Classifications

• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/201—Pre-melted polymers
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/203—Solid polymers with solid and/or liquid additives
• • 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
• • 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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/04—Monomers containing three or four carbon atoms
  • C08F10/08—Butenes
• • 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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/14—Monomers containing five or more carbon atoms
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/14—Monomers containing five or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
  • C08K5/107—Esters; Ether-esters of monocarboxylic acids with phenols with polyphenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1535—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1535—Five-membered rings
  • C08K5/1539—Cyclic anhydrides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
• • 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
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms

Definitions

• the present invention relates to a method for producing a melt-kneaded composition containing a 3-methyl-1-butene-based polymer and a melt-kneaded composition.
• 3-Methyl-1-butene-based polymers have a high melting point among thermoplastic polyolefin-based resins, and are useful as heat-resistant polyolefins.
• the 3-methyl-1-butene polymer since the 3-methyl-1-butene polymer has a high melting point, it must be melt-kneaded at a high temperature. Therefore, during melt kneading, the 3-methyl-1-butene-based polymer deteriorates (decomposes) due to heat and oxidation, resulting in a decrease in the viscosity of the melt and a decrease in the mechanical properties of the molded product. There was a problem that physical properties deteriorated.
• Patent Document 1 a combination of antioxidants is studied in view of the fact that the effects of antioxidants are lost in a short time.
• Patent Document 2 in order to prevent the 3-methyl-1-butene-based polymer from being oxidized and deteriorated during melt-kneading, the types and combinations of antioxidants to be added are studied.
• an alkyl radical scavenger may be used to ensure the stability of polyolefin during thermoforming.
• Patent Document 3 describes a polyolefin composition containing a polyolefin, a hindered phenol compound, an acrylate compound, and a phosphorus compound in order to ensure heat resistance during high-temperature processing when forming fibers, etc. ing.
• Patent Document 4 describes oxidative stabilization of polyolefin-based thermoplastic resins, including a thermoplastic resin, a phenol antioxidant, an aromatic amine and/or an N,N'-substituted oxamide antioxidant, and compositions containing lactone antioxidants have been described.
• the resin composition has poor thermal stability, reproducibility in differences between kneading devices cannot be ensured, making it difficult to stably produce a molded body. Furthermore, even if the melting and kneading time is short, it is inevitable that the cumulative melting and kneading time will become longer if scraps are recycled (material recycling).
• Patent Documents 1 and 2 In order to prevent thermal deterioration of 3-methyl-1-butene-based polymers, studies are being conducted on the use of antioxidants, alkyl radical scavengers, and the like. However, in Patent Documents 1 and 2, no study is conducted regarding the stability of physical properties against long-term heat during melt-kneading. In fact, the inventors tested the methods described in Patent Documents 1 and 2, but the compositions containing the 3-methyl-1-butene-based polymer had insufficient long-term thermal stability. In Patent Document 3, there is no study using a 3-methyl-1-butene-based polymer as the polyolefin.
• an object of the present invention is to provide a method for producing a melt-kneaded composition and a melt-kneaded composition that can maintain stability of physical properties even when melt-kneaded for a long time. More specifically, the present invention provides a melt-kneading method that can maintain stability of physical properties even after long-term melt-kneading, has good productivity, and can obtain a molded product with good mechanical properties. An object of the present invention is to provide a method for producing a composition and a melt-kneaded composition. Other issues can be understood by those skilled in the art from the disclosure of this specification.
• the present invention is as follows.
• a melt-kneaded composition comprising a step of melt-kneading a 3-methyl-1-butene-based polymer and an alkyl radical scavenger at 300 to 380°C in a lower oxygen state than in the atmosphere.
• Production method [2] The method for producing a melt-kneaded composition according to [1] above, further comprising the step of injecting an inert gas into the melt-kneader, and the melt-kneading is performed in the melt-kneader.
• a step of melt-kneading a 3-methyl-1-butene-based polymer and an alkyl radical scavenger The above melting and kneading is carried out at 300 to 380°C, and The melting and kneading is performed by injecting an inert gas into the melting and kneading machine, or Performing the melting and kneading by deaerating the inside of the melting and kneading machine under reduced pressure, A method for producing a melt-kneaded composition.
• the method for producing a melt-kneaded composition according to any one of [1] to [4] above, wherein the melt-kneading is performed for 1 to 15 minutes.
• the 3-methyl-1-butene-based polymer is a 3-methyl-1-butene homopolymer, and a copolymer of 3-methyl-1-butene and an ⁇ -olefin having 2 to 20 carbon atoms.
• R 7 and R 8 each independently represent an alkyl group having 1 to 4 carbon atoms
• R 9 and R 10 each independently represent an alkyl group having 1 to 9 carbon atoms.
