including glass), radiation-resistant films, γ ray-resistant films, and porous films; heat dissipation films or sheets, molds for electronic component encapsulant production, LED molds, laminate plates for high-frequency circuits, covering materials for high-frequency cables, optical waveguide substrates, glass fiber composites, carbon fiber composites, glass interlayers, films for safety glass, window films for building materials, arcade domes, gymnasium window glass substitutes, films for LCD substrates, bulletproof materials, films for bulletproof glass, heat shield sheets, and heat shield films; release paper such as release paper for synthetic leather, release paper for advanced composite materials, release paper for carbon fiber composite material curing, release paper for glass fiber composite material curing, release paper for aramid fiber composite material curing, release paper for nanocomposite material curing, and release paper for filler curing; and heat-resistant and water-resistant printing paper, films for packaging, mold releasing films, breathable films, reflection films, synthetic paper, films for displays, conductive films for displays, and display barrier films.
Examples of other applications include: mandrels for rubber hose production, sheaths, sheaths for rubber hose production, hoses, tubes, release paper for synthetic leather, medical tubes, industrial tubes, cooling water piping, hot water piping, wire covering materials, millimeter-wave signal cable covering materials, high-frequency signal cable covering materials, eco-wire covering materials, in-vehicle cable covering materials, signal cable covering materials, insulators for high-voltage wires, wiring ducts, tubes for cosmetics or perfume sprays, medical tubes, transfusion tubes, pipes and wire harnesses; interior and exterior materials of automobiles, motorcycles, railroad vehicles, air planes, ships, etc.; abrasion-resistant automobile interior and exterior materials; automobile interior and exterior materials such as instrument panel skins, door trim skins, rear package trim skins, ceiling skins, rear pillar skins, seat back garnishes, console boxes, arm rests, air back case lid materials, shift knobs, assist grips, side step mats, meter covers, battery caps, fuses, automatic washing sensor components, ignitions, coil bobbins, bushings, bumpers, car heater fans, radiator grills, wheel covers, electric source connectors for EV, in-vehicle display polarizing plates, louvers, armrests, rail insulators, motorcycle windshields, reclining covers, sheets in trunks, seat belt buckles, moldings such as inner or outer moldings, bumper moldings, side moldings, roof moldings, and belt moldings, air spoilers, automobile seals such as door seals and body seals, glass run channels, mudguards, kicking plates, step mats, number plate housings, automobile hose members, air duct hoses, air duct covers, air intake pipes, air dam skirts, timing belt cover seals, hood cushions, door cushions, cup holders, side brake grips, shift knob covers, seat adjustment knobs, wire harness grommets, suspension cover boots, glass guides, inner belt line seals, roof guides, trunk lid seals, molded quarter window gaskets, corner moldings, glass encapsulation, hood seals, glass run channels, secondary seals, bumper components, body panels, side shields, door skins, weather strip materials, hoses, steering wheels, wire harness covers, and seat adjuster covers; special tires such as vibration damping tires, silent tires, car race tires, and radio control tires; packings, automobile dust covers, lamp seals, automobile boots, rack and pinion boots, timing belts, wire harnesses, grommets, emblems, air filter packings, automobile connectors, ignition coils, switches, lamp reflectors, relays, electric control unit cases, sensor housings, head lamps, meter plates, insulators, bearing retainers, thrust washers, lamp reflectors, door handles, grazing, panoramic roofs, solenoid valves, ECU cases, connectors for unit connection, alternators, terminal blocks for HEV, electromagnetic valves, and coil assembly components; skin materials for furniture, shoes, cloths, bags, building materials, and the like; seal materials for architecture, waterproof sheets, building material sheets, piping joints, dressing tables, bathroom ceilings, impellers, building material gaskets, window films for building materials, iron-core protecting members, sheets for foundation improvement, water stops, joint sealing materials, gaskets, doors, door frames, window frames, cornices, baseboards, opening frames, floor materials, ceiling materials, wall paper, health supplies (e.g., nonslip mats or sheets and tip-resistant films, mats, or sheets), health appliance components, impact absorbing pads, protectors or protecting