JPS6049009A - Preparation of propylene polymer - Google Patents
Preparation of propylene polymerInfo
- Publication number
- JPS6049009A JPS6049009A JP15831783A JP15831783A JPS6049009A JP S6049009 A JPS6049009 A JP S6049009A JP 15831783 A JP15831783 A JP 15831783A JP 15831783 A JP15831783 A JP 15831783A JP S6049009 A JPS6049009 A JP S6049009A
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- Japan
- Prior art keywords
- polymerization
- hydrogen
- stage
- propylene
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（目的）
本発明はプロピレン重合体あるい（Ｌｉ共重合体の製造
法に関する。DETAILED DESCRIPTION OF THE INVENTION (Objectives) The present invention relates to a method for producing a propylene polymer or (Li copolymer).
さらに詳しくは結晶性プロピレン重合体又は共重合体本
来の優れた剛性、耐衝撃性、透明性、耐熱性等を保持し
ながら、特に真空・圧空成形 押出成形等において良好
なる成形加工性を有し、かつフィッシュアイおよび表面
肌あれ発生のトラブルが解消されたプロピレン重合体の
製造法に関する。More specifically, while maintaining the excellent rigidity, impact resistance, transparency, heat resistance, etc. inherent to crystalline propylene polymers or copolymers, it has good moldability, especially in vacuum/air pressure molding, extrusion molding, etc. , and a method for producing a propylene polymer which eliminates the problems of fish eyes and surface roughness.
（従来技術）
ポリプロピレンは、その優れた物性のために食品容器、
トレイ等の真空・圧空成形品、フィルム・シートの如き
押出成形品などの分野でも広く使−用されてい乙が、溶
融時の弾性的性質に乏［７いだめに成形時の生産性が低
く、溶融弾性の改良が強く望まれてい７こ。(Prior art) Due to its excellent physical properties, polypropylene is used for food containers,
It is widely used in the fields of vacuum and air-formed products such as trays, and extrusion molded products such as films and sheets. There is a strong desire to improve the melt elasticity.
従来、ポリプロピレンに高い溶融弾性を例りする目的で
低密度ポリエチレンなどをブレンドする方法が公知ｆあ
ル（％公昭４７−３０６１．４、′１１−開昭５０−８
８４．８など）。Conventionally, a method of blending low-density polyethylene or the like with polypropylene for the purpose of exhibiting high melt elasticity has been known.
84.8 etc.).
しかし、これらの方法では、溶融弾性は向上するものの
剛ＶＬ１ 耐熱性などのポリプロピレン本来の憂れた物
件が低下し好ましくない。そこで他樹脂との混合ではな
く、ポリプロピレン自体の分子量分布を広げることによ
り溶融弾性を向上させようとする試みが種々提案されて
いる。However, although these methods improve the melt elasticity, properties such as rigidity, VL1, and heat resistance, which are inherently poor properties of polypropylene, are deteriorated, which is not preferable. Therefore, various attempts have been made to improve the melt elasticity by broadening the molecular weight distribution of polypropylene itself, rather than by mixing it with other resins.
たとえばプロピレフの重合の際に、重合を２段階で実施
し、高分子量成分と低分子量成分とを重合槽内で生成さ
せることにより溶融弾性を向上させる手法が提案されて
いる（特開昭５４−３８３８９、特開昭５４−１４４４
４８、特開昭５５−１２３６３７、特開昭ｓ ７−１−
ｓ ｓ ３０４ ）。For example, in the polymerization of propyref, a method has been proposed in which the polymerization is carried out in two stages and a high molecular weight component and a low molecular weight component are generated in a polymerization tank to improve the melt elasticity (Japanese Patent Application Laid-Open No. 1987-1999-1). 38389, Japanese Patent Publication No. 54-1444
48, JP-A-55-123637, JP-A-S 7-1-
ss 304).
しかし、この方法では溶融弾性を向上させようとして２
ｅ、分の分子量差を大きくすれば、高分子量成分の分散
が悪くなり、成形品にフィッソユアイが多発する。However, in this method, in an attempt to improve the melt elasticity,
If the molecular weight difference between e and 2 is increased, the dispersion of the high molecular weight component becomes poor, and physoyui occurs frequently in the molded product.