• a method for producing a melt-kneaded composition that can maintain stability of physical properties even when melt-kneaded for a long time, has good productivity, and can obtain a molded article having good mechanical properties; and a melt-kneaded composition.
• melt-kneaded composition of this embodiment and its manufacturing method are as follows: A step of melt-kneading a 3-methyl-1-butene-based polymer and an alkyl radical scavenger, Melting and kneading is performed at 300 to 380°C, and In the process of melting and kneading, melting and kneading is performed by injecting an inert gas into the inside of the melting and kneading machine, or melting and kneading is performed by depressurizing and degassing the inside of the melting and kneading machine.
• 3-Methyl-1-butene-based polymers have a high melting point of about 280°C or higher, so even if the composition is added with an antioxidant, which is recommended for high-temperature molding in this field, it can be melted at a high temperature of about 300°C or higher. During kneading, the stability of physical properties could not be maintained due to thermal deterioration, resulting in a decrease in mechanical properties of the molded product.
• the present inventors focused on the fact that 3-methyl-1-butene-based polymers can undergo decomposition starting from alkyl radicals (R.) by high-temperature melt-kneading.
• a composition was prepared in which an alkyl radical scavenger was added to a polymer.
• an alkyl radical scavenger was added, it was not easy to suppress thermal deterioration caused by high-temperature melt-kneading. Therefore, the inventors thought that even if an alkyl radical scavenger was used, decomposition proceeded by oxygen before thermal decomposition, and focused on the atmospheric conditions in the apparatus during melt-kneading.
• the said "long time" is about 15 minutes, for example.
• the above-mentioned "melting-kneading step” usually includes a step of melt-kneading the 3-methyl-1-butene-based polymer and the alkyl radical scavenger inside a melt-kneading machine.
• the above method for producing a melt-kneaded composition or the above-mentioned "melt-kneading step” includes a step of injecting an inert gas into the inside of the melt-kneading machine and a step of depressurizing and degassing the inside of the melt-kneading machine. Either step may be included, or both steps may be included. For example, a step of injecting an inert gas may be carried out upstream of the melt-kneading machine, and a step of degassing under reduced pressure may be carried out downstream.
• step of injecting or “step of degassing under reduced pressure” is a step before melting and kneading the 3-methyl-1-butene-based polymer and the alkyl radical scavenger, for example, before the start of heating, before the start of shearing. , may be carried out before heating and shearing begins, and preferably continues during melt kneading.
• the 3-methyl-1-butene-based polymer may be a 3-methyl-1-butene homopolymer or a copolymer of 3-methyl-1-butene and an unsaturated hydrocarbon.
• the unsaturated hydrocarbons include ⁇ -olefins, and from the viewpoint of good copolymerizability, ⁇ -olefins having 2 to 20 carbon atoms are preferred.
• the 3-methyl-1-butene-based polymer is preferably a 3-methyl-1-butene homopolymer and a 3-methyl-1-butene homopolymer. and an ⁇ -olefin having 2 to 20 carbon atoms.
• the content of structural units derived from ⁇ -olefin in the copolymer is preferably more than 0 mol% and 20 mol% or less.
• the content of structural units derived from ⁇ -olefin in the copolymer is preferably 0.1 mol% or more, and even more preferably 0.5 mol% or more. It is.
• the content of structural units derived from ⁇ -olefin in the copolymer is preferably 15 mol% or less, and even more preferably 10 mol%.
• the content ratio of structural units derived from ⁇ -olefin in the copolymer can be determined by a Fourier transform infrared spectrophotometer (FT-IR). Specifically, it can be measured by the method described in Examples.
• FT-IR Fourier transform infrared spectrophotometer
• the ⁇ -olefin having 2 to 20 carbon atoms is preferably an ⁇ -olefin having 4 to 16 carbon atoms, more preferably an ⁇ -olefin having 4 to 12 carbon atoms. - It is an olefin. Further, the ⁇ -olefin having 2 to 20 carbon atoms may be linear or branched.
• Examples of ⁇ -olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1 -Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1- Examples include octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexene, and vinylnorbornane.
• One type of ⁇ -olefin having 2 to 20 carbon atoms may be used alone, or two or more types may be used in combination.
• the method for producing the 3-methyl-1-butene-based polymer is not particularly limited, and may be produced using a well-known catalyst such as a Ziegler-Natta catalyst or a metallocene-based catalyst.
• a method for producing a 3-methyl-1-butene-based polymer includes, for example, homopolymerization of 3-methyl-1-butene in the presence of a catalyst as described in JP-A-61-103910, or It can be obtained as a powder by copolymerizing 3-methyl-1-butene and the above ⁇ -olefin.
• the stereoregularity of the 3-methyl-1-butene polymer may be isotactic or syndiotactic.
