WO2017199870A1 - 酸化アルミニウム形成用組成物及びその製造方法並びに酸化亜鉛粒子又は酸化アルミニウム粒子を含有するポリオレフィン系ポリマーナノコンポジット及びその製造方法 - Google Patents
酸化アルミニウム形成用組成物及びその製造方法並びに酸化亜鉛粒子又は酸化アルミニウム粒子を含有するポリオレフィン系ポリマーナノコンポジット及びその製造方法 Download PDFInfo
- Publication number
- WO2017199870A1 WO2017199870A1 PCT/JP2017/018000 JP2017018000W WO2017199870A1 WO 2017199870 A1 WO2017199870 A1 WO 2017199870A1 JP 2017018000 W JP2017018000 W JP 2017018000W WO 2017199870 A1 WO2017199870 A1 WO 2017199870A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyolefin
- aluminum oxide
- aluminum
- oxide particles
- powder
- Prior art date
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 190
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 183
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 239000002245 particle Substances 0.000 title claims abstract description 137
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 111
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- -1 aluminum alkyl compound Chemical class 0.000 claims abstract description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000010409 thin film Substances 0.000 claims abstract description 71
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 239000011701 zinc Substances 0.000 claims abstract description 37
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims description 101
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 99
- 238000004519 manufacturing process Methods 0.000 claims description 97
- 239000003960 organic solvent Substances 0.000 claims description 60
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 53
- 239000000463 material Substances 0.000 claims description 35
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical group CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000006460 hydrolysis reaction Methods 0.000 claims description 28
- 239000004743 Polypropylene Substances 0.000 claims description 26
- 229920001155 polypropylene Polymers 0.000 claims description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 12
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 12
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 12
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 12
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 8
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 6
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- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 2
- 239000002904 solvent Substances 0.000 abstract description 43
- 239000002798 polar solvent Substances 0.000 abstract description 14
- 239000012454 non-polar solvent Substances 0.000 abstract description 10
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 10
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- 238000005470 impregnation Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 8
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
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- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
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- 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
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- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
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- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
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- C—CHEMISTRY; METALLURGY
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Definitions
- the present invention relates to a composition for forming aluminum oxide comprising a solution containing a partially hydrolyzed alkylaluminum, a method for producing the same, and a method for producing aluminum oxide. If the alkylaluminum partial hydrolyzate-containing solution of the present invention is used, an aluminum oxide thin film is formed on a substrate that is not resistant to polar solvents, or aluminum oxide particles are included in a substrate that is not resistant to polar solvents. Can do. Furthermore, the present invention relates to a polyolefin polymer nanocomposite containing zinc oxide particles or aluminum oxide particles and a method for producing the same.
- Aluminum oxide is widely used in various applications because it has excellent properties such as high strength, high heat resistance, high thermal conductivity, low coefficient of thermal expansion, and insulation.
- aluminum oxide thin film aluminum oxide sheet for electronic materials, preparation of aluminum oxide film, preparation of catalyst carrier, heat resistance, barrier property against air and moisture, antireflection effect, antistatic effect, antifogging effect It is used for applications such as imparting abrasion resistance and binders for ceramic production.
- Such an aluminum oxide thin film is required to have high purity (Non-Patent Document 1). Specifically, it can be applied to protective films for cutting tools, insulating films for semiconductors, magnetic materials, solar cells, surface devices, magnetic heads, infrared sensors, food, medicine, medical equipment packaging materials, optical members, etc. Can be mentioned.
- the aluminum oxide particles are used for ceramic raw materials, rubber, plastic fillers, abrasives and the like.
- Non-patent document 2 Specific examples include fillers for high thermal conductivity resins, fillers for resin adjustment such as refractive index, reflectivity, workability and flexibility, and fine ceramic sintering materials.
- the aluminum oxide thin film is produced by a method such as a sputtering method, a chemical vapor deposition (CVD) method, an atomic layer deposition (ALD) method, or the like.
- the sputtering method, the CVD method, the ALD method, and the like have problems such as the need for using a large sealed container, which increases the manufacturing cost of the aluminum oxide thin film and decreases the material usage efficiency.
- Patent Documents 1 to 4 Various studies have been made on the formation of an aluminum oxide thin film using a coating method.
- Patent Document 1 when a passivation film is produced by heat treatment (firing), it is necessary to calcinate and remove (remove) residual organic components such as a binder resin and a ligand. There is. For this reason, there is a problem that a long time is required for firing or a heat treatment at a high temperature of about 400 to 1000 ° C. is required.
- Patent Documents 3 and 4 describe an alumina thin film forming method and an alumina thin film forming composition.
- an aluminum-containing compound contained in the composition for forming an alumina thin film methylaluminoxane and the like are described.
- Patent Documents 3 and 4 have examples in which a thin film is produced using a dibutylaluminum hydride solution, a tri-n-octylaluminum solution, and a tri-n-dodecylaluminum solution.
- dibutylaluminum hydride, tri-n-octylaluminum, and tri-n-dodecylaluminum are vaporized together with the solvent when the solvent is removed by drying, and the efficiency of aluminum usage is greatly reduced. There was also a problem that it was difficult to obtain.
- a polymer-based nanocomposite is a composite material in which an inorganic oxide is dispersed in a polymer in the form of ultrafine particles of usually 1 to 100 nm. Compared to conventional inorganic oxide filler-filled polymers, the amount of inorganic oxide added is small, and the surface area of the inorganic oxide is significantly increased.
- Polymer-based nanocomposites containing zinc oxide can improve the basic properties of polymers, such as improved thermal stability, improved wear resistance, increased refractive index, and improved stability to ultraviolet rays, as a matrix polymer.
- polymers such as improved thermal stability, improved wear resistance, increased refractive index, and improved stability to ultraviolet rays, as a matrix polymer.
- Patent Document 5 It is also known that polymer nanocomposites containing zinc oxide impart functionality such as conductivity, ultraviolet absorption, antibacterial properties, and refractive index adjustment.
- the polymer-based nanocomposite containing aluminum oxide particles is also expected to impart functionality such as thermal conductivity, wear resistance, and refractive index adjustment (Patent Document 6).
- polyolefin is an excellent general-purpose plastic having low cost, high melting point, easy moldability, and good recyclability.
- studies have been actively conducted to replace inorganic materials and engineering plastics using polyolefin-based nanocomposites obtained by nanocompositing polyolefins and inorganic oxides.
- Patent Document 5 requires the addition of a thiol compound or a silane coupling agent dispersant to prevent the aggregation of inorganic oxides.
- a thiol compound or a silane coupling agent dispersant to prevent the aggregation of inorganic oxides.
- problems such as generation of malodor due to the use of thiol compounds, increase in costs due to the use of silane coupling agents, and loss of the modification effect of other additives due to the interaction between the dispersant and other additives. It was.
- Patent Document 7 It is often studied as an inorganic oxide filler-filled polymer as described in Patent Document 7 instead of a nanocomposite. In this case, it is necessary to add a dispersant in the same manner as described above. Compared to nanocomposites, the interaction between the polymer and the inorganic oxide is weak, and a large amount of inorganic oxide filler is required, so that the properties as a polymer are greatly reduced. There were problems such as.
- Patent Document 6 Although the production method of Patent Document 6 can produce a polyolefin-based nanocomposite containing aluminum oxide without using a dispersant, further improvement in the dispersion of inorganic oxides is desired.
- Patent Documents 1 to 4 When the methods or materials described in Patent Documents 1 to 4 are used, an aluminum oxide thin film cannot be formed on a substrate that is not resistant to polar solvents, and oxidation is not performed in a substrate that is not resistant to polar solvents. It is also impossible to form aluminum particles.
- the object of the first aspect of the present invention is to form an aluminum oxide thin film on a base material such as an acrylic resin or a polycarbonate resin, which is not resistant to polar solvents such as ether, alcohol, ketone, carboxylic acid and ester. It is to provide an agent capable of forming aluminum oxide particles.
- the object of the second aspect of the present invention is to contain zinc oxide particles and aluminum oxide particles in a well dispersed state in a polyolefin base material without adding a dispersant, and even when the oxide concentration is 3% by weight or more.
- An object of the present invention is to provide a polyolefin-based nanocomposite containing zinc oxide particles or aluminum oxide particles having an average particle diameter of less than 100 nm and a method for producing the same.
- the first aspect of the present invention is as follows.
- An alkylaluminum compound comprising a trialkylaluminum or a mixture thereof (provided that the alkyl group has 4 to 12 carbon atoms and may be the same or different) and a nonpolar organic solvent are added to a solution in the alkylaluminum compound.
- Adding water having a molar ratio in the range of 0.5 to 1.4 to aluminum to obtain a solution containing a partially hydrolyzed alkylaluminum A method for producing a particulate or thin film aluminum oxide-forming composition comprising an alkylaluminum partial hydrolyzate-containing solution.
- [2] The production method according to [1], wherein the trialkylaluminum is an alkylaluminum compound represented by the following general formula (1).
- R 1 represents an isobutyl group, an n-hexyl group or an n-octyl group, and the three R 1 s may be the same or different.
- [3] The production method according to [2], wherein the trialkylaluminum is triisobutylaluminum.
- [4] The production method according to any one of [1] to [3], wherein the nonpolar organic solvent is an aromatic hydrocarbon.
- [5] The production method according to [4], wherein the aromatic hydrocarbon is toluene and / or xylene.
- a composition for forming a particulate or thin film aluminum oxide comprising a solution containing a partially hydrolyzed alkylaluminum and a nonpolar organic solvent,
- the alkyl group of the alkylaluminum partial hydrolyzate is an alkyl group having 4 to 12 carbon atoms which may be the same or different, and the molar ratio of the alkyl group to the aluminum atom is in the range of 0.2 to 2,
- the composition described above, wherein the molar ratio of oxygen atom to is in the range of 1.4 to 0.5.
- composition according to [8] wherein the alkyl group is at least one selected from the group consisting of an isobutyl group, an n-hexyl group, and an n-octyl group.
- the nonpolar organic solvent is an aromatic hydrocarbon.
- the aromatic hydrocarbon is toluene and / or xylene.
- the nonpolar organic solvent is an aliphatic hydrocarbon.
- [14] [8] A method for producing an aluminum oxide thin film, comprising applying the composition according to any one of [13] to a substrate and then removing the nonpolar organic solvent to form an aluminum oxide thin film.
- the second aspect of the present invention is as follows. [16] A partial hydrolyzate-containing solution of dialkylzinc (wherein the alkyl group has 1 to 14 carbon atoms and may be the same or different) and a polyolefin powder are used, A method for producing a polyolefin-based polymer nanocomposite containing zinc oxide particles.
- the partial hydrolyzate-containing solution is prepared by adding water having a molar ratio in the range of 0.5 to 1.4 to zinc in the dialkyl zinc to a solution containing dialkyl zinc and an organic solvent. [16] to [18].
- polyolefin powder is polyethylene powder or polypropylene powder.
- polyolefin powder is a polyolefin powder prepared using a Ziegler-Natta catalyst.
- R 2 represents a methyl group, an ethyl group, an isobutyl group, an n-hexyl group or an n-octyl group, and the three R 2 s may be the same or different.
- an aluminum aluminum thin film and aluminum oxide particles are formed on a substrate that is not resistant to a polar solvent and also in a base material using an alkylaluminum hydrolyzed composition solution that does not contain a polar solvent. can do.
- the second aspect of the present invention it is possible to provide a polyolefin-based nanocomposite that contains zinc oxide particles or aluminum oxide particles having an average particle diameter of less than 100 nm in a polyolefin base material and does not contain a dispersant. it can. Further, in the nanocomposite of the present invention, even if the content of zinc oxide particles or aluminum oxide particles is 3% by weight or more, the zinc oxide particles or aluminum oxide particles are contained in a good dispersion state in the nanocomposite.
- An appearance photograph of an aluminum oxide thin film using Synthesis Example 1-1 The IR spectrum by the ATR method of the aluminum oxide thin film using the synthesis example 1-1. An appearance photograph of an aluminum oxide thin film using Synthesis Example 1-1. The IR spectrum by the ATR method of the aluminum oxide thin film using the synthesis example 1-1. IR spectrum by ATR method of acrylic resin substrate (Mitsubishi Rayon Co., Ltd., Acrylite EX). An appearance photograph of an aluminum oxide thin film using Synthesis Example 1-4. The IR spectrum by the ATR method of the aluminum oxide thin film using the synthesis example 1-4. An appearance photograph of an aluminum oxide thin film using Synthesis Example 1-4. The IR spectrum by the ATR method of the aluminum oxide thin film using the synthesis example 1-4. The IR spectrum by the ATR method of the aluminum oxide thin film using the synthesis example 1-4.