一方、フィッシュアイの発生を抑えるべく２成分の分Ｐ
吐差を小さくすれば溶融弾性がほとんど向−１ニしない
。On the other hand, in order to suppress the occurrence of fish eyes, two ingredients
If the discharge difference is made small, the melt elasticity will hardly change to -1.
従って、成形品にフィッシュアイを発生させずに溶融弾
訃を向トさせる方法は現在まで見い出されていなかった
。Therefore, no method has been found to date to prevent melt bombardment without causing fish eyes in the molded product.
（本発明の既四）
本究明者らは重合方式を］−：失することにより、溶ｉ
１！沖性の向Ｆとフィッ／ユアイの解消とを同時に実現
すべく鋭意検討を行なった。その結果重合を３段階で実
施し、第１段階と第３段階では低分子量成分を生成させ
、杭２段階で高分子量成分を生成させることにより、溶
融弾性の向上とフィンシュアイの解消とを同時に実現し
た重合体を得、本発明に到達した。(Article 4 of the present invention) The present inventors discovered that by losing the polymerization method, the soluble i
1! We conducted intensive studies to simultaneously achieve the goal of off-shore direction F and the elimination of fit/yuai. As a result, polymerization was carried out in three stages, with low molecular weight components being produced in the first and third stages, and high molecular weight components being produced in the second stage, thereby improving melt elasticity and eliminating Fin Shuai. At the same time, a polymer was obtained and the present invention was achieved.
すなわち、本発明はチタン含有固体触媒成分と有機アル
ミニウム化合物とを主体とする触媒系を用い、プロピレ
ンあるいはプロピレンと他のオレフィンとの重合を行な
ってプロピレフ ノ重合体あるいは共重合体を製造する
方法において、重合を３段階で実施し、第１段階と第３
段階では水素の存在下で重合を行ない、第２段階でｔま
実質的に無水素状態で重合を行なうことを特徴とする。That is, the present invention relates to a method for producing a propylev nopolymer or copolymer by polymerizing propylene or propylene with another olefin using a catalyst system mainly consisting of a titanium-containing solid catalyst component and an organoaluminum compound. , the polymerization was carried out in three stages, with the first and third stages
The method is characterized in that the polymerization is carried out in the presence of hydrogen in the step, and the polymerization is carried out in a substantially hydrogen-free state up to t in the second step.
プロピレン重合体あるいは共重合体を製造する方法であ
る。This is a method for producing propylene polymers or copolymers.
（具体的説明）
本発明において使用される触媒系はチタン含有固体触媒
成分と有機アルミニウム化合物とを主体とするものであ
る。(Specific Description) The catalyst system used in the present invention is mainly composed of a titanium-containing solid catalyst component and an organoaluminum compound.
チタン含有同体触媒成分は、固体のマグネシウム化合物
四ハロゲン化チタンおよび電子供与性化合物を接触させ
て得られる公知の担体相持型触媒成分、三塩化チタンを
主成分として含む公知の触媒成分から選ばれる。The titanium-containing isocatalyst component is selected from a known carrier-supported catalyst component obtained by contacting a solid magnesium compound, titanium tetrahalide, and an electron-donating compound, and a known catalyst component containing titanium trichloride as a main component.
共触媒の有機アルミニウム化合物は、一般式ＡｔＲｏＸ
８−信式中Ｒは炭素数２〜１ｏの炭化水素基を表わし、
Ｘはハロゲンを表わし、ｎは３≧ｎ〉１．５の数を表わ
す）で表わされる。チタン官有固体触媒成分が固体のマ
グネシウム化合物を含有する。担体相持型触媒成分であ
る場合はＡ１．Ｒ３ｔ：たはＡ／ ＲａとｇＲ２Ｘの混
合物を使用するのが好ましく、一方、三塩化チタンある
いは三塩化チタンを主成分として含む触媒成分である場
合はＡｔＲ２Ｘを使用するのが対重しい。The organoaluminum compound of the cocatalyst has the general formula AtRoX
In the 8-signal formula, R represents a hydrocarbon group having 2 to 1 carbon atoms,
X represents a halogen, and n represents a number of 3≧n>1.5). The titanium-functionalized solid catalyst component contains a solid magnesium compound. In the case of a carrier-supported catalyst component, A1. It is preferable to use a mixture of R3t: or A/Ra and gR2X. On the other hand, in the case of titanium trichloride or a catalyst component containing titanium trichloride as a main component, it is preferable to use AtR2X.