• the copolymer may be a random copolymer, a block copolymer, or an alternating copolymer.
• alkyl radical scavenger reacts with the alkyl radical derived from the 3-methyl-1-butene-based polymer and stabilizes the alkyl radical, thereby preventing subsequent chain carbon-carbon bonds.
• the alkyl radical scavenger preferably contains at least one selected from the group consisting of an acrylic phenol compound and a benzofuranone compound.
• One type of alkyl radical scavenger may be used alone, or two or more types may be used in combination.
• the acrylic phenol compound used in this embodiment can be represented by the following general formula (I), for example.
• R 1 represents a hydrogen atom or a methyl group
• R 2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
• R 3 , R 4 , R 5 and R 6 each independently Indicates an alkyl group having 1 to 9 carbon atoms.
• the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group, n-propyl group, and isopropyl group.
• the alkyl group having 1 to 9 carbon atoms may be linear or branched.
• alkyl group having 1 to 9 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, 1,1-dimethylpropyl group. group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Examples include octyl group and n-nonyl group.
• R 1 is preferably a hydrogen atom.
• R 2 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
• R 3 , R 4 , R 5 and R 6 are each independently preferably an alkyl group having 3 to 8 carbon atoms, more preferably an alkyl group having 5 carbon atoms, and still more preferably a 1,1-dimethylpropyl group. .
• the acrylic phenol compound represented by general formula (I) is, for example, 2,4-di-t-amyl-6-[1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl]phenyl acrylate, 2,4-di-t-butyl-6-[1-(3,5-di-t-butyl-2-hydroxyphenyl)ethyl]phenylacrylate, and 2-t-butyl-6-[(3 -t-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenylacrylate and the like.
• acrylic phenol compound represented by the general formula (I) examples include Sumilizer (registered trademark) GS manufactured by Sumitomo Chemical Co., Ltd. and Sumilizer (registered trademark) GS manufactured by Sumitomo Chemical Co., Ltd. (registered trademark) GM".
• the benzofuranone compound used in this embodiment can be represented by the following general formula (II), for example.
• R 7 and R 8 each independently represent an alkyl group having 1 to 4 carbon atoms
• R 9 and R 10 each independently represent an alkyl group having 1 to 9 carbon atoms.
• the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group.
• the alkyl group having 1 to 9 carbon atoms may be linear or branched.
• alkyl group having 1 to 9 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, 1,1-dimethylpropyl group. group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Examples include octyl group and n-nonyl group.
• R 7 and R 8 are each independently preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
• R 9 and R 10 are each independently preferably an alkyl group having 1 to 4 carbon atoms, more preferably a t-butyl group.
• the benzofuranone compound represented by general formula (II) is, for example, 5,7-di-t-butyl-3-(3,4-di-methyl-phenyl)-3H-benzofuran-2-one, 5,7 -di-t-butyl-3-(3,4-di-propyl-phenyl)-3H-benzofuran-2-one, and 4-t-butyl-2-(5-t-butyl-2-oxo-3H -benzofuran-3-yl)phenyl-3,5-di-t-butyl-4-hydroxybenzoate and the like.
• alkyl radical scavenger examples include "Irganox (registered trademark) HP-136" manufactured by BASF, and “Irganox (registered trademark) HP-136" manufactured by Chitec.
• the product name is "Revonox (registered trademark) 501".
• the amount of the alkyl radical scavenger added to 100 parts by mass of the 3-methyl-1-butene polymer is preferably 0.01 to 1.00 parts by mass. If the amount of the alkyl radical scavenger is within the above numerical range, the stability of the physical properties of the melt-kneaded composition can be maintained during melt-kneading. Furthermore, there is no risk that the physical properties required of the resin composition, such as the alkyl radical scavenger bleed out or deterioration of hygroscopicity, will be impaired. Furthermore, there is no risk of decomposition gas being generated during melt molding and resulting in molding defects.
• the amount of the alkyl radical scavenger to be blended with respect to 100 parts by mass of the 3-methyl-1-butene-based polymer is more preferably 0.02 parts by mass or more, and even more preferably 0.02 parts by mass or more. 0.05 parts by mass or more.
• the amount of the alkyl radical scavenger to be blended with respect to 100 parts by mass of the 3-methyl-1-butene-based polymer is more preferably 0.80 parts by mass or less, and more preferably 0.80 parts by mass or less. Preferably it is 0.70 parts by mass or less.
• the blending amount of the above-mentioned alkyl radical scavengers means the total blending amount of the alkyl radical scavengers.
• At least one antioxidant selected from the group consisting of phenolic antioxidants and phosphorus-based antioxidants may be further blended and melt-kneaded.
• melt-kneading may be performed without adding an antioxidant.