equipment (e.g., helmets and guards), sport goods (e.g., sport grips and protectors), sport protecting equipment, rackets, mouth guards, balls, golf balls, and carrying implements (e.g., impact absorbing grips for carrying and impact absorbing sheets); impact absorbers such as vibration damping pallets, impact absorbing dampers, insulators, impact absorbers for shoes, impact absorbing foams, and impact absorbing films or sheets; grip materials (pens and pencils, industrial tools, sporting equipment, vehicle handles, commodities, electric instruments, furniture, etc.), camera bodies and components, office automation equipment components, copier structural parts, printer structural parts, members for air planes, in-flight meal trays, facsimile structural parts, pump components, electrical tool components, drying/washing machine components, heater pump nozzles or ports, IH rice cookers, rice cooker inner lid materials, microwave oven roller stay rings, vacuum cleaner fan guides, pump or filter cases for electric rice jars, garbage disposal components or tanks or heating and drying components, meters for milk, filter bowls, escalator components, ultrasonic motor housings, absolute encoders, small pump housings, television members, hair dryer housings, lighting covers, sundries, coffee drippers, humidifier components, iron components, tap water instrument components, drinking flasks, combs, fountain pens, pencil cases, pencil sharpeners, sport leisure goods, ski goggles, karate or kendo protective gears, fins for surfing, musical instruments, fish breeding tanks, sandals, snow shovels, fishing rod cases, toys, treads, shoe soles, shoe midsoles or inner soles, soles, sandals, chair skins, bags, school bags, wears such as jumpers and coats, bands, rods, ribbons, notebook covers, book covers, keyholders, pencases, wallets, chopsticks, China spoons, microwave cooking pans, business card holders, commuter pass holders, suckers, tooth blushes, floor materials, gymnastic mats, electrical tool components, agricultural equipment components, heat dissipation materials, transparent substrates, soundproof materials, acoustic absorbents, cushion materials, wire cables, shape memory materials, connectors, switches, plugs, home electronic components (motor components, housings, etc.), medical gaskets, speaker diaphragms, medical caps, drug caps, and gaskets; packing materials for use in high-temperature treatments such as boiling treatment and high-pressure steam sterilization after filling bottles with baby food, dairy products, drugs, sterilized water, or the like; industrial seal materials, industrial sewing machine tables, number plate housings, cap liners such as PET bottle cap liners, protecting film adhesive layers, pressure-sensitive adhesive materials such as hot melt adhesive materials, stationery, and office supplies; precision measuring equipment or office automation equipment supporting members such as office automation printer legs, facsimile legs, sewing machine legs, motor supporting mats, and audio vibration-proof materials; heat-resistant packings for office automation, animal cages, physicochemical experimental equipment such as beakers and measuring cylinders, medical films or sheets, films or sheets for cell culture, syringes, optical media such as CD, DVD and Blu-ray, cells for optical measurement, cloth cases, clear cases, clear files, clear sheets, and desk mats; applications as fiber, for example, monofilaments, multifilaments, cut fiber, hollow fiber, nonwoven fabrics, stretchable nonwoven fabrics, fiber, waterproof fabrics, breathable woven fabrics and fabrics, disposable diapers, sanitary products, hygiene products, filters, bug filters, filters for dust collection, air cleaners, hollow fiber filters, water-purifying filters, filter fabrics, filter paper, gas separation membranes, artificial liver (cases and hollow fiber), filter reverse osmotic membranes, heart-lung machines, injection syringes, three-way cocks, transfusion sets, instruments for surgeons, flowmeters, dental instruments, instruments for contact lens sterilization, inhaling masks, cells for analysis, milking machines, fire alarm boxes, fire extinguishers, helmets, protecting glasses, IC carriers, pickup lenses, and burn-in sockets.
Further, the molded article of the present invention is also suitably used in coating materials, films and sheets obtained by coating, mold release materials, water-repellant materials, insulating films, adhesive materials, pressure-sensitive adhesive materials, coated paper, transparent sealants, sealants, hot melt-type pressure-sensitive adhesives or adhesives, solvent-type pressure-sensitive adhesives or adhesives, film-like pressure-sensitive adhesives or adhesives, fabric tapes, craft tapes, elastic adhesives, etc.
