WO2006109631A1 - Procede de production de polymeres du 4-methyl-1-pentene et polymeres correspondants - Google Patents

Procede de production de polymeres du 4-methyl-1-pentene et polymeres correspondants Download PDF

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Publication number
WO2006109631A1
WO2006109631A1 PCT/JP2006/307148 JP2006307148W WO2006109631A1 WO 2006109631 A1 WO2006109631 A1 WO 2006109631A1 JP 2006307148 W JP2006307148 W JP 2006307148W WO 2006109631 A1 WO2006109631 A1 WO 2006109631A1
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methyl
pentene
polymer
pentene polymer
separating
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PCT/JP2006/307148
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English (en)
Japanese (ja)
Inventor
Tetsuya Kunisada
Yukio Katsuki
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Mitsui Chemicals, Inc.
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Priority to JP2007512924A priority Critical patent/JP4913040B2/ja
Publication of WO2006109631A1 publication Critical patent/WO2006109631A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • C08F6/12—Separation of polymers from solutions
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/14—Monomers containing five or more carbon atoms
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms

Definitions

  • the present invention relates to a method for producing a 4-methyl-1 pentene polymer and a 4-methyl-1 pentene polymer.
  • Branched ⁇ -olefins such as 4-methyl-1 pentene and 3-methyl-1 pentene are homopolymerized in the presence of a Ziegler polymerization catalyst containing a titanium trihalide component, or branched ⁇ -olefins and other olefins are polymerized. Many attempts have been made so far to produce a branched, one-year-old refin polymer excellent in transparency and heat resistance.
  • the branched ⁇ -olefin polymer obtained in the presence of such a trihalogenated titanium catalyst has a broad molecular weight distribution and is excellent in melt fluidity and moldability.
  • the problem was that the regularity and rigidity were inferior, and the catalyst was inferior in polymerization activity.
  • the present applicant has developed a method for polymerizing a branched ⁇ -year-old refin in the presence of a catalyst formed from a highly active titanium catalyst component, an organoaluminum compound catalyst component, and an organosilicon compound catalyst component.
  • a catalyst formed from a highly active titanium catalyst component, an organoaluminum compound catalyst component, and an organosilicon compound catalyst component This is proposed in Japanese Patent Laid-Open No. 59-206418 (Patent Document 1).
  • Patent Document 2 A continuous polymerization process was also proposed in JP-A-2-38406 (Patent Document 2).
  • atactic polypropylene produced as a by-product in the production of polypropylene in the presence of a Ziegler polymerization catalyst containing a trihalogenated titanium component, is excellent in flexibility, a resin modifier, and a hot melt adhesive.
  • Patent Document 3 used as an asphalt modifier suitable for the production of pavement materials and waterproof coatings (Publication No. 11-504382 (Patent Document 4))
  • Patent Document 4 further improvement in heat resistance is required.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 59-206418
  • Patent Document 2 JP-A-2-38406
  • Patent Document 3 JP-A-4-46984
  • Patent Document 4 Japanese Patent Publication No. 11-504382
  • An object of the present invention is to provide a high-quality 4-methyl-1-pentene polymer excellent in heat resistance, transparency, impact strength, and the like when blended with flexibility, adhesiveness, heat resistance, and other resins. It is an object of the present invention to provide a special 4-methyl-1 pentene polymer having a high isodisperse diatomic fractional power of 0 to 95% and a method for producing them. Means for solving the problem
  • the present invention relates to
  • Step 1 of separating and recovering 4-methyl-1-pentene polymer (A) as a solid component from a polymer solution containing a solid component obtained by polymerization using 4-methyl-1-pentene polymer (B)
  • the 4-methyl-1 pentene polymer (A) is separated into the remaining polymer solution from the 4-methyl-1 pentene polymer (A). Provision of the production method of A) and (B).
  • the 4-methyl-1-pentene polymer (B) produced simultaneously after separating and recovering the 4-methyl-1-pentene polymer (A) as a solid component from the polymer solution containing the solid component obtained by Providing a method for producing 4-methyl-1 pentene polymer (B), which separates and recovers the methyl 1-pentene polymer (A) from the remaining polymer solution.
  • the two-phase flow evaporator having piston flow characteristics is a double tube flash dryer, and the linear velocity at the inlet of the double tube flash dryer is 0.03 to 30 mZ seconds and The gas superficial linear velocity at the outlet is 3 to 30000 mZ seconds, and the temperature of the 4-methyl 1-pentene polymer (B) at the outlet of the double tube flash dryer is 100 to 400 ° C.
  • 1 comprises a recurring unit 0-4 0 mole 0/0 derived from Orefin having 2 to 20 carbon atoms other than pentene, ⁇ isotactic die each time fraction of 40% to 95%, 4-methyl-1-pentene-based Provision of polymer (B).