• One type of antioxidant may be used alone, or two or more types may be used in combination.
• phenolic antioxidants include pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-t- butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris[(4-t-butyl-3-hydroxy- 2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, octadecyl-3-(3,5-di-t-butyl-4-hydroxy phenyl)propionate, thiodiethylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-
• phenolic antioxidant commercially available products may be used, and examples thereof include “ADEKA STAB (registered trademark) AO series” manufactured by ADEKA, “Irganox (registered trademark) series” manufactured by BASF Japan, etc.
• phosphorus-based antioxidants examples include 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5 ] Undecane, Tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenephosphonite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, Tris(2 , 4-di-t-butylphenyl) phosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphite, bis(2,4-di-t-butyl phenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol
• ADEKA STAB registered trademark PEP series
• ADEKA STAB registered trademark HP series
• Irgafos registered trademark
• BASF Japan BASF Japan
• HOSTANOX registered trademark
• antioxidants other antioxidants than the phenolic antioxidant and the phosphorus antioxidant may be blended as long as the effects of the present invention are not impaired.
• antioxidants other than phenolic antioxidants and phosphorus antioxidants include sulfur-based antioxidants and amine-based antioxidants.
• the amount of antioxidant added to 100 parts by mass of the 3-methyl-1-butene-based polymer is preferably 0.01 parts by mass or more, more preferably 0.10 parts by mass. That's all.
• the amount of antioxidant added to 100 parts by mass of the 3-methyl-1-butene-based polymer is preferably 1.00 parts by mass or less, more preferably 0.80 parts by mass or less.
• the blending amount of the above-mentioned antioxidants means the total blending amount of antioxidants.
• additives In the melt-kneading step, in addition to the 3-methyl-1-butene-based polymer, the alkyl radical scavenger, and the antioxidant, other additives may be further blended and melt-kneaded.
• Other additives include, for example, antacids, fillers, light stabilizers, antistatic agents, flame retardants, pigments, polymerization inhibitors, heavy metal deactivators, ultraviolet absorbers, nucleating agents, clarifying agents, and lubricants. , a fluorescent whitening agent, and a rust inhibitor.
• One type of other additives may be used alone, or two or more types may be used in combination.
• antacid From the viewpoint of suppressing deterioration due to acid components generated from residual metal components, it is preferable to further blend an antacid in the melt-kneading process.
• antacids include barium laurate, calcium stearate, zinc stearate, magnesium stearate, aluminum stearate, zinc oleate, and magnesium 12-hydroxystearate.
• One type of antacid may be used alone, or two or more types may be used in combination.
• the amount of the antacid added to 100 parts by mass of the 3-methyl-1-butene polymer can be determined as appropriate depending on the use of the melt-kneaded composition, and is, for example, 0.01 to 200 parts by mass. You can.
• a filler may be further blended and melt-kneaded in the melt-kneading step, depending on the use of the melt-kneaded composition.
• the filler may be added to the melt-kneaded composition and then melt-kneaded again.
• fillers include fibrous compounds such as glass fibers, alumina fibers, resin fibers, carbon fibers, and cellulose fibers; flat compounds such as mica, talc, montmorillonite, and flat aluminum; glass beads, shirasu balloons, acrylic balloons, etc.
• Acicular compounds such as acicular titanate metal salts, wollastonite, acicular silica, tin oxide; Powdered titanate metal salts, pulverized wood chips, titanium oxide, calcium carbonate, silica, alumina, etc. Powdered compounds; and the like.
• These fillers may be surface-treated with, for example, a silane coupling agent.
• a compatibilizer may be used to improve the dispersibility of the filler.
• One type of filler may be used alone, or two or more types may be used in combination.
• the amount of the filler to be blended with respect to 100 parts by mass of the 3-methyl-1-butene-based polymer can be determined as appropriate depending on the use of the melt-kneaded composition, and is, for example, 0.01 to 300 parts by mass. Good too.
• the production method of this embodiment includes a step of melt-kneading a 3-methyl-1-butene-based polymer and an alkyl radical scavenger at 300 to 380° C. in an oxygen condition lower than that of the atmosphere.
• a manufacturing method further includes a step of injecting an inert gas into the melt-kneading machine, and the melt-kneading is performed within the melt-kneading machine. By injecting an inert gas, preferably by continuing it, a low oxygen condition inside the melt kneader can be achieved.
• Such a manufacturing method further includes a step of depressurizing and deaerating the inside of the melt-kneading machine, and it is preferable that the melt-kneading is performed within the melt-kneading machine. By degassing under reduced pressure, preferably by continuing it, a low oxygen state inside the melt-kneader can be achieved.
• Such a manufacturing method further includes a step of injecting an inert gas into the inside of the melt-kneading machine, and a step of degassing the inside of the melt-kneading machine under reduced pressure, and the melt-kneading is carried out in the melt-kneading machine. It is preferable to do so.