- FT-IR spectrum of polypropylene nanocomposite containing 5% by weight of zinc oxide prepared in Example 2-1 (the first spectrum is a propylene homopolymer powder spectrum, the second spectrum is Example 2-1 Spectrum).
- 4 is a TEM image of a polypropylene nanocomposite containing 5% by weight of zinc oxide prepared in Example 2-1.
- FT-IR spectrum of polypropylene nanocomposite containing 5% by weight of steam-treated zinc oxide prepared in Example 2-2 (first spectrum is propylene homopolymer powder only spectrum, second spectrum is Example 2-2 spectrum). 4 is a TEM image of a nanocomposite containing 5% by weight of steam-treated zinc oxide prepared in Example 2-2. The powder X-ray diffraction spectrum of the nanocomposite containing 5% by weight of steam-treated zinc oxide prepared in Example 2-2.
- FT-IR spectrum of the polypropylene nanocomposite containing 5% by weight of aluminum oxide prepared in Example 2-3 (the first spectrum is a spectrum of propylene homopolymer powder only, the second spectrum is Example 2-3) Spectrum).
- 4 is a TEM image of a polypropylene nanocomposite containing 5% by weight of aluminum oxide prepared in Example 2-3.
- FT-IR spectrum of nanocomposite containing 5% by weight of steam-treated aluminum oxide prepared in Example 2-4 (the first spectrum is the spectrum of propylene homopolymer powder only, the first spectrum is the example 2-4 spectrum).
- 4 is a TEM image of a nanocomposite containing 5% by weight of steam-treated aluminum oxide prepared in Example 2-4.
- the present invention contains a partial hydrolyzate of a trialkylaluminum or an alkylaluminum compound comprising a mixture thereof (wherein the alkyl group has 4 to 12 carbon atoms and may be the same or different) and a nonpolar organic solvent. Adding water having a molar ratio of 0.5 to 1.4 to the aluminum in the alkylaluminum compound to obtain a solution containing a partially hydrolyzed alkylaluminum solution, The present invention relates to a method for producing a particulate or thin film aluminum oxide-forming composition comprising a solution containing a partially hydrolyzed alkylaluminum.
- the trialkylaluminum is preferably an alkylaluminum compound represented by the following general formula (1).
- R 1 represents an isobutyl group, an n-hexyl group or an n-octyl group, and the three R 1 s may be the same or different.
- Examples of the compound represented by the general formula (1) include triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tridodecylaluminum, tritetradecylaluminum and the like.
- Triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum are particularly preferred from the viewpoints that the unit mass of aluminum is inexpensive and from the viewpoint of the aluminum concentration of the solution prepared from the compound and the aluminum oxide equivalent concentration. Triisobutylaluminum is preferred.
- trimethylaluminum and triethylaluminum are not easy to control the reactivity with water without using a polar solvent, and require a special apparatus for adding water and costly. From this viewpoint, trimethylaluminum is not preferable from the viewpoint that the price for aluminum of unit mass is expensive.
- nonpolar solvent examples include aromatic hydrocarbons and aliphatic hydrocarbons.
- aromatic hydrocarbons examples include benzene, toluene, o-xylene, m-xylene, p-xylene, mixed xylene (xylene), ethylbenzene, isopropylbenzene, mesitylene, pseudocumene, amylbenzene, o-cymene, m- Examples include cymene, p-cymene, mixed cymene (cymene), o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, mixed diethylbenzene (diethylbenzene), cyclohexylbenzene, tetralin and the like.
- toluene and xylene are particularly preferable from the viewpoint that a moderately high boiling point is preferable.
- aliphatic hydrocarbons examples include pentane, methylcyclopentane, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, nonane, octane, n-decane, n-undecane, n-dodecane, tridecane, tetradecane, kerosene, decalin Petroleum ether, petroleum benzine, solvent naphtha, dipentene, turpentine, o-menthane, m-menthane, p-menthane, mixed menthane (menthane), ligroin and the like.
- the boiling point is moderately high. preferable.
- Nonpolar solvents mentioned here are the above aromatic hydrocarbons and aliphatic hydrocarbons, and polar solvents are diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, anisole, methyl- Ether solvents such as t-butyl ether; ethanol, isopropyl alcohol, butanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoacetate, ethylene glycol dibutyl ether, propylene glycol, dipropylene glycol, dipropylene Alcohol solvents such as glycol monomethyl ether and hexylene glycol; acetone, acetophenone, cyclohexano , Ketones such as diacetone alcohol, methyl isobutyl ketone and methyl ethyl ketone, aldehyde solvents;
- polarities listed here are evaluated by dielectric constant, dipole moment, solubility parameter, etc., and are classified into nonpolar solvents and polar solvents empirically as described above.
- the partial hydrolysis of the alkylaluminum compound is carried out with water in a molar ratio of 0.5 to 1.4 with respect to the alkylaluminum compound.
- the molar ratio of water to the alkylaluminum compound is less than 0.5, it is difficult to form a uniform aluminum oxide thin film and particles that are liable to become liquid after solvent drying.
- the molar ratio of water to the alkylaluminum compound is preferably 0.5 or more, and more preferably 0.8 or more.
- the molar ratio of water to the alkylaluminum compound exceeds 1.4, a gel or solid insoluble in the solvent is precipitated, and it becomes difficult to form a uniform aluminum oxide thin film and particles from the gel and solid.
- the following is preferable, and 1.3 or less is more preferable.
- the precipitated gel or solid can be removed by decantation, filtration, or the like.
- the partial hydrolysis reaction is performed by adding water to the non-polar solvent and the alkylaluminum compound in an inert gas atmosphere.
- the concentration of the alkylaluminum compound in the alkylaluminum compound solution to which water is added can be 2 to 98% by mass.
- the addition of water to the alkylaluminum compound solution can be set as appropriate depending on the type and volume of the raw material to be mixed, and can be, for example, in the range of 1 minute to 10 hours.
- the temperature at the time of addition can be arbitrarily selected from -15 to 150 ° C. However, in consideration of safety and the like, it is preferably in the range of ⁇ 15 to 80 ° C.
- an aging reaction can be performed for 0.1 to 50 hours in order to further promote the partial hydrolysis reaction of the alkylaluminum compound and water.
- the aging reaction temperature can be selected from -15 to 150 ° C. However, considering the shortening of the ripening reaction time, etc., it is preferably in the range of 25 to 150 ° C.
- the alkylaluminum compound, water, and nonpolar solvent can be introduced into the reaction vessel according to any conventional method.
- the pressure in the reaction vessel is not limited.
- the hydrolysis reaction step may be any of a batch operation method, a semi-batch operation method, and a continuous operation method, and is not particularly limited, but a batch operation method is preferable.
- the alkyl aluminum partial hydrolyzate-containing solution is obtained by the partial hydrolysis reaction.
- the alkylaluminum compound is triisobutylaluminum, analysis of the partially hydrolyzed composition has been performed for a long time, but the composition result of the product differs depending on the report, and the composition of the product is not clearly specified.
- the composition of the product also varies depending on the solvent, concentration, molar ratio of water added, addition temperature, reaction temperature, reaction time, and the like.
- the present invention relates to an aluminum oxide forming composition, which is a particulate or thin film aluminum oxide forming composition comprising a solution containing a partially hydrolyzed alkylaluminum and a nonpolar organic solvent, and the alkyl
- the alkyl group of the aluminum partial hydrolyzate is an alkyl group having 4 to 12 carbon atoms which may be the same or different, and the molar ratio of the alkyl group to the aluminum atom is in the range of 0.2 to 2, and the oxygen to the aluminum atom The molar ratio of atoms is in the range of 1.4 to 0.5.
- the alkyl group preferably has 4 to 8 carbon atoms, more preferably an isobutyl group, an n-hexyl group or an n-octyl group.
- the alkyl group is an alkyl group having 4 to 12 carbon atoms
- the molar ratio of the alkyl group to the aluminum atom is in the range of 0.2 to 2
- the molar ratio of the oxygen atom to the aluminum atom is 1 It was found that the alkylaluminum partial hydrolyzate in the range of 4 to 0.5 is soluble even in a nonpolar organic solvent.
- the molar ratio of alkyl groups to aluminum atoms is preferably in the range of 0.2-2. More preferably 0.8 to 1.8, and still more preferably 1.0 to 1.5.
- the molar ratio of oxygen atoms to aluminum atoms is preferably in the range of 1.4 to 0.5, more preferably in the range of 1.4 to 0.7, and still more preferably in the range of 1.3 to 0.9.
- the alkyl aluminum partial hydrolyzate in the method of the present invention is presumed to be a mixture of compounds containing a structural unit represented by the following general formula (2).
- R 1 is the same as R 1 in the general formula (1), m is an integer of 1 to 80.
- the solids and the like When solids or the like are deposited after completion of the partial hydrolysis reaction, the solids and the like can be removed by purification by a method such as filtration.
- the solid content concentration of the alkyl aluminum partial hydrolyzate-containing solution can be adjusted by concentration (solvent removal). Moreover, the non-polar solvent different from the solvent used for the reaction and the reaction used can be added, and the solid content concentration, polarity, viscosity, boiling point, economy, etc. can be appropriately adjusted.
- the polar solvent different from that used in the reaction can be the same solvent as the nonpolar solvent.
- the content of the alkylaluminum partial hydrolyzate in the alkylaluminum partial hydrolyzate-containing solution of the present invention can be appropriately determined according to the application.
- the content can be adjusted by adjusting the amount of the nonpolar solvent.
- the content of the alkylaluminum partial hydrolyzate can be appropriately adjusted, for example, in the range of 1 to 90% by mass. However, it is not intended to be limited to this range.
- the content of the alkylaluminum partial hydrolyzate is preferably in the range of 5 to 50% by mass in consideration of solubility and viscosity.
- the content of the alkylaluminum partial hydrolyzate is preferably 5% by mass or more from the viewpoint that it is difficult to dry because the content of the material is low and contains a large amount of solvent, and the amount of the solvent to be processed increases, and the viscosity is preferably From the viewpoint of increasing the white solid or the like during the production, the content is preferably 50% by mass or less. However, it is not intended to be limited to this range, and the content of the alkylaluminum partial hydrolyzate can be determined as appropriate according to the application.
- the mass of aluminum oxide relative to the mass of the alkylaluminum partial hydrolyzate-containing solution Percentage is defined as aluminum oxide equivalent concentration.
- the aluminum oxide equivalent concentration of the alkylaluminum partial hydrolyzate-containing solution of the present invention can be appropriately adjusted, for example, in the range of 5 to 50% by mass. However, it is not intended to be limited to this range.
- the method for producing an aluminum oxide thin film of the present invention is a method for obtaining an aluminum oxide thin film by applying the alkyl aluminum partial hydrolyzate-containing solution of the present invention to a substrate.
- Application to the substrate is performed by spin coating, dip coating, screen printing, bar coating, slit coating, die coating, gravure coating, roll coating, curtain coating, spray pyrolysis, electrostatic
- a conventional method such as a spray pyrolysis method, an ink jet method, or a mist CVD method can be used.
- Application to the substrate can be performed in an inert atmosphere or an air atmosphere.
- Application to the substrate can be carried out under pressure or reduced pressure, but it is preferable to carry out under atmospheric pressure from the viewpoint of economy because the apparatus is simple.
- the substrate is made of lead glass, soda glass, borosilicate glass, alkali-free glass, etc .; oxides such as silica, alumina, titania, zirconia, complex oxides; polyethylene (PE), polypropylene (PP), Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyphenylene sulfide (PPS), polystyrene (PS), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), Polyvinylidene chloride, cyclic polyolefin (COP), ethylene-vinyl acetate copolymer (EVA), polyimide, polyamide, polyethersulfone (PES), polyurethane, triacetate, triacetylcellulose (TAC), cellopha , Polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene
- Examples of the shape of the base material include powder, a film, a plate, or a three-dimensional structure having a three-dimensional shape.
- the substrate After applying the alkylaluminum partial hydrolyzate-containing solution, the substrate is brought to a predetermined temperature, and the solvent is dried or baked at the same temperature as the drying to form an aluminum oxide thin film.
- the substrate when coating is performed by spray pyrolysis, electrostatic spray pyrolysis, ink jet, or mist CVD, the substrate can be heated to a predetermined temperature before coating. It can be fired simultaneously.
- the predetermined temperature for drying the solvent can be selected, for example, from 20 to 250 ° C.
- the solvent can be dried, for example, over 0.5 to 60 minutes. However, it is not intended to be limited to these ranges.
- the predetermined temperature for firing for forming the aluminum oxide can be selected from 50 to 550 ° C., for example. However, considering the type of the substrate, it is appropriate to set the temperature so that the substrate is not damaged.
- the predetermined temperature for baking is the same as the predetermined temperature for drying the solvent, drying and baking of the solvent can be performed simultaneously.
- the solvent-dried precursor film can be fired, for example, over 0.5 to 300 minutes.
- the film thickness of the aluminum oxide thin film obtained as described above can be, for example, 0.005 to 3 ⁇ m. However, it is not intended to limit to this range.
- the film thickness of the aluminum oxide thin film can be increased by repeating the coating, drying, and baking steps a plurality of times as necessary.
- the aluminum oxide thin film obtained as described above can be used in an oxidizing gas atmosphere such as oxygen, a reducing gas atmosphere such as hydrogen, a water vapor atmosphere in which a large amount of moisture exists, or argon, nitrogen, oxygen, etc.
- an oxidizing gas atmosphere such as oxygen, a reducing gas atmosphere such as hydrogen, a water vapor atmosphere in which a large amount of moisture exists, or argon, nitrogen, oxygen, etc.
- the crystallinity and denseness of aluminum oxide can be improved by heating at a predetermined temperature in the plasma atmosphere. Residual organic substances and the like in the aluminum oxide thin film obtained by irradiation with light such as ultraviolet rays or microwave treatment can be removed.
- the method for producing a particulate aluminum oxide-containing substrate of the present invention comprises mixing the alkylaluminum partial hydrolyzate-containing solution of the present invention with a substrate material during the production of the substrate, and containing the particulate aluminum oxide in the substrate. It is a method of obtaining the base material to perform.
- the base material and the alkylaluminum partial hydrolyzate-containing solution can be introduced into the production apparatus according to any conventional method.
- the pressure of the manufacturing apparatus is not limited.
- the base material may be the same base material as in the production of the aluminum oxide thin film.
- the base material is a material that can be a raw material for these base materials, and is preferably a polymer material.
- the aluminum oxide produced in the method for producing an aluminum oxide thin film of the present invention and the particulate aluminum oxide formed in the substrate in the method for producing a particulate aluminum oxide-containing substrate differ depending on firing, post-treatment conditions, etc. It is presumed that the hydrated gibbsite, baiasite, boehmite, diaspore, or any of ⁇ -, ⁇ -, ⁇ -, ⁇ -, ⁇ -, ⁇ -alumina. When the treatment is performed in the water vapor atmosphere, it may be converted into aluminum hydroxide.
- aluminum oxide produced at 500 ° C. or lower is usually in an amorphous state with no clear peak observed by X-ray diffraction analysis.
- the first embodiment of the second aspect of the present invention uses a partial hydrolyzate-containing solution of dialkyl zinc (wherein the alkyl group has 1 to 14 carbon atoms and may be the same or different) and a polyolefin powder.
- the present invention relates to a method for producing a polyolefin polymer nanocomposite containing zinc oxide particles.
- the first embodiment of the second aspect of the present invention is more specifically, (A) impregnating polyolefin powder with a zinc partial hydrolyzate-containing solution of dialkylzinc (wherein the alkyl group has 1 to 12 carbon atoms and may be the same or different); (B) a step of removing the organic solvent contained in the polyolefin powder; (D) a step of melting and heating the polyolefin powder, including.
- the dialkyl zinc is preferably a dialkyl zinc represented by the following general formula (2-1).
- R 10 represents a methyl group, an ethyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group.
- the two R 10 s may be the same or different.
- Examples of the compound represented by the general formula (2-1) include dimethyl zinc, diethyl zinc, di-n-butyl zinc, diisobutyl zinc, di-sec-butyl zinc, di-tert-butyl zinc and the like. Can do. From the viewpoint that the price for zinc of unit mass is inexpensive, diethyl zinc is preferable.
- the partial hydrolyzate-containing solution is prepared by adding water having a molar ratio in the range of 0.5 to 1.4 to zinc in the dialkyl zinc to a solution containing dialkyl zinc and an organic solvent. It is preferable.
- organic solvent examples include aromatic hydrocarbons, aliphatic hydrocarbons, ether solvents that do not contain active hydrogen, and other organic solvents.
- aromatic hydrocarbons examples include benzene, toluene, o-xylene, m-xylene, p-xylene, mixed xylene (xylene), ethylbenzene, isopropylbenzene, mesitylene, pseudocumene, amylbenzene, o-cymene, m- Examples include cymene, p-cymene, mixed cymene (cymene), o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, mixed diethylbenzene (diethylbenzene), cyclohexylbenzene, tetralin and the like.
- aliphatic hydrocarbons examples include pentane, methylcyclopentane, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, nonane, octane, n-decane, n-undecane, n-dodecane, tridecane, tetradecane, kerosene, decalin Petroleum ether, petroleum benzine, solvent naphtha, dipentene, turpentine, o-menthane, m-menthane, p-menthane, mixed menthane (menthane), ligroin and the like.
- ester solvents such as ethyl acetate, acetic acid-n-butyl, acetic acid-s-butyl, and ⁇ -butyllactone, and N-methylpyrrolidone.
- the partial hydrolysis of dialkylzinc can be performed using water.
- the molar ratio of water to dialkylzinc is not particularly limited, but is preferably in the range of 0.5 to 1.4, more preferably 0.5 to 0.9. If the molar ratio of water to dialkylzinc is less than 0.5, the remaining dialkylzinc tends to impregnate the polyolefin and aggregate during drying, making it difficult to form zinc oxide having an average particle size of 100 nm or less in the polyolefin. On the other hand, when the molar ratio of water to dialkylzinc is excessively large, a gel or solid insoluble in the solvent may be precipitated. From the viewpoint of forming uniform zinc oxide particles in the polyolefin, the precipitated gel or solid is preferably removed by decantation, filtration, or the like.
- the partial hydrolysis reaction is performed by adding water to the dialkylzinc and the organic solvent in an inert gas atmosphere.
- the concentration of dialkyl zinc in the dialkyl zinc solution to which water is added can be, for example, 5 to 98% by mass.
- Water can be diluted with the organic solvent and added as a solution containing water.
- Water can be added by syringe dropping, dropping funnel or the like. Moreover, it is also possible to make it contact with pressurized nitrogen etc. using a 2 fluid spray nozzle mechanism etc., and to add as a mist-like water droplet.
- the addition of water or a solution containing water to the dialkylzinc solution can be appropriately set depending on the type and volume of the raw material to be mixed, and can be set in the range of 1 minute to 10 hours, for example.
- the temperature at the time of addition can be arbitrarily selected from -20 to 150 ° C. However, in consideration of safety and the like, it is preferably in the range of ⁇ 15 to 80 ° C.
- an aging reaction can be performed for 0.1 to 50 hours in order to further promote the partial hydrolysis reaction of the dialkylzinc and water.
- the aging reaction temperature can be selected from -15 to 150 ° C. However, considering the shortening of the ripening reaction time, etc., it is preferably in the range of 25 to 150 ° C.
- the dialkyl zinc, water, and organic solvent can be introduced into the reaction vessel according to any conventional method.
- the pressure in the reaction vessel is not limited.
- the hydrolysis reaction step may be any of a batch operation method, a semi-batch operation method, and a continuous operation method, and is not particularly limited, but a batch operation method is preferable.
- the alkylzinc partial hydrolyzate-containing solution is obtained by the partial hydrolysis reaction.
- the dialkyl zinc is diethyl zinc
- the analysis on the partially hydrolyzed composition has been performed for a long time.
- the product composition results differ depending on the report, and the product composition is not clearly specified.
- the composition of the product also varies depending on the solvent, concentration, molar ratio of water added, addition temperature, reaction temperature, reaction time, and the like.
- the alkyl zinc partial hydrolyzate in the method of the present invention is presumed to be a mixture of compounds containing a structural unit represented by the following general formula (2-3).
- R 10 is the same as R 10 in the general formula (2-1), m is an integer of 1-20.
- the solids and the like When solids or the like are deposited after completion of the partial hydrolysis reaction, the solids and the like can be removed by purification by a method such as filtration.
- the solid content concentration of the alkylzinc partial hydrolyzate-containing solution can be adjusted by concentration (solvent removal). Further, the solvent used in the reaction and an organic solvent different from that used in the reaction may be added to adjust the solid content concentration, polarity, viscosity, boiling point, economy and the like as appropriate.
- the content of the alkyl zinc partial hydrolyzate in the alkyl zinc partial hydrolyzate-containing solution of the present invention can be determined as appropriate.
- the content can be adjusted by adjusting the amount of the organic solvent.
- the content of the alkylzinc partial hydrolyzate can be appropriately adjusted, for example, in the range of 5 to 90% by mass. However, it is not intended to be limited to this range.
- the content of the alkylzinc partial hydrolyzate is preferably in the range of 5 to 50% by mass in consideration of solubility and viscosity.
- the content of the alkylzinc partial hydrolyzate is preferably 5% by mass or more from the viewpoint that the material content is low and the solvent is contained in a large amount, which makes it difficult to dry and the amount of solvent to be processed increases. From the viewpoint of increasing the viscosity and facilitating precipitation of a white solid or the like during production, the content is preferably 50% by mass or less.
- the percentage of the zinc oxide mass relative to the mass of the alkylzinc partial hydrolyzate-containing solution was calculated. It is defined as the zinc oxide equivalent concentration in the substance-containing solution.
- the zinc oxide equivalent concentration of the alkyl zinc partial hydrolyzate-containing solution can be appropriately adjusted within a range of 5 to 40% by mass, for example.
- polyolefins constituting the polyolefin powder include ethylene homopolymers; ethylene copolymers obtained by polymerizing ethylene and at least one selected from propylene and ⁇ -olefins having 4 to 8 carbon atoms; Examples thereof include propylene copolymers obtained by polymerizing propylene and at least one selected from ethylene and ⁇ -olefins having 4 to 8 carbon atoms.
- the polyolefin may contain a small amount of aromatic monomers such as dienes, vinyl acetate, unsaturated carboxylic acid, unsaturated carboxylic acid ester, styrene, and styrene derivatives as the second and third comonomers.
- the ethylene homopolymer and ethylene copolymer of the present invention are defined as polyethylene, and the polypropylene homopolymer and propylene copolymer are defined as polypropylene.
- Examples of the method for producing the polyolefin powder of the present invention include Ziegler-Natta method, metallocene method, high pressure radical polymerization method and the like. However, it is not intended to be limited to the above method.
- the polyolefin powder is preferably porous from the viewpoint that the impregnation with the alkylzinc partial hydrolyzate-containing solution can be easily performed. From the viewpoint of obtaining a porous polyolefin powder, the polyolefin powder is preferably produced by the Ziegler-Natta method.
- the polyolefin powder used in the present invention is preferably a powder obtained by the Ziegler-Natta method.
- the shape of the polyolefin is preferably a powder from the viewpoint of easy impregnation with the alkylzinc partial hydrolyzate-containing solution. Furthermore, the particle size of the particles constituting the powder is impregnated from the viewpoint of obtaining a nanocomposite in which the zinc oxide particles are present in a well dispersed state by impregnating the inside of the particles with the alkylzinc partial hydrolyzate-containing solution. Is preferably relatively small.
- the particle diameter of the particles constituting the powder is suitably in the range of, for example, 0.1 ⁇ m to 1000 ⁇ m as the average particle diameter. However, it is not intended to be limited to this range.
- the polyolefin particles are preferably porous from the viewpoint of easy impregnation with the alkylzinc partial hydrolyzate-containing solution.
- the density is suitably in the range of 0.8 to 1.0 g / cm 3 , for example. However, it is not intended to be limited to this range.
- the impregnation of the alkylzinc partial hydrolyzate-containing solution into the polyolefin powder is preferably performed in a reducing atmosphere or an inert atmosphere, and more preferably in a nitrogen atmosphere from the viewpoint of economy.
- the impregnation of the polyolefin powder can be carried out under pressure or under reduced pressure, but it is preferable to carry out under atmospheric pressure from the viewpoint of economy because the apparatus is simple.
- the aging temperature can be selected from -15 to 100 ° C. However, in consideration of shortening of the aging time and the like, the range of 25 to 100 ° C. is preferable.
- an antioxidant may be added to the partial hydrolyzate-containing solution impregnated in the polyolefin powder in order to prevent thermal degradation of the polyolefin in the (D) melt heating step described later.
- the polyolefin powder can be impregnated with the antioxidant-containing solution simultaneously with the partial hydrolyzate-containing solution.
- the polyolefin powder after impregnating the partially hydrolyzed product-containing solution can be impregnated with the antioxidant-containing solution polyolefin powder.
- the antioxidant-containing solution can be obtained by dissolving an antioxidant in an organic solvent exemplified by the partial hydrolyzate-containing solution.
- the antioxidant those known as antioxidants for polyolefins can be appropriately used.
- the amount of the antioxidant added to the polyolefin powder can be, for example, in the range of 0.01 to 1% by mass in consideration of the type of antioxidant and the type of polyolefin. However, it is not intended to be limited to this range.
- antioxidants examples include 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H ) -Trione, 4,4 ′, 4 ′ ′-(1-methylpropanyl-3-ylidene) tris (6-tert-butyl-m-cresol), 6,6′-di-tert-butyl-4, 4'-butylidene di-m-cresol, octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate], 3,9-bis ⁇ 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl ⁇ -2
- step (B) Organic solvent removal step
- the organic solvent contained in the partially hydrolyzed product-containing solution is removed from the polyolefin powder.
- the removal of the organic solvent is not particularly limited as long as it is a method capable of removing the organic solvent from the polyolefin powder obtained in the step (A).
- it can be carried out by drying the polyolefin powder obtained in the step (A) at a predetermined temperature.
- a predetermined temperature For example, an arbitrary temperature can be selected between 20 and 100 ° C., and drying can be performed under normal pressure or reduced pressure. From the viewpoint of preventing the polyolefin from melting before removing the solvent, it is preferably 100 ° C. or lower and under reduced pressure.
- the solvent can be dried, for example, over a period of 0.5 minutes to 50 hours. However, it is not intended to be limited to these ranges.
- the melt-kneading temperature can be appropriately determined depending on the type of polyolefin in consideration of its melting point. For example, 120 to 150 ° C. for polyethylene and 160 to 200 ° C. for polypropylene are preferable from the viewpoint of minimizing thermal degradation.
- the melt kneading can be performed, for example, over 1 minute to 50 hours. However, it is not intended to be limited to these ranges.
- a polyolefin polymer nanocomposite containing zinc oxide particles can be obtained by melting and heating the polyolefin powder.
- the content (concentration) of the zinc oxide particles contained in the polyolefin polymer nanocomposite produced by the production method of the present invention is not particularly limited. However, the content of zinc oxide particles is preferably 3% by weight or more. If it is less than 3% by weight, the effect of zinc oxide is hardly exhibited. On the other hand, if the upper limit exceeds 40% by weight, for example, the properties of the polyolefin are likely to be impaired, and the cost tends to increase due to an increase in the amount of zinc oxide. From such a viewpoint, it is preferable that the zinc oxide particle concentration is appropriately adjusted in the range of 3 to 40% by weight.
- the percentage of the mass of zinc oxide contained relative to the total mass of the polyolefin nanocomposite containing zinc oxide is defined as the zinc oxide content (concentration) in the nanocomposite.
- a polyolefin nanocomposite containing zinc oxide can be produced by further heating, molding, or granulating as desired.
- the shape can be a sheet, a film, a chip or the like, but is not particularly limited.
- Examples of methods for supplying moisture include impregnation, a method of exposing a polyolefin powder from which an organic solvent has been removed to the atmosphere for a sufficient time, a method of bringing the polyolefin powder into contact with water vapor in a container such as a chamber, and a container such as a chamber. And a method of exposing the polyolefin powder to wet air and a method of directly contacting water with the polyolefin powder.
- the reaction with moisture at the time of moisture supply is preferably performed at 20 to 100 ° C.
- the water supply time can be, for example, 0.5 minutes to 50 hours. However, it is not intended to be limited to these ranges.
- the present invention includes a polyolefin-based polymer nanocomposite containing a polyolefin base material and zinc oxide particles, containing no dispersant, and having an average particle diameter of less than 100 nm.
- This polyolefin polymer nanocomposite can be produced by the production method of the present invention.
- the average particle diameter of the zinc oxide particles in the polyolefin is preferably in the range of 1 nm to less than 100 nm.
- the polyolefin polymer nanocomposite of the present invention is based on a polyolefin polymer in which oxide particles are difficult to disperse, and the average particle diameter of zinc oxide particles is as fine as less than 100 nm, A nanocomposite in which zinc oxide particles are well dispersed in a substrate without containing a dispersant (without using a dispersant as a dispersion aid for zinc oxide particles).
- the dispersant not contained in the nanocomposite means a chemical used for the purpose of dispersing zinc oxide particles in a polyolefin substrate.
- Additives that can be added later to the nanocomposite described later and that have a dispersing action on the inorganic particles are not included in the dispersant described here.
- a dispersing agent is not used for the purpose of disperse
- the content (concentration) of zinc oxide particles in the polyolefin is not particularly limited, but can be, for example, 3% by weight or more.
- the percentage of the mass of zinc oxide contained relative to the total mass of the polyolefin nanocomposite containing zinc oxide of the present invention is defined as the zinc oxide content (concentration) in the nanocomposite.
- the zinc oxide concentration is preferably adjusted as appropriate in the range of 3 to 40% by weight.
- zinc oxide in the polyolefin obtained as described above can be obtained in a predetermined atmosphere under an oxidizing gas atmosphere such as oxygen, a reducing gas atmosphere such as hydrogen, or a plasma atmosphere such as argon, nitrogen or oxygen.
- oxidizing gas atmosphere such as oxygen
- reducing gas atmosphere such as hydrogen
- plasma atmosphere such as argon, nitrogen or oxygen.
- the crystallinity and crystal state of zinc oxide can be improved by heating at a temperature.
- the crystallinity and crystal state of zinc oxide can also be improved by irradiation with light such as ultraviolet rays or microwave treatment.
- the polyolefin nanocomposite containing zinc oxide particles of the present invention improves the basic properties of the polymer, such as improved thermal stability of the polymer as a matrix, improved wear resistance, adjustment of the refractive index, and improved stability to ultraviolet light. Therefore, it is possible to impart functionality such as conductivity, ultraviolet absorption, antibacterial properties, and refractive index adjustment. Therefore, a substitute for the material of the current part that is required to adjust the thermal stability, wear resistance, refractive index increase, ultraviolet stability, conductivity, ultraviolet absorption, antibacterial property, and refractive index is expected as an application.
- the polyolefin nanocomposite containing zinc oxide particles of the present invention may contain various additives as long as the effects of the zinc oxide particles contained in the composite are not impaired.
- various additives include plasticizers such as polyalkylene oxide oligomeric compounds and organophosphorus compounds, crystal horns such as talc, kaolin and organophosphorus compounds, montanic acid waxes, lithium stearate, aluminum stearate, etc.
- metal soaps include lubricants, ultraviolet light inhibitors, colorants, flame retardants, and foaming agents.
- a second embodiment of the second aspect of the present invention is a partial hydrolysis of an alkylaluminum compound comprising a trialkylaluminum or a mixture thereof (provided that the alkyl group has 1 to 12 carbon atoms and may be the same or different).
- the present invention relates to a method for producing a polyolefin polymer nanocomposite containing aluminum oxide particles, characterized by using a decomposition product-containing solution and a polyolefin powder.
- the second embodiment of the second aspect of the present invention is more specifically, (E) A polyolefin-containing powder is impregnated with a solution containing a partial hydrolyzate of an alkylaluminum compound comprising a trialkylaluminum or a mixture thereof (wherein the alkyl group has 1 to 12 carbon atoms and may be the same or different). Process, (F) a step of removing the organic solvent contained in the polyolefin powder, and (H) a step of melting and heating the polyolefin powder. including.
- the trialkylaluminum is preferably a trialkylaluminum represented by the following general formula (2-2). (Wherein R 2 represents a methyl group, an ethyl group, an isobutyl group, an n-hexyl group or an n-octyl group. The three R 2 s may be the same or different.)
- Examples of the compound represented by the general formula (2-2) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tridodecylaluminum, tritetradecylaluminum, etc. Can be mentioned. Trimethylaluminum, triethylaluminum, and triisobutylaluminum are preferable from the viewpoint that the price for unit mass of aluminum is low, and triethylaluminum and triisobutylaluminum are particularly preferable.
- water having a molar ratio of 0.5 to 1.4 with respect to the aluminum in the trialkylaluminum is added to the solution containing the trialkylaluminum and the organic solvent. It is preferable to be prepared.
- the molar ratio of water to trialkylaluminum is less than 0.5, the remaining trialkylaluminum easily impregnates the polyolefin and easily aggregates during drying, making it difficult to form aluminum oxide having an average particle size of 100 nm or less in the polyolefin. is there.
- the molar ratio of water to trialkylaluminum exceeds 1.4, a gel or solid insoluble in the solvent is precipitated, and it becomes difficult to form uniform aluminum oxide particles in the polyolefin by the gel or solid. .4 or less is preferable, and 1.3 or less is more preferable.
- the precipitated gel or solid can be removed by decantation, filtration, or the like.
- organic solvent examples include the same compounds as in the production of the polyolefin nanocomposite containing the zinc oxide.
- the partial hydrolysis reaction can be performed by adding water to the organic solvent with the trialkylaluminum in an inert gas atmosphere.
- the concentration of the trialkylaluminum in the trialkylaluminum solution to which water is added can be, for example, 5 to 98% by mass.
- Water can be diluted with the organic solvent and added as a solution containing water.
- Water can be added by a dropping method such as a syringe dropping or a dropping funnel. Moreover, it is also possible to make it contact with pressurized nitrogen etc. using a 2 fluid spray nozzle mechanism etc., and to add as a mist-like water droplet.
- the addition of water or a solution containing water to the trialkylaluminum solution can be appropriately set depending on the type and volume of the raw material to be mixed, and can be set in the range of 1 minute to 10 hours, for example.
- the temperature at the time of addition can be arbitrarily selected from -20 to 150 ° C. However, in consideration of safety and the like, it is preferably in the range of ⁇ 15 to 80 ° C.
- an aging reaction can be performed for 0.1 to 50 hours in order to further promote the partial hydrolysis reaction of the trialkylaluminum and water.
- the aging reaction temperature can be selected from -15 to 150 ° C.
- the trialkylaluminum, water, and organic solvent can be introduced into the reaction vessel according to any conventional method.
- the pressure in the reaction vessel is not limited.
- the hydrolysis reaction step may be any of a batch operation method, a semi-batch operation method, and a continuous operation method, and is not particularly limited, but a batch operation method is preferable.
- the alkylaluminum partial hydrolyzate-containing solution is obtained by the partial hydrolysis reaction. Analysis of alkylaluminum partial hydrolyzed compositions has been performed for a long time, but the composition results of the products differ from reports, and the composition of the products is not clearly specified.
- the composition of the product also varies depending on the solvent, concentration, molar ratio of water added, addition temperature, reaction temperature, reaction time, and the like.
- the alkylaluminum partial hydrolyzate in the method of the present invention is presumed to be a mixture of compounds containing a structural unit represented by the following general formula (2-5).
- R 2 is the same as R 2 in the general formula (2-2), m is an integer of 1 to 80.
- the solids and the like When solids or the like are deposited after completion of the partial hydrolysis reaction, the solids and the like can be removed by purification by a method such as filtration.
- the solid content concentration of the alkyl aluminum partial hydrolyzate-containing solution can be adjusted by concentration (solvent removal). Further, the solvent used in the reaction and an organic solvent different from that used in the reaction may be added to adjust the solid content concentration, polarity, viscosity, boiling point, economy and the like as appropriate.
- the content of the alkylaluminum partial hydrolyzate in the alkylaluminum partial hydrolyzate-containing solution can be determined as appropriate.
- the content can be adjusted by adjusting the amount of the organic solvent.
- the content of the alkylaluminum partial hydrolyzate can be appropriately adjusted, for example, in the range of 5 to 90% by mass. However, it is not intended to be limited to this range.
- the content of the alkylaluminum partial hydrolyzate is preferably in the range of 5 to 70% by mass in consideration of solubility and viscosity.
- the content of the alkylaluminum hydrolyzate is preferably 5% by mass or more from the viewpoint that it is difficult to dry because the content of the material is low and contains a large amount of solvent, and the amount of the solvent to be processed increases, and the viscosity is high From the viewpoint that white solids and the like are likely to precipitate during production, 70 mass% or less is preferable.
- the percentage of the aluminum oxide mass relative to the mass of the alkylaluminum partial hydrolyzate-containing solution is expressed as the alkylaluminum part. It is defined as the aluminum oxide equivalent concentration in the hydrolyzate-containing solution.
- the aluminum oxide equivalent concentration of the alkylaluminum partial hydrolyzate-containing solution can be appropriately adjusted within a range of 5 to 40% by mass, for example.
- polyolefin powder examples include the same polyolefin powder as in the production of the polyolefin nanocomposite containing the zinc oxide particles.
- the impregnation of the polyolefin with a solution containing an alkyl aluminum partial hydrolyzate is preferably performed in a reducing atmosphere or an inert atmosphere, and more preferably in a nitrogen atmosphere from the viewpoint of economy.
- the impregnation of the polyolefin powder can be carried out under pressure or under reduced pressure, but it is preferable to carry out under atmospheric pressure from the viewpoint of economy because the apparatus is simple.
- the aging temperature can be selected from -15 to 100 ° C. However, in consideration of shortening of the aging time and the like, the range of 25 to 100 ° C. is preferable.
- antioxidant in order to prevent thermal degradation of the polyolefin in the (H) melt heating step described later.
- antioxidant those known as antioxidants for polyolefins can be used.
- the same antioxidant as in the production of the polyolefin nanocomposite containing the zinc oxide can be mentioned.
- the percentage of the mass of aluminum oxide contained with respect to the total mass of the polyolefin nanocomposite containing aluminum oxide of the present invention is defined as the aluminum oxide concentration in the nanocomposite.
- the aluminum oxide concentration is preferably adjusted as appropriate in the range of 3 to 40% by weight.
- the organic solvent contained in the partial hydrolyzate containing solution is removed from polyolefin powder.
- the removal of the organic solvent is not particularly limited as long as the organic solvent can be removed from the polyolefin powder obtained in the step (E).
- it can be carried out by drying the polyolefin powder obtained in the step (E) at a predetermined temperature.
- the predetermined temperature for removing the organic solvent can be selected, for example, from 20 to 100 ° C., and the drying can be performed under normal pressure or reduced pressure. From the viewpoint of preventing the polyolefin from melting before removing the solvent, it is preferably 100 ° C. or lower and reduced pressure.
- the solvent can be dried, for example, over a period of 0.5 minutes to 50 hours. However, it is not intended to be limited to these ranges.
- melt heating process After carrying out the organic solvent removal process, the polyolefin powder impregnated and dried at a temperature equal to or higher than the melting temperature of the polyolefin is melt-kneaded using various mixers and extruders.
- the melt kneading temperature is preferably 120 to 150 ° C. for polyethylene and 160 to 200 ° C. for polypropylene from the viewpoint of minimizing thermal degradation.
- the melt kneading can be performed, for example, over 1 minute to 50 hours. However, it is not intended to be limited to these ranges.
- a polyolefin polymer nanocomposite containing aluminum oxide particles can be obtained by melting and heating the polyolefin powder.
- the content of the aluminum oxide particles contained in the polyolefin polymer nanocomposite produced by the production method of the present invention is not particularly limited. However, the content of aluminum oxide particles is preferably 3% by weight or more. If it is less than 3% by weight, the effect of aluminum oxide is hardly exhibited. On the other hand, if the upper limit exceeds 40% by weight, for example, the properties of the polyolefin are liable to be impaired, and the cost tends to increase due to an increase in the amount of aluminum oxide. From such a viewpoint, the content (concentration) of the aluminum oxide particles is preferably adjusted as appropriate in the range of 3 to 40% by weight.
- the percentage of the mass of aluminum oxide contained relative to the total mass of the polyolefin nanocomposite containing aluminum oxide is defined as the aluminum oxide content (concentration) in the nanocomposite.
- a polyolefin nanocomposite containing aluminum oxide is prepared by further heating, molding, or granulating.
- the shape can be a sheet, film, chip or the like.
- the reaction with moisture at the time of moisture supply is preferably performed at 20 to 100 ° C.
- the water supply time can be, for example, 0.5 minutes to 50 hours. However, it is not intended to be limited to these ranges.
- the present invention is a polyolefin-based polymer nanocomposite containing a polyolefin base material and aluminum oxide particles, containing no dispersant, and having an average particle diameter of less than 100 nm.
- This polyolefin polymer nanocomposite can be produced by the production method of the present invention.
- the average particle diameter of the aluminum oxide particles in the polyolefin is preferably in the range of 1 nm to less than 100 nm.
- the polyolefin-based polymer nanocomposite of the present invention is based on a polyolefin-based polymer in which oxide particles are difficult to disperse, and the average particle diameter of aluminum oxide particles is as fine as less than 100 nm, It is a nanocomposite in which aluminum oxide particles are well dispersed in a base material without containing a dispersant (without using a dispersant as a dispersion aid for aluminum oxide particles).
- the dispersant not contained in the nanocomposite means a chemical used for the purpose of dispersing aluminum oxide particles in a polyolefin substrate.
- Additives that can be added later to the nanocomposite described later and that have a dispersing action on the inorganic particles are not included in the dispersant described here.
- the intention is that no dispersant is used for the purpose of dispersing the aluminum oxide particles in the polyolefin substrate during the nanocomposite production process, and as a result, the nanocomposite of the present invention does not contain a dispersant.
- the content of aluminum oxide particles in the polyolefin obtained as described above is not particularly limited, but can be, for example, 3% by weight or more.
- the percentage of the mass of aluminum oxide contained relative to the total mass of the polyolefin nanocomposite containing aluminum oxide of the present invention is defined as the aluminum oxide content (concentration) in the nanocomposite.
- the concentration of the aluminum oxide increases from the viewpoint of increasing the cost due to an increase in the amount of aluminum oxide. Is preferably adjusted in the range of 3 to 40% by weight.
- the aluminum oxide in the polyolefin obtained as described above is subjected to a predetermined atmosphere under an oxidizing gas atmosphere such as oxygen, under a reducing gas atmosphere such as hydrogen, or under a plasma atmosphere such as argon, nitrogen or oxygen.
- a oxidizing gas atmosphere such as oxygen
- a reducing gas atmosphere such as hydrogen
- a plasma atmosphere such as argon, nitrogen or oxygen.
- the crystallinity and crystal state of aluminum oxide can be improved by heating at a temperature.
- the crystallinity and crystal state of aluminum oxide can also be improved by irradiation with light such as ultraviolet rays or microwave treatment.
- aluminum oxide is a hydrate such as gibbsite, baiasite, boehmite, diaspore, or ⁇ -, ⁇ -, ⁇ -, ⁇ -, ⁇ -, ⁇ -alumina, etc. It is known to become a state.
- the aluminum oxide in the polyolefin produced in the present invention is a compound containing an aluminum element and an oxygen element, and the proportion of these two elements in the aluminum oxide is 90% or more.
- aluminum oxide in the present invention varies depending on the post-treatment conditions and the like, it is presumed that the aluminum oxide is in any of the above-described generally known aluminum oxides depending on the treatment temperature and conditions. Moreover, when it is attached
- aluminum oxide produced at 500 ° C. or lower is usually in an amorphous state with no clear peak observed by powder X-ray diffraction analysis.
- the polyolefin nanocomposite containing the aluminum oxide particles of the present invention can impart functionality such as thermal conductivity, wear resistance, and refractive index adjustment in the polyolefin nanocomposite containing aluminum oxide particles. Therefore, a substitute for the material of the current part that requires adjustment of thermal conductivity, wear resistance, and refractive index is expected as an application.
- the polyolefin nanocomposite containing the aluminum oxide particles of the present invention may contain various additives as long as the effects of the aluminum oxide particles contained in the nanocomposite are not impaired.
- various additives include plasticizers such as polyalkylene oxide oligomeric compounds and organophosphorus compounds, crystal horns such as talc, kaolin and organophosphorus compounds, montanic acid waxes, lithium stearate, aluminum stearate, etc.
- plasticizers such as polyalkylene oxide oligomeric compounds and organophosphorus compounds
- crystal horns such as talc, kaolin and organophosphorus compounds
- montanic acid waxes lithium stearate, aluminum stearate, etc.
- metal soaps include lubricants, ultraviolet light inhibitors, colorants, flame retardants, and foaming agents.
- the alkyl aluminum compound-containing solution and alkyl aluminum partial hydrolyzate-containing solution of the present invention were prepared in a nitrogen gas atmosphere, and all solvents were used after dehydration and deaeration.
- the alkylaluminum partial hydrolyzate-containing solution of the present invention is obtained by performing IR measurement with a FT-IR spectroscope ("FT / IR-4100" manufactured by JASCO Corporation) after drying the solvent with an evaporator. did.
- the aluminum oxide thin film prepared by the production method of the present invention is obtained by an ATR (Attenuated Total Reflection) method using a ZnSe prism with an FT-IR spectrometer (“FT / IR-4100” manufactured by JASCO Corporation). Relative IR measurements were performed without ATR correction.
- ATR Attenuated Total Reflection
- Example 1-1 100 ⁇ l of the triisobutylaluminum hydrolyzed composition-containing toluene solution obtained in Synthesis Example 1-1 was dropped on a 15 mm square glass substrate (Eagle XG manufactured by Corning) in an air atmosphere at 25 ° C. and a relative humidity of about 40%. Then, after spin coating with a spin coater at 4000 rpm for 20 seconds, a thin film was formed by heating at 80 ° C. for 3 minutes.
- Example 1-2 A thin film was formed in the same manner as in Example 1-1 except that heating was performed at 200 ° C. for 3 minutes.
- Example 1-3 A thin film was formed in the same manner as in Example 1-1 except that a 20 mm square acrylic substrate (manufactured by Mitsubishi Rayon Co., Ltd., Acrylite EX) and 150 ⁇ l of the solution were dropped.
- FIG. 10 A transparent thin film as shown in FIG. 10 was obtained, and IR measurement by the ATR method was performed. As a result, a spectrum as shown in FIG. 11 was obtained, confirming the formation of an aluminum oxide thin film.
- the IR spectrum of the acrylic substrate itself by the ATR method is FIG. 12, which is clearly different from FIG.
- Example 1-4 The toluene solution containing the tri-n-octylaluminum hydrolyzate composition obtained in Synthesis Example 1-4 was placed on a 15 mm square glass substrate (Eagle XG manufactured by Corning) in an air atmosphere at 25 ° C. and a relative humidity of about 40%. 150 ⁇ l was added dropwise to the film, and spin coated at 4000 rpm for 20 seconds with a spin coater, followed by heating at 80 ° C. for 3 minutes to form a thin film.
- a 15 mm square glass substrate Eagle XG manufactured by Corning
- a transparent thin film as shown in FIG. 13 was obtained, and when IR measurement was performed by the ATR method, a spectrum as shown in FIG. 14 was obtained, confirming the formation of an aluminum oxide thin film.
- Example 1-5 A thin film was formed in the same manner as in Example 1-4 except that a 20 mm square acrylic resin substrate (Acrylite EX, manufactured by Mitsubishi Rayon Co., Ltd.) and 180 ⁇ l of the solution were dropped.
- a transparent thin film as shown in FIG. 15 was obtained, and when IR measurement was performed by the ATR method, a spectrum as shown in FIG. 16 was obtained, confirming the formation of an aluminum oxide thin film.
- Example 1-6 The triisobutylaluminum hydrolyzed composition-containing decane solution obtained in Synthesis Example 1-5 was subjected to 20 mm square acrylic resin substrate (Acrylite EX, manufactured by Mitsubishi Rayon Co., Ltd.) in an air atmosphere at 25 ° C. and a relative humidity of about 40%. 180 ⁇ l of the solution was dropped on the substrate, and was applied by spinning at 4000 rpm for 20 seconds with a spin coater, followed by heating at 80 ° C. for 3 minutes to form a thin film.
- Acrylic resin substrate Acrylite EX, manufactured by Mitsubishi Rayon Co., Ltd.
- a transparent thin film as shown in FIG. 17 was obtained, and IR measurement by the ATR method was performed. As a result, a spectrum as shown in FIG. 18 was obtained, confirming the formation of an aluminum oxide thin film.
- Example 1-1 A thin film was formed in the same manner as in Example 1-3, except that the solution was changed to the THF solution containing the triisobutylaluminum hydrolyzate composition obtained in Reference Synthesis Example 1-1.
- alkylzinc partial hydrolyzate-containing solution and alkylaluminum partial hydrolyzate-containing solution of the present invention were prepared in a nitrogen gas atmosphere, and all solvents were used after dehydration and deaeration.
- the polypropylene nanocomposite containing zinc oxide and the polypropylene nanocomposite containing aluminum oxide of the present invention were subjected to IR measurement by a transmission method using an FT-IR spectroscope (“FT / IR-6100” manufactured by JASCO Corporation). .
- the polypropylene nanocomposite containing zinc oxide of the present invention was subjected to powder X-ray diffraction (hereinafter referred to as XRD) measurement with a powder X-ray diffractometer (“SmartLab” manufactured by Rigaku Corporation).
- XRD powder X-ray diffraction
- the polypropylene nanocomposite containing zinc oxide and the polypropylene nanocomposite containing aluminum oxide of the present invention were cut to about 100 nm by a microtome with a diamond knife and transmitted with a transmission electron microscope (“H-7100” manufactured by Hitachi, Ltd.). TEM measurement was performed.
- Example 2-1 Propylene was polymerized using a Ziegler-Natta catalyst (TiCl 4 / MgCl 2 / dibutyl phthalate type). The resulting propylene homopolymer had a density of 0.9 g / cm 3 and a weight average molecular weight of 2.6 ⁇ 10 5 .
- the impregnated propylene homopolymer powder was vacuum-dried for 6 hours to remove the solvent.
- Solvent-removed propylene homopolymer powder was melted and heated in a mixer at 180 ° C. and 100 rpm for 15 minutes to produce a polypropylene nanocomposite containing zinc oxide. Furthermore, using a sheet molding machine, the nanocomposite heated and melted at 230 ° C. for 6 minutes was pressed and quenched to form a sheet.
- the upper spectrum is the spectrum of Example 2-1 and the lower spectrum is the spectrum of the propylene homopolymer powder only. A diffraction peak of zinc oxide was confirmed.
- Example 2-2 A polypropylene nanocomposite containing zinc oxide was formed in the same manner as in Example 2-1, except that a water supply step of reacting with water vapor at 80 ° C. for 24 hours was introduced between the solvent drying removal step and the melt heating step, A sheet was formed in the same manner as in Example 2-1.
- Example 2-3 Polypropylene nanoparticle containing aluminum oxide in the same manner as in Example 2-1, except that the ethyl zinc partial hydrolyzate-containing toluene solution of Synthesis Example 2-1 was changed to the ethyl aluminum partial hydrolyzate-containing toluene solution of Synthesis Example 2-2. A composite was formed.
- Example 2-4 15.79 g of the toluene solution containing the ethyl zinc partial hydrolyzate of Synthesis Example 2-1 was converted into 15.79 g of the toluene solution containing the ethyl aluminum partial hydrolyzate of Synthesis Example 2-2 ([oxidation in the solution containing the alkyl zinc partial hydrolyzate].
- Zinc equivalent concentration (10 wt%) / 100 ⁇ [alkyl zinc partial hydrolyzate weight] [total nanocomposite amount (polypropylene weight (30 g) + converted zinc oxide weight (10 wt% of alkyl zinc partial hydrolyzate)) )] ⁇ [Zinc oxide concentration in nanocomposite (5 wt%)] / 100), a polypropylene nanocomposite containing aluminum oxide was formed in the same manner as in Example 2-2. It was made into a sheet like 1.
- the aluminum oxide of the first aspect of the present invention imparts heat dissipation, imparts heat resistance, imparts barrier properties against air and moisture, imparts antireflection effect, imparts antistatic effect, imparts anti-fogging effect, imparts wear resistance, and provides high thermal conductivity. It can be used for filler for resin, filler for adjusting resin such as refractive index, reflectance, workability and flexibility, sintering raw material of fine ceramic, and the like.
- the polyolefin-based nanocomposite according to the second aspect of the present invention can be used as a substitute for materials of current parts that require stability, abrasion resistance, refractive index increase, UV stability, conductivity, UV absorption, and antibacterial properties.
- Alternatives to materials for current parts that require adjustment of thermal conductivity, wear resistance, and refractive index can be used for applications and the like.
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Abstract
Description
関連出願の相互参照
本出願は、2016年5月16日出願の日本特願2016-98174号および2016年11月2日出願の日本特願2016-215555号の優先権を主張し、それらの全記載は、ここに特に開示として援用される。
酸化アルミニウムは、高強度、高耐熱性、高熱伝導度、低熱膨張率、絶縁性等において優れた特性を有することから、各種用途に幅広く使用されている。
ポリマー系ナノコンポジットとは、ポリマーに無機酸化物を通常1~100nmの超微粒子の形で分散させた複合材料である。従来の無機酸化物フィラー充填ポリマーに対し、無機酸化物添加量が少量である、無機酸化物の表面積が大幅に上昇する、等の特徴を有する。
[1]
トリアルキルアルミニウム又はそれらの混合物からなるアルキルアルミニウム化合物(但し、アルキル基は炭素数4~12であり、同一又は異なってもよい)及び非極性有機溶媒を含有する溶液に、前記アルキルアルミニウム化合物中のアルミニウムに対してモル比が0.5~1.4の範囲の水を添加してアルキルアルミニウム部分加水分解物含有溶液を得ることを含む、
アルキルアルミニウム部分加水分解物含有溶液からなる、粒子状又は薄膜状酸化アルミニウム形成用組成物の製造方法。
[2]
前記トリアルキルアルミニウムが下記一般式(1)で表されるアルキルアルミニウム化合物である、[1]に記載の製造方法。
[3]
前記トリアルキルアルミニウムがトリイソブチルアルミニウムである、[2]に記載の製造方法。
[4]
前記非極性有機溶媒が芳香族系炭化水素である、[1]~[3]のいずれか1項に記載の製造方法。
[5]
前記芳香族系炭化水素が、トルエン及び/又はキシレンである、[4]に記載の製造方法。
[6]
前記非極性有機溶媒が脂肪族炭化水素である、[1]~[3]いずれか1項に記載の製造方法。
[7]
前記脂肪族炭化水素が、ヘプタン、メチルシクロヘキサン、エチルシクロヘキサン、n-デカン、n-ウンデカン、n-ドデカン及びトリデカンから成る群から選ばれる少なくとも1種である、[6]に記載の製造方法。
[8]
アルキルアルミニウム部分加水分解物と非極性有機溶媒を含有する溶液からなる粒子状又は薄膜状酸化アルミニウム形成用組成物であって、
前記アルキルアルミニウム部分加水分解物のアルキル基は、同一又は異なってもよい炭素数4~12のアルキル基であり、アルミニウム原子に対するアルキル基のモル比が0.2~2の範囲であり、アルミニウム原子に対する酸素原子のモル比が1.4~0.5の範囲である、前記組成物。
[9]
前記アルキル基はイソブチル基、n-ヘキシル基およびn-オクチル基から成る群から選ばれる少なくとも1種である、[8]に記載の組成物。
[10]
前記非極性有機溶媒が芳香族系炭化水素である、[8]又は[9]に記載の組成物。
[11]
前記芳香族系炭化水素が、トルエン及び/又はキシレンである、[10]に記載の組成物。
[12]
前記非極性有機溶媒が脂肪族炭化水素である、[8]又は[9]に記載の組成物。
[13]
前記脂肪族炭化水素が、ヘプタン、メチルシクロヘキサン、エチルシクロヘキサン、n-デカン、n-ウンデカン、n-ドデカンおよびトリデカンから成る群から選ばれる少なくとも1種である、[12]に記載の組成物。
[14]
[8]~[13]のいずれか1項に記載の組成物を基板に塗布し、次いで非極性有機溶媒を除去して、酸化アルミニウム薄膜を形成することを含む、酸化アルミニウム薄膜の製造方法。
[15]
[8]~[13]のいずれか1項に記載の組成物を基材形成用バインダーと混合し、次いで非極性有機溶媒を除去して、前記バインダー中で粒子状酸化アルミニウムを形成することを含む、粒子状酸化アルミニウムを含有する基材の製造方法。
[16]
ジアルキル亜鉛(但し、アルキル基は炭素数1~14であり、同一又は異なってもよい)の部分加水分解物含有溶液及びポリオレフィン粉末を用いることを特徴とする、
酸化亜鉛粒子を含有するポリオレフィン系ポリマーナノコンポジットの製造方法。
[17]
(A)ジアルキル亜鉛(但し、アルキル基は炭素数1~12であり、同一又は異なってもよい)の部分加水分解物含有溶液を、ポリオレフィン粉末に含浸させる工程、
(B)ポリオレフィン粉末に含有された有機溶媒を除去する工程、及び
(D)ポリオレフィン粉末を溶融加熱して酸化亜鉛粒子を含有するポリオレフィン系ポリマーナノコンポジットを得る工程、
を含む、[16]に記載の製造方法。
[18]
前記工程(B)、(D)の間に、
(C)ポリオレフィン粉末に含有された上記アルキル亜鉛部分加水分解物に水分を供給して前記部分加水分解物の加水分解を促進させる工程、
を含む、[17]に記載の製造方法。
[19]
前記部分加水分解物含有溶液は、ジアルキル亜鉛及び有機溶媒を含有する溶液に、前記ジアルキル亜鉛中の亜鉛に対してモル比が0.5~1.4の範囲の水を添加して調製される、[16]~[18]のいずれか1項に記載の製造方法。
[20]
前記ジアルキル亜鉛中の亜鉛に対する水のモル比が0.5~0.9の範囲である、[16]~[19]のいずれか1項に記載の製造方法。
[21]
前記ジアルキル亜鉛が下記一般式(2-1)で表される、[16]~[20]のいずれか1項に記載の製造方法。
[22]
前記ジアルキル亜鉛がジエチル亜鉛である、[16]~[21]のいずれか1項に記載の製造方法。
[23]
前記ポリオレフィン粉末がポリエチレン粉末、または、ポリプロピレン粉末である、[16]~[22]のいずれか1項に記載の製造方法。
[24]
前記ポリオレフィン粉末が、チーグラー・ナッタ触媒を用いて調製したポリオレフィン粉末である、[16]~[23]のいずれか1項に記載の製造方法。
[25]
ポリオレフィン基材及び酸化亜鉛粒子を含有し、分散剤を含有せず、前記酸化亜鉛粒子は平均粒子径が100nm未満であるポリオレフィン系ポリマーナノコンポジット。
[26]
前記酸化亜鉛粒子の含有量が3重量%以上である、[25]に記載のナノコンポジット。
[27]
前記酸化亜鉛粒子は、前記ポリオレフィン基材中に分散している、[25]又は[26]に記載のナノコンポジット。
[28]
トリアルキルアルミニウム又はそれらの混合物からなるアルキルアルミニウム化合物部分加水分解物含有溶液及びポリオレフィン粉末を用いることを特徴とする、酸化アルミニウム粒子を含有するポリオレフィン系ポリマーナノコンポジットの製造方法。
[29]
(E)トリアルキルアルミニウム又はそれらの混合物からなるアルキルアルミニウム化合物(但し、アルキル基は炭素数1~12であり、同一又は異なってもよい)の部分加水分解物含有溶液を、ポリオレフィン粉末に含浸させる工程、
(F)ポリオレフィン粉末に含有された有機溶媒を乾燥除去する工程、及び
(H)ポリオレフィン粉末を溶融加熱して酸化アルミニウム粒子を含有するポリオレフィン系ポリマーナノコンポジットを得る工程、
を含む、[28]に記載の製造方法。
[30]
前記工程(F)、(H)の間に、
(G)ポリオレフィン粉末に含有された上記アルキルアルミニウム部分加水分解物に水分を供給して前記部分加水分解物の加水分解を促進させる工程、
を含む、[29]に記載の製造方法。
[31]
前記部分加水分解物含有溶液は、トリアルキルアルミニウム又はそれらの混合物からなるアルキルアルミニウム化合物及び有機溶媒を含有する溶液に、前記アルキルアルミニウム化合物中のアルミニウムに対してモル比が0.5~1.4の範囲の水を添加して調製される、[28]~[30]のいずれか1項に記載の製造方法。
[32]
前記トリアルキルアルミニウムが下記一般式(2-2)で表されるアルキルアルミニウム化合物である、[28]~[31]のいずれか1項に記載の製造方法。
[33]
前記トリアルキルアルミニウムがトリエチルアルミニウムである、[28]~[32]のいずれか1項に記載の製造方法。
[34]
前記トリアルキルアルミニウムがトリイソブチルアルミニウムである、[28]~[33]のいずれか1項に記載の製造方法。
[35]
前記ポリオレフィン粉末がポリエチレン粉末、または、ポリプロピレン粉末である、[28]~[34]のいずれか1項に記載の製造方法。
[36]
前記ポリオレフィン粉末が、チーグラー・ナッタ触媒を用いて調製したポリオレフィン粉末である、[28]~[35]のいずれか1項に記載の製造方法。
[37]
ポリオレフィン基材及び酸化アルミニウム粒子を含有し、分散剤を含有せず、前記酸化アルミニウム粒子は平均粒子径が100nm未満であるポリオレフィン系ポリマーナノコンポジット。
[38]
酸化アルミニウム粒子の含有量が3重量%以上である、[37]に記載のナノコンポジット。
[39]
酸化アルミニウム粒子は、ポリオレフィン基材中に分散している、[37]又は[38]に記載のナノコンポジット。
[40]
水酸化アルミニウム粒子をさらに含有する[37]~[39]のいずれかに記載のナノコンポジット。
本発明は、トリアルキルアルミニウム又はそれらの混合物からなるアルキルアルミニウム化合物(但し、アルキル基は炭素数4~12であり、同一又は異なってもよい)の部分加水分解物及び非極性有機溶媒を含有する溶液に、前記アルキルアルミニウム化合物中のアルミニウムに対してモル比が0.5~1.4の範囲の水を添加してアルキルアルミニウム部分加水分解物含有溶液を得ることを含む、
アルキルアルミニウム部分加水分解物含有溶液からなる、粒子状又は薄膜状酸化アルミニウム形成用組成物の製造方法に関する。
本発明は、酸化アルミニウム形成用組成物に関し、この組成物は、アルキルアルミニウム部分加水分解物と非極性有機溶媒を含有する溶液からなる粒子状又は薄膜状酸化アルミニウム形成用組成物であり、前記アルキルアルミニウム部分加水分解物のアルキル基は、同一又は異なってもよい炭素数4~12のアルキル基であり、アルミニウム原子に対するアルキル基のモル比が0.2~2の範囲であり、アルミニウム原子に対する酸素原子のモル比が1.4~0.5の範囲である。アルキル基は、好ましくは炭素数4~8であり、より好ましくはイソブチル基、n-ヘキシル基またはn-オクチル基である。
本発明の酸化アルミニウム薄膜の製造方法は、前記本発明のアルキルアルミニウム部分加水分解物含有溶液を基材に塗布して酸化アルミニウム薄膜を得る方法である。
本発明の粒子状酸化アルミニウム含有基材の製造方法は、前記本発明のアルキルアルミニウム部分加水分解物含有溶液を基材製造時に基材原料に混合して、基材中に粒子状酸化アルミニウムを含有する基材を得る方法である。
本発明の第二の側面の第一の態様は、ジアルキル亜鉛(但し、アルキル基は炭素数1~14であり、同一又は異なってもよい)の部分加水分解物含有溶液及びポリオレフィン粉末を用いることを特徴とする、酸化亜鉛粒子を含有するポリオレフィン系ポリマーナノコンポジットの製造方法に関する。
(A)ジアルキル亜鉛(但し、アルキル基は炭素数1~12であり、同一又は異なってもよい)の亜鉛部分加水分解物含有溶液を、ポリオレフィン粉末に含浸させる工程、
(B)ポリオレフィン粉末に含有された有機溶媒を除去する工程、
(D)ポリオレフィン粉末を溶融加熱する工程、
を含む。
前記ジアルキル亜鉛は、下記一般式(2-1)で表されるジアルキル亜鉛であることが好ましい。
工程(B)では、部分加水分解物含有溶液に含まれていた有機溶媒をポリオレフィン粉末から除去する。前記有機溶媒の除去は、工程(A)で得られたポリオレフィン粉末から有機溶媒を除去できる方法であれば特に限定はない。例えば、工程(A)で得られたポリオレフィン粉末を所定の温度で乾燥することで実施できる。例えば、20~100℃の間で任意の温度を選択でき、乾燥は常圧または減圧下で実施できる。溶媒を除去する前にポリオレフィンが溶融することを防止する観点から100℃以下であること及び減圧下であることが好ましい。前記溶媒を、例えば、0.5分~50時間かけて乾燥させることができる。但し、これらの範囲に限定される意図ではない。
有機溶媒の除去する工程を実施した後、各種ミキサー、押出機を用いてポリオレフィンの溶融温度以上の温度で含浸、乾燥除去されたポリオレフィン粉末を溶融混練する。溶融混練温度は、ポリオレフィンの種類により、その融点を考慮して適宜決定できる。例えば、ポリエチレンの場合120~150℃、ポリプロピレンの場合160~200℃が熱劣化を最小限に留めるという観点から好ましい。溶融混練は、例えば、1分~50時間かけて行うことができる。但し、これらの範囲に限定される意図ではない。
(B)有機溶媒除去工程と(D)溶融加熱工程の間に、(C)ポリオレフィン粉末に含有された上記アルキル亜鉛部分加水分解物に水分を供給して分解を促進させる工程、を含有させることができる。
本発明は、ポリオレフィン基材及び酸化亜鉛粒子を含有し、分散剤を含有せず、前記酸化亜鉛粒子は平均粒子径が100nm未満であるポリオレフィン系ポリマーナノコンポジットを包含する。このポリオレフィン系ポリマーナノコンポジットは、上記本発明の製造方法により製造ことができる。ポリオレフィン中の酸化亜鉛粒子の平均粒子径は、好ましくは、1nm以上~100nm未満の範囲である。本発明のポリオレフィン系ポリマーナノコンポジットは、酸化物粒子が分散しにくいポリオレフィン系ポリマーを基材とするにもかかわらず、かつ酸化亜鉛粒子の平均粒子径が100nm未満と微細であるにもかかわらず、分散剤を含有することなく(分散剤を酸化亜鉛粒子の分散助剤として用いることなく)、酸化亜鉛粒子が基材中に良好に分散したナノコンポジットである。
本発明の第二の側面の第二の態様は、トリアルキルアルミニウム又はそれらの混合物からなるアルキルアルミニウム化合物(但し、アルキル基は炭素数1~12であり、同一又は異なってもよい)の部分加水分解物含有溶液及びポリオレフィン粉末を用いることを特徴とする、酸化アルミニウム粒子を含有するポリオレフィン系ポリマーナノコンポジットの製造方法に関する。
(E)トリアルキルアルミニウム又はそれらの混合物からなるアルキルアルミニウム化合物(但し、アルキル基は炭素数1~12であり、同一又は異なってもよい)の部分加水分解物含有溶液を、ポリオレフィン粉末に含浸させる工程、
(F)ポリオレフィン粉末に含有された有機溶媒を除去する工程、及び
(H)ポリオレフィン粉末を溶融加熱する工程、
を含む。
前記トリアルキルアルミニウムは、下記一般式(2-2)で表されるトリアルキルアルミニウムであることが好ましい。
工程(F)では、部分加水分解物含有溶液に含まれていた有機溶媒をポリオレフィン粉末から除去する。前記有機溶媒の除去は、工程(E)で得られたポリオレフィン粉末から有機溶媒を除去できる方法であれば特に限定はない。例えば、工程(E)で得られたポリオレフィン粉末を所定の温度で乾燥することで実施できる。前記有機溶媒を除去させるための所定の温度は、例えば、20~100℃の間で任意の温度を選択でき、乾燥は常圧または減圧下で実施できる。溶媒を除去する前にポリオレフィンが溶融することを防止する観点から100℃以下であること及び減圧であることが好ましい。前記溶媒を、例えば、0.5分~50時間かけて乾燥させることができる。但し、これらの範囲に限定される意図ではない。
有機溶媒の除去工程を実施した後、各種ミキサー、押出機を用いてポリオレフィンの溶融温度以上の温度で含浸、乾燥除去されたポリオレフィン粉末を溶融混練する。溶融混練温度は、ポリエチレンの場合120~150℃、ポリプロピレンの場合160~200℃が熱劣化を最小限に留めるという観点から好ましい。溶融混練は、例えば、1分~50時間かけて行うことができる。但し、これらの範囲に限定される意図ではない。
(F)有機溶媒除去工程と(H)溶融加熱工程の間に、(G)ポリオレフィン粉末に含有された上記アルキルアルミニウム部分加水分解物に水分を供給して分解を促進させる工程、を含有させることができる。
本発明は、ポリオレフィン基材及び酸化アルミニウム粒子を含有し、分散剤を含有せず、前記酸化アルミニウム粒子は平均粒子径が100nm未満であるポリオレフィン系ポリマーナノコンポジット。
本発明のアルキルアルミニウム化合物含有溶液およびアルキルアルミニウム部分加水分解物含有溶液の調製は、窒素ガス雰囲気下で行い、溶媒は全て脱水および脱気して使用した。
トリアルキルアルミニウムのモル数は以下の式より算出した。
[トリアルキルアルミニウムのモル数]
=[導入したトリアルキルアルミニウムの質量(g)]/[トリアルキルアルミニウムの分子量(トリイソブチルアルミニウムの場合198.33)]
本発明のアルキルアルミニウム部分加水分解物含有溶液は、溶媒をエバポレーターにより乾燥させたものを、FT-IR分光装置(日本分光社製「FT/IR-4100」)にて透過法によりIR測定を実施した。
トルエン10.00gに、トリイソブチルアルミニウム(東ソー・ファインケム社製)12.90gを20℃で加え、十分撹拌した。その後、20℃で水1.289g([水]/[トリイソブチルアルミニウム]=1.1(モル比))を30分間かけてシリンジで滴下して加えた。25℃で3時間攪拌を続けることにより熟成反応を行った後、少量の析出固体をデカント除去してトリイソブチルアルミニウム加水分解組成物含有トルエン溶液を得た。
トルエン10.00gに、トリイソブチルアルミニウム21.61gを20℃で加え、十分撹拌した。その後、20℃で水2.159g([水]/[トリイソブチルアルミニウム]=1.1(モル比))を30分間かけてシリンジで滴下して加えた。さらに、25℃で3時間攪拌を続けることにより熟成反応を行った後、少量の析出固体をデカント除去してトリイソブチルアルミニウム加水分解組成物含有トルエン溶液を得た。
トルエン1.990gに、トリ‐n-ヘキシルアルミニウム(東ソー・ファインケム社製)15.00gを20℃で加え、十分撹拌した。その後、20℃で水1.052g([水]/[トリ‐n-ヘキシルアルミニウム]=1.2(モル比))を30分間かけてシリンジで滴下して加えた。さらに、25℃で3時間攪拌を続けることにより熟成反応を行った後、少量の析出固体をデカント除去してトリ‐n-ヘキシルアルミニウム加水分解組成物含有トルエン溶液を得た。
トルエン4.890gに、トリ‐n-オクチルアルミニウム(東ソー・ファインケム社製)15.01gを20℃で加え、十分撹拌した。その後、20℃で水0.958g([水]/[トリ‐n-オクチルアルミニウム]=1.3(モル比))を30分間かけてシリンジで滴下して加えた。さらに、25℃で3時間攪拌を続けることにより熟成反応を行った後、少量の析出固体をデカント除去してトリ‐n-オクチルアルミニウム加水分解組成物含有トルエン溶液を得た。
デカン10.70gに、トリイソブチルアルミニウム12.18gを20℃で加え、十分撹拌した。その後、20℃で水1.326g([水]/[トリイソブチルアルミニウム]=1.2(モル比))を30分間かけてシリンジで滴下して加えた。さらに、25℃で3時間攪拌を続けることにより熟成反応を行った後、少量の析出固体をデカント除去してトリイソブチルアルミニウム加水分解組成物含有デカン溶液を得た。
デカン4.890gに、トリ‐n-オクチルアルミニウム15.00gを20℃で加え、十分撹拌した。その後、20℃で水0.958g([水]/[トリ‐n-オクチルアルミニウム]=1.3(モル比))を30分間かけてシリンジで滴下して加えた。さらに、25℃で3時間攪拌を続けることにより熟成反応を行った後、少量の析出固体をデカント除去してトリ‐n-オクチルアルミニウム加水分解組成物含有デカン溶液を得た。
デトラヒドロフラン(以下THF)10.00gに、トリイソブチルアルミニウム12.09gを20℃で加え、十分撹拌した。その後、20℃で水1.208g([水]/[トリイソブチルアルミニウム]=1.1(モル比))を30分間かけてシリンジで滴下して加えた。さらに、25℃で3時間攪拌を続けることにより熟成反応を行い、トリイソブチルアルミニウム加水分解組成物含有THF溶液を得た。
[参考合成例1-2]
トルエン17.41gに、トリエチルアルミニウム10.90gを20℃で加え、十分撹拌した。その後、20℃で水1.891g([水]/[トリイソブチルアルミニウム]=1.1(モル比))を30分間かけてシリンジで滴下して加えた。しかし、滴下時に副生エタンガスの異常発生、白色塊の形成が起こり、スケールを大きくした場合製造困難になることが容易に想像された。さらに、25℃で3時間攪拌を続けることにより熟成反応を行った後、多量の析出固体をデカント除去してトリイソブチルアルミニウム加水分解組成物含有トルエン溶液を得た。水の活性水素2つが全てトリエチルアルミニウムと反応し、エタンを生成し、エタンガスはガスとして全て溶液より除去されると仮定した場合の、重量収率は62%であり、その他の合成例に比べて大きく低下した。
合成例1-1で得られたトリイソブチルアルミニウム加水分解組成物含有トルエン溶液を、25℃、相対湿度約40%の空気雰囲気下、15mm角のガラス基板(コーニング社製、EagleXG)上に100μl滴下し、スピンコーターにより4000rpm、20秒間スピンして塗布した後、80℃で3分加熱することで薄膜を形成させた。
200℃で3分加熱する以外は実施例1-1と同様に薄膜を形成させた。
基板を、20mm角のアクリル基板(三菱レイヨン社製、アクリライトEX)、溶液を150μl滴下にした以外は実施例1-1と同様に薄膜を形成させた。
合成例1-4で得られたトリ‐n-オクチルアルミニウム加水分解組成物含有トルエン溶液を、25℃、相対湿度約40%の空気雰囲気下、15mm角のガラス基板(コーニング社製、EagleXG)上に150μl滴下し、スピンコーターにより4000rpm、20秒間スピンして塗布した後、80℃で3分加熱することで薄膜を形成させた。
基板を、20mm角のアクリル樹脂基板(三菱レイヨン社製、アクリライトEX)、溶液を180μl滴下した以外は実施例1-4と同様に薄膜を形成させた。
合成例1-5で得られたトリイソブチルアルミニウム加水分解組成物含有デカン溶液を、25℃、相対湿度約40%の空気雰囲気下、20mm角のアクリル樹脂基板(三菱レイヨン社製、アクリライトEX)上に180μl滴下し、スピンコーターにより4000rpm、20秒間スピンして塗布し後、80℃で3分加熱することで薄膜を形成させた。
溶液を、参考合成例1-1で得られたトリイソブチルアルミニウム加水分解組成物含有THF溶液にした以外は実施例1-3と同様に薄膜を形成させた。
本発明のアルキル亜鉛部分加水分解物含有溶液、アルキルアルミニウム部分加水分解物含有溶液の調製は、窒素ガス雰囲気下で行い、溶媒は全て脱水および脱気して使用した。
トリアルキルアルミニウムのモル数は以下の式より算出した。
[トリアルキルアルミニウムのモル数]
=[導入したトリアルキルアルミニウムの質量(g)]/[トリアルキルアルミニウムの分子量(トリエチルアルミニウムの場合114.17)]
本発明の酸化亜鉛を含有するポリプロピレンナノコンポジット、酸化アルミニウムを含有するポリプロピレンナノコンポジットは、FT-IR分光装置(日本分光社製「FT/IR-6100」)にて透過法によりIR測定を実施した。
トルエン45.0gに、ジエチル亜鉛(東ソー・ファインケム社製)8.98gを20℃で加え、十分撹拌した。その後、-15℃まで冷却し、-15℃で水を10重量%含有するテトラヒドロフラン(以後THF)溶液を7.857g([水]/[ジエチル亜鉛]=0.6(モル比))を60分間かけてシリンジで滴下して加えた。25℃まで昇温した後、25℃で3時間攪拌を続けることにより熟成反応を行った後、少量の析出固体をデカント除去してエチル亜鉛部分加水分解物含有トルエン溶液を得た。
トルエン45.00gに、トリエチルアルミニウム21.61gを20℃で加え、十分撹拌した。その後、-15℃まで冷却し、-15℃で水を10重量%含有するTHF溶液を11.09g([水]/[トリエチルアルミニウム]=1.0(モル比))を60分間かけてシリンジで滴下して加えた。25℃まで昇温した後、25℃で3時間攪拌を続けることにより熟成反応を行った後、少量の析出固体をデカント除去してエチルアルミニウム部分加水分解物含有トルエン溶液を得た。
チーグラー―ナッタ触媒(TiCl4/MgCl2/フタル酸ジブチル型)を用いてプロピレンを重合した。得られたプロピレン単独重合体の密度は0.9g/cm3、重量平均分子量は2.6×105であった。
溶媒乾燥除去工程と溶融加熱工程の間に水蒸気と80℃、24時間反応させる水分供給工程を導入した以外は実施例2-1と同様に酸化亜鉛を含有したポリプロピレンナノコンポジットを形成させ、さらに、実施例2-1と同様にシート状にした。
合成例2-1のエチル亜鉛部分加水分解物含有トルエン溶液を、合成例2-2のエチルアルミニウム部分加水分解物含有トルエン溶液にした以外実施例2-1と同様に酸化アルミニウムを含有するポリプロピレンナノコンポジットを形成させた。
合成例2-1のエチル亜鉛部分加水分解物含有トルエン溶液15.79gを、合成例2-2のエチルアルミニウム部分加水分解物含有トルエン溶液15.79g([アルキル亜鉛部分加水分解物含有溶液における酸化亜鉛換算濃度(10wt%)]/100×[アルキル亜鉛部分加水分解物重量]=[ナノコンポジット総量(ポリプロピレン重量(30g)+変換された酸化亜鉛重量(アルキル亜鉛部分加水分解物重量の10wt%))]×[ナノコンポジットにおける酸化亜鉛濃度(5wt%)]/100より算出)にした以外は実施例2-2と同様に酸化アルミニウムを含有するポリプロピレンナノコンポジットを形成させ、さらに、実施例2-1と同様にシート状にした。
Claims (40)
- トリアルキルアルミニウム又はそれらの混合物からなるアルキルアルミニウム化合物(但し、アルキル基は炭素数4~12であり、同一又は異なってもよい)及び非極性有機溶媒を含有する溶液に、前記アルキルアルミニウム化合物中のアルミニウムに対してモル比が0.5~1.4の範囲の水を添加してアルキルアルミニウム部分加水分解物含有溶液を得ることを含む、
アルキルアルミニウム部分加水分解物含有溶液からなる、粒子状又は薄膜状酸化アルミニウム形成用組成物の製造方法。 - 前記トリアルキルアルミニウムがトリイソブチルアルミニウムである、請求項2に記載の製造方法。
- 前記非極性有機溶媒が芳香族系炭化水素である、請求項1~3のいずれか1項に記載の製造方法。
- 前記芳香族系炭化水素が、トルエン及び/又はキシレンである、請求項4に記載の製造方法。
- 前記非極性有機溶媒が脂肪族炭化水素である、請求項1~3いずれか1項に記載の製造方法。
- 前記脂肪族炭化水素が、ヘプタン、メチルシクロヘキサン、エチルシクロヘキサン、n-デカン、n-ウンデカン、n-ドデカン及びトリデカンから成る群から選ばれる少なくとも1種である、請求項6に記載の製造方法。
- アルキルアルミニウム部分加水分解物と非極性有機溶媒を含有する溶液からなる粒子状又は薄膜状酸化アルミニウム形成用組成物であって、
前記アルキルアルミニウム部分加水分解物のアルキル基は、同一又は異なってもよい炭素数4~12のアルキル基であり、アルミニウム原子に対するアルキル基のモル比が0.2~2の範囲であり、アルミニウム原子に対する酸素原子のモル比が1.4~0.5の範囲である、前記組成物。 - 前記アルキル基はイソブチル基、n-ヘキシル基およびn-オクチル基から成る群から選ばれる少なくとも1種である、請求項8に記載の組成物。
- 前記非極性有機溶媒が芳香族系炭化水素である、請求項8又は9に記載の組成物。
- 前記芳香族系炭化水素が、トルエン及び/又はキシレンである、請求項10に記載の組成物。
- 前記非極性有機溶媒が脂肪族炭化水素である、請求項8又は9に記載の組成物。
- 前記脂肪族炭化水素が、ヘプタン、メチルシクロヘキサン、エチルシクロヘキサン、n-デカン、n-ウンデカン、n-ドデカンおよびトリデカンから成る群から選ばれる少なくとも1種である、請求項12に記載の組成物。
- 請求項8~13のいずれか1項に記載の組成物を基板に塗布し、次いで非極性有機溶媒を除去して、酸化アルミニウム薄膜を形成することを含む、酸化アルミニウム薄膜の製造方法。
- 請求項8~13のいずれか1項に記載の組成物を基材形成用バインダーと混合し、次いで非極性有機溶媒を除去して、前記バインダー中で粒子状酸化アルミニウムを形成することを含む、粒子状酸化アルミニウムを含有する基材の製造方法。
- ジアルキル亜鉛(但し、アルキル基は炭素数1~14であり、同一又は異なってもよい)の部分加水分解物含有溶液及びポリオレフィン粉末を用いることを特徴とする、
酸化亜鉛粒子を含有するポリオレフィン系ポリマーナノコンポジットの製造方法。 - (A)ジアルキル亜鉛(但し、アルキル基は炭素数1~12であり、同一又は異なってもよい)の部分加水分解物含有溶液を、ポリオレフィン粉末に含浸させる工程、
(B)ポリオレフィン粉末に含有された有機溶媒を除去する工程、及び
(D)ポリオレフィン粉末を溶融加熱して酸化亜鉛粒子を含有するポリオレフィン系ポリマーナノコンポジットを得る工程、
を含む、請求項16に記載の製造方法。 - 前記工程(B)、(D)の間に、
(C)ポリオレフィン粉末に含有された上記アルキル亜鉛部分加水分解物に水分を供給して前記部分加水分解物の加水分解を促進させる工程、
を含む、請求項17に記載の製造方法。 - 前記部分加水分解物含有溶液は、ジアルキル亜鉛及び有機溶媒を含有する溶液に、前記ジアルキル亜鉛中の亜鉛に対してモル比が0.5~1.4の範囲の水を添加して調製される、請求項16~18のいずれか1項に記載の製造方法。
- 前記ジアルキル亜鉛中の亜鉛に対する水のモル比が0.5~0.9の範囲である、請求項16~19のいずれか1項に記載の製造方法。
- 前記ジアルキル亜鉛がジエチル亜鉛である、請求項16~21のいずれか1項に記載の製造方法。
- 前記ポリオレフィン粉末がポリエチレン粉末、または、ポリプロピレン粉末である、請求項16~22のいずれか1項に記載の製造方法。
- 前記ポリオレフィン粉末が、チーグラー・ナッタ触媒を用いて調製したポリオレフィン粉末である、請求項16~23のいずれか1項に記載の製造方法。
- ポリオレフィン基材及び酸化亜鉛粒子を含有し、分散剤を含有せず、前記酸化亜鉛粒子は平均粒子径が100nm未満であるポリオレフィン系ポリマーナノコンポジット。
- 前記酸化亜鉛粒子の含有量が3重量%以上である、請求項25に記載のナノコンポジット。
- 前記酸化亜鉛粒子は、前記ポリオレフィン基材中に分散している、請求項25又は26に記載のナノコンポジット。
- トリアルキルアルミニウム又はそれらの混合物からなるアルキルアルミニウム化合物部分加水分解物含有溶液及びポリオレフィン粉末を用いることを特徴とする、酸化アルミニウム粒子を含有するポリオレフィン系ポリマーナノコンポジットの製造方法。
- (E)トリアルキルアルミニウム又はそれらの混合物からなるアルキルアルミニウム化合物(但し、アルキル基は炭素数1~12であり、同一又は異なってもよい)の部分加水分解物含有溶液を、ポリオレフィン粉末に含浸させる工程、
(F)ポリオレフィン粉末に含有された有機溶媒を乾燥除去する工程、及び
(H)ポリオレフィン粉末を溶融加熱して酸化アルミニウム粒子を含有するポリオレフィン系ポリマーナノコンポジットを得る工程、
を含む、請求項28に記載の製造方法。 - 前記工程(F)、(H)の間に、
(G)ポリオレフィン粉末に含有された上記アルキルアルミニウム部分加水分解物に水分を供給して前記部分加水分解物の加水分解を促進させる工程、
を含む、請求項29に記載の製造方法。 - 前記部分加水分解物含有溶液は、トリアルキルアルミニウム又はそれらの混合物からなるアルキルアルミニウム化合物及び有機溶媒を含有する溶液に、前記アルキルアルミニウム化合物中のアルミニウムに対してモル比が0.5~1.4の範囲の水を添加して調製される、請求項28~30のいずれか1項に記載の製造方法。
- 前記トリアルキルアルミニウムがトリエチルアルミニウムである、請求項28~32のいずれか1項に記載の製造方法。
- 前記トリアルキルアルミニウムがトリイソブチルアルミニウムである、請求項28~33のいずれか1項に記載の製造方法。
- 前記ポリオレフィン粉末がポリエチレン粉末、または、ポリプロピレン粉末である、請求項28~34のいずれか1項に記載の製造方法。
- 前記ポリオレフィン粉末が、チーグラー・ナッタ触媒を用いて調製したポリオレフィン粉末である、請求項28~35のいずれか1項に記載の製造方法。
- ポリオレフィン基材及び酸化アルミニウム粒子を含有し、分散剤を含有せず、前記酸化アルミニウム粒子は平均粒子径が100nm未満であるポリオレフィン系ポリマーナノコンポジット。
- 酸化アルミニウム粒子の含有量が3重量%以上である、請求項37に記載のナノコンポジット。
- 酸化アルミニウム粒子は、ポリオレフィン基材中に分散している、請求項37又は38に記載のナノコンポジット。
- 水酸化アルミニウム粒子をさらに含有する請求項37~40のいずれかに記載のナノコンポジット。
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JPWO2017199870A1 (ja) | 2019-03-22 |
TWI737730B (zh) | 2021-09-01 |
US11795277B2 (en) | 2023-10-24 |
JP2021155741A (ja) | 2021-10-07 |
JP6944443B2 (ja) | 2021-10-06 |
KR20190008266A (ko) | 2019-01-23 |
US20220145042A1 (en) | 2022-05-12 |
CN109153580A (zh) | 2019-01-04 |
CN109153580B (zh) | 2022-03-22 |
US11267940B2 (en) | 2022-03-08 |
TW201806868A (zh) | 2018-03-01 |
US20220144657A1 (en) | 2022-05-12 |
US11820871B2 (en) | 2023-11-21 |
JP7162402B2 (ja) | 2022-10-28 |
US20190276612A1 (en) | 2019-09-12 |
KR102324241B1 (ko) | 2021-11-09 |
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