  • a high stereoregularity containing magnesium, titanium, halogen and an electron donor as essential components can be used, for example, so-called Ziegler catalyst, metallocene catalyst and the like.
  • Titanium catalyst component, (b) organic aluminum A catalyst formed from an organic compound catalyst component and (C) an electron donor component is preferably used.
  • the highly stereoregular titanium catalyst contains magnesium, titanium, halogen, and an electron donor as essential components.
  • a titanium catalyst component (a) preferably has a magnesium atom Z titanium atom (atomic ratio) of 2 to 100, more preferably 4 to 70, and preferably a halogen atom Z titanium atom (atomic ratio). It is 4 to 100, more preferably 6 to 40, and the electron donor Z titanium atom (atomic ratio) is preferably in the range of 0.2 to 10, more preferably 0.4 to 6.
  • the specific surface area of highly stereoregular titanium catalyst component (a) is preferably 3m 2 Zg or more, still more preferably 40 m 2 / g or more, particularly preferably 100m 2 / g ⁇ 8000m 2 / g Desirable.
  • Such a titanium catalyst component (a) is usually washed simply with hexane at room temperature.
  • titanium catalyst component (a) has an amorphous power, regardless of the starting magnesium compound used for the catalyst preparation, or a normal, commercially available magnesium alloy. Compared to that of muhalide, it is desirable to be in a very amorphous state. Titanium catalyst component (a), in addition to the essential components, unless the catalyst performance is greatly deteriorated
  • the titanium catalyst component (a) contains other components such as other elements, metals, diluents, etc.
  • the titanium catalyst component (a) It is preferable to show a specific surface area value as described above and to show amorphousness when removed.
  • the titanium catalyst component (a) has an average particle diameter of usually 1 to 200 / ⁇ ⁇ , preferably 5 to LOO m, and a geometric standard deviation ⁇ g of the particle size distribution is usually less than 2.1 , Preferably 1
  • the particle shape is a perfect shape such as a true sphere, an oval sphere, or a granule.
  • a magnesium compound (or magnesium metal) is used.
  • Titanium compounds and electron donors or electron donor-forming compounds Titanium compounds and electron donors or electron donor-forming compounds (electron donors).
  • electron donors The compound to be formed may be brought into contact with each other with or without other reaction reagents.
  • the titanium catalyst component (a) in order to produce the titanium catalyst component (a), it may be applied in accordance with a conventionally known method for preparing a highly active titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components.
  • Preparation methods of such a highly active titanium catalyst component (a) include, for example, JP-A-50-108385, JP-A-50-126590, JP-A-51-20297, JP JP 51-28189, JP 51-64586, JP 51-92885, JP 51-136625, JP 52-87489, JP 52-100596 JP, JP 52-147688, JP 52-104593, JP 53-2580, JP 53-40093, JP 53-43094, JP Sho 55-135102, Sho 55-135103, Sho 56-811, Sho 56-11908, Sho 56-18606, Sho 58-83006 JP, 58-138705, JP 58-138706, JP 58-138707, JP 58-138708, JP 58-138709, JP Sho 58-138710, JP Sho 58-138715 It is disclosed in etc..
  • a method using a liquid halogenated titanium or a method using a halogenated hydrocarbon after or when using a titanium compound is preferred.
  • the electron donor used in the above preparation diesters or diester-forming compounds, alcohols, phenols, aldehydes, ketones, ethers, carboxylic acids, strong rubonic anhydrides, carbonates, monoesters, amines, etc. Can be mentioned.
  • a dicarboxylic acid ester in which two carboxyl groups are bonded to one carbon atom or a dicarboxylic acid in which a carboxyl group is bonded to two adjacent carbon atoms, respectively.
  • Esters are preferably used.
  • the magnesium compound used for the preparation of the highly stereoregular titanium catalyst component (a) is a magnesium compound having a reducing ability or a magnesium compound having no reducing ability.
  • the magnesium compound having a reducing ability include a magnesium compound having a magnesium 'carbon bond or a magnesium-hydrogen bond.
  • a magnesium compound having no reducing ability is preferable, and a halogen-containing compound is particularly preferable.
  • Magnesium-containing compounds, particularly magnesium chloride, alkoxy magnesium chloride, aryloxy salt and magnesium are preferably used.
  • Titanium compounds used for the preparation of the titanium catalyst component (a) include, for example, Ti (OR) X g
  • halogen-containing titanium compounds particularly tetrahalogen titanium, are preferred, and tetrasalt titanium is more preferred.
  • a compound having at least one A1-carbon bond in the molecule can be used.
  • M ⁇ IR 1 wherein M 1 is Li, Na, K and R 1 is the same as above
  • trialkylaluminum such as triethylaluminum and tributylaluminum, or alkylaluminum in which two or more of the above aluminum compounds are combined! /.