• an inert gas is injected into the melt-kneader. Melting and kneading is performed, or the inside of a melting and kneading machine is depressurized and degassed to perform melting and kneading.
• the manufacturing method of this embodiment suppresses deterioration of the physical properties of the melt-kneaded composition due to oxygen, effectively exhibits the function of the alkyl radical scavenger, and makes it possible to obtain a molded article with good mechanical properties.
• it is important to perform melt-kneading under an inert atmosphere or under low oxygen conditions.
• "low oxygen state” means that by depressurizing and degassing the inside of the melting and kneading machine, the oxygen concentration inside the melting and kneading machine has become lower than before depressurizing and degassing. state.
• the concept of "hypoxic state” may include a state "under an inert atmosphere.”
• the oxygen concentration inside the melt kneading machine is preferably 5% or less, more preferably 2% or less, and further preferably 1% or less.
• the oxygen concentration is measured using an oxygen concentration meter, preferably a diaphragm type galvanic type, more preferably a diaphragm type galvanic battery type or galvanic battery type oxygen concentration meter.
• the oxygen concentration can be measured by the method described in Examples.
• the oxygen concentration meter for example, "XP-3180E” (diaphragm type galvanic battery type) manufactured by Shin Cosmos Electric Co., Ltd. and its successor "XP-3380II-E” (galvanic battery type) can be used.
• a method of melting and kneading by injecting an inert gas into the inside of a melting and kneading machine is, for example, a method of melting and kneading by injecting each component into the melting and kneading machine while injecting an inert gas into the inside of the melting and kneading machine.
• an inert gas is added after each component is introduced into the melt-kneading machine, preferably before starting heating or starting shearing, more preferably before starting heating and starting shearing.
• each component may be introduced from a sealed supply section to perform melting and kneading. Further, during melting and kneading, the inert gas may continue to be injected into the melting and kneading machine.
• the method of injecting the inert gas can be carried out depending on the equipment installed in each melting and kneading machine. This may be carried out from a supply section for each component provided in the melt-kneading machine, or may be carried out from a gas vent provided in the melt-kneading machine.
• the inert gas can be injected into the entire area from the inert gas supply section to the heating section where melting and kneading is carried out for melting and kneading.
• the inert gas include nitrogen gas, helium gas, neon gas, argon gas, krypton gas, and carbon dioxide gas, and nitrogen gas is preferred from the viewpoint of high availability and versatility.
• the method of melting and kneading by degassing the inside of the melting and kneading machine is, for example, by introducing each component into the melting and kneading machine while degassing the inside of the melting and kneading machine under reduced pressure.
• the inside of the melting and kneading machine is Melting and kneading may be performed by degassing under reduced pressure, or melting and kneading may be performed by deaerating the interior of the melting and kneading machine under reduced pressure and then introducing each component from a sealed supply section. Further, during the melting and kneading, the vacuum degassing inside the melting and kneading machine may be performed intermittently or continuously.
• the method of depressurizing and deaerating the inside of the melt-kneading machine can be carried out depending on the equipment provided in each melt-kneading machine, and for example, it may be carried out from a vacuum vent.
• a vacuum pump can be used for vacuum degassing.
• the inside of the melt-kneading machine can be in a vacuum state of, for example, 50 kPa or less and 0.1 kPa or more.
• the melt kneading machine is a facility that can perform melting and kneading by injecting an inert gas into the inside of the melting and kneading machine, or it can perform melting and kneading by depressurizing and deaerating the inside of the melting and kneading machine.
• a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, etc. equipped with such equipment can be used.
• the injection of the above-mentioned inert gas and vacuum degassing may be used together.
• the above melting and kneading is performed at 300 to 380°C. If the melt-kneading temperature is less than 300°C, the 3-methyl-1-butene-based polymer will not be sufficiently melted, resulting in insufficient dispersion of the alkyl radical scavenger and additives. If the melt-kneading temperature exceeds 380° C., the decomposition of raw materials such as the 3-methyl-1-butene polymer and the alkyl radical scavenger will become significant, making it impossible to obtain sufficient effects of the invention.
• the melt-kneading temperature is preferably 300°C or higher, more preferably 310°C or higher. Further, from the viewpoint of suppressing significant decomposition of the raw materials, the melting and kneading temperature is preferably 380°C or lower, more preferably 360°C or lower.
• the melting and kneading time can be adjusted depending on the size of the kneading device and the like.
• the melting and kneading time may be 1 to 15 minutes, but is not limited to the numerical range of the melting and kneading time.