さらに本発明方法においては上記触媒および共触媒成分
のほかに第３成分として公知の電子供与性化合物を使用
することができる。Furthermore, in the method of the present invention, in addition to the above catalyst and cocatalyst components, a known electron-donating compound can be used as a third component.
重合反応はたとえばヘキサノ、ヘプタンなどの不活性溶
媒の存在下でも、不存在下すなわち液状プロピレンの存
在下あるいけ気相プロピレン中でも行なうことができる
。The polymerization reaction can be carried out in the presence or absence of an inert solvent such as hexano, heptane, etc., ie in the presence of liquid propylene or in gas phase propylene.
捷だ、プロピレンと共重合される他のオレフイントシて
ハ、エチレン、ブテン−１、ヘキセン−】、オクテン−
１等を用いることができる。Other olefins copolymerized with propylene include ethylene, butene, hexene, and octene.
1st grade can be used.
重合は３段階で行なわれる。触媒は、第１段階重合前に
添加されるのが一般的である。第２段階、第３段階重合
過程において触媒を補充することは必ずしも排除するも
のではないが、樹脂のブレンドでは得られない特性を得
ることを目的としていることに徴し、触媒は第１段階で
添加するのが好ましい。Polymerization takes place in three stages. The catalyst is generally added before the first stage polymerization. Although replenishing the catalyst in the second and third stage polymerization processes is not necessarily excluded, the catalyst is added in the first stage because the purpose is to obtain properties that cannot be obtained by blending resins. It is preferable to do so.
第１段階重合は、プロピレンあるいはプロピレンと他の
オレフィンとを水素の共存下に重合する。In the first stage polymerization, propylene or propylene and other olefins are polymerized in the presence of hydrogen.
水素は、第１段階重合によって得られる重合体のＭＦＲ
が０．１〜２００の範囲となるように制御される。一般
には水素濃度（スラＩＪ ｌ−重合においては気相部濃
度、無溶媒液状プロピレン中の重合あるいは気相法にお
いてはモノマー中の含有量を指す。以下同じ）が０．１
〜３０モル係好１しくは０．３〜２０モル係添加される
。Hydrogen increases the MFR of the polymer obtained by the first stage polymerization.
is controlled to be in the range of 0.1 to 200. In general, the hydrogen concentration (in slough IJ l-polymerization, it refers to the concentration in the gas phase; in polymerization in solvent-free liquid propylene or in the gas phase method, it refers to the content in the monomer; the same applies hereinafter) is 0.1
It is added in an amount of 1 to 30 mol, or 0.3 to 20 mol.
プロピレンと共重合される他のオレフィンは、間歇的に
添加することもできるし、寸だ、プロピレン等と共に連
続的に供給することもできる、第１段階の重合温度は一
般に４０〜９０℃、対重しくけ５０〜８０℃であり、他
のオレフィンの供給晴は第１段階重合で得られる重合体
中の他のオレフィンの含有量が、ランダム重合において
け０〜２０重届°係、ブロック共重合体においては０〜
５重量俸となるように調節されるのが望ましい。Other olefins to be copolymerized with propylene can be added intermittently or continuously together with propylene, etc. The polymerization temperature in the first stage is generally 40 to 90°C, The temperature of the other olefins is 50 to 80°C, and the content of other olefins in the polymer obtained in the first stage polymerization is 0 to 20°C in random polymerization, and the block co-monitoring temperature is 50 to 80°C. In polymers, 0-
It is desirable that the weight salary be adjusted to 5.
第１段階重合によってＭＦＲ（ＡＳＴＭＤ−１２＋３８
）が０．１〜２００、対重しくは０．５〜１ （１（
］の範囲の重合体を全重合体の：３ｏ〜６０重喰係、好
ましくは３５〜５５重量係となるように行なわれる。MFR (ASTMD-12+38
) is 0.1-200, weight is 0.5-1 (1(
] The weight ratio of the total polymer is 30 to 60, preferably 35 to 55.
第１段階重合終了後、直ちに第２段階重合に移行する。Immediately after the first stage polymerization is completed, the second stage polymerization begins.
