JPS6226328B2 - - Google Patents
Info
- Publication number
- JPS6226328B2 JPS6226328B2 JP54108207A JP10820779A JPS6226328B2 JP S6226328 B2 JPS6226328 B2 JP S6226328B2 JP 54108207 A JP54108207 A JP 54108207A JP 10820779 A JP10820779 A JP 10820779A JP S6226328 B2 JPS6226328 B2 JP S6226328B2
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- ethylene
- polymerization
- block copolymer
- stage
- 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
Links
- 238000006116 polymerization reaction Methods 0.000 claims description 41
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 36
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 35
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 27
- 239000005977 Ethylene Substances 0.000 claims description 27
- 229920001400 block copolymer Polymers 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 7
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 6
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical group Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Description
本発明は衝撃強度を維持した透明性と光沢性の
良好な射出ならびに押出成形用プロピレン共重合
体の製造法に関する。さらにくわしくは、プロピ
レンを重合後、エチレン含有プロピレンをこれに
重合させ、さらにエチレンもしくはエチレン高含
有のプロピレンを重合させてプロピレンブロツク
共重合体を３段階の重合により製造する方法に関
する。
従来、衝撃強度の大なる射出あるいは押出成形
用のポリプロピレンは、プロピレンをホモ重合し
た後、エチレン含有プロピレンをブロツク共重合
して得られているが、成形品とした場合、透明性
が劣るので、とくに瓶類では中味では中味が見え
にくく、また光沢性にも欠けるので、とかく商品
価値を低下させるという欠点があつた。単に透明
性や光沢性が良いものとしては、プロピレンをホ
モ重合させたものが知られているが、衝撃強度が
著しく劣るので、これを必要とする射出成形品用
や押出成形品用としては不適である。また、フイ
ルム用としては光沢性の良好なものが知られてい
るが、剛性や衝撃強度などが低く、一般成形品用
としては不向きである。
ここにおいて本発明者は衝撃強度が大で、しか
も透明性や光沢性の良いプロピレン重合体の製造
法について種々研究を重ねた結果、プロピレンブ
ロツク共重合体を３段階の重合により製造する
際、第１段目の重合において、プロピレンを全ブ
ロツク共重合体の0.01ないし１重量％の範囲で重
合したのち、これに第２段目の重合において、エ
チレンを１ないし10容量％含有するエチレン、プ
ロピレン混合物を全ブロツク共重合体の65ないし
95重量％の範囲で重合させ、さらに第３段目の重
合において、エチレンもしくはエチレンを15容量
％以上含有するエチレン、プロピレン混合物を重
合させることにより、衝撃強度を維持した透明性
ならびに光沢性の良好なプロピレンブロツク共重
合体を製造し得ることを見出すに至つた。なお本
発明の第１段目の重合において、プロピレンの重
合をおこなうのは、第２段目の重合時にかさ密度
の異常に低いものが生じ重合操作を困難にするこ
とを防止するためであり、その重合量は全ブロツ
ク共重合体の0.01ないし１重量％となるようにす
るが、好ましくは0.05ないし0.5重量％であり、
重合量が多すぎると第２段目のランダムである共
重合性を損ない、製品の透明光沢性を悪化するの
で好ましくない。なお第１段目の重合は常温常圧
でもおこなうことができる。第２段目の重合はラ
ンダム共重合になるが、これをおこなうためエチ
レン含量をエチレン、プロピレン混合物１ないし
10容量％とするが、好ましくは２ないし６容量％
とし、エチレン含量が大だとアタクチツクポリプ
ロピレンの剛性を大にし、製品の耐熱性を低下さ
せる傾向がある。第２段目の重合は全ブロツク共
重合体の65ないし95重量％の範囲でおこなうが、
65重量％以下では製品の透明性および剛性が低下
し、95重量％以上では製品の衝撃度が低下するの
で好ましくない。また、第３段目の重合はエチレ
ンのホモ重合かあるいはランダム共重合になる
が、これをおこなうためエチレン単独か、もしく
はエチレン含量をエチレン、プロピレン混合物中
15容量％以上とするが、エチレン含量が小では製
品の衝撃強度を低下するので好ましくない。
第２段目ならびに第３段目の重合の重合温度、
圧力については第１段目の重合同様、とくに限度
はないが、50ないし70℃、７ないし10Kg／cm2程度
が好適である。
本発明のプロピレンブロツク共重合体の製造に
用いられる重合触媒は、一般に知られているプロ
ピレン重合用のものが使用可能であり、たとえば
三塩化チタンと有機金属化合物からなるものであ
り、有機金属化合物はジエチル・アルミニウムク
ロライドが好適である。そして重合は溶媒あるい
は無溶媒スラリー重合法によるものが好適であ
る。なお重合に際し、分子量調節のため常法によ
り水素の添加をおこなう。
つぎに本発明を実施例によりさらに具体的に説
明する。
実施例 １
三塩化チタンとジエチル・アルミニウムクロラ
イドからなる触媒を用い、ヘプタン溶媒下、プロ
ピレンの重合量が0.35ｇとなるように、常温常圧
で６時間撹拌し第１段目の重合をおこない、つい
で、これにエチレンを９容量％含有するエチレ
ン、プロピレン混合物を毎分4.4Nl供給し、かつ
分子量調節用に水素を気相中４容量％となるよう
にして、70℃、10Kg／cm2で１時間30分第２段目の
重合をおこない、さらにエチレンを20容量％含有
するエチレン、プロピレン混合物を毎分4.9Nl供
給し、かつ第２段目の重合と同目的で水素を気相
中５容量％となるようにして、52℃、７Kg／cm2で
１時間第３段目の重合をおこないプロピレンブロ
ツク共重合製品を得た。なお、このプロピレンブ
ロツク共重合製品における各重合ブロツクの構成
比は、第１段目の重合で得られたものから順次約
