JP2023514429A - 多段階重合プロセスにおいてアルファ-オレフィンポリマーを製造するための方法 - Google Patents
多段階重合プロセスにおいてアルファ-オレフィンポリマーを製造するための方法 Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F210/06—Propene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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Abstract
Description
a)第1気相重合反応器中、アルファ-オレフィン重合触媒および第1反応ガス混合物の存在下で、第1アルファ-オレフィンポリマーを重合し、第1アルファ-オレフィンポリマーおよび前記第1反応ガス混合物を形成する工程;
b)その中に分散した前記アルファ-オレフィン重合触媒を含む第1アルファ-オレフィンポリマーと共に、前記第1反応ガス混合物を第1気相重合反応器から連続的または間欠的に取り出し、第1生成物ストリームを形成する工程;
c)前記第1生成物ストリームを第1出口容器に導き、前記第1出口容器においてアルファ-オレフィンポリマーの層(bed)を形成する工程;
d)前記第1反応ガス混合物のストリームを前記第1出口容器から取り出し、これを前記第1気相重合反応器内に戻す工程;
e)前記出口容器から前記第1アルファ-オレフィンポリマーを連続的または間欠的に取り出し、第2生成物ストリームを形成する工程;
f)前記第2生成物ストリームを第2気相重合反応器内に導き、アルファ-オレフィン重合触媒および第2反応ガス混合物の存在下で前記第1アルファ-オレフィンポリマーを重合し、第2アルファ-オレフィンポリマーおよび前記第2反応ガス混合物を形成する工程;
g)その中に分散したアルファ-オレフィン重合触媒を含む前記第2アルファ-オレフィンポリマーと共に、前記第2反応ガス混合物を第2気相重合反応器から連続的または間欠的に取り出し、第3生成物ストリームを形成する工程;および
h)前記第3生成物ストリームを第2出口容器に導き、前記第2出口容器においてアルファ-オレフィンポリマーの層(bed)を形成する工程;
ここで、前記第2気相重合反応器から取り出された未反応ガスは圧縮機で圧縮され、該圧縮されたガスは、前記第1出口容器と前記第2気相重合反応器との間の出口に供給される。
本発明の方法で重合されるモノマーは、典型的には、2~12個の炭素原子、好ましくは2~10個の炭素原子を有するアルファ-オレフィンである。好ましくは、オレフィンはエチレンまたはプロピレンであり、場合により2~8個の炭素原子を有する1つ以上の他のアルファ-オレフィンを伴う。とりわけ好ましくは、本発明の方法は、場合により4~8個の炭素原子を有するアルファ-オレフィンから選択される1つまたは複数のコモノマーと共に、エチレンを重合するために;または、場合によりエチレンおよび4~8個の炭素原子を有するアルファ-オレフィンから選択される1つまたは複数のコモノマーと共に、プロピレンを重合するために使用される。
気相-固相オレフィン重合反応器における重合は、オレフィン重合触媒の存在下で行われる。触媒は、所望のオレフィンポリマーを生成することができる任意の触媒であり得る。適当な触媒は、とりわけ、チタン、ジルコニウムおよび/またはバナジウム触媒などの遷移金属に基づくチーグラー・ナッタ触媒である。特にチーグラー・ナッタ触媒は、幅広い範囲の分子量で、高い生産性でオレフィンポリマーを製造できるため、有用である。
第1気相重合反応器での重合は、予備重合またはスラリー相または気相で行われる別の重合段階などの、前重合段階によって先行されてもよい。このようなスラリー相反応器としては、ループ反応器が好ましい。このような重合段階は、存在する場合、当技術分野で周知の手順に従って行うことができる。本発明の重合プロセスに先行する重合および他のプロセス段階を含む適当なプロセスは、以下に開示されている:WO-A-92/12182、WO-A-96/18662、EP-A-1415999、WO-A-98/58976、EP-A-887380、WO-A-98/58977、EP-A-1860125、GB-A-1580635、US-A-4582816、US-A-3405109、US-A-3324093、EP-A-479186およびUS-A-5391654。当業者によく理解されるように、触媒は前重合段階の後も活性を維持する必要がある。
気相アルファ-オレフィン重合において、ガス状のアルファ-オレフィンモノマーがそれぞれの気相重合反応器に導入され、重合中にポリマー粒子が成長する。
ポリマー材料は、気体-固体オレフィン重合反応器から抜き出される。ポリマー材料はまた、適当な領域から、特に好ましくは流動層反応器の中間ゾーンから、気体-固体オレフィン重合反応器から排出され得る。以下では、流動層反応器について議論する。しかし、本発明の方法は、同様に、任意の他の既知のタイプの気相重合反応器で行うことができる。