• the "melting and kneading time" indicates the time during which the mixer is rotating in a batch type kneader, and the residence time of the raw materials in the apparatus in the case of a continuous extrusion type kneader. It is preferable that the above-mentioned low oxygen state is continuously maintained throughout the entire melting and kneading time.
• the manufacturing method of this embodiment is less likely to cause deterioration in physical properties due to high-temperature melting and kneading. Therefore, the longer the melt-kneading time (approximately 15 minutes in this embodiment), the more stable the physical properties of the melt will be, and the more the melt-kneaded resin composition will be able to obtain a molded product with good mechanical properties. , the effect of the present invention that it can be manufactured with high productivity is easily exhibited. As the melt-kneading machine becomes larger, the production volume increases and the above-mentioned melt-kneading time tends to become longer, which increases the possibility that the physical properties of the melt-kneaded composition will deteriorate. However, with the manufacturing method of the present embodiment, the stability of the physical properties can be maintained, so it is possible to manufacture a melt-kneaded resin composition with good productivity and good mechanical properties.
• the mixer rotation speed during melt-kneading may be 80 rpm or more or 100 rpm or more, or 400 rpm or less or 350 rpm or less.
• the melt-kneaded composition is removed from the melt-kneader and cooled.
• melt-kneaded composition manufactured by the method for manufacturing a melt-kneaded composition described above.
• a part of the 3-methyl-1-butene-based polymer is heated at high temperature during melt-kneading, and in some cases by high temperature and shearing. Since there is a possibility of decomposition and the amount of the alkyl radical scavenger blended is small, it is difficult to accurately define the decomposed alkyl radical scavenger.
• melt-kneaded composition containing the above-mentioned decomposition products and reaction products of a 3-methyl-1-butene-based polymer and an alkyl radical scavenger.
• the melt-kneaded composition produced by the above-mentioned method for producing a melt-kneaded composition may be produced by a method other than the above-mentioned method for producing a melt-kneaded composition, as illustrated in the Examples section. It is clear that the stability of physical properties is maintained compared to the melt-kneaded composition. Note that it is possible to detect part or all of the undecomposed alkyl radical scavenger present in the melt-kneaded composition.
• the total content of the 3-methyl-1-butene polymer and the alkyl radical scavenger in the melt-kneaded composition is preferably 99.0% by mass or more, more preferably 99.0% by mass or more. It is 5% by mass or more.
• the upper limit of the total content ratio is not limited as long as it does not impair the effects of the invention, and may be, for example, 100% by mass or less, or 99.9% by mass or less.
• the total content of the 3-methyl-1-butene polymer, the alkyl radical scavenger, and the antioxidant in the melt-kneaded composition is preferably 99.0 mass % or more, more preferably 99.5% by mass or more.
• the upper limit of the total content ratio is not limited as long as it does not impair the effects of the invention, and may be, for example, 100% by mass or less, or 99.9% by mass or less.
• the said "content ratio" shall be calculated based on the compounding quantity of each component used for a melt kneading composition.
• the melt-kneaded composition of this embodiment preferably has a melting point of 280 to 310°C.
• the melting point of the melt-kneaded composition is within the above range, it has excellent heat resistance and can suitably exhibit the characteristics of a 3-methyl-1-butene-based polymer.
• the melting point of the melt-kneaded composition of this embodiment has almost no difference from the melting point of the 3-methyl-1-butene-based polymer used as a raw material. Therefore, in this specification, the melting point of the 3-methyl-1-butene-based polymer used as a raw material can be regarded as the melting point of the melt-kneaded composition.
• the melting point can be measured by the method described in the Examples.
• the melt-kneaded composition of this embodiment has a melt viscosity of preferably 10 to 1000 Pa ⁇ s, more preferably 20 to 500 Pa ⁇ s at a barrel temperature of 320° C. and a shear rate of 1220 sec ⁇ 1 . If the melt viscosity of the melt-kneaded composition is 10 Pa ⁇ s or more, the strength of the molded article will be good. Further, if the melt viscosity of the melt-kneaded composition is 1000 Pa ⁇ s or less, the fluidity during molding will be good.
• the melt viscosity of the melt-kneaded composition can be measured by the method described in Examples.
• melt-kneaded composition 3-methyl-1-butene-based polymer, alkyl radical scavenger, and other additives such as antioxidants and fillers that are added as necessary are melt-kneaded. Molding may be performed continuously with the step of Alternatively, the melt-kneaded composition may be once taken out and then melt-molded again.
• general molding methods such as injection molding, extrusion molding, blow molding, and vacuum molding can be used.
• the melt-kneaded composition of the present embodiment has a molded article having a breaking strength of preferably 10 MPa or more, more preferably 25 MPa or more, as measured in accordance with JIS K 7161-1:2014. If the breaking strength is 10 MPa or more, it can be said to have good mechanical strength. Breaking strength can be measured by the method described in Examples.