0.04、76、24重量％であつた。
実施例 ２
第２段目の重合時のエチレンプロピレン混合物
のエチレン含有量を５容量％とし、これらを毎分
4Nlに、第３段目の重合時のそれを23容量％と
し、これらを毎分5.2Nlに、かつ水素含量を８容
量％にした以外は実施例１と同様におこないプロ
ピレンブロツク共重合製品を得た。なお、このプ
ロピレンブロツク共重合製品における各重合ブロ
ツクの構成比は、第１段目の重合で得られたもの
から順次約0.05、82、18重量％であつた。
実施例 ３
三塩化チタンとジエチル・アルミニウムクロラ
イドからなる触媒を用い、ヘプタン溶媒下、プロ
ピレンの重合量が0.55ｇとなるように、常温常圧
で６時間撹拌し第１段目の重合をおこない、つい
で、これにエチレンを２容量％含有するエチレ
ン、プロピレン混合物を毎分5.0Nl供給し、かつ
分子量調節用に水素を気相中10容量％となるよう
にして、70℃、10Kg／cm2で１時間30分第２段目の
重合をおこない、さらにエチレンを18容量％含有
するエチレン、プロピレン混合物を毎分4.2Nl供
給し、かつ第２段目の重合と同目的で水素を気相
中５容量％となるようにして、52℃、７Kg／cm2で
30分第３段目の重合をおこないプロピレンブロツ
ク共重合製品を得た。なお、このプロピレンブロ
ツク共重合製品における各重合ブロツクの構成比
は、第１段目の重合で得られたものから順次約
0.05、91、９重量％であつた。
以上の実施例で得られた各共重合製品の諸物性
を従来品と比較し第１表に示す。ここで従来品は
第１段目の重合なしに実施例２の第２段目の重合
に相当するところをプロピレン単独でおこない、
これに同じく第３段目の重合をほどこして得られ
たものであり、プロピレンのホモ重合体ブロツク
82重量％とプロピレン・エチレンランダム共重合
ブロツク18重量％を有するプロピレンブロツク共
重合体である。
The present invention relates to a method for producing a propylene copolymer for injection and extrusion molding that maintains impact strength and has good transparency and gloss. More specifically, the present invention relates to a method for producing a propylene block copolymer through a three-step polymerization process, in which propylene is polymerized, ethylene-containing propylene is polymerized thereto, and ethylene or ethylene-rich propylene is further polymerized. Conventionally, polypropylene for injection or extrusion molding with high impact strength has been obtained by homopolymerizing propylene and then block copolymerizing ethylene-containing propylene, but when made into molded products, the transparency is poor, so In particular, bottles have the disadvantage that it is difficult to see the contents and they also lack gloss, which lowers their commercial value. Homopolymerized propylene is known as a material that simply has good transparency and gloss, but its impact strength is extremely poor, so it is not suitable for injection molded products or extrusion molded products that require this. It is. In addition, although films with good gloss are known, they have low rigidity and impact strength, making them unsuitable for general molded products. As a result of various research into methods for producing propylene polymers that have high impact strength, transparency, and gloss, the present inventors found that when producing propylene block copolymers through three-stage polymerization, In the first stage polymerization, propylene is polymerized in a range of 0.01 to 1% by weight of the total block copolymer, and then in the second stage polymerization, an ethylene and propylene mixture containing 1 to 10% by volume of ethylene is added. 65 or more of the whole block copolymer
By polymerizing in a range of 95% by weight, and then in the third stage polymerizing ethylene or an ethylene/propylene mixture containing 15% or more by volume of ethylene, it has good transparency and gloss while maintaining impact strength. We have now discovered that it is possible to produce a propylene block copolymer. In the first stage polymerization of the present invention, propylene is polymerized in order to prevent an abnormally low bulk density from occurring during the second stage polymerization and making the polymerization operation difficult. The polymerized amount is 0.01 to 1% by weight of the total block copolymer, preferably 0.05 to 0.5% by weight,