  • the electron donor (c) includes amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphorylamides, esters, thioethers, and thioesters. , Acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (ary oxy) silanes, organic acids, and metal amides and salts belonging to Groups I to IV of the periodic table, etc. Can be mentioned.
  • the salt can be obtained, for example, by reacting an organic acid with an organometallic compound used as the catalyst component (b).
  • the compound force exemplified above as the electron donor contained in the titanium catalyst component (a) can be selected.
  • organic acid esters alkoxy (ary oxy) silane compounds, ethers, ketones, acid anhydrides, amines, and the like.
  • the electron donor in the titanium catalyst component (a) is a monocarboxylic acid ester
  • the electron donor component (c) is an alkyl group of an aromatic carboxylic acid. It is preferred to be an ester!
  • the electron donor in the titanium catalyst component (a) is an ester obtained by the reaction of a dicarboxylic acid and an alcohol having 2 or more carbon atoms, the general formula R Si (OR 1 ) (In the formula
  • R, R 1 are hydrocarbon groups (0 ⁇ n ⁇ 4), alkoxy (ary oxy) silane compounds, or steric hindrance! /, And amines are preferably used as the electron donor component (c). U ,.
  • alkoxy (ary oxy) silane compounds trimethyl methoxy silane, trimethyl ethoxy silane, trimethyl n -propoxy silane, triethyl methoxy silane, tri n-propyl methoxy silane, tri iso propyl methoxy silane, Triphenylmethoxysilane and the like are preferable.
  • amines include 2, 2, 6, 6-tetramethinoleviperidine, 2, 2, 5, 5-tetramethylpyrrolidine, or derivatives thereof, and tetramethylmethylenediamine. be able to.
  • polymerization refers to homopolymerization or copolymerization.
  • 4-Methyl-1 pentene polymer (A) and 4-Methyl-1 pentene polymer (B) can be obtained by homopolymerization of 4-methyl-1 pentene or copolymerization of 4-methyl-1 pentene with olefins other than 4 methyl-1 pentene. Can be obtained at The olefins copolymerized with 4-methyl-1-pentene may be linear or have side chains, but linear olefins are particularly preferred.
  • a linear olefin having a carbon atom number in the range of 2 to 20 is usually used.
  • Such straight chain olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene. 1—Eicosen.
  • linear olefins in particular, 1-hexene, 1-octene, 1-decene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, etc.
  • Olefin is preferably used.
  • These olefins can also be used in combination of two or more.
  • the 4-methyl-1 pentene polymer ( ⁇ ) and 4-methyl-1 pentene of the present invention In the manufacturing method of the system polymer (B), 4-methyl-1-pentene 60 to: LOO mol 0/0, preferably from 70 to 99 mole 0/0, more preferably 80 to 95 mole 0/0, 4-methyl-1- Orefuin other than pentene 0-40 mole 0/0, preferably 1 to 30 mol 0/0, more preferably 5 to 20 mol 0/0 (if the wherein 4-methyl-1-pentene and 4 Orefuin other than methyl 1-pentene Can be obtained by polymerizing in a hydrocarbon solvent using the aforementioned polymerization catalyst.
  • polymerization is usually performed in a hydrocarbon solvent as an inert medium.
  • inert media include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, and kerosene; alicyclic hydrocarbons such as cyclopentane and cyclohexane; benzene, Aromatic hydrocarbons such as toluene and xylene; Halogenated hydrocarbons such as dichloroethane, methylene chloride, and chlorobenzene; or a mixture thereof. Of these, aliphatic hydrocarbons are particularly preferably used.
  • polymerization may be carried out in the monomer using 4-methyl-1 pentene, which is a monomer that does not exist in the inert medium, as the hydrocarbon solvent, and the monomer and the inert medium. You can use both in combination.
  • a 4-methyl-1 pentene polymer is produced in the presence of the catalyst as described above.
  • preliminary polymerization as described below is performed prior to performing such polymerization. May be.
  • the catalyst in the main polymerization exhibits a large polymerization activity, and a high bulk density powdery 4-methyl-1-pentene polymer (A) can be obtained. it can. That is, the polymer yield per unit catalyst amount increases, and the stericity of the resulting polymer tends to improve.
  • a catalyst that also forms at least a part of the titanium catalyst component (a), the organoaluminum compound catalyst component (b) and at least a part of the electron donor component (c) is used as described above.
  • olefins are reacted in an amount of 1 to 1000 g per millimole of titanium in the titanium catalyst component (a).
  • the olefin used in the prepolymerization is not particularly limited, but usually has 5 carbon atoms.
  • the organoaluminum compound catalyst component (b) and the Z or electron donor component (c) are newly added during the main polymerization. May be used additionally.
  • the organoaluminum compound catalyst component (b) is usually 1 to: LOOO mole, preferably 10 to 1000 moles per mole of titanium, and the electron donor component (c) is treated with the organoaluminum catalyst component. (b) It may be additionally used in an amount of usually 0.005 to 2 mol, preferably 0.01 to 1 mol, per mol.