• the peak area of the bending vibration 1,461 cm -1 derived from the main chain methylene group of the 3-methyl-1-butene homopolymer and the bending vibration 727 cm -1 derived from the side chain methylene group of the ⁇ -olefin homopolymer A calibration curve was created from the ratio to the peak area of and the addition ratio of each resin.
• the above IR measurement was performed on the 3-methyl-1-butene-based copolymer obtained in the production example, the obtained measurement value was inserted into the above calibration curve, and ⁇ -olefins other than 3-methyl-1-butene were measured. The content ratio of the derived structural units was determined.
• the copolymer or homopolymer obtained in the production example was heated at 10°C/10°C from 30°C to 320°C under a nitrogen flow rate (100 mL/min) using a differential scanning calorimeter (“DSC25” manufactured by TA Instrument). The temperature was raised to 320°C for 5 minutes, and then the temperature was lowered to -70°C at a rate of 10°C/min. After holding at -70°C for 5 minutes, the temperature was raised to 320°C at a rate of 10°C/min, and the melting point was measured.
• DSC25 differential scanning calorimeter
• melt viscosity In Examples 1, 7, and 8, after blending each component shown in Table 1, using a capillary rheometer ("Capillography 1C" manufactured by Toyo Seiki Seisakusho Co., Ltd.), the barrel temperature was 320°C, and the shear rate was 1220 sec -1 (capillary rheometer). The melt viscosity (Pa ⁇ s) of the melt-kneaded composition was measured under the following conditions: inner diameter 1.0 mm x length 10 mm, extrusion speed 10 mm/min).
• melt-kneaded composition was depressurized to -0.1 MPaG using an oil rotary pump using a decompression hot press device (IMC-1 83B manufactured by Imoto Seisakusho Co., Ltd.) and preheated at 320°C for 2 minutes. , and pressed for 2 minutes at 70 kN (1.7 MPa). Thereafter, it was pressed for 2 minutes at 70 kgf/cm 2 (6.9 MPa) using a cooling press equipped with water cooling to produce a pressed plate with a thickness of 0.5 mm. A test sheet was cut into a cylindrical shape with a diameter of 8 mm from the obtained press plate.
• a decompression hot press device IMC-1 83B manufactured by Imoto Seisakusho Co., Ltd.
• Example 1 [Breaking strength]
• each component shown in Table 1 or 2 was melt-kneaded at 200 rpm and 320° C. in a nitrogen atmosphere using a small kneader (“Micro 15 Compounder” manufactured by DSMXplore).
• a small injection molding machine (“MicroInjection Molding Machine 10cc” manufactured by DSMXplore) at an injection pressure of 0.3 MPa
• a small test piece (1BA type dumbbell test piece described in Appendix A of JIS7161-2) was
• the breaking strength (MPa) was measured at a tensile rate of 5 mm/min at 49% humidity. The measurements were performed five times each, and the average value was used.
• the strength retention rate was calculated based on the following formula from the above-mentioned breaking strength of the dumbbell test pieces produced under the conditions 4 minutes and 15 minutes after the start of melt-kneading.
• Strength retention rate (%) (breaking strength of dumbbell test piece prepared under conditions 15 minutes after the start of kneading/breaking strength of dumbbell test piece prepared under conditions 4 minutes after start of kneading) x 100
• the evaluation results are summarized in Table 3. The larger the strength retention rate (%), the better the tensile properties are maintained.
• A-2 5,7-di-t-butyl-3-(3,4-dimethyl-phenyl)-3H-benzofuran-2-one, manufactured by Tokyo Kasei Kogyo Co., Ltd.
• C-2 A composition whose main component is tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenephosphonite, Product name: “HOSTANOX (registered trademark) P-EPQ”, manufactured by Clariant (sulfur-based antioxidant)
• ⁇ D-1 2,2-bis ⁇ [3-(dodecylthio)-1-oxopropoxy]methyl ⁇ propane-1,3-diylbis[3-(dodecylthio)propionate], trade name "ADEKASTAB (registered trademark) AO" -412S”, manufactured by ADEKA ⁇ Catechols>
• ⁇ E-1 4-t-butyl-pyrocatechol, manufactured by Tokyo Kasei Kogyo Co., Ltd.
• the temperature of the mixed solution was raised to 110°C over 2 hours, and when it reached 110°C, 42.4 mL (160 mmol) of dibutyl phthalate was added, and the mixture was maintained at the same temperature for 2 hours while stirring. . After 2 hours of reaction, the mixture was allowed to stand and the supernatant liquid was removed. Decane and hexane were added thereto, and the solid components were washed three times, then resuspended in 2 L of titanium tetrachloride, and heated to react again at 110° C. for 2 hours.
