JPH0373571B2 - - Google Patents
Info
- Publication number
- JPH0373571B2 JPH0373571B2 JP58066920A JP6692083A JPH0373571B2 JP H0373571 B2 JPH0373571 B2 JP H0373571B2 JP 58066920 A JP58066920 A JP 58066920A JP 6692083 A JP6692083 A JP 6692083A JP H0373571 B2 JPH0373571 B2 JP H0373571B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- ethylene
- butene
- propylene
- film
- 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.)
- Expired - Lifetime
Links
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 11
- -1 stretched tapes Substances 0.000 description 11
- 238000000465 moulding Methods 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
本発明はエチレン重合体に関し、詳しくは機械
的強度が高く、かつインフレーシヨン成形性に優
れているエチレン重合体に関する。
高密度ポリエチレンは機械的強度が比較的良好
なため、射出および中空成形品、延伸テープ、繊
維等に広く用いられている。しかし、このポリエ
チレンを加工する場合、樹脂圧力が高いため、
インフレーシヨン成形時に多大の消費電力エネル
ギーを要し、また吐出量が少ない、バブル安定
性が悪い、高速成形時にフイルム表面がさめ肌
状になり商品価値を低下させるなど多くの問題点
を有している。また、高密度ポリエチレンの機械
的強度は、前述したように、比較的高いものであ
るが、単位重量当りのフイルム生産性をより一層
向上するために、さらにフイルム強度の向上が望
まれている。
本発明者らは、上記問題点を解消するために鋭
意研究した結果、所定の物性を有し、所定量のブ
テン−１およびプロピレンを含有するエチレン重
合体が機械的強度などの物性が優れている上に加
工性、生産性等も優れ、これらのバランスが良好
であることを見い出し、本発明を完成するに至つ
た。
すなわち本発明は、エチレン単位、プロピレン
単位およびブテン−１単位を含有し、密度0.935
〜0.960ｇ／cm3、極限粘度〔η〕1.5〜5.5dl／ｇ，
エチレン含量92.5〜99.7重量％，プロピレン含量
3.5〜0.1重量％，ブテン−１含量4.0〜0.2重量％
であり、かつメチル分枝数／エチル分枝数が0.06
〜10であるエチレン重合体を提供するものであ
る。
本発明のエチレン重合体はエチレンをベースと
してプロピレンおよびブテン−１が共重合したも
のあるいは該共重合体とポリエチレンとの混合物
等を包含するものである。このエチレン重合体は
密度が0.935〜0.960ｇ／cm3、好ましくは0.940〜
0.955ｇ／cm3のものである。密度が0.935ｇ／cm3未
満であると、フイルムの腰が弱いものとなり、
0.960ｇ／cm3を超えると、フイルム強度が低下し
たりフイツシユアイが発生しやすくなり好ましく
ない。また、極限粘度〔η〕は1.5〜5.5dl／ｇ、
好ましくは2.5〜5.0dl／ｇ、さらに好ましくは3.0
〜4.0dl／ｇである。〔η〕が1.5dl／ｇ未満であ
ると、フイルム強度が低下し、5.5dl／ｇを超え
ると、流動性、成形性が悪化して実用に供し得な
いものとなる。
本発明のエチレン重合体は、上記の如き密度、
〔η〕を有しており、さらにエチレン，プロピレ
ンおよびブテン−１のそれぞれの含量が特定され
たものである。エチレン含量は本発明の重合体中
にエチレン単位として含まれる量であつて92.5〜
99.7重量％、好ましくは96.7〜99.2重量％である。
これらの中にはポリエチレンにおけるエチレン単
位も含まれる。エチレン単位は本発明の重合体の
ベースとなるものであつて、92.5重量％未満であ
ると、エチレン重合体としての特性が低下するた
め好ましくない。プロピレン含量とは本発明の重
合体中にメチル分枝を有するエチレン単位の含ま
れる量を意味し、3.5〜0.1重量％、好ましくは1.8
〜0.5重量％である。プロピレン含量が0.1重量％
未満であると、フイルム成形時のバブル安定性が
悪化し、3.5重量％を超えると、フイルムの衝撃
強度が低下して実用に供し得なくなる。また、ブ
テン−１含量とは本発明の重合体中にエチル分枝
を有するエチレン単位の含まれる量を意味し、
4.0〜0.2重量％、好ましくは1.8〜0.3重量％であ
る。ブテン−１の含量が0.2重量％未満であると、
フイルム強度が低下し、かつフイルム外観が悪化
し、4.0重量％を超えると、フイルム成形時のバ
ブル安定性が悪化する。さらに、本発明の重合体
はメチル分枝数／エチル分枝数が0.06〜10、好ま
しくは0.5〜５の条件を満足するものでなければ
ならない。ここでメチル分枝数は主にプロピレン
含量にエチル分枝数は主にブテン−１含量により
決定されるものである。両者の比、すなわち前
者／後者が0.06未満であると、フイルム成形時の
バブルが不安定となり成形性が悪化し、フイルム
にしわ、たるみが発生する。一方、10を超える
と、フイルム強度が低下しかつ樹脂圧力が高くな
るためシヤークスキンが発生し、フイルム外観が
悪化する。したがつて、プロピレンおよびブテン
−１の含量は本発明の重合体の使用目的を考慮し
て適切に選定すべきである。
本発明のエチレン重合体は以上の如き物性等を
有しているものであれば良く、他には制限はない
がインフレーシヨン成形におけるバブル安定性の
面から溶融張力が10〜25ｇ、好ましくは12〜20
ｇ、より好適には14〜18ｇであるものが望まし
い。溶融張力が10ｇ未満であると、バブル安定性
が悪化して横揺れが生じフイルムにしわ、たるみ
が発生するとともにフイルム強度が低下する。一
方、25ｇを超えると、やはりバブル安定性が悪化