  • hydrogen or halogenated hydrocarbons may coexist for the purpose of adjusting the molecular weight or molecular weight distribution.
  • the polymerization temperature at which suspension polymerization is preferred as the polymerization method is a temperature within a range where suspension polymerization is possible, and is 0 ° C or higher, preferably within a range of 25 to 70 ° C. It is preferable.
  • the polymerization pressure is desirably in the range of, for example, atmospheric pressure to 20 MPa, preferably atmospheric pressure to 10 MPa.
  • the polymerization time is preferably set so that the amount of (co) polymer produced is lOOOOg or more, preferably 5000 g or more, per 1 mmol of titanium in the titanium catalyst component. Further, this polymerization may be carried out in one step or in multiple steps.
  • the polymerization proceeds in a slurry state, that is, in a suspended state in a hydrocarbon solvent, and as the polymerization proceeds, 4-methyl-1 as a solid component insoluble in the hydrocarbon solvent used as the polymerization solvent.
  • a polymer solution containing a pentene polymer (A) and a 4-methyl-1-pentene polymer (B) soluble in a hydrocarbon solvent as a polymerization solvent is obtained.
  • the polymer solution is introduced into a solid-liquid separator and separated into a 4-methyl-1 pentene polymer (A) and a polymer solution in which the 4-methyl-1-pentene polymer (B) is dissolved. Is done.
  • a conventionally known separation method such as centrifugation or filtration can be used, and the solid component obtained by separation is dried. By processing, a powdery 4-methyl-1 pentene polymer (A) can be obtained.
  • the 4-methyl-1-pentene polymer (B) is separated and recovered by precipitation.
  • a deposition method a method using a thin film evaporator or a method using a two-phase flow type evaporator having piston flow properties can be arbitrarily selected, and a combination of a plurality of deposition methods can be used. It is preferable to use at least a two-phase flow evaporator having flow characteristics.
  • An evaporation device having piston flowability means a facility through which an object to be evaporated flows in a certain direction from upstream to downstream of the device.
  • a two-phase flow evaporator is an evaporator that has at least a gas-liquid or gas-solid two-phase flow, and gas-liquid solid three-phase coexist.
  • Typical examples of these are kneaders and double-pipe heat exchangers.
  • tube-type pipes that form at least one of a wavy flow, slag flow, annular flow, and spray flow.
  • An evaporator is particularly preferred.
  • a device in which the flow state is formed by a gas generated inside the evaporation device is most preferred.
  • a double tube flash dryer is preferably used.
  • the double tube flash dryer has a heating medium flow path on the outside and a double flow path for the polymer solution after separating and recovering the 4-methyl-1-pentene polymer (A) on the inner side. It is a heat exchanger composed of tubes, and steam, electric heating equipment, hot oil, dowtherm, etc. can be used as the heating medium.
  • the flow state inside the double tube flash dryer is the temperature, concentration, and concentration of the remaining polymer solution separated and recovered from 4-methyl-1 pentene polymer (A) supplied to the double tube flash dryer. Although it depends on the pressure, etc., it is in the following fluid state.
  • the temperature, concentration, and concentration of the remaining polymer solution obtained by separating and recovering the 4-methyl-1 pentene polymer (A) supplied to the double tube flash dryer are Volatile formation by heating with a heat medium such as steam, which varies depending on the pressure, etc., and the temperature distribution, concentration distribution, pressure distribution, etc. inside the double tube flash dryer
  • the portion evaporates and forms a wavy flow, a slag flow, an annular flow, and a spray flow through a bubble flow or the like.
  • the applied heat is immediately consumed by the latent heat of evaporation, and the temperature rise inside the evaporation facility can be suppressed and the temperature of the heat source required for evaporation can be kept low.
  • the cost per unit of energy can be kept low.
  • 4-methyl-1-pentene polymer (A) is the remaining polymer solution that has been separated and recovered 4-methyl-1 pentene polymer (B) is generally used in the conventional thin film evaporators for separation and recovery.
  • the torque load on the drive device such as a motor generated by the concentration of the polymer solution is large and the equipment cost is high, and the carbonization remaining in the resulting 4-methyl-1 monopentene polymer (B). It is difficult to reduce the amount of hydrogen solvent.
  • double-tube flash dryers do not have a drive unit, are easy to maintain and maintain, and are low in cost.
  • since it can be dried in a very short time it is also suitable for drying materials that are sensitive to heat.
  • the 4-methyl-1 pentene polymer in the remaining polymer solution from which the 4-methyl-1 pentene polymer (A) is separated and recovered is recovered.
  • the concentration of the polymer (B) is usually preferably adjusted to 1 to 30% by weight.
  • the polymer solution may be preheated, but is usually heated with a double tube flash dryer.
