JPH083008B2 - Polypropylene resin composition - Google Patents
Polypropylene resin compositionInfo
- Publication number
- JPH083008B2 JPH083008B2 JP62288303A JP28830387A JPH083008B2 JP H083008 B2 JPH083008 B2 JP H083008B2 JP 62288303 A JP62288303 A JP 62288303A JP 28830387 A JP28830387 A JP 28830387A JP H083008 B2 JPH083008 B2 JP H083008B2
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene
- syndiotactic polystyrene
- weight
- resin composition
- polypropylene resin
- 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 - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は剛性、ヘイズなどの物性の良好なポリプロピ
レン樹脂組成物に関する。詳しくは、特定の化合物を含
むポリプロピレン樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polypropylene resin composition having good physical properties such as rigidity and haze. Specifically, it relates to a polypropylene resin composition containing a specific compound.
ポリプロピレンは耐熱性、剛性に優れた安価な樹脂で
あるが、結晶化度が比較的小さいので通常の方法で成型
したのでは、成型物の剛性が樹脂本来のものに比較して
不良であるという問題があり、この問題を種々の核剤添
加して解決することが試みられており、中でもある種の
高分子化合物を添加する方法（例えば、特開昭60−1397
31号公報）は添加物が成型物表面に浮きだすといった問
題もなく、しかも比較的少量の添加で効果的であるなど
優れた方法である。Polypropylene is an inexpensive resin with excellent heat resistance and rigidity, but because of its relatively low degree of crystallinity, it is said that the rigidity of the molded product is inferior to that of the original resin when molded by an ordinary method. There is a problem, and attempts have been made to solve this problem by adding various nucleating agents. Among them, a method of adding a certain kind of polymer compound (for example, JP-A-60-1397).
No. 31) is an excellent method in which there is no problem that the additive floats on the surface of the molded product, and the addition of a relatively small amount is effective.
しかしながら、ある種の高分子化合物を添加する方法
は上記したように優れているが、用いられる高分子化合
物はその合成方法が難しく、入手し難たいという問題が
あり、さらに有用な他の化合物が望まれている。However, although the method of adding a certain type of polymer compound is excellent as described above, the polymer compound used has a problem that its synthesis method is difficult and difficult to obtain, and further useful other compounds are available. Is desired.
本発明者らは、ポリプロピレンの結晶化度を向上させ
うる新たな高分子化合物について鋭意探索し、特定の高
分子化合物の添加がポリプロピレンの結晶化度を大幅に
向上させうることを見出し、本発明を完成した。The present inventors have diligently searched for a new polymer compound that can improve the crystallinity of polypropylene, and found that the addition of a specific polymer compound can significantly improve the crystallinity of polypropylene. Was completed.
即ち、本発明はシンジオタクチックポリスチレン或い
はその水素化物をポリプロピレンに対して0.00001重量
％以上１重量％未満含有することを特徴とするポリプロ
ピレン樹脂組成物である。That is, the present invention is a polypropylene resin composition characterized by containing syndiotactic polystyrene or its hydride in an amount of 0.00001% by weight or more and less than 1% by weight based on polypropylene.
本発明において、ポリプロピレンとしては結晶性のポ
リプロピレンであるかぎりプロピレンの単独重合体のみ
ならずエチレン、ブテン−１、ヘキセン−１等の他のオ
レフィンとのランダム共重合体やブロック共重合体であ
ってもよく、公知のチーグラー・ナッタ触媒を用いプロ
ピレンを重合することで製造できる。また市場で広く入
手するものも支障なく使用できる。In the present invention, polypropylene is not only a homopolymer of propylene as long as it is a crystalline polypropylene, but also a random copolymer or block copolymer with other olefins such as ethylene, butene-1, and hexene-1. Alternatively, it can be produced by polymerizing propylene using a known Ziegler-Natta catalyst. Also, those widely available in the market can be used without any trouble.