The 4-methyl-1-pentene polymer (X) may be processed into fine powders by crushing. The obtained fine powders can be used, for example, as an additive for ink compositions or coating compositions, as an additive for metallurgical powder compositions, as an additive for powder compositions for ceramic sintering, as an additive for pressure-sensitive adhesives, as an additive for rubbers, as a mold release agent for toner, or as a die mold release agent. Further, the obtained fine powders can also be used as a resin additive for shafts, gear wheels, cams, electric components, camera components, automobile components, components intended for household goods, or as a resin additive for waxes, greases, engine oils, fine ceramics, plating, etc.
Next, the present invention will be described in detail with reference to Examples. However, the present invention is not limited by these Examples.
Dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butyl-fluorenyl)zirconium dichloride was synthesized by the method described in International Publication No. WO 2001/027124. This compound is also referred to as a “catalyst (A)”.
A magnetic stirrer was placed in a Schlenk flask thoroughly dried and purged with nitrogen, and 30.7 mmol of the catalyst (A) was placed therein as a bridged metallocene compound. A suspension (n-hexane solvent) containing 500 equivalents (based on an aluminum atom) of modified methylaluminoxane with respect to the catalyst (A) was added thereto at room temperature with stirring, and decane was added in an amount that would adjust the catalyst (A) to 5.0 mmol/mL to prepare a catalyst solution (slurry solution (A-1)).
The slurry solution (A-1) thus prepared was charged with 2.0 mL of a decane solution of diisobutyl aluminum hydride (2.0 mmol/mL based on an aluminum atom) and further with 7.5 mL (5.0 g) of 3-methyl-1-pentene under a stream of nitrogen. The stirring was terminated 1.5 hours later, and the obtained prepolymerization catalyst component was washed three times with 50 mL of decane by decantation. This prepolymerization catalyst component was suspended in decane to obtain 50 mL of decane slurry (A-2).
Diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butyl-fluorenyl)zirconium dichloride was synthesized by the method described in International Publication No. WO 2005/121192. This compound is also referred to as a “catalyst (B)”.
A magnetic stirrer was placed in a Schlenk flask thoroughly dried and purged with nitrogen, and 32.8 mmol of the catalyst (B) was placed therein as a bridged metallocene compound. A suspension (n-hexane solvent) containing 500 equivalents (based on an aluminum atom) of modified methylaluminoxane with respect to the catalyst (B) was added thereto at room temperature with stirring, and decane was added in an amount that would adjust the catalyst (B) to 2.5 mmol/mL to prepare a catalyst solution (slurry solution (B-1)).
The slurry solution (B-1) thus prepared was charged with 2.0 mL of a decane solution of diisobutyl aluminum hydride (2.0 mmol/mL based on an aluminum atom) and further with 7.5 mL (5.0 g) of 3-methyl-1-pentene under a stream of nitrogen. The stirring was terminated 1.5 hours later, and the obtained prepolymerization catalyst component was washed three times with 50 mL of decane by decantation. This prepolymerization catalyst component was suspended in decane to obtain 50 mL of decane slurry (B-2).
Dimethyl[3-tert-butyl-5-methyl-cyclopentadienyl](fluorenyl)zirconium dichloride was synthesized by the method described in International Publication No. WO 2001/027124. This compound is also referred to as a “catalyst (C)”.
A magnetic stirrer was placed in a Schlenk flask thoroughly dried and purged with nitrogen, and 32.8 mmol of the catalyst (C) was placed therein as a bridged metallocene compound. A suspension (n-hexane solvent) containing 500 equivalents (based on an aluminum atom) of modified methylaluminoxane with respect to the catalyst (C) was added thereto at room temperature with stirring, and decane was added in an amount that would adjust the catalyst (C) to 2.5 mmol/mL to prepare a catalyst solution (slurry solution (C-1)).
The slurry solution (C-1) thus prepared was charged with 2.0 mL of a decane solution of diisobutyl aluminum hydride (2.0 mmol/mL based on an aluminum atom) and further with 7.5 mL (5.0 g) of 3-methyl-1-pentene under a stream of nitrogen. The stirring was terminated 1.5 hours later, and the obtained prepolymerization catalyst component was washed three times with 50 mL of decane by decantation. This prepolymerization catalyst component was suspended in decane to obtain 50 mL of decane slurry (C-2).
