JP2015140420A - Spherocrystal growth rate retardant for polyethylene - Google Patents
Spherocrystal growth rate retardant for polyethylene Download PDFInfo
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- JP2015140420A JP2015140420A JP2014015568A JP2014015568A JP2015140420A JP 2015140420 A JP2015140420 A JP 2015140420A JP 2014015568 A JP2014015568 A JP 2014015568A JP 2014015568 A JP2014015568 A JP 2014015568A JP 2015140420 A JP2015140420 A JP 2015140420A
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- polyethylene
- molecular weight
- growth rate
- spherulite
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- 229920000573 polyethylene Polymers 0.000 title claims abstract description 121
- -1 polyethylene Polymers 0.000 title claims abstract description 98
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 91
- 238000005259 measurement Methods 0.000 claims abstract description 14
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 239000003112 inhibitor Substances 0.000 claims description 35
- 238000005194 fractionation Methods 0.000 claims description 26
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 5
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 18
- 238000002156 mixing Methods 0.000 abstract description 8
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- 238000000926 separation method Methods 0.000 abstract 2
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- 238000000465 moulding Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
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- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
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- QEIQEORTEYHSJH-UHFFFAOYSA-N Armin Natural products C1=CC(=O)OC2=C(O)C(OCC(CCO)C)=CC=C21 QEIQEORTEYHSJH-UHFFFAOYSA-N 0.000 description 2
- PXTQVTSYGRRBPC-UHFFFAOYSA-L CC1=C2C=CC(C2=C(C)C=C1)[Zr](Cl)(Cl)(C1C=CC=C1)=[Si](C)C Chemical compound CC1=C2C=CC(C2=C(C)C=C1)[Zr](Cl)(Cl)(C1C=CC=C1)=[Si](C)C PXTQVTSYGRRBPC-UHFFFAOYSA-L 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- XRSFQLOANYRGRT-UHFFFAOYSA-N n,n-dimethyldocosan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCCCCC[NH+](C)C XRSFQLOANYRGRT-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 229910052726 zirconium Inorganic materials 0.000 description 2
- KZWFMOHCIQNTCU-AUYXYSRISA-N (z)-n-methyl-n-[(z)-octadec-9-enyl]octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(C)CCCCCCCC\C=C/CCCCCCCC KZWFMOHCIQNTCU-AUYXYSRISA-N 0.000 description 1
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- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
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- IYVBNEJDHFJJEM-UHFFFAOYSA-N 22-methyltricosan-1-amine Chemical compound CC(C)CCCCCCCCCCCCCCCCCCCCCN IYVBNEJDHFJJEM-UHFFFAOYSA-N 0.000 description 1
- 101000573147 Arabidopsis thaliana Pectinesterase 6 Proteins 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- YWZRYRRNCJPOEE-UHFFFAOYSA-N N-ethyl-N-methyldocosan-1-amine hydrochloride Chemical compound [Cl-].C[NH+](CCCCCCCCCCCCCCCCCCCCCC)CC YWZRYRRNCJPOEE-UHFFFAOYSA-N 0.000 description 1
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- JQALJEWGZIIUNK-UHFFFAOYSA-L [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1C2=CC(=CC=C2C=2C=CC(=CC1=2)C(C)(C)C)C(C)(C)C)C1C=CC=C1 Chemical compound [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1C2=CC(=CC=C2C=2C=CC(=CC1=2)C(C)(C)C)C(C)(C)C)C1C=CC=C1 JQALJEWGZIIUNK-UHFFFAOYSA-L 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical group [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- QRUYYSPCOGSZGQ-UHFFFAOYSA-L cyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 QRUYYSPCOGSZGQ-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- ICZKASVWFUJTEI-UHFFFAOYSA-N n,n-dimethyldocosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCN(C)C ICZKASVWFUJTEI-UHFFFAOYSA-N 0.000 description 1
- YBQSEDBKAFGAPG-UHFFFAOYSA-N n,n-dimethylhexacosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCN(C)C YBQSEDBKAFGAPG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ポリエチレンの球晶成長速度を抑制する効率に優れるポリチレン用球晶成長速度抑制剤に関するものであり、特にポリエチレンに配合することにより、ポリエチレンの球晶成長速度を遅くし、球晶サイズの小さいポリエチレンとすることにより、高いバリヤー性、透明性を付与することが可能となるポリエチレン用球晶成長速度抑制剤に関するものである。 The present invention relates to a spherulite growth rate inhibitor for polyethylene which is excellent in efficiency for suppressing the spherulite growth rate of polyethylene, and in particular, by blending with polyethylene, the spherulite growth rate of polyethylene is reduced, and the spherulite size is reduced. The present invention relates to a spherulite growth rate inhibitor for polyethylene that can impart high barrier properties and transparency by using a small polyethylene.
ポリエチレン、ポリプロピレン等に代表されるポリオレフィンは、各種包装用材料、構造用材料等として用いられており、一部の用途においては、見た目、内容物の視認性等の観点から透明性に優れることが求められており、その透明性を改良する方法として、各種の透明化剤が提案されている（例えば特許文献１〜３参照。）。 Polyolefins typified by polyethylene, polypropylene, etc. are used as various packaging materials, structural materials, etc., and in some applications, they may be excellent in transparency from the viewpoint of appearance, content visibility, etc. As a method for improving the transparency, various clarifying agents have been proposed (see, for example, Patent Documents 1 to 3).
しかし、特許文献１〜３に記載された透明化剤は、ポリオレフィンとは異なる異種の材よりなるものであり、ポリオレフィンとの混合性、透明性等にまだまだ課題を有するものであった。 However, the clarifying agents described in Patent Documents 1 to 3 are made of different materials different from polyolefin, and still have problems in the mixing property and transparency with polyolefin.
そこで、本発明は、ポリエチレンとの混合性に優れ、ポリエチレンの球晶の成長を遅くし、球晶サイズを小さくすることが可能となることから、透明性に優れるポリエチレンを供することが可能となるポリエチレン用球晶成長速度抑制剤を提供するものである。 Therefore, the present invention is excellent in mixing with polyethylene, slows the growth of polyethylene spherulites, and makes it possible to reduce the size of spherulites, thereby providing polyethylene having excellent transparency. The present invention provides a spherulite growth rate inhibitor for polyethylene.
本発明者らは、上記課題を達成するため鋭意検討の結果、特定のエチレン系重合体がポリエチレンの球晶の成長速度を遅くし、球晶サイズの小さいポリエチレンとなり、透明性に優れるポリエチレンとすることが可能となることを見出し、本発明を完成させるに至った。 As a result of intensive studies in order to achieve the above-mentioned problems, the present inventors have made a specific ethylene-based polymer slow the growth rate of polyethylene spherulites, resulting in polyethylene having a small spherulite size, and having excellent transparency. As a result, the present invention has been completed.
即ち、本発明は、密度（ｋｇ／ｍ３）が９１０以上９６０以下、メルトフローレート（ｇ／１０分）が０．０１以上１００以下、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）による分子量測定において２つのピークを示し、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が２．０から７．０の範囲であり、分子量分別した際のＭｎが１０万以上である成分の割合がポリマー全体の４０％未満であり、かつ分子量分別した際のＭｎが１０万以上のフラクション中に長鎖分岐を主鎖１０００炭素数あたり０．１５個以上有するエチレン系重合体であることを特徴とするポリエチレン用球晶成長速度抑制剤に関するものである。 That is, in the present invention, the density (kg / m 3 ) is 910 or more and 960 or less, the melt flow rate (g / 10 minutes) is 0.01 or more and 100 or less, and the molecular weight is measured by gel permeation chromatography (GPC). Two peaks are shown, the ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) is in the range of 2.0 to 7.0, and Mn when molecular weight fractionation is 100,000 or more An ethylene polymer in which the proportion of a certain component is less than 40% of the whole polymer, and 0.15 or more long-chain branches per 1000 carbons in the main chain in a fraction having a Mn of 100,000 or more when molecular weight fractionation is performed. The present invention relates to a spherulite growth rate inhibitor for polyethylene.
以下に本発明を詳細に説明する。 The present invention is described in detail below.
本発明のポリエチレン用球晶成長速度抑制剤は、密度（ｋｇ／ｍ３）が９１０以上９６０以下、メルトフローレート（ＭＦＲ）（ｇ／１０分）が０．０１以上１００以下、ゲル・パーミエーション・クロマトグラフィーによる分子量測定において２つのピークを示し、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が２．０から７．０の範囲であり、分子量分別した際のＭｎが１０万以上である成分の割合がポリマー全体の４０％未満であり、かつ分子量分別した際のＭｎが１０万以上のフラクション中に長鎖分岐を主鎖１０００炭素数あたり０．１５個以上有するエチレン系重合体よりなるものである。該ポリエチレン用球晶成長速度抑制剤は、ポリエチレンに配合することによりポリエチレンの球晶の成長速度を遅くすることから、その球晶サイズを小さくするものである。その結果、球晶サイズの小さいポリエチレンは透明性に優れるものとなる。 The spherulite growth rate inhibitor for polyethylene of the present invention has a density (kg / m 3 ) of 910 to 960, a melt flow rate (MFR) (g / 10 min) of 0.01 to 100, and gel permeation. When the molecular weight measurement by chromatography shows two peaks, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) is in the range of 2.0 to 7.0, and the molecular weight fractionation The proportion of the component having Mn of 100,000 or more is less than 40% of the whole polymer, and 0.15 long-chain branches per 1000 carbon atoms in the fraction having Mn of 100,000 or more when molecular weight fractionation is performed It consists of an ethylene polymer having the above. Since the spherulite growth rate inhibitor for polyethylene slows down the growth rate of spherulites of polyethylene by being blended with polyethylene, the spherulite size is reduced. As a result, polyethylene with a small spherulite size is excellent in transparency.