し、上下動するようになり好ましくない。本発明
のエチレ−プロピレン−ブテン−１三元共重合体
の成形性がよい原因は必ずしも明確ではないが、
共重合組成によりその分子量分布が微妙に変化
し、成形性に好影響を与えるためと考えられる。
本発明のエチレン重合体は、種々の方法で製造
することが可能である。例えば、チーグラー型触
媒を用いて単段で所定量のエチレン，プロピレン
およびブテン−１を圧力0.5〜15Kg／cm2、温度50
〜95℃の条件下で共重合させる方法などがあげら
れるが、特に効率良く製造するためには以下の如
き２段階による方法が好ましい。
まず、第１段階においてエチレンのみを高活性
のチーグラー型触媒の存在下で〔η〕が0.4〜1.0
dl／ｇ、好ましくは0.5〜0.8dl／ｇ、エチレン重
合量25〜80重量％、好ましくは35〜65重量％とな
るような条件下で反応せしめる。さらに、第２段
階においては、得られたポリエチレンにエチレ
ン，プロピレンおよびブテン−１を加えてエチレ
ン含量，プロピレン含量およびブテン−１含量が
所定量となるように重合を行なう。この第２段階
では〔η〕が4.0〜8.0dl／ｇ、好ましくは5.0〜
7.0dl／ｇ、重合量75〜20重量％、好ましくは65
〜35重量％となるような条件で反応せしめ、前記
物性等を有する本発明のエチレン重合体を得る。
ここで、高活性のチーグラー型触媒としては各種
のものを用い得るが、例えば特願昭57−222161号
明細書に開示されている触媒は好適に使用するこ
とができる。
２段階による重合方法において懸濁重合、溶液
重合、気相重合などいずれも可能であり、また連
続式も回分式も可能である。例えば、懸濁二段重
合を行なう場合は、溶媒としてペンタン，ｎ−ヘ
キサン，シクロヘキサン，ヘプタン，ベンゼン，
トルエンなどの不活性溶媒を用い、第１段目では
温度70〜95℃、好ましくは80〜90℃、圧力0.5〜
15Kg／cm2、好ましくは４〜10Kg／cm2、反応時間１
〜３時間で重合を行ない、第２段目では温度50〜
90℃、好ましくは60〜80℃、圧力0.5〜15Kg／cm2、
好ましくは３〜10Kg／cm2、反応時間0.5〜1.5時間
で重合を行なうことにより本発明のエチレン重合
体を得ることができる。また、極限粘度は分子量
調節剤（例えば水素など）の種類、濃度などを変
化させることにより調節可能である。
本発明のエチレン重合体は機械的強度、特にフ
イルム強度が高いため、その生産性が優れてい
る。また、フイルム成形用、押出成形用、中空成
形用の組成物として優れた加工特性を有し、特に
高密度ポリエチレンの薄肉強化フイルム用として
適している。さらに、インフレーシヨン成形に供
した場合、高速成形性にすぐれ、バブルの安定性
も良く、かつフイルム外観も良好で、樹脂圧力が
低く成形性に優れている。
次に、実施例により本発明を詳しく説明する。
製造例
固体触媒成分の製造
ｎ−ヘプタン50ml中にマグネシウムジエトキシ
ド1.0ｇ（8.8ミリモル）および市販の無水硫酸マ
グネシウム1.06ｇ（8.8ミリモル）を懸濁させ、
さらに四塩化ケイ素1.5ｇ（8.8ミリモル）とエタ
ノール1.6ｇ（35.2ミリモル）を加えて80℃で１
時間反応を行なつた。次いで、四塩化チタン５ml
（45ミリモル）を加えて98℃で３時間反応させた。
反応後、冷却静置し上澄液を傾斜法により除去し
た。次いで、新たにｎ−ヘプタン100mlを加えて
撹拌、静置、上澄液除去の洗浄操作を３回行なつ
た後、ｎ−ヘプタン200mlを加えて固体触媒成分
の分散液を得た。このもののチタン担持量を比色
法により求めた結果、42mg−Ti／ｇ−担体であ
つた。
実施例 １〜５
２容のステンレス製、オートクレーブを乾燥
窒素で置換した後、乾燥ヘキサン0.5、上記(1)
で製造した固体触媒成分を0.08ミリモル，トリエ
チルアルミニウム0.21ミリモルおよびジエチルア
ルミニウムクロライドを0.59ミリモル加えた。
次に、ポリエチレンが第１表に示す極限粘度と
なるよう計量された水素および反応器の全圧が
8.7Kg／cm2Ｇになるようにエチレンを連続的に供
給し、90℃で120分間撹拌しながら反応を行なつ
た。
次いで、反応器を40℃まで冷却後、脱気して乾
燥窒素置換した後、0.5の乾燥ヘキサンを追加
投入した。しかる後、エチレン，プロピレンおよ
びブテン−１の各所定量と第１表に示す極限粘度
となるように計量された水素を加え、全圧8.3
Kg／cm2Ｇ、温度80℃で30分間撹拌しながら反応を
行なつた。
反応終了後、得られたエチレン重合体を洗浄、
乾燥した後、その物性を測定した。結果を第１表
に示す。
比較例 １〜５
エチレン，プロピレンおよびブテン−１の配合
量を変えたこと以外は実施例と同様に行なつた。
結果を第１表に示す。
The present invention relates to an ethylene polymer, and more particularly to an ethylene polymer that has high mechanical strength and excellent inflation moldability. High-density polyethylene has relatively good mechanical strength, so it is widely used in injection and blow molded products, stretched tapes, fibers, etc. However, when processing this polyethylene, the resin pressure is high, so