  • the heating temperature is sufficient to sufficiently evaporate the solvent in the polymer solution, and the 4-methyl-1 pentene polymer in the polymer solution in a double tube flash dryer ( It is preferable to give the polymer solution a quantity of heat so that B) does not solidify, i.e.
  • the temperature of the combined body (B) is 100 to 400 ° C, preferably 100 to 300 ° C, more preferably 130 to 250 ° C, particularly 140 to 250 ° C.
  • the heating temperature is higher than the above lower limit temperature, the 4-methyl-1 pentene polymer (B) flows without solidification in the double tube flash dryer, which is preferable and the heating temperature is lower than the above upper limit value. Is preferable because it can prevent thermal degradation of the polymer (B).
  • the amount of heat to be applied can be appropriately set according to the type of hydrocarbon solvent used, the heat transfer area of the double tube flash dryer, the pressure distribution, the treatment rate of the polymer solution, and the like.
  • the polymer solution preferably subjected to the heating step as described above is a polymerization solvent that is flash-dried and then vaporized by a drum or the like installed at the outlet of a double tube flash dryer. It is separated into a hydrocarbon solvent, unreacted olefin and the like, and 4-methyl-1 pentene polymer (B).
  • the linear velocity at the inlet of the double tube flash dryer is Is from 0.03 to 30 mZ seconds, preferably from 0.1 to LOmZ seconds, and the gas superficial line velocity at the exit of the double tube flash dryer is 3 to 30000 mZ seconds, preferably 10 to: LOOOOm Z seconds It is desirable to be.
  • the remaining polymer solution obtained by separating and recovering the 4-methyl-1 pentene polymer (A) is flash-dried, whereby unreacted olefins and a part of the remaining V-solvent solvent. And 4-methyl-1 pentene polymer (B) can be obtained.
  • the resulting 4-methyl-1-pentene polymer (B) is excellent in flexibility, adhesiveness, heat resistance and dispersibility.
  • the 4-methyl-1-pentene polymer (A) of the present invention is a homopolymer of 4-methyl-1-pentene or an olefin other than 4-methyl-1-pentene and 4-methyl-1-pentene. It is a copolymer with in. It is preferable that the polymer (A) is a copolymer of 4-methyl-1-pentene and 4-olefin-1-olefin other than olefin, because of excellent impact resistance.
  • the olefin that is copolymerized with 4-methyl-1 pentene may be linear or side chain, but is preferably linear olefin.
  • olefins having 2 to 20 carbon atoms are usually used.
  • Such linear olefins include ethylene, propylene, 1-butene, 1 pentene, 1 hexene, 1 octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 -You can list Eikosen.
  • 4-methyl-1-pentene polymer of the present invention (Alpha) is 4-methyl-1 content force of the constituent unit derived from pentene 3 ⁇ 40 ⁇ 100 mole 0/0, 4 preferably 90 to 99.9 mole 0/0 (where the total amount of Orefin other than methyl 1-pentene and 4-methyl-1-pentene is 100 mole 0/0).
  • the molecular weight of 4-methyl-1 pentene polymer ( ⁇ ), that is, MFR (260 ° C, 5 kg load) is 0.01 to: L00 g / 10 min, preferably 0.1 to 20 g / 10 min. .
  • the molecular weight can be controlled by adding hydrogen to the polymerization temperature or reaction system.
  • the melting point measured by DSC once completely melted and then cooled to a temperature of 30 ° C at a rate of 10 ° CZ and solidified, and then increased again from a temperature of 30 ° C to a rate of 10 ° CZ.
  • the maximum endothermic peak when heated is 200-240 ° C, preferably 220-240 ° C.
  • the bulk density of the powder which is a solid component obtained by separation and recovery from a polymer solution by a conventionally known method such as filtration and then drying, is preferably 300 to 450 kgZm 3. .
  • the 4-methyl-1 pentene polymer (A) of the present invention may contain an acid oxidant, a higher fatty acid metal salt, and an acid absorbent such as Z or hydrated talcite, if necessary.
  • organic peroxides and other additives can be blended and used. When blending the additives, dry blend them with an ordinary tumbler or Henschel mixer, and melt-knead them with an ordinary kneader such as a banner mixer, pressure-one-der, single-screw extruder, or twin-screw extruder. Can be prepared.
  • the 4-methyl-1-pentene polymer (B) of the present invention is a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene and olefins other than 4-methyl-1-pentene. Copolymers of 4-methyl-1-pentene and olefins other than 4-methyl-1-pentene are preferred because they are more flexible.
  • the olefin that is copolymerized with 4-methyl-1 pentene may be linear or side chain, but is preferably linear olefin.
  • olefins having 2 to 20 carbon atoms are usually used.
  • Such linear olefins include ethylene, propylene, 1-butene, 1 pentene, 1 hexene, 1 octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 -You can list Eikosen.