• the reaction mixture was allowed to stand again using decane and hexane, and the supernatant liquid was removed repeatedly until sufficient washing was performed until no free titanium compound was detected in the washing liquid.
• the obtained suspended component was dried under reduced pressure at room temperature for 6 hours to obtain a dried titanium catalyst component.
• the composition of the obtained titanium catalyst component was 4.0% by mass of titanium, 56.0% by mass of chlorine, 17.0% by mass of magnesium, and 11.0% by mass of dibutyl phthalate.
• copolymer (A) which is a copolymer of 3-methyl-1-butene and 1-decene.
• the copolymer (A) thus obtained was subjected to the above measurements and found to have a melting point of 296°C. Further, the content of the structural unit derived from the comonomer 1-decene in the copolymer (A) was 1.1 mol%. Further, the melt viscosity of the melt-kneaded composition obtained in Example 1 was 104 Pa ⁇ s.
• Example 1 Using each component shown in Table 1, the melt-kneaded composition was evaluated according to the above-mentioned evaluation methods for [stability of physical properties in melt-kneading] and [strength retention]. Regarding the evaluation results of the above-mentioned [Analysis of the amount of additives contained in the melt-kneaded composition], the amount of additives contained in the injection molded piece after kneading for 4 minutes was 520 mass for A-1. ppm, B-1 was 1,100 mass ppm, and C-1 was 490 mass ppm. The amount of additives contained in the injection molded pieces after kneading for 15 minutes was 170 mass ppm for A-1, 520 mass ppm for B-1, and 130 mass ppm for C-1.
• Examples 2 to 8 and Comparative Examples 1 to 8 The same test as in Example 1 was conducted and evaluated, except that each component and the blending amount of the composition were changed as shown in the table. The results are shown in Table 1 or 2.
• Comparative Example 5 regarding the evaluation results of the above-mentioned [Analysis of the amount of additives contained in the melt-kneaded composition], the amount of additives contained in the injection-molded piece for which the kneading time was 4 minutes was A -1 was 400 mass ppm, B-1 was 965 mass ppm, and C-1 was 536 mass ppm. The amount of additives contained in the injection molded pieces after kneading for 15 minutes was 61 mass ppm for A-1, 1183 mass ppm for B-1, and 263 mass ppm for C-1.
• Comparative Example 1 contained a large amount of antioxidant but did not contain an alkyl radical scavenger, so the complex shear viscosity from 60 seconds to 900 seconds was The absolute value of the numerical value indicating the slope of the logarithm of was large, and both the viscosity retention rate and strength retention rate were small, which means that the 3-methyl-1-butene-based polymer deteriorated quickly during melt-kneading. I understand that. In addition, from the comparison between Example 1 and Comparative Example 1, it was found that the smaller the absolute value of the slope of the logarithm of the complex shear viscosity from the measurement time of 60 seconds to 900 seconds, the higher the strength retention.
• Example 2 it can be seen that even when the alkyl radical scavenger is benzofuranones, the effects of the present invention can be achieved.
• Examples 1, 3, and 4 show that the alkyl radical scavenger alone is effective in suppressing the deterioration of a 3-methyl-1-butene-based polymer during melt-kneading, regardless of the presence or absence of an antioxidant.
• Comparative Example 3 shows that there is no effect without the alkyl radical scavenger.
• Examples 1 and 5 show that even when the amount of the alkyl radical scavenger added is 0.02 parts by mass, it is effective in suppressing the deterioration of the 3-methyl-1-butene-based polymer during melt-kneading. From Example 6 and Comparative Example 2, it was found that the composition containing the antioxidant described in Patent Document 1 suppressed the deterioration of the 3-methyl-1-butene-based polymer during melt-kneading more than the composition without the addition of a stabilizer. Although the suppressing effect is somewhat effective, it is insufficient, indicating that an alkyl radical scavenger is required.
• Comparative Example 4 shows that the composition containing the antioxidant described in Patent Document 2 is insufficient in suppressing deterioration of the 3-methyl-1-butene-based polymer during melt-kneading. From Examples 7 and 8, even 3-methyl-1-butene-based copolymers and 3-methyl-1-butene homopolymers with high copolymerization ratios suppress deterioration during melt kneading by the alkyl radical scavenger. It turns out that it is effective.
• Example 1 and Comparative Examples 1, 5, and 6 the effect of suppressing the deterioration of the 3-methyl-1-butene-based polymer during melt-kneading using the alkyl radical scavenger was found to be significant under conditions of lower oxygen than in the atmosphere, such as inert It can be seen that this is achieved by kneading in an atmosphere. From Example 1 and Comparative Example 7, it can be seen that catechols have no effect of suppressing the deterioration of the 3-methyl-1-butene-based polymer during melt-kneading.

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