Inflation molding requires a large amount of power and energy, and has many problems such as low discharge volume, poor bubble stability, and the film surface becomes rough during high-speed molding, reducing product value. ing. Further, as mentioned above, the mechanical strength of high-density polyethylene is relatively high, but in order to further improve the film productivity per unit weight, it is desired to further improve the film strength. As a result of intensive research to solve the above problems, the present inventors found that an ethylene polymer having predetermined physical properties and containing a predetermined amount of butene-1 and propylene has excellent physical properties such as mechanical strength. In addition, they have found that they have excellent workability, productivity, etc., and have a good balance between these, leading to the completion of the present invention. That is, the present invention contains ethylene units, propylene units and butene-1 units, and has a density of 0.935
~0.960g/ cm3 , intrinsic viscosity [η]1.5~5.5dl/g,
Ethylene content 92.5-99.7% by weight, propylene content
3.5-0.1% by weight, butene-1 content 4.0-0.2% by weight
and the number of methyl branches/number of ethyl branches is 0.06
10. The ethylene polymer of the present invention includes a copolymer of propylene and butene-1 based on ethylene, or a mixture of the copolymer and polyethylene. This ethylene polymer has a density of 0.935 to 0.960 g/cm 3 , preferably 0.940 to
It has a weight of 0.955g/ cm3 . If the density is less than 0.935g/cm 3 , the film will be stiff,
If it exceeds 0.960 g/cm 3 , it is not preferable because the film strength decreases and fish eyes tend to occur. In addition, the intrinsic viscosity [η] is 1.5 to 5.5 dl/g,
Preferably 2.5 to 5.0 dl/g, more preferably 3.0
~4.0dl/g. If [η] is less than 1.5 dl/g, the film strength will decrease, and if it exceeds 5.5 dl/g, the fluidity and moldability will deteriorate, making it impossible to put it into practical use. The ethylene polymer of the present invention has a density as described above,
[η], and the respective contents of ethylene, propylene and butene-1 were specified. The ethylene content is the amount contained as ethylene units in the polymer of the present invention, and is from 92.5 to
99.7% by weight, preferably 96.7-99.2% by weight.
These include ethylene units in polyethylene. Ethylene units form the base of the polymer of the present invention, and if the amount is less than 92.5% by weight, the properties of the ethylene polymer will deteriorate, which is not preferred. By propylene content is meant the amount of ethylene units with methyl branching in the polymer of the invention, 3.5 to 0.1% by weight, preferably 1.8% by weight.
~0.5% by weight. Propylene content 0.1% by weight
If it is less than 3.5% by weight, the bubble stability during film molding will deteriorate, and if it exceeds 3.5% by weight, the impact strength of the film will decrease, making it impossible to put it into practical use. In addition, the butene-1 content means the amount of ethylene units having ethyl branches contained in the polymer of the present invention,
4.0-0.2% by weight, preferably 1.8-0.3% by weight. When the content of butene-1 is less than 0.2% by weight,
The film strength decreases and the film appearance deteriorates, and if it exceeds 4.0% by weight, the bubble stability during film molding deteriorates. Furthermore, the polymer of the present invention must satisfy the condition that the number of methyl branches/the number of ethyl branches is 0.06 to 10, preferably 0.5 to 5. Here, the number of methyl branches is mainly determined by the propylene content, and the number of ethyl branches is mainly determined by the butene-1 content. If the ratio between the two, ie, the former/latter, is less than 0.06, bubbles during film molding will become unstable, resulting in poor moldability and causing wrinkles and sag in the film. On the other hand, if it exceeds 10, the film strength decreases and the resin pressure increases, causing shark skin and deteriorating the film appearance. Therefore, the contents of propylene and butene-1 should be appropriately selected in consideration of the intended use of the polymer of the present invention. The ethylene polymer of the present invention may have the physical properties as described above, and there are no other restrictions, but from the viewpoint of bubble stability in inflation molding, the melt tension is preferably 10 to 25 g. 12～20
g, more preferably 14 to 18 g. If the melt tension is less than 10 g, the bubble stability deteriorates and lateral vibration occurs, causing wrinkles and sagging of the film, and the film strength decreases. On the other hand, if it exceeds 25 g, the bubble stability will deteriorate and the bubble will move up and down, which is not preferable. Although the reason for the good moldability of the ethylene-propylene-butene-1 terpolymer of the present invention is not necessarily clear,
This is thought to be because the molecular weight distribution changes slightly depending on the copolymer composition, which has a favorable effect on moldability. The ethylene polymer of the present invention can be produced by various methods. For example, using a Ziegler type catalyst, predetermined amounts of ethylene, propylene, and butene-1 are fed in a single stage at a pressure of 0.5 to 15 kg/cm 2 and a temperature of 50 kg/cm 2 .
Examples include a method of copolymerizing under conditions of ~95°C, but for particularly efficient production, the following two-step method is preferred. First, in the first step, only ethylene is mixed with [η] of 0.4 to 1.0 in the presence of a highly active Ziegler type catalyst.
The reaction is carried out under conditions such that the amount of ethylene polymerized is 25 to 80% by weight, preferably 35 to 65% by weight. Furthermore, in the second step, ethylene, propylene and butene-1 are added to the obtained polyethylene and polymerization is carried out so that the ethylene content, propylene content and butene-1 content become predetermined amounts. In this second stage, [η] is 4.0 to 8.0 dl/g, preferably 5.0 to
7.0dl/g, polymerization amount 75-20% by weight, preferably 65
The reaction is carried out under conditions such that the concentration is 35% by weight to obtain the ethylene polymer of the present invention having the above-mentioned physical properties.
Here, various highly active Ziegler type catalysts can be used, and for example, the catalyst disclosed in Japanese Patent Application No. 57-222161 can be suitably used. In the two-stage polymerization method, suspension polymerization, solution polymerization, gas phase polymerization, etc. are all possible, and both continuous and batch methods are possible. For example, when performing suspension two-stage polymerization, the solvent may be pentane, n-hexane, cyclohexane, heptane, benzene,
Using an inert solvent such as toluene, the temperature in the first stage is 70-95°C, preferably 80-90°C, and the pressure is 0.5-95°C.
15Kg/cm 2 , preferably 4-10Kg/cm 2 , reaction time 1
Polymerization takes ~3 hours, and the temperature in the second stage is 50 ~
90℃, preferably 60~80℃, pressure 0.5~15Kg/ cm2 ,
The ethylene polymer of the present invention can be obtained by polymerizing preferably at 3 to 10 kg/cm 2 and for a reaction time of 0.5 to 1.5 hours. Moreover, the intrinsic viscosity can be adjusted by changing the type, concentration, etc. of the molecular weight modifier (for example, hydrogen). Since the ethylene polymer of the present invention has high mechanical strength, particularly film strength, its productivity is excellent. It also has excellent processing properties as a composition for film molding, extrusion molding, and blow molding, and is particularly suitable for thin reinforced films of high-density polyethylene. Furthermore, when subjected to inflation molding, it has excellent high-speed moldability, good bubble stability, good film appearance, low resin pressure, and excellent moldability. Next, the present invention will be explained in detail with reference to Examples. Production Example Production of Solid Catalyst Component 1.0 g (8.8 mmol) of magnesium diethoxide and 1.06 g (8.8 mmol) of commercially available anhydrous magnesium sulfate were suspended in 50 ml of n-heptane.
Furthermore, 1.5 g (8.8 mmol) of silicon tetrachloride and 1.6 g (35.2 mmol) of ethanol were added and
A time reaction was performed. Next, 5 ml of titanium tetrachloride
(45 mmol) was added and reacted at 98°C for 3 hours.
After the reaction, the mixture was cooled and left to stand, and the supernatant liquid was removed by a decanting method. Next, 100 ml of n-heptane was newly added and washing operations of stirring, standing, and removing the supernatant liquid were performed three times, and then 200 ml of n-heptane was added to obtain a dispersion of the solid catalyst component. The amount of titanium supported on this product was determined by a colorimetric method and was found to be 42 mg-Ti/g-support. Examples 1 to 5 A 2-volume stainless steel autoclave was replaced with dry nitrogen, and then 0.5% of dry hexane was added to the above (1).
0.08 mmol of the solid catalyst component prepared above, 0.21 mmol of triethylaluminum, and 0.59 mmol of diethylaluminum chloride were added. Next, hydrogen was measured so that the polyethylene had the intrinsic viscosity shown in Table 1, and the total pressure of the reactor was
Ethylene was continuously supplied at a rate of 8.7 Kg/cm 2 G, and the reaction was carried out at 90° C. for 120 minutes with stirring. Next, the reactor was cooled to 40°C, degassed and replaced with dry nitrogen, and then 0.5 ml of dry hexane was added. Thereafter, predetermined amounts of ethylene, propylene, and butene-1 and hydrogen weighed to give the intrinsic viscosity shown in Table 1 were added, and the total pressure was reduced to 8.3.