  • 4-methyl-1-pentene polymer of the present invention is 60 to a constituent unit - derived in 4-methyl-1-pentene: LOO mol 0/0, preferably from 65 to 99 mole 0/0, more preferably from 70 to 95 mole 0/0, and, 4-methyl-1 0 to 40 mol Orefin non-pentene 0/0, good Mashiku 1 to 35 mole 0/0, more preferably in an amount of 5 to 30 mole 0/0 (the total amount of the herein 4-methyl 1-pentene and 4 Orefin other than methyl 1-pentene is 100 mole 0/0).
  • the 4-methyl-1 pentene polymer ( ⁇ ) of the present invention has a isotactic diad fraction measured by 13 C-NMR of 40 to 95%, preferably 50 to 90%.
  • the isotactic diat fraction (also called diad tacticity (m fraction)) Is obtained by the following method.
  • the dyadic tacticity (m fraction) of 4-methyl-1 pentene copolymer is the isobutyl branching of any two head-to-tail linked 4-methyl-1 pentene unit chains expressed in a planar zigzag structure in the polymer chain.
  • m fraction the isobutyl branching of any two head-to-tail linked 4-methyl-1 pentene unit chains expressed in a planar zigzag structure in the polymer chain.
  • m and r represent the absorption intensity derived from the main chain methylene of 4-methyl-1-pentene units bonded at the head-tail as shown below.
  • the 13 C—NMR ⁇ vector uses a nuclear magnetic resonance apparatus with an iH resonance frequency of 400 MHz.
  • the solution was completely dissolved in about 0.5 ml of a solvent obtained by adding about 0.05 ml of deuterated benzene as a lock solvent, and then measured at 120 ° C. by a proton complete decoupling method. Select the measurement conditions as flip angle 45 ° and norse interval 5 sec or more.
  • the chemical shift was set at 127.7 ppm for benzene, and the chemical shifts for other carbon peaks were based on this.
  • the region of 41.5 to 43.3 ppm was divided by the minimum points of the peak profile, and the high magnetic field side was classified as the first region and the low magnetic field side was classified as the second region.
  • the 4-methyl-1 pentene unit shown in (m) 2 The main chain methylene in the 2 chain resonates.
  • the methylene peak linked to the comonomer also overlaps, so 34.5-53.5 ppm from the above 1st region. No The peak value derived from the monomer was doubled and the integrated value was designated as “m”.
  • the 4-methyl-1-pentene polymer (B) of the present invention has an intrinsic viscosity [r?] Of 0.1 to 3. OdlZg, preferably 0. 2 ⁇ 2. Melting point measured by Odl / g, DSC (Once completely melted, solidify by cooling to a temperature of 30 ° C at a rate of 10 ° CZ and solidify again. Maximum endothermic peak when the temperature is raised at a rate of ° CZ min) Force S140 to 199 ° C, preferably 140 to 180 ° C.
  • Such a 4-methyl-1 pentene polymer (B) is obtained by separating the 4-methyl-1 pentene polymer (A) by the production method of the present invention. It can be obtained by precipitating the methyl-1-pentene polymer (B).
  • the 4-methyl-1-pentene polymer (B) of the present invention may have any shape, for example, a pellet shape, a bale shape, or a sheet shape, depending on the intended use. Can be molded into powder form.
  • the 4-methyl-1 pentene polymer (B) of the present invention includes, as necessary, an acid pickling agent, a higher fatty acid metal salt, and an acid absorbent such as Z or Hyde mouth talcite, If necessary, organic peroxides and other additives can be blended and used. When blending the additives, dry blend them with an ordinary tumbler or Henschel mixer, and melt-knead them with an ordinary kneader such as a banner mixer, pressure-one-der, single-screw extruder, or twin-screw extruder. Can be prepared.
  • the 4-methyl-1 pentene polymer (B) of the present invention is excellent in adhesiveness and dispersibility in other resins, and excellent in flexibility and heat resistance.
  • the 4-methyl-1 pentene polymer (B) of the present invention is chemically stable, has a low melt viscosity, is excellent in adhesiveness, and is compatible with various plastics. In addition, because of its characteristics such as excellent balance between electrical properties, flexibility and heat resistance, various hot-melt adhesives, rubber, plastic workability improvers, modifiers, paving materials, etc. Widely used. [0066] [Resin modifier]
  • the resin modifier is a modifier added to improve the moldability, appearance, mechanical properties, etc. of olefin-based resin and elastomer.
  • the 4-methyl-1 pentene polymer (B) of the present invention is excellent in dispersibility in various types of greaves, and is particularly easily mixed with solvents and fats and oils that are highly compatible with olefin polymers. And excellent heat resistance, it can be suitably used as a resin modifier.
  • An asphalt modifier is an additive added for the purpose of modifying the properties of asphalt.