該ポリエチレン用球晶成長速度抑制剤がポリエチレンの球晶成長速度を遅くする理由は明らかでないが、該ポリエチレン用球晶成長速度抑制剤を配合したポリエチレンでは冷却結晶化時に形成される球晶数が著しく増加することが確認されており、球晶数の増加により個々の球晶の成長が阻害されて、成長速度が低下するものと考えられる。すなわち、本
発明のポリエチレン用球晶成長速度抑制剤はポリエチレンに対して結晶核剤的働きを有するものと推察される。
The reason why the spherulite growth rate inhibitor for polyethylene slows down the spherulite growth rate of polyethylene is not clear, but in the case of polyethylene blended with the spherulite growth rate inhibitor for polyethylene, the number of spherulites formed during cooling crystallization is low. It is confirmed that the number of spherulites increases significantly, and the growth of individual spherulites is inhibited by the increase in the number of spherulites, and the growth rate is considered to decrease. That is, the spherulite growth rate inhibitor for polyethylene of the present invention is presumed to have a crystal nucleating agent function for polyethylene.
本発明のポリエチレン用球晶成長速度抑制剤は、密度が９１０ｋｇ／ｍ３以上９６０ｋｇ／ｍ３以下のエチレン系重合体よりなるものであり、特にポリエチレンに配合した際に透明性、耐熱性にも優れるものとなることから９２５ｋｇ／ｍ３以上９４５ｋｇ／ｍ３以下のものであることが好ましい。ここで、密度が９１０ｋｇ／ｍ３未満である場合、ポリチレンと配合した際の耐熱性が劣るものとなる。一方、密度が９６０ｋｇ／ｍ３を超えるものである場合、ポリエチレンと配合した際の相溶性に劣り、透明性にも劣るものとなる。 The spherulite growth rate inhibitor for polyethylene of the present invention is composed of an ethylene polymer having a density of 910 kg / m 3 or more and 960 kg / m 3 or less, and especially when blended with polyethylene, transparency and heat resistance are also achieved. it is preferred because it becomes excellent those 925 kg / m 3 or more 945 kg / m 3 or less. Here, when the density is less than 910 kg / m 3 , the heat resistance when blended with polytylene is inferior. On the other hand, when the density exceeds 960 kg / m 3 , the compatibility when blended with polyethylene is poor and the transparency is also poor.
本発明のポリエチレン用球晶成長速度抑制剤は、ＭＦＲが０．０１ｇ／１０分以上１００ｇ／１０分以下のエチレン系重合体よりなるものであり、特にポリエチレンに配合した際に透明性、成形加工性に優れるものとなることから０．０５ｇ／１０分以上５０ｇ／１０分以下のものであることが好ましい。ここで、ＭＦＲが０．０１ｇ／１０分未満である場合、ポリエチレンと配合した際の相溶性、成形加工性に劣り、透明性にも劣るものとなる。一方、ＭＦＲが１００ｇ／１０分を超えるものである場合、ポリエチレンの球晶成長速度抑制効果が乏しく、ポリエチレンと配合してもポリエチレンの球晶サイズが大きなものとなり、透明性に劣るものとなる。 The spherulite growth rate inhibitor for polyethylene of the present invention is composed of an ethylene polymer having an MFR of 0.01 g / 10 min or more and 100 g / 10 min or less, particularly when blended with polyethylene, transparency and molding processing. It is preferable that it is 0.05 g / 10 min or more and 50 g / 10 min or less because it becomes excellent in property. Here, when MFR is less than 0.01 g / 10 min, the compatibility and the moldability when blended with polyethylene are inferior, and the transparency is also inferior. On the other hand, when MFR exceeds 100 g / 10 min, the effect of suppressing the spherulite growth rate of polyethylene is poor, and even when blended with polyethylene, the spherulite size of polyethylene becomes large and the transparency is poor.
本発明のポリエチレン用球晶成長速度抑制剤は、ＧＰＣによる分子量測定において溶出曲線が２つのピークを示すエチレン系重合体よりなるものである。ここで、溶出曲線のピークが１つ又は３つ以上のものである場合、ポリエチレンの球晶成長速度抑制効果が乏しく、ポリエチレンと配合してもポリエチレンの球晶サイズが大きなものとなり、透明性に劣るものとなる。 The spherulite growth rate inhibitor for polyethylene of the present invention is composed of an ethylene polymer whose elution curve shows two peaks in the molecular weight measurement by GPC. Here, when the peak of the elution curve is one or more than three, the effect of suppressing the spherulite growth rate of polyethylene is poor, and even when blended with polyethylene, the spherulite size of polyethylene becomes large, and transparency is improved. It will be inferior.
本発明のポリエチレン用球晶成長速度抑制剤は、ＧＰＣによる測定においてＭｗ／Ｍｎが２．０から７．０の範囲のエチレン系重合体よりなるものであり、特にポリエチレンに配合した際に成形加工性、クリーン性に優れるものとなることから３．０から６．０の範囲であることが好ましい。ここで、Ｍｗ／Ｍｎが２．０未満である場合、ポリエチレンと配合した際の相溶性、成形加工性に劣り、透明性にも劣るものとなる。一方、Ｍｗ／Ｍｎが７．０を超える場合、ポリエチレンの球晶成長速度抑制効果が乏しく、ポリエチレンと配合してもポリエチレンの球晶サイズが大きなものとなり、透明性に劣るものとなる。Ｍｗ／Ｍｎは、有機変性粘土（Ｂ）合成時の有機化合物添加量の低減、重合時の温度低下、エチレン以外のオレフィン添加量の増加により大きくすることができる。 The spherulite growth rate inhibitor for polyethylene of the present invention is composed of an ethylene-based polymer having a Mw / Mn in the range of 2.0 to 7.0 as measured by GPC, particularly when blended with polyethylene. In the range of 3.0 to 6.0, it is preferable because of excellent properties and cleanliness. Here, when Mw / Mn is less than 2.0, compatibility with polyethylene and molding processability are inferior, and transparency is also inferior. On the other hand, when Mw / Mn exceeds 7.0, the effect of suppressing the spherulite growth rate of polyethylene is poor, and even when blended with polyethylene, the spherulite size of polyethylene is large and the transparency is poor. Mw / Mn can be increased by reducing the amount of organic compound added during synthesis of the organically modified clay (B), lowering the temperature during polymerization, and increasing the amount of olefin other than ethylene.
本発明のポリエチレン用球晶成長速度抑制剤は、分子量分別した際のＭｎが１０万以上である成分の割合が４０％未満であるエチレン系重合体からなるものであり、特にポリエチレンと配合した際にポリエチレンの球晶成長速度抑制効果に優れることから３５％以下であることが好ましい。ここで、Ｍｎが１０万以上である成分の割合が４０％以上である場合、ポリエチレンの球晶成長速度抑制効果に劣り、球晶サイズの大きなものとなる結果、透明性に劣るものとなる。分子量分別で得られたＭｎが１０万以上のフラクションの割合については、有機変性粘土（Ｂ）合成時の有機化合物添加量の低減、重合時の水素添加量の減少、重合時のエチレン以外のオレフィン添加量の増加により増加させることができる。また、遷移金属化合物（Ａ）の配位子の種類によっても制御が可能である。 The spherulite growth rate inhibitor for polyethylene of the present invention is composed of an ethylene-based polymer in which the proportion of components having Mn of 100,000 or more when molecular weight fractionation is less than 40%, particularly when blended with polyethylene. Furthermore, it is preferably 35% or less because it is excellent in the effect of suppressing the spherulite growth rate of polyethylene. Here, when the ratio of the component whose Mn is 100,000 or more is 40% or more, the effect of suppressing the spherulite growth rate of polyethylene is inferior, and as a result of the large spherulite size, the transparency is inferior. Regarding the proportion of fractions with Mn of 100,000 or more obtained by molecular weight fractionation, the amount of organic compound added during the synthesis of organically modified clay (B), the amount of hydrogen added during polymerization, the olefin other than ethylene during polymerization It can be increased by increasing the amount added. Control is also possible by the type of ligand of the transition metal compound (A).
また、本発明のポリエチレン用球晶成長速度抑制剤は、分子量分別した際のＭｎが１０万以上のフラクション中にヘキシル基以上の長鎖分岐を主鎖１０００炭素数あたり０．１５個以上有するエチレン系重合体よりなるものである。ここで、長鎖分岐が主鎖１０００炭素数あたり０．１５未満である場合、ポリエチレンの球晶成長速度抑制効果に劣り、球晶サイズの大きなものとなる結果、透明性に劣るものとなる。分子量分別で得られたＭｎが１０万以上のフラクションの長鎖分岐数は、有機変性粘土（Ｂ）合成時の有機化合物添加量の低減、重合時のエチレン以外のオレフィン添加量の増加により増加させることができる。また、遷移金属化合物（Ａ）の配位子の種類によっても制御が可能である。 Further, the spherulite growth rate inhibitor for polyethylene of the present invention is an ethylene having 0.15 or more long-chain branches having a hexyl group or more per 1000 carbon atoms in a fraction having a Mn of 100,000 or more when molecular weight fractionation is performed. It consists of a polymer. Here, when the long chain branching is less than 0.15 per 1000 carbon atoms of the main chain, the effect of suppressing the spherulite growth rate of polyethylene is inferior, and as a result of the large spherulite size, the transparency is inferior. The number of long-chain branches in the fraction obtained by molecular weight fractionation with Mn of 100,000 or more is increased by reducing the amount of organic compound added during synthesis of the organically modified clay (B) and increasing the amount of olefin other than ethylene during polymerization. be able to. Control is also possible by the type of ligand of the transition metal compound (A).
