JP2017165916A5

JP2017165916A5 -

Info

Publication number: JP2017165916A5
Application number: JP2016054559A
Authority: JP
Filing date: 2016-03-17
Publication date: 2019-02-07
Anticipated expiration: 2036-03-17

Description

すなわち、本発明は以下のエチレン系マクロモノマーの製造方法を提供するものである。
［１］下記条件（イ）〜（ハ）を満たすエチレン系マクロモノマー
（イ）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が１．０以上４．０未満、
（ロ）炭素数１０００個当たりのビニル基数（Ｖ_１）が０．２５個〜１０個であり、かつ、Ｚ_１（＝Ｖ _１ ×Ｍｎ／１４０００）が０．５０〜１．１である、および
（ハ）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される重量平均分子量（Ｍｗ）が３０００〜１０００００である、
を得るための製造方法であって、
下記必須成分（Ａ）および（Ｂ）を含むオレフィン重合用触媒
成分（Ａ）：遷移金属元素を含む架橋シクロペンタジエニルインデニル化合物、および
成分（Ｂ）：層状ケイ酸塩、
を用いて、エチレンを単独重合またはエチレン以外のα−オレフィンと共重合することを特徴とするエチレン系マクロモノマーの製造方法。 That is, the present invention provides the following method for producing an ethylene macromonomer.
[1] Ethylene-based macromonomer satisfying the following conditions (A) to (C) (A) Ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (Mw / Mn) is 1.0 or more and less than 4.0,
(B) The number of vinyl groups per 1000 carbon atoms (V ₁ ) is 0.25 to 10 and Z ₁ (= V ₁ × Mn / 14000 ) is 0.50 to 1.1. And (c) the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 3000 to 100,000.
A manufacturing method for obtaining
Olefin polymerization catalyst component (A) containing the following essential components (A) and (B): a bridged cyclopentadienyl indenyl compound containing a transition metal element, and component (B): a layered silicate,
A process for producing an ethylene-based macromonomer, characterized in that ethylene is homopolymerized or copolymerized with an α-olefin other than ethylene.

２．本発明で製造されるエチレン系マクロモノマーの特性
本発明により得られるエチレン系マクロモノマーは、下記条件（イ）〜（ハ）を満足する。
（イ）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が１．０以上４．０未満
（ロ）炭素数１０００個当たりのビニル基数（Ｖ_１）が０．２５個〜１０個であり、かつ、Ｚ_１（＝Ｖ _１ ×Ｍｎ／１４０００）が０．５０〜１．１である
（ハ）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される重量平均分子量（Ｍｗ）が３０００〜１０００００である 2. Characteristics of the ethylene-based macromonomer produced according to the present invention The ethylene-based macromonomer obtained according to the present invention satisfies the following conditions (A) to (C).
(A) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 1.0 or more and less than 4.0 (b) 1000 carbon atoms. (C) Gel permeation chromatography wherein the number of vinyl groups per unit (V ₁ ) is from 0.25 to 10 and Z ₁ (= V ₁ × Mn / 14000 ) is from 0.50 to 1.1. The weight average molecular weight (Mw) measured by chromatography (GPC) is 3000 to 100,000.

２−２．条件（ロ）ビニル基数Ｖ_１
本発明により得られるエチレン系マクロモノマーの炭素数１０００個当たりのビニル基数（Ｖ_１）は０．２５個〜１０個であり、好ましくは０．２８個〜７個であり、より好ましくは０．３０個〜５個であり、更に好ましくは０．３２個〜３個であり、かつ、Ｚ_１（＝Ｖ _１ ×Ｍｎ／１４０００）は０．５０〜１．１であり、好ましくは０．５５〜１．０である。 2-2. Condition (b) Number of vinyl groups V ₁
The number of vinyl groups (V ₁ ) per 1000 carbon atoms of the ethylene-based macromonomer obtained according to the present invention is 0.25 to 10, preferably 0.28 to 7, more preferably 0.8. 30 to 5, more preferably 0.32 to 3, and Z ₁ (= V ₁ × Mn / 14000 ) is 0.50 to 1.1, preferably 0.55. -1.0.