The reaction was carried out at Kg/cm 2 G and a temperature of 80° C. for 30 minutes with stirring. After the reaction is completed, the obtained ethylene polymer is washed,
After drying, its physical properties were measured. The results are shown in Table 1. Comparative Examples 1 to 5 The same procedures as in Examples were carried out except that the amounts of ethylene, propylene and butene-1 were changed.
The results are shown in Table 1.
【表】【table】
【表】【table】
Claims (1)
−１単位を含有し、密度0.935〜0.960ｇ／cm3，極
限粘度1.5〜5.5dl／ｇ，エチレン含量92.5〜99.7
重量％，プロピレン含量3.5〜0.1重量％，ブテン
−１含量4.0〜0.2重量％であり、かつメチル分枝
数／エチル分枝数が0.06〜10であるエチレン重合
体。1 Contains ethylene units, propylene units and butene-1 units, density 0.935-0.960 g/cm 3 , intrinsic viscosity 1.5-5.5 dl/g, ethylene content 92.5-99.7
% by weight, a propylene content of 3.5 to 0.1 weight %, a butene-1 content of 4.0 to 0.2 weight %, and a methyl branch number/ethyl branch number of 0.06 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6692083A JPS59193914A (en) | 1983-04-18 | 1983-04-18 | Ethylene polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6692083A JPS59193914A (en) | 1983-04-18 | 1983-04-18 | Ethylene polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59193914A JPS59193914A (en) | 1984-11-02 |
| JPH0373571B2 true JPH0373571B2 (en) | 1991-11-22 |
Family
ID=13329892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6692083A Granted JPS59193914A (en) | 1983-04-18 | 1983-04-18 | Ethylene polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59193914A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5610506A (en) * | 1979-07-09 | 1981-02-03 | Mitsui Petrochem Ind Ltd | Production of ethylene polymer composition |
| JPS5692937A (en) * | 1979-12-26 | 1981-07-28 | Nippon Oil Co Ltd | Resin composition for molding polyethylene film |
-
1983
- 1983-04-18 JP JP6692083A patent/JPS59193914A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5610506A (en) * | 1979-07-09 | 1981-02-03 | Mitsui Petrochem Ind Ltd | Production of ethylene polymer composition |
| JPS5692937A (en) * | 1979-12-26 | 1981-07-28 | Nippon Oil Co Ltd | Resin composition for molding polyethylene film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59193914A (en) | 1984-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR940008983B1 (en) | Process for the preparation of polyethylene | |
| JP2005510589A (en) | Transparent and flexible propylene polymer composition | |
| EP3851462A1 (en) | Catalyst for olefin polymerization | |
| JPS623177B2 (en) | ||
| JPH0330605B2 (en) | ||
| JPH09324022A (en) | Polypropylene block copolymer | |
| JPS6150084B2 (en) | ||
| JPH0368890B2 (en) | ||
| JPH0373571B2 (en) | ||
| KR20020077193A (en) | Polypropylene-based resin composition, process for producing the same and stretched film containing the same | |
| US5576400A (en) | Process for producing olefin polymer | |
| JP3397095B2 (en) | Highly transparent film and method for producing the same | |
| JPH0415820B2 (en) | ||
| JPH044324B2 (en) | ||
| JP3060085B2 (en) | Polystyrene-based copolymer, method for producing polystyrene-based copolymer, and injection-molded product | |
| JP3325420B2 (en) | Method for producing propylene-ethylene block copolymer | |
| JP3355816B2 (en) | Manufacturing method and molded product of modified polypropylene | |
| CN114539456B (en) | Preparation method of poly (1-butene) polymer, preparation method of poly (1-butene) base membrane material master batch and poly (1-butene) membrane | |
| JPH0348926B2 (en) | ||
| JP3341568B2 (en) | Propylene / ethylene block copolymer composition and method for producing the same | |
| JPH0313244B2 (en) | ||
| JPH02135243A (en) | Highly rigid polypropylene composition | |
| JP2733060B2 (en) | Propylene copolymer composition | |
| JPS6226328B2 (en) | ||
| JP2507509B2 (en) | Method for producing opaque polypropylene film |