Synthesis of (8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)) zirconium dichloride (catalyst D)
In a nitrogen atmosphere, a 200 ml three-neck flask was charged with 40 ml of a tert-butyl methyl ether solution of ethyl magnesium bromide having a concentration of 1.0 M. While this solution was cooled in an ice bath, 2.64 g of cyclopentadiene was added dropwise thereto over 20 minutes. The mixture was brought back to room temperature and stirred for 17 hours to prepare solution D-1.
In a nitrogen atmosphere, a 500 ml three-neck flask was charged with 200 ml of diisopropyl ether and 0.36 g of copper(II) trifluoromethanesulfonate. To this solution, the preceding solution D-1 prepared was added dropwise over 20 minutes in a water bath. A solution prepared by dissolving 4.30 g of 1-bromoadamantane in 40 mL of diisopropyl ether was added dropwise thereto, and the mixture was stirred at 70° C. for 10 hours. The reaction solution was cooled to room temperature, and then, 200 ml of a saturated aqueous solution of ammonium chloride was added thereto in a water bath. The organic layer was separated, and the aqueous layer was subjected to extraction with 200 ml of hexane. The hexane extracts and the preceding organic layer were combined, and the obtained organic solution was washed with water. This organic solution was dried over magnesium sulfate, and then, the solvent was distilled off. The obtained solid matter was purified using a silica gel column chromatograph to obtain 4.2 g of a crude product.
In a nitrogen atmosphere, a 100 ml Schlenk flask was charged with 4.2 g of the obtained crude product and 20 mL of hexane. To this solution, 13.8 mL of a hexane solution of 1.6 M n-butyl lithium was added dropwise over 20 minutes in an ice bath, and the mixture was brought back to room temperature and stirred for 17 hours. Precipitates were collected by filtration from this reaction solution and washed with hexane to obtain the target 1-adamantylcyclopentadienyl lithium. The yield was 2.70 g, and the % yield was 66%.
The target compound was identified from measurement results of 1H-NMR. The measurement results are as follows.
1H-NMR (THF-d8): δ 5.57-5.55 (2H, m), 5.52-5.50 (2H, m), 1.96 (3H, s), 1.87 (6H, s), 1.74 (6H, s).
In a nitrogen atmosphere, a 100 ml three-neck flask was charged with 40 ml of THF and 1.57 g of magnesium chloride. To this solution, a solution obtained by dissolving 3.09 g of 1-adamantylcyclopentadienyl lithium in 10 ml of THF was added dropwise over 5 minutes, and the mixture was stirred at room temperature for 2 hours and further at 50° C. for 3 hours. A solution obtained by dissolving 1.96 g (15.75 mmol) of 1-acetylcyclohexene in 10 ml of THF was added dropwise thereto over 10 minutes in an ice/acetone bath, and the mixture was stirred at room temperature for 19 hours. 1.0 ml of acetic acid and 3.1 ml of pyrrolidine were charged thereinto in an ice/acetone bath, and the mixture was stirred at room temperature for 17 hours. To this solution, 30 ml of a saturated aqueous solution of ammonium chloride was added in an ice/acetone bath. To this solution, 100 ml of hexane was added. Then, the organic layer was separated, and the aqueous layer was subjected to extraction with 200 ml of hexane. The hexane extracts and the preceding organic layer were combined, and the obtained organic solution was washed twice with water. This organic solution was dried over magnesium sulfate, and then, the solvent was distilled off. The obtained solid matter was recrystallized from methanol to obtain the target 2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene. The yield was 2.134 g, and the % yield was 47%.
The target compound was identified from measurement results of 1H-NMR and GC-MS. The measurement results are as follows.
1H-NMR (Toluene-d8): δ6.06 (1H, s), 5.98 (1H, s), 2.88-2.78 (2H, m), 1.98-1.13 (26H, m).
GC-MS: m/Z=306 (M+).