第２段階重合は、重合槽中の残存ガスを放出して重合槽
中の水素を除いた後、水素の供給を停止ｈＬでもモノマ
ーのみを供給することによって実質的に無水素状態とし
て重合が行なわれる。In the second stage polymerization, after releasing the residual gas in the polymerization tank and removing the hydrogen in the polymerization tank, the hydrogen supply is stopped, and even if only the monomer is supplied, the polymerization is carried out in a substantially hydrogen-free state. It will be done.
第２段階重合においては、高分子蛋重合体め形成を目的
とすることから、重合温度は高温を避けるのが一般的で
あり、通常、４０〜９０℃、好１しくけ４０〜７５℃、
４．１ｉ′に好ましくは５０〜７０℃で行なわれる。In the second stage polymerization, since the purpose is to form a high-molecular protein polymer, high temperatures are generally avoided, and the polymerization temperature is usually 40-90°C, preferably 40-75°C,
4.1i' is preferably carried out at 50-70°C.
他のオレフィンの供給は、ブロック共重合の場合には、
第２段階重合によって得られるポリマー中の他のオレフ
ィンの含有量がＯ〜８０重Ｑ条、ランタン、共重合にお
いては０〜２０中量係となるように供給される。In the case of block copolymerization, the supply of other olefins is
The content of other olefins in the polymer obtained by the second stage polymerization is O to 80 FQ, lanthanum, and 0 to 20 MQ in the case of copolymerization.
＆）２段階ｊｌｊ今によって得られる重合体は、重置平
均分子量が８０万以上、好唸しくは１００万」ヅ、Ｌと
し、全重合体中の第２段階重合によって得られた重合体
の占める割合が、１〜３（）市へ（°係となるようにす
るのが卵重［７い、
重量平均分子量が８０万に達し７ないときは溶融弾性の
向−」―が小さく好−土しくない。&) The polymer obtained by the second stage polymerization has a weighted average molecular weight of 800,000 or more, preferably 1,000,000 L, and the polymer obtained by the second stage polymerization in the total polymer The proportion of egg weight should be between 1 and 3 (). It doesn't look earthy.
重量平均分子用゛は、ＧＰＣを用いて第１段階祁合によ
って得られた重合体と、第２段階重合後の重合体の両者
をｊｌｌｌ定し、両者の差と、第１段階及び第２段階の
重合量との関係から重批半均分子量を算出することによ
って得ることができる。For weight-average molecules, both the polymer obtained by the first-stage polymerization and the polymer after the second-stage polymerization are determined using GPC, and the difference between the two and the first- and second-stage polymers are determined. It can be obtained by calculating the half-average molecular weight from the relationship with the polymerization amount of each step.
第２段階重合終了後、再度水素の共存下に第３段階重合
が行なわれる。重合条件は、第１段階重合と同じ条件範
囲で行なうことができ、第３段階で得られる重合体のＭ
ＦＲｌｄｏ、１−２００、好ましくは０．５〜Ｚｏｏが
望ましく、全重合体中に占める第３段階重合によって得
られた重合体の飢は３０〜６０重１％、好ましくは３５
〜５５重拵チが適当である。After the second stage polymerization is completed, the third stage polymerization is carried out again in the presence of hydrogen. The polymerization conditions can be carried out in the same range as the first stage polymerization, and the M of the polymer obtained in the third stage can be
FRldo, 1-200, preferably 0.5-Zoo, and the proportion of the polymer obtained by the third stage polymerization in the total polymer is 30-60% by weight, preferably 35
~55 heavy Koshiraechi is appropriate.
第１段階重合で得られた重合体と第３段階重合によって
得られた重合体の割合は、■、２〜２：１の１；、０合
が望ましい。The ratio of the polymer obtained in the first stage polymerization to the polymer obtained in the third stage polymerization is preferably 1:0, 2 to 2:1.
なお、第３段階重合によって得られた重合体のＭ Ｆ”
Ｒは、第２段重合後の重合体と第３段重合後の重合体
の夫々のＭＩｉ’Ｒを測定し、第２段重合後の重合体：
茂と第３段階重合によって得られた重合体のｍ″とから
算出することによって得ることができる。In addition, M F'' of the polymer obtained by the third stage polymerization
R is determined by measuring the MIi'R of the polymer after the second stage polymerization and the polymer after the third stage polymerization, and the polymer after the second stage polymerization:
It can be obtained by calculating from the number m and the m'' of the polymer obtained by the third stage polymerization.