容器出口を通してポリマー材料を出口容器から回収する際に、ポリマー材料から残留炭化水素を除去するためのプロセス工程を施すことができる。このようなプロセスは当技術分野で周知であり、減圧ステップ、パージステップ、ストリッピングステップ、抽出ステップなどを含むことができる。また、異なるステップの組み合わせも可能である。
Claims (11)
- 少なくとも2つの気相反応器を含む多段階重合プロセスにおいてアルファ-オレフィンポリマー組成物を製造するための方法であって、該方法は以下の工程:
a)第1気相重合反応器中、アルファ-オレフィン重合触媒および第1反応ガス混合物の存在下で、第1アルファ-オレフィンポリマーを重合し、第1アルファ-オレフィンポリマーおよび前記第1反応ガス混合物を形成する工程;
b)その中に分散した前記アルファ-オレフィン重合触媒を含む第1アルファ-オレフィンポリマーと共に、前記第1反応ガス混合物を第1気相重合反応器から連続的または間欠的に取り出し、第1生成物ストリームを形成する工程;
c)前記第1生成物ストリームを第1出口容器に導き、前記第1出口容器においてアルファ-オレフィンポリマーの層を形成する工程;
d)前記第1反応ガス混合物のストリームを前記第1出口容器から取り出し、これを前記第1気相重合反応器内に戻す工程;
e)前記出口容器から前記第1アルファ-オレフィンポリマーを連続的または間欠的に取り出し、第2生成物ストリームを形成する工程;
f)前記第2生成物ストリームを第2気相重合反応器内に導き、アルファ-オレフィン重合触媒および第2反応ガス混合物の存在下で前記第1アルファ-オレフィンポリマーを重合し、第2アルファ-オレフィンポリマーおよび前記第2反応ガス混合物を形成する工程;
g)その中に分散したアルファ-オレフィン重合触媒を含む前記第2アルファ-オレフィンポリマーと共に、前記第2反応ガス混合物を第2気相重合反応器から連続的または間欠的に取り出し、第3生成物ストリームを形成する工程;および
h)前記第3生成物ストリームを第2出口容器に導き、前記第2出口容器においてアルファ-オレフィンポリマーの層を形成する工程;
を含み、
前記第2気相重合反応器から取り出された未反応ガスは圧縮機で圧縮され、圧縮されたガスは、前記第1出口容器と前記第2気相重合反応器との間の出口に供給されることを特徴とする、方法。 - 第1気相重合反応器の上流に、少なくとも1つのスラリー反応器、好ましくはループ反応器を含む、請求項1に記載の方法。
- 第2気相重合反応器の下流に少なくとも1つのさらなる気相重合反応器を含む、請求項1または2に記載の方法。
- 前記少なくとも1つのさらなる気相重合反応器から取り出された未反応ガスを圧縮機で圧縮し、該圧縮ガスを、前記少なくとも1つのさらなる気相重合反応器のすぐ上流の気相重合反応器の出口容器に、前記出口容器と前記少なくとも1つのさらなる気相重合反応器との間の出口内へ供給する、請求項3に記載の方法。
- 気相重合反応器の出口容器の圧力が、それぞれの生成物ストリームが取り出される重合段階の圧力の10%以内である、請求項1~4のいずれかに記載の方法。
- 前記第1反応ガス混合物の前記流れが、前記出口容器内の前記のアルファ-オレフィンポリマー層のレベルより上から取り出される、請求項1~5のいずれかに記載の方法。
- アルファ-オレフィンポリマーが、前記出口容器内で、沈下した下向きのアルファ-オレフィンポリマーの移動層を形成する、請求項1~6のいずれかに記載の方法。
- 前記第2気相重合反応器は、前記第1反応ガス混合物の組成とは少なくとも1つの成分に関して異なる第2反応ガス混合物を含有し、前記第1反応ガス混合物とは異なる第2ガスが前記出口容器のいずれかに導入される、請求項1~7のいずれかに記載の方法。
- 前記第2ガスの少なくとも一部が液体の形態で導入される、請求項8に記載の方法。
- 前記第2ガスは、前記第2ガス混合物と同じ組成を有する、請求項8または9に記載の方法。
- 前記少なくとも1つのアルファ-オレフィンモノマーは、エチレン、プロピレン、1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、または1-オクテン、1-デセンおよびそれらの混合物からなる群から選択される、請求項1~10のいずれかに記載の方法。
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PCT/EP2021/054379 WO2021170552A1 (en) | 2020-02-24 | 2021-02-23 | Process for producing alpha-olefin polymers in a multistage polymerization process |
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