In a nitrogen atmosphere, a 30 ml Schlenk flask was charged with 1.546 g of octamethylfluorene and 40 ml of tert-butyl methyl ether. To this solution, 2.62 ml of a hexane solution of 1.6 M n-butyl lithium was added dropwise over 15 minutes in an ice/acetone bath. The mixture was stirred for 22 hours while gradually brought back to room temperature. To this solution, 1.349 g of 2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene was added. The mixture was stirred at room temperature for 19 hours and further at 50° C. for 8 hours. Then, the reaction solution was added to 100 ml of a saturated aqueous solution of ammonium chloride. The organic layer was separated, and the aqueous layer was subjected to extraction with 100 ml of hexane. The hexane extracts and the preceding organic layer were combined, and the obtained organic solution was washed twice with water. This organic solution was dried over magnesium sulfate, and then, the solvent was distilled off. The obtained solid was washed with acetone to obtain the target 8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene). The yield was 1.51 g, and the % yield was 54%.
The target compound was identified from measurement results of FD-MS. The measurement results are as follows.
FD-MS: m/Z=693 (M+).
The obtained 8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene) was confirmed from measurement results of 1H-NMR to be a mixture of a plurality of isomers.
In a nitrogen atmosphere, a 100 ml Schlenk flask was charged with 1.039 g of 8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene), 0.47 ml of a-methylstyrene, 30 ml of hexane, and 2.62 ml of cyclopentyl methyl ether. To this solution, 2.18 ml of a hexane solution of 1.6 M n-butyl lithium was added dropwise over 10 minutes in an oil bath of 25° C. After stirring at 50° C. for 4 hours, precipitates were filtered and washed with hexane to obtain a pink powder. A 100 ml Schlenk flask was charged with this pink powder and 30 ml of diethyl ether. This solution was cooled in a dry ice/acetone bath. Then, to this solution, 0.385 g (1.65 mmol) of zirconium tetrachloride suspended in 30 ml of diethyl ether was added. Then, the mixture was stirred for 16 hours while the temperature was gradually increased to room temperature.
The solvent was distilled off under reduced pressure, and then, soluble matter was extracted from the residue using approximately 70 ml of dichloromethane. The obtained extracts were concentrated. Then, 50 ml of hexane was added thereto, and insoluble mater was removed by filtration. This solution was concentrated to approximately 10 ml and then left standing overnight at −30° C. The precipitated powder was collected by filtration and washed with hexane to obtain 0.384 g of an orange powder. This orange powder was dissolved by the addition of 5 ml of diethyl ether and left standing overnight at −30° C. The precipitated powder was collected by filtration and washed with hexane to obtain the target (8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)) zirconium dichloride (catalyst D). The yield was 0.220 g, and the % yield was 17%.
The target compound was identified from measurement results of 1H-NMR. The measurement results are as follows.
1H-NMR (270 MHz, CDCl3, TMS reference): δ7.98 (1H, s), 7.86 (1H, s), 7.60 (1H, s), 7.37 (1H, s), 6.19 (1H, J=1.6Hz, d), 5.33 (1H, J=1.6Hz, d), 3.58-3.44 (2H, m), 2.35-2.28 (1H, m), 2.18 (3H, s), 1.94-1.18 (54H, m).
A 100 mL three-neck flask equipped with a stirrer and thoroughly purged with nitrogen was charged with 32 mL of purified decane and 14.65 mmol (based on an aluminum atom) of solid polymethylaluminoxane (manufactured by Tosoh Finechem Corp.) at 30° C. under a stream of nitrogen to prepare a suspension. To the suspension, 12.75 mL of a 4.6 mmol/L solution of 50 mg (0.059 mmol based on a zirconium atom) of the preceding catalyst (D) synthesized in toluene was added with stirring. The stirring was terminated 1.5 hours later, and the obtained catalyst component was washed three times with 50 mL of decane by decantation and suspended in decane to prepare 50 mL of a slurry solution (D-2). In this catalyst component, the supporting rate of Zr was 100%.
The slurry solution (D-2) thus prepared was charged with 2.0 mL of a decane solution of diisobutyl aluminum hydride (2.0 mmol/mL based on an aluminum atom) and further with 7.5 mL (5.0 g) of 3-methyl-1-pentene under a stream of nitrogen. The stirring was terminated 1.5 hours later, and the obtained prepolymerization catalyst component was washed three times with 50 mL of decane by decantation. This prepolymerization catalyst component was suspended in decane to obtain 50 mL of decane slurry (D-3).
A SUS polymerization vessel (internal capacity: 1 L) equipped with a stirrer was charged with 425 mL of purified decane and 0.5 mL (1 mol) of a decane solution of diisobutyl aluminum hydride (2.0 mmol/mL based on an aluminum atom) at room temperature under a stream of nitrogen. Subsequently, 0.0005 mmol (based on a zirconium atom) of the preceding decane slurry (A-2) of the prepolymerization catalyst component of the catalyst (A) prepared was added thereto, and 50 NmL of hydrogen was charged thereinto (first hydrogen charging). Subsequently, the polymerization vessel was continuously charged with 250 mL of 4-methyl-1-pentene at a given rate over 2 hours. The start of this charging was referred to as the start of polymerization. The temperature was increased to 45° C. over 0.5 hours from the start of polymerization and then kept at 45° C. for 4 hours. 90 NmL of hydrogen was charged thereinto 3 hours after the start of polymerization (second hydrogen charging). After a lapse of 4.5 hours from the start of polymerization, the temperature was decreased to room temperature, followed by depressurization. Immediately thereafter, the polymerization solution containing a white solid was filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80° C. for 8 hours to obtain a polymer [X-1]. The yield was 131 g. Results of measuring physical properties are shown in Table 1.
120 g of a polymer [X-2] was obtained by the same reaction as in Example 1 except that the decane slurry (B-2) was used instead of the decane slurry (A-2). Results of measuring physical properties are shown in Table 1.
115 g of a polymer [X-3] was obtained by the same reaction as in Example 1 except that the decane slurry (C-2) was used instead of the decane slurry (A-2), and the polymerization temperature was set to 100° C. Results of measuring physical properties are shown in Table 1.
A SUS polymerization vessel (internal capacity: 1 L) equipped with a stirrer was charged with 425 mL of purified decane and 0.5 mL (1 mol) of a decane solution of diisobutyl aluminum hydride (2.0 mmol/mL based on an aluminum atom) at room temperature under a stream of nitrogen. Subsequently, 0.0005 mmol (based on a zirconium atom) of the preceding decane slurry (C-2) of the prepolymerization catalyst component of the catalyst (C) prepared was added thereto, and 50 NmL of hydrogen was charged thereinto (first hydrogen charging). Subsequently, the polymerization vessel was continuously charged with a mixed solution of 250 mL of 4-methyl-1-pentene and 3.3 mL of 1-decene at a given rate over 2 hours. The start of this charging was referred to as the start of polymerization. The temperature was increased to 45° C. over 30 minutes from the start of polymerization and then kept at 45° C. for 4 hours. 90 NmL of hydrogen was charged thereinto 3 hours after the start of polymerization (second hydrogen charging). After a lapse of 4.5 hours from the start of polymerization, the temperature was decreased to room temperature, followed by depressurization. Immediately thereafter, the polymerization solution containing a white solid was filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80° C. for 8 hours to obtain a polymer [X-4]. The yield was 125 g. Results of measuring physical properties are shown in Table 1.
115 g of a polymer [X-5] was obtained by the same reaction as in Example 4 except that 2.0 mL of 1-hexene was added instead of adding 3.3 mL of 1-decene as a copolymerizable monomer. Results of measuring physical properties are shown in Table 1.
135 g of a polymer [X′-1] was obtained by the same reaction as in Example 1 except that: the number of hydrogen charges was set to a total of 3; in addition to the first hydrogen charging before the start of polymerization as in Example 1, the second hydrogen charging was performed 1 hour after the start of polymerization, and the third hydrogen charging was performed 2 hours after the start of polymerization; and the first, second, and third amounts of hydrogen charged were each set to 0.5 NmL. Results of measuring physical properties are shown in Table 1.
150 g of a polymer [X′-2] was obtained by the same reaction as in Example 2 except that: the number of hydrogen charges was set to a total of 3; in addition to the first hydrogen charging before the start of polymerization as in Example 2, the second hydrogen charging was performed 1 hour after the start of polymerization, and the third hydrogen charging was performed 2 hours after the start of polymerization; and the first, second, and third amounts of hydrogen charged were each set to 0.5 NmL. Results of measuring physical properties are shown in Table 1.
A polymer [X′-3] was obtained by changing the proportions of 4-methyl-1-pentene, 1-decene, and hydrogen according to the method of Comparative Example 7 of International Publication No. WO 2006/054613. Results of measuring physical properties are shown in Table 1.
115 g of a polymer [X′-4] was obtained by the same reaction as in Example 4 except that the decane slurry (D-3) was used instead of the decane slurry (C-2). Results of measuring physical properties are shown in Table 1.
A polymer [X′-5] was obtained by the same polymerization reaction as in Comparative Example 4 except that: the number of hydrogen charges was set to a total of 3; in addition to the first hydrogen charging before the start of polymerization as in Comparative Example 4, the second hydrogen charging was performed 1 hour after the start of polymerization, and the third hydrogen charging was performed 2 hours after the start of polymerization; and the first, second, and third amounts of hydrogen charged were each set to 50 NmL. The yield was 131 g.
A polymer in an amount sufficient for pellet preparation was provided by carrying out the polymerization of Example or Comparative Example described above a plurality of times, if necessary. 100 parts by mass of each polymer were mixed with 0.1 parts by mass of tri(2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and 0.1 parts by mass of n-octadecyl-3-(4′-hydroxy-3′,5′-di-t-butylphenyl) propionate as a heat stabilizer. After a lapse of appropriate time, the mixture was granulated under conditions of a set temperature of 260° C., an amount of the resin extruded of 60 g/min and the number of revolutions of 200 rpm using a twin-screw extruder BT-30 manufactured by PLABOR Research Laboratory of Plastics Technology Co., Ltd. (screw diameter: 30 mmφ, L/D: 46) to obtain pellets for evaluation.
The obtained pellets for evaluation were subjected to DSC measurement and melt tension measurement by methods mentioned later. The results are shown in Table 1.
Hereinafter, the methods for evaluating the polymer and the pellets for evaluation will be specifically described. The evaluation results are shown in Table 1.
The content of the constitutional unit derived from at least one olefin (comonomer) selected from ethylene and an α-olefin having 3 to 20 carbon atoms (except for 4-methyl-1-pentene) in the 4-methyl-1-pentene polymer was calculated from 13C-NMR spectra using the following apparatus and conditions.
The measurement was performed using AVANCE III cryo-500 nuclear magnetic resonance apparatus manufactured by Bruker BioSpin under the following conditions: solvent: an o-dichlorobenzene/benzene-d6 (4/1 v/v) mixed solvent; sample concentration: 55 mg/0.6 mL; measurement temperature: 120° C.; observed nucleus: 13C (125 MHz); sequence: single-pulse proton broadband decoupling; pulse width: 5.0 μsec (45° pulse), repetition time: 5.5 sec; the number of integrations: 64; and chemical shift reference value: 128 ppm of benzene-d6. The content of the constitutional unit derived from the comonomer was calculated using an integrated value of the backbone methine signals according to the following expression.
Content of the constitutional unit derived from the comonomer (%)=[P/(P+M)]×100
wherein P represents the total peak area of comonomer backbone methine signals, and M represents the total peak area of 4-methyl-1-pentene backbone methine signals.
The meso diad fraction (also referred to as diad isotacticity or meso diad isotacticity) of the 4-methyl-1-pentene polymer was defined as the fraction of isobutyl branches having the same orientation when the head-to-tail linkage of arbitrary two 4-methyl-1-pentene units in the polymer chain is expressed by planar zigzag arrangement, and determined from 13C-NMR spectra according to the following expression.
Meso diad fraction (diad isotacticity) (m) (%)=[m/(m+r)]×100
wherein m and r each represent absorption intensity derived from the backbone methylenes of head-to-tail linked 4-methyl-1-pentene units represented by the formula given below.
The 13C-NMR spectra were measured using AVANCE III cryo-500 nuclear magnetic resonance apparatus manufactured by Bruker BioSpin under the following conditions: solvent: an o-dichlorobenzene/benzene-d6 (4/1 v/v) mixed solvent; sample concentration: 60 mg/0.6 mL; measurement temperature: 120° C.; observed nucleus: 13C (125 MHz); sequence: single-pulse proton broadband decoupling; pulse width: 5.0 μsec (45° pulse), repetition time: 5.5 sec; and chemical shift reference value: 128 ppm of benzene-d6.