本発明において使用するシンジオタクチックポリスチ
レンとしては、特開昭62−104818号公報にその製造方法
が詳しく開示されている方法により製造されたものが挙
げられるが、他の製造方法によって製造されたものでも
使用可能である。Examples of syndiotactic polystyrene used in the present invention include those produced by the method disclosed in detail in JP-A-62-104818, but those produced by other production methods. But it can be used.
シンジオタクチックポリスチレンのタクチシティは13
C−NMRで測定できる（特開昭62−104818号公報参照）
が、その値は100％である必要はなく、80％以上シンジ
オタクチックであれば充分であり、簡便には沸騰メチル
エチルケトン抽出残率で求めることが可能であり、その
抽出残率が80％以上であれば本発明で使用することがで
きる。Tacticity of syndiotactic polystyrene is 13
It can be measured by C-NMR (see JP-A-62-104818).
However, the value does not need to be 100%, 80% or more syndiotactic is sufficient, and it is possible to easily calculate it by boiling methyl ethyl ketone extraction residual ratio, and the extraction residual ratio is 80% or higher. If so, it can be used in the present invention.
本発明においてはシンジオタクチックポリスチレンの
水素化物についても使用できる。なお、その水素化率に
ついて制限は無いが、50％以上が水素化されたものを利
用すると得られる組成物の透明性が良好となり、特にフ
ィルム等に利用すると好ましい。シンジオタクチックポ
リスチレンの水素化の方法についても特に制限はなく、
芳香環を水素化する通常の条件で行う方法があれば良
く、具体的には、パラジウムカーボン等の水素化触媒と
シンジオタクチックポリスチレンを溶解した溶液、好ま
しくは脂環族炭化水素溶媒が利用されるが、からなるス
ラリーを水素の加圧下に加熱する方法で例示できる。In the present invention, a hydride of syndiotactic polystyrene can also be used. The hydrogenation rate is not limited, but the transparency of the obtained composition is improved when a hydrogenated 50% or more is used, and it is particularly preferably used for a film or the like. There is no particular limitation on the method for hydrogenating syndiotactic polystyrene,
A method for hydrogenating an aromatic ring may be used under ordinary conditions. Specifically, a solution in which a hydrogenation catalyst such as palladium carbon and syndiotactic polystyrene are dissolved, preferably an alicyclic hydrocarbon solvent is used. However, it can be exemplified by a method of heating a slurry consisting of
本発明において上記ポリプロピレンとシンジオタクチ
ックポリスチレン或いはその水素化物とを混合する方法
についても特に制限はなく、単に両者を混合溶融する方
法、シンジオタクチックポリスチレンを含む触媒を用い
てポリプロピレンを重合しポリプロピレンにシンジオタ
クチックポリスチレンを分散せしめる方法などによって
本発明の組成物を作ることができる。There is no particular limitation on the method of mixing the polypropylene with syndiotactic polystyrene or a hydride thereof in the present invention, a method of simply mixing and melting the both, polypropylene is polymerized with a catalyst containing syndiotactic polystyrene to give polypropylene. The composition of the present invention can be prepared by, for example, a method of dispersing syndiotactic polystyrene.
シンジオタクチックポリスチレン或いはその水素化物
のポリプロピレンに対する使用割合としては0.00001重
量％以上１重量％未満、好ましくは0.0001重量％以上１
重量％未満である。0.00001重量％未満の使用では添加
の効果が殆ど得られず、また、１重量％以上添加しても
格別その効果は増大せず、むしろヘイズが悪化するだけ
である。The use ratio of syndiotactic polystyrene or its hydride to polypropylene is 0.00001% by weight or more and less than 1% by weight, preferably 0.0001% by weight or more and 1
% By weight. If it is used in an amount of less than 0.00001% by weight, the effect of the addition is hardly obtained, and even if it is added in an amount of 1% by weight or more, the effect is not particularly increased, but the haze is rather deteriorated.