本発明のポリエチレン用球晶成長速度抑制剤は、ポリエチレンに配合することにより、ポリエチレンの球晶成長速度を遅くする結果、球晶サイズを小さくすることが可能となり、ポリエチレンの耐熱性を低下させることなく、透明性を大幅に高めることが可能となる。さらには、驚くべきことに、ポリエチレンのガスバリア性をも改善される効果を発現する場合も見られる。 When the spherulite growth rate inhibitor for polyethylene of the present invention is blended with polyethylene, the spherulite growth rate of polyethylene is reduced, and as a result, the spherulite size can be reduced and the heat resistance of polyethylene is reduced. Therefore, it becomes possible to greatly increase transparency. Furthermore, surprisingly, there are cases where the effect of improving the gas barrier properties of polyethylene is also exhibited.
本発明のポリエチレン用球晶成長速度抑制剤の配合量は、特に制限されるものではないが、ポリエチレン１００重量部に対して、通常１〜３０重量部を配合して使用できる。 Although the compounding quantity of the spherulite growth rate inhibitor for polyethylene of this invention is not restrict | limited in particular, 1-30 weight part can be normally mix | blended and used with respect to 100 weight part of polyethylene.
本発明のポリエチレン用球晶成長速度抑制剤を配合するポリエチレンとしては、一般的にポリエチレンと称される範疇に属するものであれば如何なるものであってもよく、例えば高圧法低密度ポリエチレン、直鎖状低密度ポリエチレン、高密度ポリエチレン等を挙げることができ、その中でも、耐熱性、透明性のバランスに優れる直鎖状低密度ポリエチレン（エチレン−α−オレフィン共重合体）であることが好ましい。その中でも容器用として、耐熱性、透明性、クリーン性のバランスに極めて優れるものとなることから、ＪＩＳ Ｋ６９２２−１に準拠し、１９０℃、荷重２．１６ｋｇで測定したＭＦＲが０．１〜１５．０ｇ／１０分、ＪＩＳ Ｋ６９２２−１に準拠した密度が８９０〜９４０ｋｇ／ｍ３の直鎖状低密度ポリエチレンであることが好ましい。 The polyethylene to which the spherulite growth rate inhibitor for polyethylene of the present invention is blended may be any as long as it belongs to a category generally referred to as polyethylene, for example, high pressure method low density polyethylene, linear In particular, linear low-density polyethylene (ethylene-α-olefin copolymer) having an excellent balance of heat resistance and transparency is preferable. Among them, for containers, since the balance of heat resistance, transparency, and cleanness is extremely excellent, the MFR measured at 190 ° C. and a load of 2.16 kg is 0.1 to 15 in accordance with JIS K6922-1. It is preferably a linear low density polyethylene having a density of 890 to 940 kg / m 3 according to JIS K6922-1 for 0.0 g / 10 minutes.
本発明のポリエチレン用球晶成長速度抑制剤を構成するエチレン系重合体の製造方法としては、密度が９１０ｋｇ／ｍ３以上９６０ｋｇ／ｍ３以下、ＭＦＲが０．０１ｇ／１０分以上１００ｇ／１０分以下、ＧＰＣによる分子量測定において２つのピークを示し、Ｍｗ／Ｍｎが２．０から７．０の範囲であり、分子量分別した際のＭｎが１０万以上である成分の割合がポリマー全体の４０％未満であり、かつ分子量分別した際のＭｎが１０万以上のフラクション中に長鎖分岐を主鎖１０００炭素数あたり０．１５個以上有するエチレン系重合体の製造が可能であれば如何なる方法を用いてもよく、例えばメタロセン系重合触媒の存在下、エチレン、場合によってはプロピレン、ブテン−１、ヘキセン−１、オクテン−１等のα−オレフィンの（共）重合を行なう方法を挙げることができる。 As a method for producing an ethylene polymer constituting the spherulite growth rate inhibitor for polyethylene of the present invention, the density is 910 kg / m 3 or more and 960 kg / m 3 or less, and the MFR is 0.01 g / 10 min or more and 100 g / 10 min. Hereinafter, GPC shows two peaks in the molecular weight measurement, Mw / Mn is in the range of 2.0 to 7.0, and the proportion of the component having Mn of 100,000 or more when molecular weight fractionation is 40% of the whole polymer. Any method can be used as long as it can produce an ethylene polymer having 0.15 or more long-chain branches per 1000 carbon atoms in the fraction having a molecular weight fractionation of Mn of 100,000 or more. For example, in the presence of a metallocene polymerization catalyst, ethylene, and in some cases, α-olefin such as propylene, butene-1, hexene-1, octene-1, etc. A method of performing (co) polymerization can be mentioned.
その際のメタロセン系重合触媒としては、例えばビス（シクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイルビス（シクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイル（シクロペンタジエニル）（４，７−ジメチル−１−インデニル）ジルコニウムジクロリド、ジメチルシランジイル（シクロペンタジエニル）（２，４，７−トリメチル−１−インデニル）ジルコニウムジクロリドおよびイソプロピリデン（シクロペンタジエニル）（２，７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロライドなどのジルコニウム化合物、ジルコニウム原子をチタン原子、ハフニウム原子に変えた化合物や上記遷移金属化合物のジクロロ体をジメチル体、ジエチル体、ジヒドロ体、ジフェニル体、ジベンジル体に変えた遷移金属化合物（Ａ）；Ｎ，Ｎ−ジメチル−ベヘニルアミン塩酸塩、Ｎ−メチル−Ｎ−エチル−ベヘニルアミン塩酸塩、Ｎ−メチル−Ｎ−ｎ−プロピル−ベヘニルアミン塩酸塩、Ｎ−メチル−Ｎ−イソプロピル−ベヘニルアミン塩酸塩、Ｎ−メチル−Ｎ−ｎ−ブチル−ベヘニルアミン塩酸塩、Ｐ，Ｐ−ジメチル−ベヘニルホスフィン塩酸塩、Ｐ，Ｐ−ジエチル−ベヘニルホスフィン塩酸塩、Ｐ，Ｐ−ジプロピル−ベヘニルホスフィン塩酸塩等の有機酸塩により変性された有機変性粘土（Ｂ）及びトリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウムなどのアルキルアルミニウム（Ｃ）を含んでなるメタロセン系触媒を挙げることができる。 Examples of the metallocene polymerization catalyst at that time include bis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4,7-dimethyl- 1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride and isopropylidene (cyclopentadienyl) (2,7-di-t-butyl) -9-fluorenyl) zirconium dichloride, zirconium compounds, compounds in which zirconium atoms are changed to titanium atoms, hafnium atoms, and dichloro isomers of the above transition metal compounds are dimethyl, diethyl, dihydro, diphenyl, Transition metal compound (A) changed to benzyl form; N, N-dimethyl-behenylamine hydrochloride, N-methyl-N-ethyl-behenylamine hydrochloride, N-methyl-Nn-propyl-behenylamine hydrochloride N-methyl-N-isopropyl-behenylamine hydrochloride, N-methyl-Nn-butyl-behenylamine hydrochloride, P, P-dimethyl-behenylphosphine hydrochloride, P, P-diethyl-behenylphosphine hydrochloride A metallocene catalyst comprising an organically modified clay (B) modified with an organic acid salt such as P, P-dipropyl-behenylphosphine hydrochloride and an alkylaluminum (C) such as trimethylaluminum, triethylaluminum and triisobutylaluminum Can be mentioned.
該遷移金属化合物（Ａ）、有機変性粘土（Ｂ）およびアルキルアルミニウム（Ｃ）を含んでなるメタロセン系触媒を調製する方法に関して制限はなく、調製の方法として、各成分に関して不活性な溶媒中あるいは重合を行うエチレン、場合によってはα−オレフィンを溶媒として用い、混合する方法などを挙げることができる。また、これらの成分を反応させる順番に関しても制限はなく、この処理を行う温度、処理時間も制限はない。また、有機変性粘土（Ｂ）成分、アルキルアルミニウム（Ｃ）を２種類以上用いてエチレン系重合体製造用触媒を調製することも可能である。 There is no limitation on the method for preparing the metallocene catalyst comprising the transition metal compound (A), the organically modified clay (B), and the alkylaluminum (C). Examples thereof include a method of mixing by using ethylene for polymerization, and optionally α-olefin as a solvent. Moreover, there is no restriction | limiting also about the order which makes these components react, and the temperature and processing time which perform this process also have no restriction | limiting. It is also possible to prepare an ethylene polymer production catalyst using two or more kinds of organically modified clay (B) component and alkylaluminum (C).
また、本発明のポリエチレン用球晶成長速度抑制剤であるエチレン系重合体の製造の際には、通常の重合プロセス、例えばスラリー重合、気相重合、高圧重合、溶液重合、塊状重合のいずれのプロセスも用いることができる。 また、本発明のポリエチレン用球晶成長速度抑制剤を構成するエチレン系重合体は、特開２０１１−１０５９３４号公報等の公知の方法により製造することができる。 In the production of the ethylene polymer that is a spherulite growth rate inhibitor for polyethylene of the present invention, any of ordinary polymerization processes such as slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization, and bulk polymerization may be used. A process can also be used. Moreover, the ethylene polymer which comprises the spherulite growth rate inhibitor for polyethylene of this invention can be manufactured by well-known methods, such as Unexamined-Japanese-Patent No. 2011-105934.
本発明によれば、ポリエチレンに配合することにより、ポリエチレンの結晶化度を低下させることなく、ポリエチレンの球晶成長速度を遅くし、球晶サイズの小さいポリエチレンとすることが可能となり、高いバリヤー性、透明性を付与したポリエチレンを提供することができる。 According to the present invention, by blending with polyethylene, it is possible to reduce the spherulite growth rate of polyethylene without decreasing the crystallinity of polyethylene, and to make polyethylene with a small spherulite size, and high barrier properties. Further, it is possible to provide polyethylene having transparency.
以下実施例によって本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、断りのない限り用いた試薬等は市販品、あるいは既知の方法に従って合成したものを用いた。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise noted, the reagents used were commercially available products or those synthesized according to known methods.
有機変性粘土の粉砕にはジェットミル（セイシン企業社製（商品名）ＣＯ−ＪＥＴ ＳＹＳＴＥＭ α ＭＡＲＫ ＩＩＩを用い、粉砕後の粒径はマイクロトラック粒度分布測定装置（日機装株式会社製（商品名）ＭＴ３０００）を用いてエタノールを分散剤として測定した。 A jet mill (CO-JET SYSTEM α MARK III manufactured by Seishin Enterprise Co., Ltd. (trade name) was used for pulverization of the organically modified clay. ) Was used as a dispersant.
エチレン系重合体製造用触媒の調製、エチレン系重合体の製造および溶媒精製は全て不活性ガス雰囲気下で行った。トリイソブチルアルミニウムのヘキサン溶液（２０ｗｔ％）は東ソーファインケム（株）製を用いた。 Preparation of the ethylene polymer production catalyst, production of the ethylene polymer and solvent purification were all carried out under an inert gas atmosphere. A hexane solution (20 wt%) of triisobutylaluminum manufactured by Tosoh Finechem Co., Ltd. was used.
さらに、ポリエチレン用球晶成長速度抑制剤等の諸物性等は、以下に示す方法により測定した。 Furthermore, various physical properties such as a spherulite growth rate inhibitor for polyethylene were measured by the following methods.
＜分子量、分子量分布＞
重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、重量平均分子量と数平均分子量の比（Ｍｗ／Ｍｎ）およびピークトップ分子量（Ｍｐ）は、ＧＰＣによって測定した。ＧＰＣ装置（東ソー（株）製（商品名）ＨＬＣ−８１２１ＧＰＣ／ＨＴ）およびカラム（東ソー（株）製（商品名）ＴＳＫｇｅｌ ＧＭＨｈｒ−Ｈ（２０）ＨＴ）を用い、カラム温度を１４０℃に設定し、溶離液として１，２，４−トリクロロベンゼンを用いて測定した。測定試料は１．０ｍｇ／ｍｌの濃度で調製し、０．３ｍｌ注入して測定した。分子量の検量線は、分子量既知のポリスチレン試料を用いて校正した。なお、ＭｗおよびＭｎは直鎖状ポリエチレン換算の値として求めた。
<Molecular weight, molecular weight distribution>
Weight average molecular weight (Mw), number average molecular weight (Mn), ratio of weight average molecular weight to number average molecular weight (Mw / Mn) and peak top molecular weight (Mp) were measured by GPC. The column temperature was set to 140 ° C. using a GPC device (trade name: HLC-8121 GPC / HT, manufactured by Tosoh Corporation) and a column (trade name: TSKgel GMHhr-H (20) HT, manufactured by Tosoh Corporation). The measurement was performed using 1,2,4-trichlorobenzene as an eluent. A measurement sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected and measured. The calibration curve of molecular weight was calibrated using a polystyrene sample having a known molecular weight. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion.
＜分子量分別＞
分子量分別は、カラムとしてガラスビーズ充填カラム（直径：２１ｍｍ、長さ：６０ｃｍ）を用い、カラム温度を１３０℃に設定して、サンプル１ｇをキシレン３０ｍＬに溶解させたものを注入する。次に、キシレン／２−エトキシエタノールの比率が５／５のものを展開溶媒として用い、留出物を除去する。その後、キシレンを展開溶媒として用い、カラム中に残った成分を留出させ、ポリマー溶液を得る。得られたポリマー溶液に５倍量のメタノールを添加しポリマー分を沈殿させ、ろ過および乾燥することにより、Ｍｎが１０万以上である成分を回収した。
<Molecular weight fractionation>
For molecular weight fractionation, a glass bead packed column (diameter: 21 mm, length: 60 cm) is used as the column, the column temperature is set to 130 ° C., and 1 g of sample dissolved in 30 mL of xylene is injected. Next, distillate is removed by using a xylene / 2-ethoxyethanol ratio of 5/5 as a developing solvent. Thereafter, using xylene as a developing solvent, the components remaining in the column are distilled off to obtain a polymer solution. A component having Mn of 100,000 or more was recovered by adding 5-fold amount of methanol to the obtained polymer solution to precipitate the polymer, filtering and drying.
＜長鎖分岐＞
長鎖分岐数は、日本電子（株）製ＪＮＭ−ＧＳＸ４００型核磁気共鳴装置を用いて、１３Ｃ−ＮＭＲによってヘキシル基以上の分岐数を測定した。溶媒はベンゼン−ｄ６／オルトジクロロベンゼン（体積比３０／７０）である。主鎖メチレン炭素（化学シフト：３０ｐｐｍ）１，０００個当たりの個数として、α−炭素（３４．６ｐｐｍ）およびβ−炭素（２７．３ｐｐｍ）のピークの平均値から求めた。
<Long chain branching>
The number of long-chain branches was determined by 13C-NMR using a JNM-GSX400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd., and the number of branches equal to or greater than the hexyl group. The solvent is benzene-d6 / orthodichlorobenzene (volume ratio 30/70). The number per 1,000 main chain methylene carbons (chemical shift: 30 ppm) was determined from the average value of the peaks of α-carbon (34.6 ppm) and β-carbon (27.3 ppm).
＜密度＞
密度は、ＪＩＳ Ｋ６９２２−１に準拠して密度勾配管法で測定した。
<Density>
The density was measured by a density gradient tube method in accordance with JIS K6922-1.
＜ＭＦＲ＞
ＭＦＲ（メルトフローレート）は、ＪＩＳ Ｋ６９２２−１に準拠して測定を行った。
<MFR>
MFR (melt flow rate) was measured according to JIS K6922-1.
＜透明性（光線透過率）＞
圧縮成形機（（株）神藤金属工業所製、型式ＡＷＦＡ．５０）を用いて、成形温度１８０℃、冷却温度３０℃で厚み０．５ｍｍの圧縮成形シートを得た。このシートから、幅１０ｍｍ×長さ５０ｍｍの試験片を切出し、紫外可視分光光度計（日本分光株式会社製 型式Ｖ−５３０）を用いて、純水中で波長４５０ｎｍにおける光線透過率を測定した。
<Transparency (light transmittance)>
Using a compression molding machine (Model AWFA.50, manufactured by Shindo Metal Industry Co., Ltd.), a compression molded sheet having a molding temperature of 180 ° C., a cooling temperature of 30 ° C. and a thickness of 0.5 mm was obtained. A test piece having a width of 10 mm and a length of 50 mm was cut out from this sheet, and the light transmittance at a wavelength of 450 nm was measured in pure water using an ultraviolet-visible spectrophotometer (model number V-530 manufactured by JASCO Corporation).
＜透湿度（バリアー性）＞
前記圧縮成形シートを用いて、ＪＩＳ Ｋ ７１２９ Ａ法（感湿センサー法）に準拠して、水蒸気透過度計（Ｌｙｓｓｙ社製、型式 Ｌ８０−５０００）により透湿度を測定した。
<Moisture permeability (barrier property)>
Using the compression molded sheet, moisture permeability was measured with a water vapor permeability meter (Lyssy, model L80-5000) in accordance with JIS K 7129 A method (humidity sensitive sensor method).
＜球晶成長速度＞
試料をカバーグラスとスライドグラス間に挟み、温度可変可能なホットステージ（ＭＥＴＴＬＥＲ製、ＦＰ９０）上で１９０℃、２分間融解後、５℃／分で結晶化温度まで冷却し、等温結晶化過程の球晶直径の変化を偏光顕微鏡（（株）ニコン製、型式ＯＰＴＩＰＨＯＴ２−ＰＯＬ）により観察し、写真撮影した。球晶成長速度は、球晶出現直後および１分経過後の球晶直径を写真から読み取り、下式により算出した。
球晶成長速度［μｍ／分］＝（［１分後の球晶直径］−［球晶出現直後の直径］）×１／２
＜球晶数＞
前記球晶出現１分後の撮影写真から単位面積中に存在する球晶数［個／０．０１ｍｍ２］を算出した。
<Spherulite growth rate>
A sample is sandwiched between a cover glass and a slide glass, melted at 190 ° C. for 2 minutes on a hot stage (manufactured by METTLER, FP90), cooled to a crystallization temperature at 5 ° C./minute, and subjected to an isothermal crystallization process. The change in spherulite diameter was observed with a polarizing microscope (manufactured by Nikon Corporation, model OPTIPHOT2-POL), and photographed. The spherulite growth rate was calculated by the following formula after reading the spherulite diameter immediately after the appearance of spherulites and after 1 minute from the photograph.
Spherulite growth rate [μm / min] = ([spherulite diameter after 1 minute] − [diameter immediately after appearance of spherulites]) × 1/2
<Number of spherulites>
From the photograph taken 1 minute after the appearance of the spherulites, the number of spherulites [units / 0.01 mm 2 ] present in the unit area was calculated.