If the amount of polymerization is too large, the random copolymerizability of the second stage will be impaired, and the transparent glossiness of the product will be deteriorated, which is not preferable. The first stage polymerization can also be carried out at room temperature and pressure. The second stage of polymerization is random copolymerization, and in order to carry out this, the ethylene content is adjusted to 1 to 1 to 1 to 1.
10% by volume, preferably 2 to 6% by volume
However, if the ethylene content is high, the rigidity of the atactic polypropylene increases and the heat resistance of the product tends to decrease. The second stage polymerization is carried out in a range of 65 to 95% by weight of the total block copolymer.
If it is less than 65% by weight, the transparency and rigidity of the product will decrease, and if it is more than 95% by weight, the impact strength of the product will decrease, which is not preferable. In addition, the third stage of polymerization is homopolymerization or random copolymerization of ethylene, and in order to perform this, ethylene is used alone or the ethylene content is reduced in a mixture of ethylene and propylene.
The content should be 15% by volume or more, but a low ethylene content is not preferred because it will reduce the impact strength of the product. Polymerization temperature of the second stage and third stage polymerization,
As with the first stage polymerization, there is no particular limit to the pressure, but 50 to 70°C and about 7 to 10 kg/cm 2 are suitable. The polymerization catalyst used in the production of the propylene block copolymer of the present invention can be any commonly known catalyst for propylene polymerization, such as one consisting of titanium trichloride and an organometallic compound; Diethyl aluminum chloride is preferred. The polymerization is preferably carried out by a solvent or solvent-free slurry polymerization method. During the polymerization, hydrogen is added by a conventional method to adjust the molecular weight. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Using a catalyst consisting of titanium trichloride and diethyl aluminum chloride, the first stage polymerization was carried out by stirring at room temperature and pressure for 6 hours so that the amount of polymerized propylene was 0.35 g in a heptane solvent, Next, an ethylene/propylene mixture containing 9% by volume of ethylene was supplied at 4.4Nl/min, and hydrogen was added to the gas phase to adjust the molecular weight to 4% by volume, and the mixture was heated at 70°C and 10Kg/cm2. The second stage polymerization was carried out for 1 hour and 30 minutes, and a mixture of ethylene and propylene containing 20% by volume of ethylene was supplied at 4.9 Nl per minute, and hydrogen was added in the gas phase for the same purpose as the second stage polymerization. The third stage polymerization was carried out at 52° C. and 7 kg/cm 2 for 1 hour to obtain a propylene block copolymer product. The composition ratio of each polymer block in this propylene block copolymer product is approximately
