JPS5911308A - Purification of atactic polypropylene - Google Patents
Purification of atactic polypropyleneInfo
- Publication number
- JPS5911308A JPS5911308A JP11970682A JP11970682A JPS5911308A JP S5911308 A JPS5911308 A JP S5911308A JP 11970682 A JP11970682 A JP 11970682A JP 11970682 A JP11970682 A JP 11970682A JP S5911308 A JPS5911308 A JP S5911308A
- Authority
- JP
- Japan
- Prior art keywords
- atactic polypropylene
- chlorine
- polypropylene
- atactic
- contact treatment
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
本発明は比較的多量の触媒残渣を含有する粗アタクチツ
クボリグロビレンがら触媒残渣を除去する方法に関する
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for removing catalyst residues from crude atactic polyglobylene containing relatively large amounts of catalyst residues.
立体規則性ポリプロピレン又は他のオレフィンとプロピ
レンの共重合体を製造する際に副生ずるいわゆるアタク
チックポリプロピレンは立体規則性のポリマーの物性を
損ねろため製品のポリマーから除去される。塩素含有触
媒を用いて重合により立体規則性ポリマーを得る方法に
於て、通常の溶媒法では、ポリマースラリーをアルコー
ル、水等で処理して触媒残渣を除去した後製品のポリマ
ーが不溶部として得しれろ。又可溶部としてアタクチッ
クポリプロピレン溶液が得られ、次いで溶媒を蒸発除去
して得られるアタクチックポリプロピレンは塩素として
は１００〜３００ｐｐｍ、場合によっては５０ ｐｐｍ
以下のものが得られる。しかしながら近来の触媒性能の
向上によって、生成ポリマースラリー中の触媒残渣の除
去法が簡略化され、単に触媒残渣を溶媒に可溶化するだ
けで水洗を行うことなく、溶媒かも濾過などの方法で分
離することにょつて製品を得ることが可能となっている
。So-called atactic polypropylene, which is a by-product during the production of stereoregular polypropylene or copolymers of propylene with other olefins, is removed from the product polymer so as not to impair the physical properties of the stereoregular polymer. In the method of obtaining a stereoregular polymer by polymerization using a chlorine-containing catalyst, in the usual solvent method, the polymer slurry is treated with alcohol, water, etc. to remove catalyst residue, and then the product polymer is obtained as an insoluble part. Do it. In addition, an atactic polypropylene solution is obtained as the soluble portion, and the atactic polypropylene obtained by evaporating and removing the solvent contains 100 to 300 ppm of chlorine, and in some cases 50 ppm.
You will get: However, with recent improvements in catalyst performance, the method for removing catalyst residues from the produced polymer slurry has been simplified, and by simply solubilizing the catalyst residues in a solvent, the solvent can be separated by methods such as filtration without washing with water. It is now possible to obtain products at any time.
又プロピレン自身を媒体とする重合方法に於ては、触媒
当りのポリマーの取れ高が比較的大きいため触媒残渣を
プロピレンに可溶化した後ろ過などによって媒体から分
離することによってプロピレン不溶部として製品を得る
ことができる。上記の方法では製品中の触媒残渣を少な
くすることは可能であるが、一方分離後のアククチツク
ポリプロピレンの媒体済液中には、触媒残渣が濃縮され
て存在することになるため、単にこの媒体を蒸発除去す
るだけでは得られたアタクチックポリプロピレン中の触
媒残渣が非常に多くなる。In addition, in polymerization methods that use propylene itself as a medium, the yield of polymer per catalyst is relatively large, so the catalyst residue is solubilized in propylene and then separated from the medium by filtration, etc. to produce the product as a propylene-insoluble part. Obtainable. Although it is possible to reduce the amount of catalyst residue in the product with the above method, on the other hand, the catalyst residue is concentrated in the medium liquid of the active polypropylene after separation, so it is possible to reduce the amount of catalyst residue in the product. If the medium is simply removed by evaporation, a large amount of catalyst residue will remain in the obtained atactic polypropylene.
アタクチックポリプロピレンは、他の樹脂とのブレンド
床材として或は接着剤等に用いられるが、多量の塩素を
含有するものでは、その腐食性のために用途が限定され
るので、腐食性のない比較的不純物のないアタクチック
ポリプロピレンを得る方法が望まれている。Atactic polypropylene is used as a blended flooring material with other resins or as adhesives, etc. However, if it contains a large amount of chlorine, its corrosive nature limits its use, so it must be used as a non-corrosive material. A method for obtaining atactic polypropylene that is relatively free of impurities is desired.
本発明者らは比較的塩素含有量の多いアク（３）
クチツクポリプロピレンを処理し腐食性のないアククツ
クポリプロピレンケ得ろ方法について検討した結果、特
定の処理方法を行うことによって極めて簡単に腐食性の
ないアククチツクポリプロピレンを得ることが可能で）
、ることを見い出し本発明を完成した。The present inventors investigated a method for obtaining non-corrosive aqueous polypropylene by treating aqueous polypropylene with a relatively high chlorine content (3). It is possible to obtain acid-free polypropylene)
, and completed the present invention.
本発明の目的は比較的多量の塩素を含有するアククチツ
クポリプロピレンを処理して腐食性のないアククチツク
ポリプロピレンを提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a non-corrosive acidic polypropylene by treating an active polypropylene containing a relatively large amount of chlorine.
本発明は、触媒残渣として塩素分を比較的多ｔに含有す
るアタクチックポリプロピレンを処理して腐食性のない
アタクチックポリプロピレンを得る方法に於て塩素１９
に対してハイドロタルサイト類を帆５２以上の割合でア
タクチックポリプロピレンに添加して１００℃以上の温
度で接触処理を行ない、次いでアククチツクポリプロピ
レンから不浴部を分離除去することを特徴とするアクク
チツクポリプロピレンの精製方法に関する。The present invention provides a method for obtaining non-corrosive atactic polypropylene by treating atactic polypropylene containing a relatively large amount of chlorine as a catalyst residue.
The method is characterized in that hydrotalcites are added to atactic polypropylene at a ratio of 52 or more, and a contact treatment is carried out at a temperature of 100°C or more, and then the non-bath portion is separated and removed from the atactic polypropylene. The present invention relates to a method for purifying acidic polypropylene.
（４）
本発明の方法が適用されるアタクチックポリプロピレン
については特に制限はないが、１３５℃、テトラリン清
液で測定した極限粘度数が０．０５〜５．０、好ましく
は０．１〜３．０でありプロピレンの他にエチレン、ブ
テン、ブタジェン、イソプロピレン等のコモノマーを含
有していてもよい。含有する触媒残渣は塩素分を比較的
多量、例えばｌ ０００ ｐ、ｐｍ以上含有し、灰分と
しては１０００〜５００００ｐｐｍ程度含有するもので
ある。(4) The atactic polypropylene to which the method of the present invention is applied is not particularly limited, but has an intrinsic viscosity of 0.05 to 5.0, preferably 0.1 to 3, as measured with tetralin liquid at 135°C. .0, and may contain comonomers such as ethylene, butene, butadiene, and isopropylene in addition to propylene. The catalyst residue contained contains a relatively large amount of chlorine, for example, 1000 p, pm or more, and the ash content is about 1000 to 50000 ppm.
接触処理に用いられるハイドロタルサイト類は一般式
”ｇ Ｈ１／４／Ｘ （ＯＨ）２ ＡＸ−ｍ）（２ｏ
（式中人は２価のアニオンを示し、０ ＜ ｘ （０
，５ｒｍ ン０ ）で表わされる。Ａは通常Ｃ〇七
又はＳＯ４であり好ましくはＣ０１−である〇ハイドロ
タルサイト類の使用割合は塩素１２に対して０．５１以
上、好ましくは１〜５１であり、０．５ｆ未満では耐腐
食性が劣り、又多くても耐腐食性の効果はほとんど変ら
ない。Hydrotalcites used in contact treatment have the general formula
”g H1/4/X (OH)2 AX-m) (2o
(The person in the formula represents a divalent anion, and 0 < x (0
,5rm n0 ). A is usually C〇7
or SO4, preferably C01-. The ratio of hydrotalcites used is 0.51 or more, preferably 1 to 51 to 12 chlorine. If it is less than 0.5f, corrosion resistance will be poor, and if it is less than 0.5f, corrosion resistance will be poor, and However, the corrosion resistance effect remains almost unchanged.
接触処理の温度は１００℃以上でその好ましい温度はア
タクチックポリプロピレンの性状によって異なるが通常
は環球法で求めた軟化点以上である。接触処理はできる
だけ良い接触を行うのが好ましく、強い攪拌手段を用い
るのがよい。接触時間は前述の接触手段及びアタクチッ
クポリプロピレンの粘度によって適肖な時間に設定され
るべきである。The temperature of the contact treatment is 100°C or higher, and the preferable temperature varies depending on the properties of the atactic polypropylene, but is usually higher than the softening point determined by the ring and ball method. In the contact treatment, it is preferable to achieve as good a contact as possible, and it is preferable to use strong stirring means. The contact time should be set appropriately depending on the above-mentioned contact means and the viscosity of the atactic polypropylene.
次いで上記の接触処理を行ったアタクチックポリプロピ
レンから不溶部が分離除去される。この分離はろ過、デ
カンテーション等の公知の方法が可能である。Next, the insoluble portion is separated and removed from the atactic polypropylene subjected to the above contact treatment. This separation can be carried out by known methods such as filtration and decantation.
上記の操作によって耐腐食性の良いアタクチックポリプ
ロピレンを得ることが可能であり工業的意義が犬である
。By the above-mentioned operation, it is possible to obtain atactic polypropylene with good corrosion resistance, and it has great industrial significance.
以下に実施例を示し本発明をさらに詳細に説明する。The present invention will be explained in more detail with reference to Examples below.
実施例及び比較例に於て発生塩酸はポリマーを１ｏｒ１
１００ｍ１．のフラスコに取り、２５０℃に保って発生
する塩酸又は塩素を窒素で同伴して水に吸収させ、吸収
されたαイオンを定量し測定した。In Examples and Comparative Examples, the generated hydrochloric acid was
100m1. The sample was placed in a flask and kept at 250°C, and the generated hydrochloric acid or chlorine was entrained with nitrogen and absorbed into water, and the absorbed α ions were quantitatively measured.
腐食性は２ｃｒｎｘｌＯｔ−ｎｎのみがいた銅板を内径
３ ｃｍの試験管に入れアタクチックポリプロピレンを
３０２人れ突気中で２００℃で１０時間加熱し銅板の腐
食度を目視で判定する。Corrosion was determined by placing a copper plate containing only 2 crnxlOt-nn in a test tube with an inner diameter of 3 cm, heating atactic polypropylene at 200°C for 10 hours in an atmosphere filled with 302 people, and visually determining the degree of corrosion of the copper plate.
塩素含量１０ ｐｐｍ、発生塩酸３ ｐｐｍのアタクチ
ックポリプロピレンを１とし処理前のアタクチックポリ
プロピレン（塩素含ｉ１．２ｗｔ憾、発生塩酸４００
ｐｐｍのもの）を５とし、５段階で評価した。Atactic polypropylene with a chlorine content of 10 ppm and generated hydrochloric acid of 3 ppm was used as 1, and atactic polypropylene before treatment (chlorine content of 1.2 wt, generated hydrochloric acid of 400
ppm) was set as 5 and evaluated on a 5-level scale.
実施例１．２；比較例Ｉ、２：
塩素含ｊｙｔ１．２ｗｔ％のアタクチックポリプロピレ
ン（ホモポリプロピレンで極限粘度数０．２３ ） １
００ ｙを用いて第１表に示す添加剤を加えて１ｆｉＯ
℃で３０分間攪拌しながら処理し１６０℃で２時間静置
し透明な上部を取り出し、得られた処理済のアクチツク
ボリブロピレンを用いて発生塩酸及び腐食性、及び灰分
を測定した。Example 1.2; Comparative Examples I and 2: Atactic polypropylene containing 1.2 wt% chlorine (homopolypropylene, intrinsic viscosity number 0.23) 1
Using 00y, add the additives shown in Table 1 and make 1fiO
The solution was treated at 160 DEG C. with stirring for 30 minutes, left at 160 DEG C. for 2 hours, the transparent upper part was taken out, and the generated hydrochloric acid, corrosivity, and ash content were measured using the treated active polypropylene obtained.
比較例１は対比のため処理前のアククチツ（７） クポリプロピレンについての結果を示す。Comparative example 1 is Akuchitsu (7) before treatment for comparison. The results are shown for polypropylene.
（８）(8)
Claims (1)
クチックポリプロピレンを処理して腐食性のないアタク
チックポリプロピレンを得る方法において、塩素ｌｆ当
りハイドロタルサイト類を０．５を以上の割合でアタク
チックポリプロピレンに添加シて１００℃以上の温度で
接触処理を行ない、次いでアタクチックポリプロピレン
から不溶部分を分離除去することを特徴とする、アクク
チツクポリプロピレンの精製方法。 ２）上記接触処理がアタクチックポリプロピレンの軟化
点以上の温度で行われる特許請求の範囲第１項の方法。[Scope of Claims] l) A method for obtaining non-corrosive atactic polypropylene by treating atactic polypropylene containing a relatively large amount of chlorine as a catalyst residue, in which 0.5 hydrotalcites are added per lf of chlorine. A method for purifying atactic polypropylene, which comprises adding atactic polypropylene at the above ratio, carrying out a contact treatment at a temperature of 100° C. or higher, and then separating and removing an insoluble portion from the atactic polypropylene. 2) The method according to claim 1, wherein the contact treatment is carried out at a temperature equal to or higher than the softening point of atactic polypropylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11970682A JPS5911308A (en) | 1982-07-12 | 1982-07-12 | Purification of atactic polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11970682A JPS5911308A (en) | 1982-07-12 | 1982-07-12 | Purification of atactic polypropylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5911308A true JPS5911308A (en) | 1984-01-20 |
| JPS62165B2 JPS62165B2 (en) | 1987-01-06 |
Family
ID=14768070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11970682A Granted JPS5911308A (en) | 1982-07-12 | 1982-07-12 | Purification of atactic polypropylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5911308A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003059917A1 (en) * | 2002-01-11 | 2003-07-24 | Sunoco, Inc. (R & M) | Synthetic hydrotalcites, syntheses and uses |
| US6979708B2 (en) | 2001-08-23 | 2005-12-27 | Sunoco, Inc. (R&M) | Hydrotalcites, syntheses, and uses |
-
1982
- 1982-07-12 JP JP11970682A patent/JPS5911308A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6846870B2 (en) | 2001-08-23 | 2005-01-25 | Sunoco, Inc. (R&M) | Hydrotalcites, syntheses, and uses |
| US6979708B2 (en) | 2001-08-23 | 2005-12-27 | Sunoco, Inc. (R&M) | Hydrotalcites, syntheses, and uses |
| WO2003059917A1 (en) * | 2002-01-11 | 2003-07-24 | Sunoco, Inc. (R & M) | Synthetic hydrotalcites, syntheses and uses |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62165B2 (en) | 1987-01-06 |
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