なお、本発明で、エチレン系マクロモノマーの全１０００炭素原子あたりのビニル基数（Ｖ_１）、ビニリデン基数（Ｖ_２）、ビニレン基数（Ｖ_３）、三置換不飽和結合数（Ｖ_４）は、^１Ｈ−核磁気共鳴法（^１Ｈ−ＮＭＲ）で測定したものをいう。また、Ｚ_２（＝Ｖ _２ ×Ｍｎ／１４０００）、Ｚ_３（＝Ｖ _３ ×Ｍｎ／１４０００）、Ｚ_４（＝Ｖ _４ ×Ｍｎ／１４０００）は、それぞれマクロモノマー分子１本当たりのビニリデン基数、ビニレン基数、三置換不飽和結合数を近似する値である。ビニル基数（Ｖ１）、ビニリデン基数（Ｖ２）、ビニレン基数（Ｖ３）、三置換不飽和結合数（Ｖ４）は、それぞれ以下の構造式で表わされる基を１個として数える。 In the present invention, the number of vinyl groups (V ₁ ), the number of vinylidene groups (V ₂ ), the number of vinylene groups (V ₃ ) and the number of trisubstituted unsaturated bonds (V ₄ ) per 1000 carbon atoms of the ethylene macromonomer are: ^This is measured by ¹ H-nuclear magnetic resonance method ( ¹ H-NMR). Z ₂ (= V ₂ × Mn / 14000 ), Z ₃ (= V ₃ × Mn / 14000 ), Z ₄ (= V ₄ × Mn / 14000 ) is the number of vinylidene groups per macromonomer molecule , It is a value approximating the number of vinylene groups and the number of trisubstituted unsaturated bonds . The number of vinyl groups (V1), the number of vinylidene groups (V2), the number of vinylene groups (V3), and the number of trisubstituted unsaturated bonds (V4) are each counted as one group represented by the following structural formula.

４．評価
表２及び表３に示す実験結果を参酌しながら、実験結果を説明する。
実施例１は、触媒の重合活性が良好であり、メルトフローレート（ＭＦＲ）の点でも生産性の障害にならない良好な流動性を示した。実施例１で得られたエチレン系マクロモノマー（エチレン・１−ヘキセン共重合体）の特性をみると、Ｍｗ／Ｍｎ値（条件（イ））が２．２であることから狭い分子量分布を有し、炭素数１０００個当たりのビニル基数（Ｖ_１）（条件（ロ−１））が０．５１であり、Ｚ_１（＝Ｖ _１ ×Ｍｎ／１４０００）（条件（ロ−２））が０．６０であり、かつＶ_１／Ｖ_２値（条件（ホ））が５１超であることから良好な重合反応性を発揮できる高い末端ビニル含有率を有するが成形加工性等を悪化させるほど過剰な量の末端ビニルを含んでおらず、Ｍｗ値（条件（ハ））が３６２００であることから成形加工性等の点で良好な低分子量を有し、分子量３０００から１００万の間での分岐指数ｇ’の最低値（ｇＬ）（条件（ニ））が０．９２であることから分岐構造が少なくてマクロモノマーとして好ましく、エチレン以外のα−オレフィン含量も適切であった。
実施例２は、触媒成分当りのマクロモノマーの生産性を向上させることを目的として、重合条件のエチレン分圧を大きくしたこと以外は実施例１と同様に重合反応を行ったところ、狙い通り触媒の重合活性が実施例１よりも大きくなった。また、得られたマクロモノマーの物性は実施例１で得られたものと同様に良好であった。
実施例３は、重合体粒子の溶融付着が生じにくい低温重合でもマクロモノマーが高い生産性で製造可能か確認することを目的として、重合条件のエチレン分圧を大きくし、重合温度を低くしたこと以外は実施例１と同様に重合反応を行ったところ、触媒の重合活性が実施例１よりも小さくなったが、重合温度が低いことを考慮すると触媒の重合活性は良好であり、比較例１よりも遙かに高い重合活性であった。また、得られたマクロモノマーの物性は実施例１で得られたものと同様に良好であった。
一方、比較例１は、触媒成分（Ａ）として実施例１と同じ錯体１を用いるが、触媒成分（Ｂ）層状ケイ酸塩を用いる代わりにメチルアルミノキサンを用いて固体触媒を合成し、当該固体触媒を用いて実施例１と同じ条件でエチレン系マクロモノマー（エチレン・１−ヘキセン共重合体）を製造した実験例である。比較例１を実施例１と対比すると、触媒の重合活性が低く、メルトフローレート（ＭＦＲ）の点では明らかに流動性が悪かった。
比較例１で得られたエチレン系マクロモノマーの特性をみると、Ｍｗ／Ｍｎ値（条件（イ））が４．０であることから実施例１よりも広い分子量分布を有し、炭素数１０００個当たりのビニル基数（Ｖ_１）（条件（ロ−１））が０．４２であり、Ｚ_１（＝Ｖ _１ ×Ｍｎ／１４０００）（条件（ロ−２））が０．５３であり、かつＶ_１／Ｖ_２値（条件（ホ））が２１であることから実施例１よりも低い末端ビニル含有率を有し、Ｍｗ値（条件（ハ））が７１５００であることから成形加工性等の点で実施例１よりも高い分子量を有し、分子量３０００から１００万の間での分岐指数ｇ’の最低値（ｇＬ）（条件（ニ））が０．５４であることから実施例１よりも分岐構造が多かった。
また比較例１で得られたエチレン系マクロモノマーは、炭素数１０００個当たりのビニレン基数（Ｖ_３）、炭素数１０００個当たりの三置換不飽和結合数（Ｖ_４）、これらに対応するマクロモノマー分子一本当たりのビニレン基数の近似値（Ｚ_３＝Ｖ _３ ×Ｍｎ／１４０００）およびマクロモノマー分子一本当たりの三置換不飽和結合数の近似値（Ｚ_４＝Ｖ _４ ×Ｍｎ／１４０００）が、実施例１と比べて低かった。 4). Evaluation The experimental results will be described with reference to the experimental results shown in Tables 2 and 3.
In Example 1, the polymerization activity of the catalyst was good, and good fluidity that did not hinder productivity in terms of melt flow rate (MFR) was exhibited. Looking at the characteristics of the ethylene-based macromonomer (ethylene / 1-hexene copolymer) obtained in Example 1, the Mw / Mn value (condition (ii)) is 2.2, so that it has a narrow molecular weight distribution. And the number of vinyl groups per 1000 carbon atoms (V ₁ ) (condition (B-1)) is 0.51, and Z ₁ (= V ₁ × Mn / 14000 ) (condition (B-2)) is 0. .60, and the V ₁ / V ₂ value (condition (e)) is more than 51, so that it has a high terminal vinyl content capable of exhibiting good polymerization reactivity, but is excessive so as to deteriorate the molding processability and the like. It has a low molecular weight that is good in terms of molding processability, etc., and has a molecular weight of between 3000 and 1,000,000 because it does not contain a large amount of terminal vinyl and the Mw value (condition (c)) is 36200. The minimum value (gL) (condition (d)) of the index g ′ is 0.92. Preferably a less macromonomer branched structure and a, alpha-olefin content other than ethylene was also appropriate.
In Example 2, the polymerization reaction was carried out in the same manner as in Example 1 except that the ethylene partial pressure of the polymerization conditions was increased for the purpose of improving the productivity of the macromonomer per catalyst component. The polymerization activity of was higher than that of Example 1. Further, the physical properties of the obtained macromonomer were as good as those obtained in Example 1.
In Example 3, the ethylene partial pressure of the polymerization conditions was increased and the polymerization temperature was lowered for the purpose of confirming whether the macromonomer can be produced with high productivity even at low temperature polymerization in which the polymer particles are less likely to melt and adhere. Except for the above, the polymerization reaction was carried out in the same manner as in Example 1. As a result, the polymerization activity of the catalyst was smaller than that in Example 1. However, considering that the polymerization temperature was low, the polymerization activity of the catalyst was good. The polymerization activity was much higher than that. Further, the physical properties of the obtained macromonomer were as good as those obtained in Example 1.
On the other hand, Comparative Example 1 uses the same complex 1 as Example 1 as the catalyst component (A), but instead of using the catalyst component (B) layered silicate, a solid catalyst is synthesized using methylaluminoxane, and the solid This is an experimental example in which an ethylene-based macromonomer (ethylene / 1-hexene copolymer) was produced under the same conditions as in Example 1 using a catalyst. When Comparative Example 1 was compared with Example 1, the polymerization activity of the catalyst was low, and the fluidity was clearly poor in terms of melt flow rate (MFR).
Looking at the characteristics of the ethylene-based macromonomer obtained in Comparative Example 1, the Mw / Mn value (condition (A)) is 4.0, so that it has a molecular weight distribution wider than that of Example 1, and has a carbon number of 1000 The number of vinyl groups per unit (V ₁ ) (condition (B-1)) is 0.42, Z ₁ (= V ₁ × Mn / 14000 ) (condition (B-2)) is 0.53, In addition, since the V ₁ / V ₂ value (condition (e)) is 21, the terminal vinyl content is lower than in Example 1, and the Mw value (condition (c)) is 71500, so that the molding processability is achieved. The molecular weight higher than that of Example 1 in terms of the above, etc., and the minimum value (gL) (condition (d)) of the branching index g ′ between 3000 and 1,000,000 is 0.54. There were more branch structures than 1.
In addition, the ethylene-based macromonomer obtained in Comparative Example 1 has the number of vinylene groups per 1000 carbon atoms (V ₃ ), the number of trisubstituted unsaturated bonds per 1000 carbon atoms (V ₄ ), and the macromonomer corresponding thereto. The approximate number of vinylene groups per molecule (Z ₃ = V ₃ × Mn / 14000 ) and the approximate number of trisubstituted unsaturated bonds per macromonomer molecule (Z ₄ = V ₄ × Mn / 14000 ) It was low compared with Example 1.