  • asphalt has various uses, for example, it is used as a waterproof coating material used for covering a roof, a material for paving a road, and the like.
  • atactic polypropylene is conventionally used as a modifier for asphalt.
  • the 4-methyl 1-pentene polymer (B) of the present invention is excellent in flexibility, adhesiveness, and dispersibility in asphalt, as in the case of atactic polypropylene, and in particular, has a higher softness temperature than atactic polypropylene and heat resistance. Therefore, it can be suitably used as an asphalt modifier.
  • Hot melt adhesives are adhesives that are solid at room temperature with thermoplastic resin as the main component. They become liquid when heated and show fluidity. When cooled, they return to the original solid and have adhesive strength. It is a kind of a simple adhesive using heat.
  • As the main component of the hot melt adhesive depending on the intended use, conventionally, atactic polypropylene, ethylene vinyl acetate copolymer, etc. are generally used.
  • the hot-melt adhesive is used by heating, it is necessary that the hot-melt adhesive does not change in quality due to continuous heating.
  • the 4-methyl-1 pentene polymer (B) of the present invention has excellent heat resistance, is relatively inexpensive, can be bonded quickly, and does not contain a solvent, making it suitable for hot melt adhesive applications. It can be used as an industrial adhesive for packaging materials such as cardboard, woodwork, bookbinding and shoemaking.
  • Anhydrous magnesium chloride 75g, decane 288.3 g, and 2-ethylhexyl alcohol 308.3 g were heated at 130 ° C for 3 hours to form a homogeneous solution. Then, 2-isobutyl-1,2-isopropyl-1, , 3 Dimethoxypropane (22.2 ml) was added, and the mixture was further stirred and mixed at 100 ° C for 1 hour.
  • the solid titanium catalyst component (a) prepared by the above operation was stored as a decanslurry, but a portion of this was collected and dried for the purpose of examining the catalyst composition. In this way, the composition of titanium 3.9 mass% of the obtained solid material titanium catalyst components (a), magnesium 17.0 wt%, 57 wt chlorine 0/0, 2 Isobuchiru 2 isopropyl 1, 3-dimethoxypropane 14. hexyl alcohol to 8 mass 0/0 and 2 Echiru 2. was 9 wt%.
  • the polymer slurry is separated and recovered by filtration of the polymer slurry and dried to obtain a powdery 4-methyl- 1 A pentene polymer (A) was obtained.
  • the remaining polymer solution obtained by separating and recovering the 4-methyl-1-pentene polymer (A) separated by filtration uses a double-tube flash method, and is stored in a double-tube flash dryer.
  • 4-Methyl- 1 at the outlet The temperature of the pentene polymer (B) is 200 ° C, the linear velocity at the inlet is 0.8 mZ seconds, and the gas superficial linear velocity at the outlet is lOOOOmZ seconds. 1 Recovered pentene polymer (B)
  • the physical properties of the obtained 4-methyl-1 pentene polymer (A) and (B) are 10 MFR (temperature 260 ° C, 5 kg load) of the 4-methyl-1 pentene polymer (A), respectively. . Og / 10 min, a melting point of 225 ° C, 1 Desen content is 4 mol 0/0, 4-methyl-1 pent emissions based polymer (B) having an intrinsic viscosity [7?] is 0. 98DlZg, melting point 169 ° C, the comonomer content of 9.4 mole 0/0, ⁇ isotactic die each time fraction was 83%.
  • the residual amount of n-decane in the 4-methyl 1-pentene polymer (B) was 2% by mass.
  • the remaining polymer solution obtained by separating and recovering the 4-methyl-1-pentene polymer (A) obtained in the same manner as in Example 1 was recovered using a thin film evaporator to recover the 4-methyl-1-pentene polymer (B).
  • the residual amount of n-decane in the obtained 4-methyl-1-pentene polymer (B) was 20% by mass.
  • the production method of the present invention comprises a high-quality 4-methyl-l-pentene polymer (A) excellent in heat resistance, transparency, impact strength, etc., and flexibility, adhesiveness, heat resistance, and other oils. It is possible to obtain a special 4-methyl-1-pentene polymer (B) with an isotactic diat fractional force of 0-95%, which is excellent in dispersibility, and is extremely excellent in production efficiency. Furthermore, the 4-methyl-1 pentene polymer (B) of the present invention is characterized by being chemically stable and having excellent electrical properties such as compatibility with various plastics having low melt viscosity. Therefore, it is suitably used for various hot melt adhesives and modifiers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un polymère (A) du 4-méthyl-1-pentène de qualité élevée et offrant d'excellentes caractéristiques de résistance à la chaleur, transparence, résistance aux chocs, etc. ; un polymère spécial (B) du 4-méthyl-1-pentène dont la teneur en diades isotactiques est comprise entre 40 et 95 % et offrant d'excellentes caractéristiques de souplesse, adhérence, résistance à la chaleur et dispersibilité dans d'autres résines ; et un procédé de production de ces polymères. Le procédé de production des polymères (A) et (B) du 4-méthyl-1-pentène comprend les étapes consistant à : polymériser le 4-méthyl-1-pentène soit seul, soit avec une oléfine en C2 à C20 autre que le 4-méthyl-1-pentène, dans un solvant hydrocarboné et avec l'aide d'un catalyseur de polymérisation, afin d'obtenir une solution de polymère contenant des ingrédients solides ; séparer et récupérer à partir de ladite solution le polymère (A) du 4-méthyl-1-pentène en tant qu'ingrédient solide ; et enfin séparer et récupérer le polymère (B) du 4-méthyl-1-pentène à partir de la solution de polymère résiduelle. Le polymère (B) comprend de 60 à 100 % en moles de motifs 4-méthyl-1-pentène et de 0 à 40 % en moles de l'autre oléfine (la somme des motifs de 4-méthyl-1-pentène et des motifs de l'autre oléfine étant égale à 100 % en moles) et il contient de 40 à 95 % de diades isotactiques.
PCT/JP2006/307148 2005-04-11 2006-04-04 Procede de production de polymeres du 4-methyl-1-pentene et polymeres correspondants WO2006109631A1 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
EP2172496A1 (fr) * 2007-07-10 2010-04-07 Mitsui Chemicals, Inc. Polymère du 4-méthyl-1-pentène, procédé pour la production de celui-ci et utilisation de celui-ci
EP2308924A1 (fr) * 2008-08-01 2011-04-13 Mitsui Chemicals, Inc. Composition de résine de poly(4-méthyl-1-pentène), film la contenant, film microporeux, séparateur de batterie et batterie au lithium-ion
JP2012097208A (ja) * 2010-11-02 2012-05-24 Mitsui Chemicals Inc ４−メチル−１−ペンテン（共）重合体および該重合体から得られるブロー成形体
WO2018124070A1 (fr) 2016-12-27 2018-07-05 三井化学株式会社 Composition d'huile lubrifiante, modificateur de viscosité pour huile lubrifiante, et composition d'additif pour huile lubrifiante
US11873462B2 (en) 2019-08-29 2024-01-16 Mitsui Chemicals, Inc. Lubricating oil composition

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JPH07118327A (ja) * 1993-10-26 1995-05-09 Mitsubishi Chem Corp α−オレフイン低重合体の製造方法

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JPH07118327A (ja) * 1993-10-26 1995-05-09 Mitsubishi Chem Corp α−オレフイン低重合体の製造方法

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2172496A1 (fr) * 2007-07-10 2010-04-07 Mitsui Chemicals, Inc. Polymère du 4-méthyl-1-pentène, procédé pour la production de celui-ci et utilisation de celui-ci
EP2172496A4 (fr) * 2007-07-10 2011-01-12 Mitsui Chemicals Inc Polymère du 4-méthyl-1-pentène, procédé pour la production de celui-ci et utilisation de celui-ci
US8058379B2 (en) 2007-07-10 2011-11-15 Mitsui Chemicals, Inc. 4-methyl-1-pentene polymer, process for producing the same and use thereof
EP2308924A1 (fr) * 2008-08-01 2011-04-13 Mitsui Chemicals, Inc. Composition de résine de poly(4-méthyl-1-pentène), film la contenant, film microporeux, séparateur de batterie et batterie au lithium-ion
EP2308924A4 (fr) * 2008-08-01 2011-10-26 Mitsui Chemicals Inc Composition de résine de poly(4-méthyl-1-pentène), film la contenant, film microporeux, séparateur de batterie et batterie au lithium-ion
US8211981B2 (en) 2008-08-01 2012-07-03 Mitsui Chemicals, Inc. Poly(4-methyl-1-pentene) resin composition, film containing same, microporous film, battery separator and lithium ion battery
JP5501233B2 (ja) * 2008-08-01 2014-05-21 三井化学株式会社 ポリ４−メチル−１−ペンテン樹脂組成物、それを含むフィルム、微多孔フィルム、電池用セパレータおよびリチウムイオン電池
JP2012097208A (ja) * 2010-11-02 2012-05-24 Mitsui Chemicals Inc ４−メチル−１−ペンテン（共）重合体および該重合体から得られるブロー成形体
WO2018124070A1 (fr) 2016-12-27 2018-07-05 三井化学株式会社 Composition d'huile lubrifiante, modificateur de viscosité pour huile lubrifiante, et composition d'additif pour huile lubrifiante
US11162050B2 (en) 2016-12-27 2021-11-02 Mitsui Chemicals, Inc. Lubricating oil composition, viscosity modifier for lubricating oil, and additive composition for lubricating oil
US11873462B2 (en) 2019-08-29 2024-01-16 Mitsui Chemicals, Inc. Lubricating oil composition

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