Peak regions were classified into a first region on a high-magnetic field side and a second region on a low-magnetic field side by delimiting a region of 41.5 to 43.3 ppm at the local minimum point of a peak profile.
In the first region, the backbone methylenes in the linkage of the two 4-methyl-1-pentene units represented by (m) resonated, and the integrated value of these units regarded as a 4-methyl-1-pentene homopolymer was referred to as “m”. In the second region, the backbone methylenes in the linkage of the two 4-methyl-1-pentene units represented by (r) resonated, and the integrated value thereof was referred to as “r”. A value less than 0.01% was equal to or lower than the detection limit.
The weight-average molecular weight (Mw) and the number-average molecular weight (Mn) were measured by GPC. The GPC measurement was performed under conditions given below. Also, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) were determined on the basis of the conversion method described below by preparing a calibration curve using commercially available polystyrene monodisperse standards.
Apparatus: gel permeation chromatograph HLC-8321 GPC/HT (manufactured by Tosoh Corp.)
Organic solvent: o-dichlorobenzene
Column: two columns of TSKgel GMH6-HT and two columns of TSKgel GMH6-HTL (all manufactured by Tosoh Corp.)
Flow rate: 1.0 ml/min
Sample: 0.15 mg/mL o-dichlorobenzene solution
Temperature: 140° C.
Molecular weight conversion: general calibration method based on PS
Coefficients of the Mark-Houwink viscosity equation were used in the calculation of general calibration. The values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970)) were used as respective Mark-Houwink coefficients of PS.
In this GPC chart based on PS, the ratio of the integrated area value of components having a molecular weight of 1,000,000 or larger to the total integrated area of the chart was referred to as the proportion of a component having a molecular weight of 1×106 or larger.
The melt flow rate (MFR) was measured under conditions of 260° C. and a 5 kg load in conformity to ASTM D1238.
(Measurement Condition)
Apparatus: CFC2 cross fractionation chromate graph (Polymer Characterization, S.A)
Detector (built-in): IR4 infrared spectrophotometer (Polymer Characterization, S.A)
Sample concentration: 60 mg/30 mL
Injection volume: 0.5 mL
Mobile phase: o-dichlorobenzene (ODCB) supplemented with BHT
Flow rate: 1.0 mL/min
A sample of 60 mg of the polymer added to 30 mL of o-dichlorobenzene (ODCB) was inserted to an apparatus cell and kept at 145° C. for a given time so that the polymer was thoroughly dissolved to obtain a sample. Then, for the progression of crystallization, the temperature of the sample was decreased to 0° C. at 1° C./min and kept at this temperature for a given time. Then, the amount of a resin eluted while the temperature of the sample was increased to 145° C. in stages at intervals of 5° C. was measured as needed.
From the results, the proportion of a polymer eluted at 80° C. or lower to all polymers was calculated, and this proportion was defined as the “amount of a component eluted at a low temperature” (cumulative weight fraction).
An aluminum pan for measurement was covered with approximately 5 mg of a sample, and the temperature was increased to 280° C. at 10° C./min using a DSC measurement apparatus manufactured by Seiko Instruments Inc. (DSC220C). The temperature was kept at 280° C. for 5 minutes and then decreased to 20° C. at 10° C./min. The temperature was kept at 20° C. for 5 minutes and then increased to 280° C. at 10° C./min. A temperature at which the summit of a crystal melting peak appeared, observed in the second temperature increase was referred to as the melting point. The heat of fusion was calculated from the integrated value of this crystal melting peak.
The melt tension was measured using an apparatus Capilograph 1D manufactured by Toyo Seiki Seisaku-sho, Ltd. A sample was added to a melting furnace (diameter: 9.55 mm) set to 260° C., thoroughly melted, then passed through a capillary having L/D of 8/2.095 mm and an inflow angle of 180° at an extrusion rate of 15 mm/min, and passed through a pulley mounted at a position of 58 cm from the lower part of the capillary. Stress applied to the pulley when the melted resin was taken up at a rate of 15 m/min was measured. The stress was referred to as the melt tension.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017-061220 | Mar 2017 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2017/045515 | 12/19/2017 | WO | 00 |