３段階の重合によって得られた最終重合体のＭＦＲは０
．１〜１０、好ましくは０．５〜５、他のオレフィンの
含有量は２０重ｉ％以下、好ましくは１５重耽チ以下で
ある。The MFR of the final polymer obtained by three-stage polymerization is 0.
．． The content of other olefins is 20% by weight or less, preferably 15% by weight or less.
特開昭５４．−３８３８９および特開昭５５−１２３６
３７に示されるような２段階重合では、重合体の溶融弾
性は向上するものの高分子量成分の分散不良によりフィ
ッシュアイが多発し、商品価値が失われる。これに対し
本発明の３段階重合では、高分子量成分生成の前後で低
分子量成分を生成させるために高分子量成分が低分子量
成分中に均一に分散し、その結果溶融弾性がさらに向」
−シ、フイツンユアイの発生が抑制されるものと推察さ
れる。Japanese Patent Application Publication No. 1983. -38389 and JP-A-55-1236
In the two-step polymerization as shown in No. 37, although the melt elasticity of the polymer is improved, fish eyes occur frequently due to poor dispersion of high molecular weight components, and commercial value is lost. In contrast, in the three-stage polymerization of the present invention, in order to generate a low molecular weight component before and after the high molecular weight component is generated, the high molecular weight component is uniformly dispersed in the low molecular weight component, and as a result, the melt elasticity is further improved.
- It is presumed that the occurrence of ``shi'' and ``fuitsunyuai'' will be suppressed.
以下、本発明を実施例によってさらに詳訊１に説明する
が、本発明はその要旨をこえない限り以下の実施例に限
定されるものではない。なお、実施例中、重合体の各種
物性の評価方法は次の通りである。Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In addition, in the examples, evaluation methods for various physical properties of the polymer are as follows.
■■、アイツタクチツクインデックスは製品パウダーの
沸ルｅｎ−へブタン抽出残の全体に対する割合としてめ
たものである。■■ The index is determined as the ratio of the boiling en-hebutane extraction residue in the product powder to the total amount.
Ｍ Ｆ Ｒ：メルトフローレイトの測定はＡＳＴＭ−ｌ
） −１２３８に準じて行なった、ＭＴ メルトテンン
ヨンの測定は東洋精機製作新製のメルトテンションテス
ターを用いて、シリンダ一温度１９０℃、オリフィスの
Ｌ ／ Ｄ ＝８／′２．１、押出速度１０ ｍｍ ／
ｍｉ ｎ引張速度３．９ｍ ／ ｍｉｄで行なった。MFR: Measurement of melt flow rate is ASTM-1
) -1238, the MT melt tension was measured using a new melt tension tester manufactured by Toyo Seiki Co., Ltd., at a cylinder temperature of 190°C, orifice L/D = 8/'2.1, and an extrusion speed of 10 mm. /
It was carried out at a min tensile speed of 3.9 m/mid.
フ・１ノンユアイ 以下の条件で製造したノートについ
て直径０．２＋ｎｍ以上のフィンンユアイの有無を判定
した。スクリュー径が；３５陥でＬ／１〕が２８の押出
機を用いてダイ温度２５０℃で幅：３００ ｍｍのコー
トハンガーダイから押出し、２５℃の冷却水が内部で循
環しているキャスティングドラノ、表面（硬質クロムメ
ッキ加工を施しである）に、空気送風機でおさえつけ、
厚さ０．３順のノートを製造した。1. Non-Yui Notes manufactured under the following conditions were evaluated for the presence or absence of fins with a diameter of 0.2+nm or more. Using an extruder with a screw diameter of 35 holes and L/1] of 28, the product was extruded from a coat hanger die with a width of 300 mm at a die temperature of 250°C, and a casting drano with 25°C cooling water circulating inside. , the surface (which is hard chrome plated) is pressed down with an air blower,
Notebooks with a thickness of 0.3 were manufactured.
真空成形・；（Ｌ 上述のようにして製造したノートを
用いて真空成形試験機で真空成形性のテストを実施した
。Vacuum forming: (L) A vacuum formability test was conducted using a vacuum forming tester using the notebook manufactured as described above.