Claims

Ethylene-based macromonomer satisfying the following conditions (a) to (c) (a) Ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (Mw / Mn) 1.0 or more and less than 4.0,
(B) The number of vinyl groups per 1000 carbon atoms (V ₁ ) is 0.25 to 10 and Z ₁ (= V ₁ × Mn / 14000 ) is 0.50 to 1.1. And (c) the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 3000 to 100,000.
A manufacturing method for obtaining
Olefin polymerization catalyst component (A) containing the following essential components (A) and (B): a bridged cyclopentadienyl indenyl compound containing a transition metal element, and component (B): a layered silicate,
A process for producing an ethylene-based macromonomer, characterized in that ethylene is homopolymerized or copolymerized with an α-olefin other than ethylene.

The said essential component (A) is a compound represented by the following general formula (1c), The manufacturing method of the ethylene-type macromonomer of Claim 1 characterized by the above-mentioned.

[In the formula (1c), M ^1c represents a transition metal of Ti, Zr or Hf. X ^1c and X ^2c each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, or 1 to 20 carbon atoms. A hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ^1c and Q ^2c each independently represent a carbon atom, a silicon atom, or a germanium atom. R ^1c independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of the four R ^1cs are bonded to form a ring together with Q ^1c and Q ^2c. Also good. ^mc is 0 or 1, and when ^mc is 0, Q ^1c is directly bonded to a conjugated 5-membered ring containing R ^2c . R ^2c and R ^4c are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 carbon atom. -20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing an oxygen atom, or a C1-C20 hydrocarbon group-substituted silyl group. R ^3c represents a substituted aryl group represented by the following general formula (1-ac). ]

[In the formula (1-ac), Y ^1c represents an atom of Group 14, 15 or 16 of the periodic table. R ^5c , R ^6c , R ^7c , R ^8c and R ^9c are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, a carbon number containing oxygen or nitrogen 1-20 hydrocarbon group, C1-C20 hydrocarbon group-substituted amino group, C1-C20 alkoxy group, C1-C18 silicon-containing hydrocarbon group containing 1-6 silicon atoms, carbon A halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, and each group of R ^5c , R ^6c , R ^7c , R ^8c and R ^9c is an adjacent group They may be bonded to form a ring together with the atoms bonded to them. n ^c is 0 or 1, if ^{n c} is ^0, there is no substituent ^{R 5c} to ^{Y 1c.} ^pc is 0 or 1, and when ^pc is 0, the carbon atom to which R ^7c is bonded and the carbon atom to which R ^9c are bonded are directly bonded. When Y ^1c is a carbon atom, at least one of R ^5c , R ^6c , R ^7c , R ^8c , and R ^9c is not a hydrogen atom. ^Pc is 0 when R ^2c is not a five-membered ring structure substituent. That is, at least one of R ^2c and R ^3c is a substituent having a five-membered ring structure. ]

3. The essential component (A) is a bridged cyclopentadienyl indenyl compound containing a transition metal element having a five-membered ring structure substituent on the indenyl ring. Of producing an ethylene-based macromonomer.

The said essential component (B) is the layered silicate processed with the acid or metal salt, The manufacturing method of the ethylene-type macromonomer as described in any one of Claims 1-3 characterized by the above-mentioned.

The method for producing an ethylene macromonomer according to any one of claims 1 to 4, wherein the ethylene macromonomer further satisfies the following condition (2).
(2) The lowest value (g _L ) of the branching index g ′ measured by a GPC measuring apparatus in which a differential refractometer, a viscosity detector, and a light scattering detector are combined between 3000 and 1,000,000 is 0. 75-1.00.

The method for producing an ethylene macromonomer according to any one of claims 1 to 5, wherein the ethylene macromonomer further satisfies the following condition (e).
(E) is the ratio of the vinyl groups _{(V 1)} per number 1000 carbon vinylidene groups per number 1000 carbon _{_{(V 2) (V 1 /}} V 2) is 22 or more.

The ethylene-based macromonomer according to any one of claims 1 to 6, wherein ethylene is homopolymerized or copolymerized with an α-olefin other than ethylene under the following conditions (1) to (3). Production method.
[Polymerization conditions]
(1) Polymerization temperature: 30 ° C. or more and less than 90 ° C. (2) Ethylene partial pressure: 0.3 MPa or more and less than 3 MPa (3) Polymerization time: 0.3 hour or more and less than 30 hours