They were 0.04, 76, and 24% by weight. Example 2 The ethylene content of the ethylene propylene mixture during the second stage polymerization was set to 5% by volume, and the ethylene content was
A propylene block copolymer product was produced in the same manner as in Example 1, except that the polymerization rate was 23% by volume during the third stage polymerization, 5.2Nl per minute, and the hydrogen content was 8% by volume. Obtained. The composition ratio of each polymerization block in this propylene block copolymer product was approximately 0.05, 82, and 18% by weight, in order from that obtained in the first stage polymerization. Example 3 Using a catalyst consisting of titanium trichloride and diethyl aluminum chloride, the first stage polymerization was carried out in a heptane solvent by stirring at room temperature and pressure for 6 hours so that the amount of polymerized propylene was 0.55 g, Next, an ethylene/propylene mixture containing 2% by volume of ethylene was supplied at 5.0Nl/min, and hydrogen was added to the gas phase to adjust the molecular weight at 10% by volume at 70°C and 10Kg/ cm2. The second stage polymerization was carried out for 1 hour and 30 minutes, and an ethylene/propylene mixture containing 18% by volume of ethylene was supplied at 4.2 Nl/min, and hydrogen was added in the gas phase for the same purpose as the second stage polymerization. At 52℃, 7Kg/cm 2 so that the capacity is %.
The third stage polymerization was carried out for 30 minutes to obtain a propylene block copolymer product. The composition ratio of each polymer block in this propylene block copolymer product is approximately
They were 0.05, 91, and 9% by weight. The physical properties of each copolymer product obtained in the above examples are shown in Table 1 in comparison with conventional products. Here, in the conventional product, the part corresponding to the second stage polymerization of Example 2 was carried out using propylene alone without the first stage polymerization,
It was also obtained by performing the third stage of polymerization, and is a homopolymer block of propylene.
It is a propylene block copolymer having 82% by weight and 18% by weight of propylene/ethylene random copolymer blocks.
【表】【table】
【表】
上表においてヘイズは30ミクロンの厚さのフイ
ルムについての測定値であり、％の小なほうが透
明性大であり、また光沢性は射出形成品について
の測定値であり、％の大なほうが光沢性良好を意
味している。従来品はアイゾツト衝撃強度におい
て上表よりもさらに大なるものがみうけられるけ
れども、透明光沢性は上表のとき本発明によるも
のよりもはるかに劣る。[Table] In the table above, haze is a measured value for a film with a thickness of 30 microns, and the smaller the percentage, the greater the transparency.The glossiness is the measured value for an injection molded product, and the larger the percentage. This means that the gloss is better. Although the conventional products have higher Izot impact strength than those shown in the above table, the transparent glossiness is far inferior to the products according to the present invention in the above table.
Claims (1)
により製造する際、第１段目の重合において、プ
ロピレンを全ブロツク共重合体の0.01ないし１重
量％の範囲で重合したのち、これに第２段目の重
合において、エチレンを１ないし10容量％含有す
るエチレン、プロピレン混合物を全ブロツク共重
合体の65ないし95重量％の範囲で重合させ、さら
に第３段目の重合において、エチレンもしくはエ
チレンを15容量％以上含有するエチレン、プロピ
レン混合物を重合させることを特徴とするプロピ
レンブロツク共重合体の製造法。 ２ 第２段目の重合を70℃、10Kg／cm2でおこなう
特許請求の範囲第１項記載のプロピレンブロツク
共重合体の製造法。 ３ 第３段目の重合を52℃、７Kg／cm2でおこなう
特許請求の範囲第１項記載のプロピレンブロツク
共合体の製造法。 ４ 重合用触媒が三塩化チタンとジエチル・アル
ミニウムクロライドである特許請求の範囲第１項
記載のプロピレンブロツク共重合体の製造法。[Claims] 1. When producing a propylene block copolymer by three-stage polymerization, in the first stage polymerization, propylene is polymerized in a range of 0.01 to 1% by weight of the entire block copolymer, and then, In the second stage of polymerization, an ethylene/propylene mixture containing 1 to 10% by volume of ethylene is polymerized in a range of 65 to 95% by weight of the total block copolymer, and then in the third stage of polymerization, A method for producing a propylene block copolymer, which comprises polymerizing ethylene or a mixture of ethylene and propylene containing 15% by volume or more of ethylene. 2. The method for producing a propylene block copolymer according to claim 1, wherein the second stage polymerization is carried out at 70° C. and 10 kg/cm 2 . 3. The method for producing a propylene block copolymer according to claim 1, wherein the third stage polymerization is carried out at 52° C. and 7 kg/cm 2 . 4. The method for producing a propylene block copolymer according to claim 1, wherein the polymerization catalyst is titanium trichloride and diethyl aluminum chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10820779A JPS5632516A (en) | 1979-08-27 | 1979-08-27 | Production of propylene block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10820779A JPS5632516A (en) | 1979-08-27 | 1979-08-27 | Production of propylene block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5632516A JPS5632516A (en) | 1981-04-02 |
| JPS6226328B2 true JPS6226328B2 (en) | 1987-06-08 |
Family
ID=14478725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10820779A Granted JPS5632516A (en) | 1979-08-27 | 1979-08-27 | Production of propylene block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5632516A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5661416A (en) * | 1979-10-24 | 1981-05-26 | Sumitomo Chem Co Ltd | Preparation of propylene-ethylene block copolymer |
| JPS5767611A (en) * | 1980-10-15 | 1982-04-24 | Mitsubishi Petrochem Co Ltd | Preparation of propylene copolymer |
| JPS5959741A (en) * | 1982-09-30 | 1984-04-05 | Daicel Chem Ind Ltd | Organic pigment |
| JPS59195290U (en) * | 1983-06-14 | 1984-12-25 | 株式会社 潤工社 | Open tube for pipe fittings |
| TW593374B (en) | 1999-12-17 | 2004-06-21 | Idemitsu Petrochemical Co | Propylene-ethylene block copolymer, resin composition, and blow-molded article |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4924593A (en) * | 1972-06-28 | 1974-03-05 | ||
| JPS50115296A (en) * | 1974-02-27 | 1975-09-09 | ||
| JPS5335789A (en) * | 1976-09-16 | 1978-04-03 | Mitsui Toatsu Chem Inc | Preparation of propylene-ethylene copolymer |
| JPS5366984A (en) * | 1976-11-27 | 1978-06-14 | Mitsui Toatsu Chem Inc | Laminated container |
| JPS54113695A (en) * | 1978-02-27 | 1979-09-05 | Tokuyama Soda Co Ltd | Preparation of block copolymer |
| JPS5571712A (en) * | 1978-11-24 | 1980-05-30 | Mitsubishi Petrochem Co Ltd | Preparation of modified polypropylene |
-
1979
- 1979-08-27 JP JP10820779A patent/JPS5632516A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4924593A (en) * | 1972-06-28 | 1974-03-05 | ||
| JPS50115296A (en) * | 1974-02-27 | 1975-09-09 | ||
| JPS5335789A (en) * | 1976-09-16 | 1978-04-03 | Mitsui Toatsu Chem Inc | Preparation of propylene-ethylene copolymer |
| JPS5366984A (en) * | 1976-11-27 | 1978-06-14 | Mitsui Toatsu Chem Inc | Laminated container |
| JPS54113695A (en) * | 1978-02-27 | 1979-09-05 | Tokuyama Soda Co Ltd | Preparation of block copolymer |
| JPS5571712A (en) * | 1978-11-24 | 1980-05-30 | Mitsubishi Petrochem Co Ltd | Preparation of modified polypropylene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5632516A (en) | 1981-04-02 |
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