実施例１および比較ｆＩ／ｌｌ １．２内容（−Ｊ ２
００ ｔのステンレス製オートクレーブにｎ−へブタン
７０ｔ１三塩化チタン（Ｔｉα３］、 ／ ３ Ａ／’
Ｃ／３東）ＩＳ チタニウＡ ”ｄ製ＡＡグレード）２
０ｇおよび／エチルア／ｌミニウ１１り［２ライド：（
０７を加え、７０℃に昇温し、水素とプロピレンを供給
して、ＭＦＲ／１．４の重合体を全重合体の４５チ製造
した、
次に、未反応ガスを放出し、新たにプロピレンのみを供
給して無水素重合を行ない、全重合体の１０％を製造し
た。最後に水素とプロピレンを供給してＭ Ｆ Ｒ４，
４の重合体を全重合体の４５％製造した。その後、未反
応ガスを放出し、ｎ−ブタノールを２を加えてＩｔ拌し
、生成固体重合体をヘプタン溶液と分離し、水洗したの
ち乾燥したところ製品重合体は１７．８に７であった。Example 1 and comparison fI/ll 1.2 Contents (-J 2
00 t stainless steel autoclave with n-hebutane 70 t1 titanium trichloride (Tiα3), / 3 A/'
C/3 East) IS Titanium A “d made AA grade) 2
0g and /ethylua/l miniu 11ri [2 rides: (
07 was added, the temperature was raised to 70°C, hydrogen and propylene were supplied, and 45 of the total polymers with MFR/1.4 were produced.Next, unreacted gas was released and new propylene was added. Anhydrous polymerization was carried out by supplying only 10% of the total polymer. Finally, hydrogen and propylene are supplied and M F R4,
Polymer No. 4 was produced as 45% of the total polymer. After that, unreacted gas was released, n-butanol was added with 2 ml of n-butanol, and the resulting solid polymer was separated from the heptane solution, washed with water, and then dried. The product polymer was 17.8 to 7. .
このときの重合結果と品質計画結果を比較例１．２と共
に表１および第１図に示しだ。比較例１け２段階重合で
、第１段階で無水素重合を実施しだものであり、比較例
２は同じく２段階重合で、第２段階で無水素重合を実施
しまたものである。表１から明らかなように実施例１は
フィッ／ユアイが全く発光せず、比較例１．２に比べて
格段に優れている。さらに溶融弾性においても比較例１
．２よりも上廻っており、それは第１図の真空成形性の
結果が優れていることと符合している。The polymerization results and quality planning results at this time are shown in Table 1 and FIG. 1 together with Comparative Example 1.2. Comparative Example 1 was a two-stage polymerization in which anhydrous polymerization was carried out in the first stage, and Comparative Example 2 was also a two-stage polymerization in which anhydrous polymerization was carried out in the second stage. As is clear from Table 1, Example 1 did not emit light at all, and was significantly superior to Comparative Examples 1.2. Furthermore, in terms of melt elasticity, Comparative Example 1
．． 2, which is consistent with the excellent vacuum formability results shown in FIG.
実施例２〜５
各段の生成Ｉ、１合とＭＦＲを変化させること以外は実
施例１と同様にして実験を行なった結果を表２に示１．
だ。表２から明らかな」：うに、各実施例ともフィッシ
ュアイの発生が無く、しかも大きな溶ｊｉｌｌｌｉ弾性
を丞している。Examples 2 to 5 Table 2 shows the results of an experiment conducted in the same manner as in Example 1 except for changing the generation I and 1 of each stage and the MFR.
is. It is clear from Table 2 that in each of the Examples, no fish eyes occurred, and moreover, they had high melting elasticity.
（以トー余白）
表１
、モ）２段目と３°段目のＭＦＲは、各殺菌後のＭＦＲ
測定結求から計算によりめた。(Table 1, Mo) The MFR of the 2nd and 3rd stage is the MFR after each sterilization.
It was determined by calculation from the measurement results.
計算式： ａ、ｍｇ ＭＦＲ（Ａ）＋ｂｚｏｇＭＩｉ”
Ｒ（１３）＝（ａ＋ｂ）ａｇ ＭＦ”ＪＲ（Ａ十Ｂ）
＊＊）１段日のＭＦＲが実測てきなかったので重合条件
から推定した値である。Calculation formula: a, mg MFR (A) + bzogMIi”
R (13) = (a + b) ag MF''JR (A + B) **) Since the MFR on the 1st stage was not actually measured, this is the value estimated from the polymerization conditions.
林−ＸＫ）洲（水素重合前後の重合体のＧ Ｐ Ｃを測
定１７、その両者の差から無水素重合時に生成した重合
体の重量平均分子…゛をめたところ １１０５てあつ：
Ｖ、。(Hayashi-XK) (Measuring the GPC of the polymer before and after hydrogen polymerization17, and determining the weight average molecule of the polymer produced during anhydrous polymerization from the difference between the two.1105Test:
V.
表２Table 2
第１図は、本発明によって得られた重合体と従来法によ
って得られた重合体の／−１垂れ試験結果を示す図であ
る。
特許出ｈｊ人 王菱油化株式会社
代理人 弁理士 古 川 秀 利
（他１名）
第１図
加熱時間（才少）FIG. 1 is a diagram showing the results of a /-1 sag test of a polymer obtained by the present invention and a polymer obtained by a conventional method. Patent issuer: Agent of Wangling Oil & Chemical Co., Ltd. Patent attorney Hidetoshi Furukawa (and 1 other person) Figure 1 Heating time (skilled)
Claims (1)
主体とする触媒系を用い、プロピレンあるいはプロピレ
ンと他のオレフィンとの重合を行なって、プロピレンの
重合体あるいは共重合体を製造する方法において、重合
を３段階で実施し、第１段階と第３段階では水素の存在
下で重合を行ない第２段階では実質的に無水素状態で重
合を行なうことを特徴とするプロピレン重合体あるいは
共重合体を製造する方法。A method for producing a propylene polymer or copolymer by polymerizing propylene or propylene with another olefin using a catalyst system mainly consisting of a titanium-containing solid catalyst component and an organoaluminum compound. Propylene polymer or copolymer is produced by polymerizing in the presence of hydrogen in the first and third stages and in a substantially hydrogen-free state in the second stage. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15831783A JPS6049009A (en) | 1983-08-30 | 1983-08-30 | Preparation of propylene polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15831783A JPS6049009A (en) | 1983-08-30 | 1983-08-30 | Preparation of propylene polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6049009A true JPS6049009A (en) | 1985-03-18 |
| JPH0420003B2 JPH0420003B2 (en) | 1992-03-31 |
Family
ID=15668988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15831783A Granted JPS6049009A (en) | 1983-08-30 | 1983-08-30 | Preparation of propylene polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6049009A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4950720A (en) * | 1988-04-29 | 1990-08-21 | Exxon Chemical Patents Inc. | Modified polypropylene, process for making and article made from the same |
| US5519090A (en) * | 1991-06-12 | 1996-05-21 | Basf Aktiengesellschaft | High-flow blend of different propylene polymers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54139693A (en) * | 1978-04-21 | 1979-10-30 | Sumitomo Chem Co Ltd | Preparation of propylene-ethylene block copolymer |
| JPS5516048A (en) * | 1978-07-20 | 1980-02-04 | Sumitomo Chem Co Ltd | Preparation of propylene-ethylene block copolymer |
| JPS5734112A (en) * | 1980-08-07 | 1982-02-24 | Sumitomo Chem Co Ltd | Production of propylene block copolymer |
-
1983
- 1983-08-30 JP JP15831783A patent/JPS6049009A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54139693A (en) * | 1978-04-21 | 1979-10-30 | Sumitomo Chem Co Ltd | Preparation of propylene-ethylene block copolymer |
| JPS5516048A (en) * | 1978-07-20 | 1980-02-04 | Sumitomo Chem Co Ltd | Preparation of propylene-ethylene block copolymer |
| JPS5734112A (en) * | 1980-08-07 | 1982-02-24 | Sumitomo Chem Co Ltd | Production of propylene block copolymer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4950720A (en) * | 1988-04-29 | 1990-08-21 | Exxon Chemical Patents Inc. | Modified polypropylene, process for making and article made from the same |
| US5519090A (en) * | 1991-06-12 | 1996-05-21 | Basf Aktiengesellschaft | High-flow blend of different propylene polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0420003B2 (en) | 1992-03-31 |
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