＜球晶サイズ＞
前記球晶出現１分後の撮影写真から球晶直径の平均値［μｍ］を算出した。
<Spherulite size>
The average value [μm] of spherulite diameter was calculated from a photograph taken 1 minute after the appearance of the spherulites.
実施例、比較例では、下記の方法により製造した樹脂および市販品を用いた。
（１）エチレン系重合体（ポリエチレン用球晶成長速度抑制剤）
調製例１（ＰＥ−１）
［粘土の変性］
１リットルのフラスコに工業用アルコール（日本アルコール販売社製（商品名）エキネンＦ−３）３００ｍｌ及び蒸留水３００ｍｌを入れ、濃塩酸１５．０ｇ及びジメチルベヘニルアミン（ライオン株式会社製（商品名）アーミンＤＭ２２Ｄ）４２．４ｇ（１２０ｍｍｏｌ）を添加し、４５℃に加熱して合成ヘクトライト（Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ社製（商品名）ラポナイトＲＤＳ）を１００ｇ分散させた後、６０℃に昇温させてその温度を保持したまま１時間攪拌した。このスラリーを濾別後、６０℃の水６００ｍｌで２回洗浄し、８５℃の乾燥機内で１２時間乾燥させることにより１２２ｇの有機変性粘土を得た。この有機変性粘土はジェットミル粉砕して、メジアン径を１５μｍとした。
［触媒懸濁液の調製］
温度計と還流管が装着された３００ｍ１のフラスコを窒素置換した後に（１）で得られた有機変性粘土２５．０ｇとヘキサンを１０８ｍ１入れ、次いでジメチルシリレン（シクロペンタジエニル）（２，４，７−トリメチル−１−インデニル）ジルコニウムジクロリド／０．４４０６ｇ、及び２０％トリイソブチルアルミニウム１４２ｍｌを添加して６０℃で３時間攪拌した。４５℃まで冷却した後に上澄み液を抜き取り、２００ｍＬのヘキサンにて５回洗浄後、ヘキサンを２００ｍｌ加えて触媒懸濁液を得た（固形重量分：１１．５ｗｔ％）。
［重合］
２リットルのオートクレーブにヘキサンを１．２リットル、２０％トリイソブチルアルミニウムを１．０ｍｌ、［触媒懸濁液の調製］で得られた触媒懸濁液を６４ｍｇ（固形分７．３ｍｇ相当）加え、７０℃に昇温後、１−ブテンを１７．６ｇ加え、分圧が０．８０ＭＰａになるようにエチレン／水素混合ガスを連続的に供給した（エチレン／水素混合ガス中の水素の濃度：５７０ｐｐｍ）。９０分経過後に脱圧し、スラリーを濾別後、乾燥することで６１．７ｇのエチレン系重合体を得た。
In Examples and Comparative Examples, resins manufactured by the following method and commercial products were used.
(1) Ethylene polymer (spherulite growth rate inhibitor for polyethylene)
Preparation Example 1 (PE-1)
[Modification of clay]
Into a 1 liter flask, 300 ml of industrial alcohol (trade name Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 ml of distilled water are placed, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (trade name, manufactured by Lion Corporation, Armin) DM22D) 42.4 g (120 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. to raise the temperature. Stirring was continued for 1 hour. The slurry was separated by filtration, washed twice with 600 ml of 60 ° C. water, and dried in an oven at 85 ° C. for 12 hours to obtain 122 g of an organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
[Preparation of catalyst suspension]
After replacing the nitrogen of a 300 ml flask equipped with a thermometer and a reflux tube, 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2, 4, 7-trimethyl-1-indenyl) zirconium dichloride / 0.4406 g and 142 ml of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 11.5 wt%).
[polymerization]
To a 2 liter autoclave was added 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum, and 64 mg (corresponding to a solid content of 7.3 mg) of the catalyst suspension obtained in [Preparation of catalyst suspension] After raising the temperature to 70 ° C., 17.6 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure was 0.80 MPa (the concentration of hydrogen in the ethylene / hydrogen mixed gas: 570 ppm). ). After 90 minutes, the pressure was released, the slurry was filtered, and dried to obtain 61.7 g of an ethylene polymer.
得られたエチレン系重合体は、ＭＦＲ＝１．４ｇ／１０分、密度は９２９ｋｇ／ｍ３であった。また、数平均分子量は１９，０００、重量平均分子量は９３，０００であり、Ｍｗ／Ｍｎ＝４．８、分子量測定による２つのピークが観測された。また、分子量分別した際のＭｎ１０万以上のフラクション中に含まれる長鎖分岐数は、主鎖１０００炭素数あたり０．３１個であり、分子量分別した際のＭｎ１０万以上のフラクションの割合は、全ポリマーの２１．８ｗｔ％であった。 The obtained ethylene polymer had MFR = 1.4 g / 10 min and a density of 929 kg / m 3 . Moreover, the number average molecular weight was 19,000, the weight average molecular weight was 93,000, Mw / Mn = 4.8, and two peaks by molecular weight measurement were observed. The number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 0.31 per 1000 carbons of the main chain, and the proportion of the fraction of Mn of 100,000 or more when molecular weight fractionation is It was 21.8 wt% of the polymer.
調製例２（ＰＥ−２）
［粘土の変性］
１リットルのフラスコに工業用アルコール（日本アルコール販売社製（商品名）エキネンＦ−３）３００ｍｌ及び蒸留水３００ｍｌを入れ、濃塩酸１８．８ｇ及びジメチルヘキサコシルアミン（Ｍｅ２Ｎ（Ｃ２６Ｈ５３）、常法によって合成）４９．１ｇ（１２０ｍｍｏｌ）を添加し、４５℃に加熱して合成ヘクトライト（Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ社製（商品名）ラポナイトＲＤＳ）を１００ｇ分散させた後、６０℃に昇温させてその温度を保持したまま１時間攪拌した。このスラリーを濾別後、６０℃の水６００ｍｌで２回洗浄し、８５℃の乾燥機内で１２時間乾燥させることにより１４０ｇの有機変性粘土を得た。この有機変性粘土はジェットミル粉砕して、メジアン径を１４μｍとした。
［触媒懸濁液の調製］
温度計と還流管が装着された３００ｍＬのフラスコを窒素置換した後に［粘土の変性］
で得られた有機変性粘土２５．０ｇとヘキサンを１０８ｍｌ入れ、次いでジメチルシリレン（シクロペンタジエニル）（２、４，７−トリメチル−１−インデニル）ジルコニウムジクロリドを０．４４０６ｇ、及び２０％トリイソブチルアルミニウム１４２ｍｌを添加して６０℃で３時間攪拌した。４５℃まで冷却した後に上澄み液を抜き取り、２００ｍｌのヘキサンにて５回洗浄後、ヘキサンを２００ｍｌ加えて触媒懸濁液を得た（固形重量分：１２．０ｗｔ％）
［重合］
２リットルのオートクレーブにヘキサンを１．２リットル、２０％トリイソブチルアルミニウムを１．０ｍｌ、［触媒懸濁液の調製］で得られた触媒懸濁液を７５ｍｇ（固形分９．０ｍｇ相当）加え、８０℃に昇温後、１−ブテンを８．３ｇ加え、分圧が０．８５ＭＰａになるようにエチレン／水素混合ガスを連続的に供給した（エチレン／水素混合ガス中の水素の濃度：８５０ｐｐｍ）。９０分経過後に脱圧し、スラリーを濾別後、乾燥することで５８．５ｇのエチレン系重合体を得た。
Preparation Example 2 (PE-2)
[Modification of clay]
Into a 1 liter flask, 300 ml of industrial alcohol (trade name: Echinen F-3, manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 ml of distilled water were added, and 18.8 g of concentrated hydrochloric acid and dimethylhexacosylamine (Me 2 N (C 26 H 53 ), Synthesized by a conventional method) 49.1 g (120 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 600 ml of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 140 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 14 μm.
[Preparation of catalyst suspension]
After replacing a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen [denaturation of clay]
25.0 g of the organically modified clay obtained in the above and 108 ml of hexane were added, and then 0.4406 g of dimethylsilylene (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride and 20% triisobutyl. 142 ml of aluminum was added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 ml of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).
[polymerization]
To a 2 liter autoclave was added 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum, and 75 mg (corresponding to a solid content of 9.0 mg) of the catalyst suspension obtained in [Preparation of catalyst suspension] After raising the temperature to 80 ° C., 8.3 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.85 MPa (the concentration of hydrogen in the ethylene / hydrogen mixed gas: 850 ppm). ). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 58.5 g of an ethylene polymer.
得られたエチレン系重合体は、ＭＦＲ＝４．０ｇ／１０分、密度は９４１ｋｇ／ｍ３であり、数平均分子量は２１，０００、重量平均分子量は７４，０００であり、Ｍｗ／Ｍｎ＝３．７、分子量測定による２つのピークが観測された。分子量分別した際のＭｎ１０万以上のフラクション中に含まれる長鎖分岐数は、主鎖１０００炭素数あたり０．１８個であった。また、分子量分別した際のＭｎ１０万以上のフラクションの割合は、全ポリマーの１４．８ｗｔ％であった。 The obtained ethylene polymer has MFR = 4.0 g / 10 min, density is 941 kg / m 3 , number average molecular weight is 21,000, weight average molecular weight is 74,000, and Mw / Mn = 3. .7, two peaks were observed by molecular weight measurement. The number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.18 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn of 100,000 or more when molecular weight fractionation was 14.8 wt% of the total polymer.
調製例３（ＰＥ−３）
［粘土の変性］
調整例１と同様に行なった
［触媒懸濁液の調製］
調製例１と同様に行った。
［重合］
２リットルのオートクレーブにヘキサンを１．２リットル、２０％トリイソブチルアルミニウムを１．０ｍｌ、［触媒懸濁液の調製］で得られた触媒懸濁液を６０ｍｇ（固形分７．２ｍｇ相当）加え、８０℃に昇温後、１−ブテンを８．３ｇ加え、分圧が０．８５ＭＰａになるようにエチレン／水素混合ガスを連続的に供給した（エチレン／水素混合ガス中の水素の濃度：３５０ｐｐｍ）。９０分経過後に脱圧し、スラリーを濾別後、乾燥することで５４．０ｇのエチレン系重合体を得た。
Preparation Example 3 (PE-3)
[Modification of clay]
Performed in the same manner as in Preparation Example 1 [Preparation of catalyst suspension]
Performed in the same manner as in Preparation Example 1.
[polymerization]
To a 2 liter autoclave was added 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum, and 60 mg (corresponding to a solid content of 7.2 mg) of the catalyst suspension obtained in [Preparation of catalyst suspension] After the temperature was raised to 80 ° C., 8.3 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.85 MPa (the concentration of hydrogen in the ethylene / hydrogen mixed gas: 350 ppm). ). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 54.0 g of an ethylene polymer.
得られたエチレン系重合体は、ＭＦＲ＝０．３５ｇ／１０分、密度は９３５ｋｇ／ｍ３であり、数平均分子量は３５，５００、重量平均分子量は１２４，０００であり、Ｍｗ／Ｍｎ＝３．５、分子量測定による２つのピークが観測された。また、分子量分別した際のＭｎ１０万以上のフラクション中に含まれる長鎖分岐数は、主鎖１０００炭素数あたり０．２０個であった。また、分子量分別した際のＭｎ１０万以上のフラクションの割合は、全ポリマーの１７．０ｗｔ％であった。 The obtained ethylene polymer had MFR = 0.35 g / 10 min, a density of 935 kg / m 3 , a number average molecular weight of 35,500, a weight average molecular weight of 124,000, and Mw / Mn = 3. .5, two peaks observed by molecular weight measurement were observed. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.20 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 17.0 wt% of the total polymer.
調製例４（ＰＥ−４）
［粘土の変性］
１リットルのフラスコに工業用アルコール（日本アルコール販売社製（商品名）エキネンＦ−３）３００ｍ１及び蒸留水３００ｍ１を入れ、濃塩酸１８．８ｇ及びメチルジオレイルアミン（ライオン株式会社製（商品名）アーミンＭ２Ｏ）５３．１ｇ（１００ｍｍｏｌ）を添加し、４５℃に加熱して（Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ社製（商品名）ラポナイトＲＤ）を１００ｇ分散させた後、６０℃に昇温させてその温度を保持したまま１時間攪拌した。このスラリーを濾別後、６０℃の水６００ｍ１で２回洗浄し、８５℃の乾燥機内で１２時間乾燥させることにより１３８ｇの有機変性粘土を得た。この有機変性粘土はジェットミル粉砕して、メジアン径を１２μｍとした。
［触媒懸濁液の調製］
温度計と還流管が装着された３００ｍリットルのフラスコを窒素置換した後に（１）で得られた有機変性粘土２５．０ｇとヘキサンを１０８ｍＬ入れ、次いでジメチルシリレン（シクロペンタジエニル）（４，７−ジメチル−１−インデニル）ジルコニウムジクロリドを０．４２６６ｇ、及び２０％トリイソブチルアルミニウム１４２ｍｌを添加して６０℃で３時間攪拌した。４５℃まで冷却した後に上澄み液を抜き取り、２００ｍｌのヘキサンにて５回洗浄後、ヘキサンを２００ｍｌ加えて触媒懸濁液を得た（固形重量分：１２．０ｗｔ％）。
［重合］
２リットルのオートクレーブにヘキサンを１．２リットル、２０％トリイソブチルアルミニウムを１．０ｍｌ、［触媒懸濁液の調製］で得られた触媒懸濁液を６６ｍｇ（固形分７．９ｍｇ相当）加え、７０℃に昇温後、１−ブテンを２３．８ｇ加え、分圧が１．２０ＭＰａになるようにエチレンガスを連続的に供給した。９０分経過後に脱圧し、スラリーを濾別後、乾燥することで４３．６ｇのエチレン系重合体を得た。
Preparation Example 4 (PE-4)
[Modification of clay]
Into a 1 liter flask, 300 ml of industrial alcohol (trade name Echinen F-3 manufactured by Japan Alcohol Sales Co., Ltd.) and 300 ml of distilled water were added, 18.8 g of concentrated hydrochloric acid and methyl dioleylamine (trade name, manufactured by Lion Corporation, Armin) (M2O) 53.1 g (100 mmol) was added and heated to 45 ° C. to disperse 100 g of (Rockwood Additives (trade name) Laponite RD), and then the temperature was raised to 60 ° C. and the temperature was maintained. Stir for 1 hour. The slurry was separated by filtration, washed twice with 600 ml of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 138 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 12 μm.
[Preparation of catalyst suspension]
After a 300 ml flask equipped with a thermometer and a reflux tube was purged with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (4,7 -Dimethyl-1-indenyl) zirconium dichloride (0.4266 g) and 20% triisobutylaluminum (142 ml) were added, and the mixture was stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 ml of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).
[polymerization]
To a 2 liter autoclave was added 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum, and 66 mg (corresponding to a solid content of 7.9 mg) of the catalyst suspension obtained in [Preparation of catalyst suspension] After raising the temperature to 70 ° C., 23.8 g of 1-butene was added, and ethylene gas was continuously supplied so that the partial pressure was 1.20 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 43.6 g of an ethylene polymer.
得られたエチレン系重合体は、ＭＦＲ＝７２．４ｇ／１０分、密度は９５４ｋｇ／ｍ３であり、数平均分子量は１６，０００、重量平均分子量は３７，０００であり、Ｍｗ／Ｍｎ＝２．４、分子量測定による１つのピークが観測された。また、分子量分別した際のＭｎ１０万以上のフラクション中に含まれる長鎖分岐数は、主鎖１０００炭素数あたり０．０１個未満であった。また、分子量分別した際のＭｎ１０万以上のフラクションの割合は、全ポリマーの５．０ｗｔ％であった。 The obtained ethylene polymer had MFR = 72.4 g / 10 min, a density of 954 kg / m 3 , a number average molecular weight of 16,000, a weight average molecular weight of 37,000, and Mw / Mn = 2. .4, one peak by molecular weight measurement was observed. Moreover, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was less than 0.01 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 5.0 wt% of the total polymer.
調製例５（ＰＥ−５）
［粘土の変性］
調製例５と同様に行った
［触媒懸濁液の調製］
温度計と還流管が装着された３００ｍｌのフラスコを窒素置換した後に［粘土の変性］
で得られた有機変性粘土２５．０ｇとヘキサンを１０８ｍｌ入れ、次いでジメチルシリレンビス（シクロペンタジエニル）ジルコニウムジクロリドを０．３４８５ｇ、及び２０％トリイソブチルアルミニウム１４２ｍｌを添加して６０℃で３時間攪拌した。４５℃まで冷却した後に上澄み液を抜き取り、２００ｍｌのヘキサンにて５回洗浄後、ヘキサンを２００ｍｌ加えて触媒懸濁液を得た。（固形重量分：１２．０ｗｔ％）
［重合］
２リットルのオートクレーブにヘキサンを１．２リットル、２０％トリイソブチルアルミニウムを１．０ｍｌ、［触媒懸濁液の調製］で得られた触媒懸濁液を１１０ｍｇ（固形分１３．２ｍｇ相当）加え、８５℃に昇温後、分圧が１．２０ＭＰａになるようにエチレンを連続的に供給した。９０分経過後に脱圧し、スラリーを濾別後、乾燥することで７２．６ｇのエチレン系重合体を得た。
Preparation Example 5 (PE-5)
[Modification of clay]
Performed in the same manner as in Preparation Example 5 [Preparation of catalyst suspension]
After replacing a 300 ml flask equipped with a thermometer and a reflux tube with nitrogen [denaturation of clay]
25.0 g of the organically modified clay obtained in the above and 108 ml of hexane were added, and then 0.3485 g of dimethylsilylenebis (cyclopentadienyl) zirconium dichloride and 142 ml of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. did. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 ml of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension. (Solid weight: 12.0wt%)
[polymerization]
To a 2 liter autoclave was added 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum, and 110 mg (corresponding to solid content of 13.2 mg) of the catalyst suspension obtained in [Preparation of catalyst suspension] After raising the temperature to 85 ° C., ethylene was continuously supplied so that the partial pressure was 1.20 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 72.6 g of an ethylene polymer.
得られたエチレン系重合体は、ＭＦＲ＝２００ｇ／１０分以上であり、密度は９４４ｋｇ／ｍ３であり、数平均分子量は９，０００、重量平均分子量は２０，０００、Ｍｗ／Ｍｎ＝２．２、分子量測定による１つのピークが観測された。また、分子量分別した際のＭｎ１０万以上のフラクションは得られなかった。 The obtained ethylene polymer has MFR = 200 g / 10 min or more, a density of 944 kg / m 3 , a number average molecular weight of 9,000, a weight average molecular weight of 20,000, and Mw / Mn = 2. 2. One peak by molecular weight measurement was observed. Further, a fraction with Mn of 100,000 or more when molecular weight fractionation was not obtained.
調整例６（ＰＥ−６）
［粘土の変性］
調製例５と同様に行った。
［触媒懸濁液の調製］
温度計と還流管が装着された３００ｍｌのフラスコを窒素置換した後に［粘土の変性］
で得られた有機変性粘土２５．０ｇをヘキサン１６５ｍｌに懸濁させ、ジメチルシランジイルビス（シクロペンタジエニル）ジルコニウムジクロリド０．３４８５ｇおよびトリエチルアルミニウムのヘキサン溶液（１．１８Ｍ）８５ｍｌを添加して６０℃で３時間撹拌した。静置して室温まで冷却後に上澄み液を抜き取り、１％トリイソブチルアルミニウムのヘキサン溶液２００ｍｌにて２回洗浄した。洗浄後の上澄み液を抜き出し、５％トリイソブチルアルミニウムのヘキサン溶液にて全体を２５０ｍｌとした。次いで、別途ジフェニルメチレン（１−シクロペンタジエニル）（２，７−ジ−ｔｅｒｔ−ブチル−９−フルオレニル）ジルコニウムジクロライド０．１１６５ｇのヘキサン１０ｍｌ懸濁液に２０％トリイソブチルアルミニウムのヘキサン溶液（０．７１Ｍ）５ｍｌを加えることにより調製した溶液を添加して、室温で６時間撹拌した。静置して上澄み液を除去、ヘキサン２００ｍｌにて２回洗浄後、ヘキサンを２００ｍｌ加えて触媒懸濁液を得た。（固形重量分：１２．０ｗｔ％）
［重合］
２リットルのオートクレーブにヘキサンを１．２リットル、２０％トリイソブチルアルミニウムを１．０ｍｌ、［触媒懸濁液の調製］で得られた触媒懸濁液を１２５ｍｇ（固形分１５．０ｍｇ相当）加え、８５℃に昇温後、１−ブテンを２．４ｇ加え、分圧が０．９０ＭＰａになるようにエチレンを連続的に供給した。９０分経過後に脱圧し、スラリーを濾別後、乾燥することで４５．０ｇのエチレン系重合体を得た。
Adjustment example 6 (PE-6)
[Modification of clay]
Performed in the same manner as in Preparation Example 5.
[Preparation of catalyst suspension]
After replacing a 300 ml flask equipped with a thermometer and a reflux tube with nitrogen [denaturation of clay]
25.0 g of the organically modified clay obtained in 1 above was suspended in 165 ml of hexane, 0.3485 g of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride and 85 ml of a hexane solution of triethylaluminum (1.18 M) were added thereto, and 60 ml was added. Stir at 0 ° C. for 3 hours. After allowing to stand and cooling to room temperature, the supernatant was taken out and washed twice with 200 ml of a 1% triisobutylaluminum hexane solution. The supernatant liquid after washing was extracted to make a total of 250 ml with 5% triisobutylaluminum hexane solution. Separately, diphenylmethylene (1-cyclopentadienyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride 0.1165 g in hexane 10 ml suspension in 20% triisobutylaluminum hexane solution (0 .71M) The solution prepared by adding 5 ml was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and after washing twice with 200 ml of hexane, 200 ml of hexane was added to obtain a catalyst suspension. (Solid weight: 12.0wt%)
[polymerization]
To a 2 liter autoclave was added 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum, and 125 mg (corresponding to a solid content of 15.0 mg) of the catalyst suspension obtained in [Preparation of catalyst suspension] After raising the temperature to 85 ° C., 2.4 g of 1-butene was added, and ethylene was continuously supplied so that the partial pressure became 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 45.0 g of an ethylene polymer.
得られたエチレン系重合体は、ＭＦＲ＝４．４ｇ／１０分であり、密度は９５１ｋｇ／ｍ３であり、数平均分子量は９，０００、重量平均分子量は７７，０００あり、Ｍｗ／Ｍｎ＝８．５、分子量測定による２つのピークが観測された。また、分子量分別した際のＭｎ１０万以上のフラクション中に含まれる長鎖分岐数は、主鎖１０００炭素数あたり０．２４個であった。また、分子量分別した際のＭｎ１０万以上のフラクションの割合は、全ポリマーの１５．７ｗｔ％であった。 The obtained ethylene polymer has MFR = 4.4 g / 10 min, a density of 951 kg / m 3 , a number average molecular weight of 9,000, a weight average molecular weight of 77,000, and Mw / Mn = 8.5. Two peaks were observed by molecular weight measurement. Moreover, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.24 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn of 100,000 or more when molecular weight fractionation was 15.7 wt% of the total polymer.
調製例７（ＰＥ−７）
［粘土の変性］
調製例５と同様に行った。
［触媒懸濁液の調製］
温度計と還流管が装着された３００ｍｌのフラスコを窒素置換した後に［粘土の変性］
で得られた有機変性粘土２５．０ｇをヘキサン１６５ｍｌに懸濁させ、ジメチルシリレン（シクロペンタジエニル）（２，４，７−トリメチル−１−インデニル）ジルコニウムジクロリドを０．４４０６ｇおよびトリエチルアルミニウムのヘキサン溶液（１．１８Ｍ）８５ｍｌを添加して６０℃で３時間撹拌した。静置して室温まで冷却後に上澄み液を抜き取り、１％トリイソブチルアルミニウムのヘキサン溶液２００ｍｌにて２回洗浄した。洗浄後の上澄み液を抜き出し、５％トリイソブチルアルミニウムのヘキサン溶液にて全体を２５０ｍｌとした。次いで、別途ジフェニルメチレン（１−シクロペンタジエニル）（９−フルオレニル）ジルコニウムジクロライド０．０６２ｇのヘキサン１０ｍｌ懸濁液に２０％トリイソブチルアルミニウムのヘキサン溶液（０．７１Ｍ）５ｍｌを加えることにより調製した溶液を添加して、室温で６時間撹拌した。静置して上澄み液を除去、ヘキサン２００ｍｌにて２回洗浄後、ヘキサンを２００ｍＬ加えて触媒懸濁液を得た（固形重量分：１２．０ｗｔ％）。
［重合］
２リットルのオートクレーブにヘキサンを１．２リットル、２０％トリイソブチルアルミニウムを１．０ｍｌ、［触媒懸濁液の調製］で得られた触媒懸濁液を９２ｍｇ（固形分１１．０ｍｇ相当）加え、８５℃に昇温後、１−ブテンを１６．６ｇ加え、分圧が０．８０ＭＰａになるようにエチレンを連続的に供給した。９０分経過後に脱圧し、スラリーを濾別後、乾燥することで５９．７ｇのエチレン系重合体を得た。
Preparation Example 7 (PE-7)
[Modification of clay]
Performed in the same manner as in Preparation Example 5.
[Preparation of catalyst suspension]
After replacing a 300 ml flask equipped with a thermometer and a reflux tube with nitrogen [denaturation of clay]
25.0 g of the organically modified clay obtained in 1 above was suspended in 165 ml of hexane, 0.4406 g of dimethylsilylene (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride and hexane of triethylaluminum. 85 ml of the solution (1.18M) was added and stirred at 60 ° C. for 3 hours. After allowing to stand and cooling to room temperature, the supernatant was taken out and washed twice with 200 ml of a 1% triisobutylaluminum hexane solution. The supernatant liquid after washing was extracted to make a total of 250 ml with 5% triisobutylaluminum hexane solution. Subsequently, it was prepared by separately adding 5 ml of a 20% triisobutylaluminum hexane solution (0.71 M) to a suspension of 0.062 g of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride in 10 ml of hexane. The solution was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and after washing twice with 200 ml of hexane, 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).
[polymerization]
To a 2-liter autoclave, 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum, and 92 mg (corresponding to a solid content of 11.0 mg) of the catalyst suspension obtained in [Preparation of catalyst suspension] were added. After raising the temperature to 85 ° C., 16.6 g of 1-butene was added, and ethylene was continuously supplied so that the partial pressure was 0.80 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 59.7 g of an ethylene polymer.
得られたエチレン系重合体は、ＭＦＲ＝１２．２ｇ／１０分であり、密度は９３２ｋｇ／ｍ３であり、数平均分子量は２０，０００、重量平均分子量は７４，０００であり、Ｍｗ／Ｍｎ＝３．８、分子量測定による１つのピークが観測された。また、分子量分別した際のＭｎ１０万以上のフラクション中に含まれる長鎖分岐数は、主鎖１０００炭素数あたり０．０７個であった。また、分子量分別した際のＭｎ１０万以上のフラクションの割合は、全ポリマーの１２．５ｗｔ％であった。
（２）ポリエチレン
参考例１（ＬＬ−１）
［粘土の変性］
水１，５００ｍｌに３７％塩酸３０ｍｌおよびＮ，Ｎ−ジメチル−ベヘニルアミンを１０６ｇ加え、Ｎ，Ｎ−ジメチル−ベヘニルアンモニウム塩酸塩水溶液を調製した。平均粒径７．８μｍのモンモリロナイト３００ｇ（クニミネ工業製、商品名クニピアＦをジェット粉砕機で粉砕することによって調製した）を上記塩酸塩水溶液に加え、６時間反応させた。反応終了後、反応溶液を濾過し、得られたケーキを６時間減圧乾燥し、変性粘土化合物３７０ｇを得た。
［触媒懸濁液の調製］
窒素雰囲気下の２０Ｌステンレス容器にヘプタン２．５Ｌ、トリエチルアルミニウムのヘプタン溶液（２０ｗｔ％希釈品）をアルミニウム原子当たり４．５ｍｏｌ（３．６Ｌ）および上記で得られた変性粘土化合物３００ｇを加えて１時間撹拌した。そこへジフェニルメチレン（シクロペンタジエニル）（２，７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロライドをジルコニウム原子当たり１０ｍｍｏｌ加えて１２時間撹拌した。得られた懸濁系に脂肪族系飽和炭化水素溶媒（出光石油化学製、商品名ＩＰソルベント２８３５）８．７Ｌを加えることにより、触媒を調製した。（ジルコニウム濃度０．６７ｍｍｏｌ／Ｌ）
［重合］
高温高圧重合用に装備された槽型反応器を用い、エチレンおよび１−ヘキセンを連続的に反応器に圧入して、全圧を９０ＭＰａ、１−ヘキセン濃度を９ｍｏｌ％、水素濃度を２ｍｏｌ％になるように設定した。そして反応器を１，５００ｒｐｍで撹拌し、上記により得られた重合触媒を反応器の供給口より連続的に供給し、平均温度を２２０℃に保ち重合反応を行なった。得られた直鎖状低密度ポリエチレンはＭＦＲ＝２．０ｇ／１０分、密度９３０ｋｇ／ｍ３であった。
The obtained ethylene polymer has MFR = 12.2 g / 10 min, a density of 932 kg / m 3 , a number average molecular weight of 20,000, a weight average molecular weight of 74,000, and Mw / Mn = 3.8, one peak observed by molecular weight measurement was observed. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.07 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 12.5 wt% of the total polymer.
(2) Polyethylene Reference Example 1 (LL-1)
[Modification of clay]
To 1,500 ml of water, 30 ml of 37% hydrochloric acid and 106 g of N, N-dimethyl-behenylamine were added to prepare an aqueous solution of N, N-dimethyl-behenylammonium hydrochloride. 300 g of montmorillonite having an average particle size of 7.8 μm (manufactured by Kunimine Kogyo Co., Ltd., prepared by pulverizing trade name Kunipia F with a jet pulverizer) was added to the above hydrochloride aqueous solution and reacted for 6 hours. After completion of the reaction, the reaction solution was filtered, and the resulting cake was dried under reduced pressure for 6 hours to obtain 370 g of a modified clay compound.
[Preparation of catalyst suspension]
To a 20 L stainless steel container in a nitrogen atmosphere, add 2.5 L of heptane, a heptane solution of triethylaluminum (diluted at 20 wt%), 4.5 mol (3.6 L) per aluminum atom, and 300 g of the modified clay compound obtained above. Stir for hours. Diphenylmethylene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride was added thereto at 10 mmol per zirconium atom and stirred for 12 hours. A catalyst was prepared by adding 8.7 L of an aliphatic saturated hydrocarbon solvent (trade name IP Solvent 2835, manufactured by Idemitsu Petrochemical Co., Ltd.) to the obtained suspension system. (Zirconium concentration 0.67 mmol / L)
[polymerization]
Using a tank reactor equipped for high-temperature and high-pressure polymerization, ethylene and 1-hexene were continuously injected into the reactor so that the total pressure was 90 MPa, the 1-hexene concentration was 9 mol%, and the hydrogen concentration was 2 mol%. Was set to be. And the reactor was stirred at 1,500 rpm, the polymerization catalyst obtained by the above was continuously supplied from the supply port of the reactor, and the polymerization reaction was carried out while maintaining the average temperature at 220 ° C. The obtained linear low-density polyethylene had MFR = 2.0 g / 10 min and a density of 930 kg / m 3 .
参考例２（ＬＬ−２）下記市販の直鎖状低密度ポリエチレンを用いた。 Reference Example 2 (LL-2) The following commercially available linear low density polyethylene was used.
東ソー（株）製、（商品名）ニポロン−Ｚ ＺＦ２３０（ＭＦＲ＝２．０ｇ／１０分、密度＝９２０ｋｇ／ｍ３）
参考例３（ＬＤ−１）下記市販の高圧法低密度ポリエチレンを用いた。
Tosoh Co., Ltd., (trade name) Nipolon-Z ZF230 (MFR = 2.0 g / 10 min, density = 920 kg / m 3 )
Reference Example 3 (LD-1) The following commercially available high pressure method low density polyethylene was used.
東ソー（株）製、（商品名）ペトロセン １７５Ｋ（ＭＦＲ＝０．６ｇ／１０分、密度＝９２２ｋｇ／ｍ３） Tosoh Co., Ltd., (trade name) Petrocene 175K (MFR = 0.6 g / 10 min, density = 922 kg / m 3 )
実施例１
表１に示すポリエチレンと表２に示すポリエチレン用球晶成長速度抑制剤を表３に示す比率で配合し、６０ｃｃのインターナルミキサー（東洋精機製作所製、商品名ラボプラストミル）を用いて、温度１８０℃、回転数３０ｒｐｍで１５分間溶融混練した。次いで、得られた樹脂組成物をホットステージ付き偏光顕微鏡により観察して、球晶成長速度、球晶数および球晶サイズを算出した。また、得られた樹脂組成物を圧縮成形したシートを用いて光線透過率および透湿度を測定した。結果を表３に示す。
Example 1
The polyethylene spherulite growth rate inhibitor shown in Table 1 and the polyethylene spherulite growth rate inhibitor shown in Table 2 were blended in the ratio shown in Table 3, and the temperature was measured using a 60 cc internal mixer (trade name: Labo Plast Mill, manufactured by Toyo Seiki Seisakusho). It was melt-kneaded for 15 minutes at 180 ° C. and 30 rpm. Subsequently, the obtained resin composition was observed with a polarizing microscope with a hot stage, and the spherulite growth rate, spherulite number, and spherulite size were calculated. Moreover, the light transmittance and moisture permeability were measured using the sheet | seat which compression-molded the obtained resin composition. The results are shown in Table 3.
実施例２〜４、比較例１〜４
ポリエチレンおよびポリエチレン用球晶成長速度抑制剤を表３および表４に示すように変更した以外は、実施例１と同様にして樹脂組成物を作製し、評価を行った。結果を表３および表４に示す。
Examples 2-4, Comparative Examples 1-4
A resin composition was prepared and evaluated in the same manner as in Example 1 except that polyethylene and the spherulite growth rate inhibitor for polyethylene were changed as shown in Tables 3 and 4. The results are shown in Table 3 and Table 4.
比較例５
ポリエチレン用球晶成長速度抑制剤（ＰＥ−１）を高圧法低密度ポリエチレン（ＬＤ−１）とした以外は、実施例２と同様にして樹脂組成物を作製し、評価を行った。結果を表４に示す。尚、ＬＤ−１の特性を表２の参考例３に示した。
Comparative Example 5
A resin composition was prepared and evaluated in the same manner as in Example 2 except that the spherulite growth rate inhibitor for polyethylene (PE-1) was changed to high-pressure low-density polyethylene (LD-1). The results are shown in Table 4. The characteristics of LD-1 are shown in Reference Example 3 in Table 2.
比較例６
ポリエチレン用球晶成長速度抑制剤（ＰＥ−１）を配合しない以外は、実施例１、２と同様の評価を行った。結果を表４に示す。
Comparative Example 6
The same evaluation as in Examples 1 and 2 was performed except that the spherulite growth rate inhibitor for polyethylene (PE-1) was not blended. The results are shown in Table 4.
比較例７
ポリエチレン用球晶成長速度抑制剤（ＰＥ−２）を配合しない以外は、実施例３と同様の評価を行った。結果を表４に示す。
比較例８
ポリエチレン用球晶成長速度抑制剤（ＰＥ−３）を配合しない以外は、実施例４と同様の評価を行った。結果を表４に示す。
Comparative Example 7
The same evaluation as in Example 3 was performed except that the spherulite growth rate inhibitor for polyethylene (PE-2) was not blended. The results are shown in Table 4.
Comparative Example 8
Evaluation similar to Example 4 was performed except not mix | blending the spherulite growth rate inhibitor for polyethylene (PE-3). The results are shown in Table 4.
本発明によれば、ポリエチレンに配合することにより、高いバリヤー性、透明性を付与したポリエチレンを効率よく提供することが可能となり、その産業上の利用可能性は極めて高いものである。 According to the present invention, by blending with polyethylene, it is possible to efficiently provide polyethylene having high barrier properties and transparency, and its industrial applicability is extremely high.
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| JP2022132652A (en) * | 2017-03-28 | 2022-09-08 | 東ソー株式会社 | Resin composition and film made of the same |
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| JP2011105934A (en) * | 2009-10-22 | 2011-06-02 | Tosoh Corp | Manufacturing method for catalyst for ethylenic polymer production, manufacturing method for ethylenic polymer, and ethylenic polymer |
| JP2012126862A (en) * | 2010-12-17 | 2012-07-05 | Tosoh Corp | Blow container |
| JP2013204028A (en) * | 2012-03-29 | 2013-10-07 | Japan Polyethylene Corp | Polyethylene based resin composition and molded body of the same |
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| JP2011105934A (en) * | 2009-10-22 | 2011-06-02 | Tosoh Corp | Manufacturing method for catalyst for ethylenic polymer production, manufacturing method for ethylenic polymer, and ethylenic polymer |
| JP2012126862A (en) * | 2010-12-17 | 2012-07-05 | Tosoh Corp | Blow container |
| JP2013204028A (en) * | 2012-03-29 | 2013-10-07 | Japan Polyethylene Corp | Polyethylene based resin composition and molded body of the same |
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| JP2017122141A (en) * | 2016-01-05 | 2017-07-13 | 東ソー株式会社 | Polyethylene resin composition and medical container formed from the same |
| JP2022132652A (en) * | 2017-03-28 | 2022-09-08 | 東ソー株式会社 | Resin composition and film made of the same |
| JP7310992B2 (en) | 2017-03-28 | 2023-07-19 | 東ソー株式会社 | Resin composition and film made of the same |
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