本発明の組成物には、安定剤、紫外線吸収剤、滑剤、
顔料、着色剤、界面活性剤などの通常ポリプロピレンに
添加される各種添加剤が添加されていても構わない。The composition of the present invention includes a stabilizer, an ultraviolet absorber, a lubricant,
Various additives usually added to polypropylene, such as pigments, colorants, and surfactants, may be added.
以下、実施例をあげ本発明を更に説明する。 Hereinafter, the present invention will be further described with reference to examples.
実施例１ ３のオートクーブにｎ−ヘプタン１、丸紅ソルベ
ー社製三塩化チタン触媒“TGY−24″300mgおよびジエチ
ルアルミニウムクロライド1mlを加え、プロピレンガス
を挿入して5kg/cm2とし、次いで水素0.4Nlを加えたのち
加熱して内温を70℃とした。その後プロピレンを挿入な
がら圧力を5kg/cm2で３時間重合した。メタノールで触
媒を失活し、水洗して触媒残分を除去し、濾過乾燥して
パウダー850gを得た。得られたパウダーの極限粘度は1.
78（135℃テトラリン溶液で測定）であり、沸騰ｎ−ヘ
プタン抽出残率は98.2％（熊川式抽出器を用い、６時間
抽出）であった。Example 1 To the autoclave of Example 3, n-heptane 1, 300 mg of "TGY-24" titanium trichloride catalyst manufactured by Marubeni Solvay and 1 ml of diethylaluminum chloride were added, and propylene gas was added to make 5 kg / cm 2, and then 0.4 Nl of hydrogen was added. Was added and heated to bring the internal temperature to 70 ° C. Then, the polymerization was carried out at a pressure of 5 kg / cm 2 for 3 hours while inserting propylene. The catalyst was deactivated with methanol, washed with water to remove the catalyst residue, and dried by filtration to obtain 850 g of powder. The obtained powder has an intrinsic viscosity of 1.
It was 78 (measured with a tetralin solution at 135 ° C.), and the boiling n-heptane extraction residual rate was 98.2% (extracted for 6 hours using a Kumakawa type extractor).
一方、特開昭62−104818号公報の実施例１に従って重
合してシンジオタクチックポリスチレンを得た。収量は
14.1gであり、その沸騰メチルエチルケトン抽出残率は9
6.2％であった。On the other hand, polymerization was carried out according to Example 1 of JP-A-62-104818 to obtain syndiotactic polystyrene. The yield is
14.1g, the boiling methyl ethyl ketone extraction residual rate is 9
It was 6.2%.
上記で得たポリプロピレン１に対して得られたシンジ
オタクチックポリスチレン0.1重量％、ステアリン酸カ
ルシウム0.02重量部および2,6−ジターシャリーブチル
−４−クレゾール0.01重量部を混合し、溶融プレスして
シートを作り下記物性を測定した。0.1% by weight of the syndiotactic polystyrene obtained with respect to the polypropylene 1 obtained above, 0.02 part by weight of calcium stearate and 0.01 part by weight of 2,6-ditertiarybutyl-4-cresol were mixed and melt-pressed to form a sheet. The following physical properties were measured.
・引っ張り降伏強さ（ASTM D638−64T）:365kg/cm2 ・曲げ弾性率（ASTM D790−63）:21000kg/cm2 ・結晶化温度:121.3℃（DSCを用い、10℃/minで降温し
て測定） ・ヘイズ（ASTM D1003）:68％ 比較例１ シンジオタクチックポリスチレンを用いることなく成
型して物性を測定した他は実施例１と同様にしたとこ
ろ、引っ張り降伏強さ330kg/cm2、曲げ弾性率18000kg/c
m2、結晶化温度112.5℃、ヘイズ72％と実施例１に比べ
劣っていた。・ Tensile yield strength (ASTM D638-64T): 365kg / cm 2・ Flexural modulus (ASTM D790-63): 21000kg / cm 2・ Crystallization temperature: 121.3 ℃ (Use DSC to cool at 10 ℃ / min. Haze (ASTM D1003): 68% Comparative Example 1 The same procedure as in Example 1 was conducted except that the physical properties were measured by molding without using syndiotactic polystyrene, and the tensile yield strength was 330 kg / cm 2 , Flexural modulus 18000kg / c
m 2 , crystallization temperature 112.5 ° C., haze 72%, which were inferior to those of Example 1.
比較例２ シンジオタクチックポリスチレンの添加量を２重量％
とした他は実施例１と同様にしたところ、引っ張り降伏
強さは360kg/cm2、曲げ弾性率は20500kg/cm2、結晶化温
度は120.8℃、ヘイズは82％であった。Comparative Example 2 The amount of syndiotactic polystyrene added was 2% by weight.
Otherwise in the same manner as in Example 1, the tensile yield strength was 360 kg / cm 2 , the flexural modulus was 20500 kg / cm 2 , the crystallization temperature was 120.8 ° C., and the haze was 82%.
実施例２ 実施例１で得たシンジオタクチックポリスチレンをデ
カリン中でパラジウム（10％）カーボンを触媒とし、水
素気流下150℃で20時間撹拌処理して水素化した。1H−N
MRにより分析したところ水素化率は85％であった。Example 2 The syndiotactic polystyrene obtained in Example 1 was hydrogenated in decalin using palladium (10%) carbon as a catalyst under a hydrogen stream at 150 ° C. for 20 hours with stirring. 1 H-N
When analyzed by MR, the hydrogenation rate was 85%.
この水素化したシンジオタクチックポリスチレンをシ
ンジオタクチックポリスチレンに代えて用いた他は実施
例１と同様にしたところ、引っ張り降伏強さは350kg/cm
2、曲げ弾性率は20500kg/cm2であり、結晶化温度は120.
2℃、ヘイズは65％であった。A tensile yield strength of 350 kg / cm was obtained in the same manner as in Example 1 except that this hydrogenated syndiotactic polystyrene was used in place of syndiotactic polystyrene.
2 , the flexural modulus is 20500kg / cm 2 , the crystallization temperature is 120.
The haze was 2% and 65%.
本発明の組成物は物性に優れ、工業的に極めて価値が
ある。The composition of the present invention has excellent physical properties and is extremely valuable industrially.
Claims (1)
の水素化物をポリプロピレンに対して0.00001重量％以
上１重量％未満含有することを特徴とするポリプロピレ
ン樹脂組成物。1. A polypropylene resin composition comprising syndiotactic polystyrene or a hydride thereof in an amount of 0.00001% by weight or more and less than 1% by weight based on polypropylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62288303A JPH083008B2 (en) | 1987-11-17 | 1987-11-17 | Polypropylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62288303A JPH083008B2 (en) | 1987-11-17 | 1987-11-17 | Polypropylene resin composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2075499A Division JPH07100723B2 (en) | 1990-03-27 | 1990-03-27 | Syndiotactic vinyl cyclohexane polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01131263A JPH01131263A (en) | 1989-05-24 |
| JPH083008B2 true JPH083008B2 (en) | 1996-01-17 |
Family
ID=17728424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62288303A Expired - Fee Related JPH083008B2 (en) | 1987-11-17 | 1987-11-17 | Polypropylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH083008B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2597375B2 (en) * | 1987-12-29 | 1997-04-02 | 出光興産株式会社 | Vinylcyclohexane-based polymer and method for producing the same |
| US5187250A (en) * | 1989-06-05 | 1993-02-16 | Mitsui Toatsu Chemicals, Incorporated | Poly-α-olefins |
| JP7828423B1 (en) * | 2024-12-05 | 2026-03-11 | 株式会社ダイセル | Release film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0755995B2 (en) * | 1986-05-06 | 1995-06-14 | 出光興産株式会社 | Thermoplastic resin composition |
-
1987
- 1987-11-17 JP JP62288303A patent/JPH083008B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01131263A (en) | 1989-05-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |