JPH01131263A - Polypropylene resin composition - Google Patents
Polypropylene resin compositionInfo
- Publication number
- JPH01131263A JPH01131263A JP28830387A JP28830387A JPH01131263A JP H01131263 A JPH01131263 A JP H01131263A JP 28830387 A JP28830387 A JP 28830387A JP 28830387 A JP28830387 A JP 28830387A JP H01131263 A JPH01131263 A JP H01131263A
- Authority
- JP
- Japan
- Prior art keywords
- component
- polypropylene
- resin composition
- syndiotactic polystyrene
- 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.)
- Granted
Links
- -1 Polypropylene Polymers 0.000 title claims abstract description 17
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 16
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 16
- 239000011342 resin composition Substances 0.000 title claims abstract description 6
- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims abstract description 17
- 150000004678 hydrides Chemical class 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000000605 extraction Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000000704 physical effect Effects 0.000 abstract description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract description 2
- 229920001400 block copolymer Polymers 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- 239000004793 Polystyrene Substances 0.000 abstract 1
- 229920005630 polypropylene random copolymer Polymers 0.000 abstract 1
- 229920002223 polystyrene Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WCVOGSZTONGSQY-UHFFFAOYSA-N 2,4,6-trichloroanisole Chemical compound COC1=C(Cl)C=C(Cl)C=C1Cl WCVOGSZTONGSQY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は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 [Industrial Field of Application] The present invention relates to a polypropylene resin composition with good physical properties. Specifically, the present invention 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５９−１３
９７３１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 its crystallinity is relatively low, so when molded using normal methods, the rigidity of the molded product is inferior to that of the original resin. There is a problem, and attempts have been made to solve this problem by adding various nucleating agents, among which methods of adding certain polymer compounds (for example, Japanese Patent Application Laid-Open No. 59-13
No. 9731) is an excellent method because it does not cause the problem of additives floating on the surface of the molded product and is effective even when added in a relatively small amount.
しんしながら、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、入手し難だいという問題があ
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 is difficult to synthesize and is difficult to obtain. is desired.
〔問題点を解決するための手段］
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
上させうろことを見出し、本発明を完成した。[Means for Solving the Problems] The present inventors have earnestly searched for a new polymer compound that can improve the crystallinity of polypropylene, and have found that the addition of a specific polymer compound can significantly increase the crystallinity of polypropylene. He discovered that the scales can be improved and completed the present invention.
即ち、本発明はシンジオタクチックポリスチレン或いは
その水素化物を含有することを特徴とすポリプロピレン
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.
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・ナツ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 includes not only propylene homopolymers but also random copolymers and block copolymers with other olefins such as ethylene, butene-1, hexene-1, etc., as long as they are crystalline polypropylene. It can also be produced by polymerizing propylene using a known Ziegler-Natsuta catalyst. Also, those widely available on the market can be used without any problem.
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 the syndiotactic polystyrene used in the present invention include those manufactured by the method disclosed in detail in JP-A-62-104818, but those manufactured by other manufacturing methods can be mentioned. It can also 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
ｃ４門Ｒ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（，８０
％以上シンジオタクチンクであれば充分であり、筒便に
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。The tacticity of syndiotactic polystyrene is 13.
It can be measured with c4 gate R (see JP-A-62-104818), but the value does not need to be 100% (,80%).
It is sufficient if the syndiotactic concentration is 80% or more, and the feces can be determined by the extraction residual rate of boiling methyl ethyl ketone, and if the extraction residual rate is 80% or more, 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であれば良く
、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）８解した）８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, hydrides of syndiotactic polystyrene can also be used. There is no limit to the hydrogenation rate, but if 50% or more is hydrogenated, the resulting composition will have good transparency, and it is particularly preferable to use it for films and the like. There are no particular restrictions on the method of hydrogenating syndiotactic polystyrene.
Any method may be used as long as it is carried out under normal conditions for hydrogenating aromatic rings. Specifically, a hydrogenation catalyst such as palladium carbon and syndiotactic polystyrene (8) solution, preferably an alicyclic hydrocarbon, are used. Although a solvent is used, an example is a method in which a slurry consisting of the solvent is heated under pressure of hydrogen.
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。In the present invention, there is no particular restriction on the method of mixing the above-mentioned polypropylene and syndiotactic polystyrene, tyrene, or a hydride thereof. The composition of the present invention can be made by a method such as dispersing syndiotactic polystyrene in polypropylene.
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０．００００
１〜１０重量％、好しくは０．０００１〜１重四％が適
当である。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、１０重量％を越えて添加し
ても格別その効果は増大しない。The usage ratio of syndiotactic polystyrene or its hydride to polypropylene is 0.0000
A suitable amount is 1 to 10% by weight, preferably 0.0001 to 1% by weight. If less than 0.00001% by weight is used, almost no effect will be obtained, and if more than 10% by weight is added, the effect will not be particularly increased.
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 may contain various additives that are normally added to polypropylene, such as stabilizers, ultraviolet absorbers, lubricants, pigments, colorants, and surfactants.
（実施例） 以下、実施例をあげ本発明を更に説明する。(Example) The present invention will be further explained below with reference to Examples.
実施例１
３Ｎのオートクープに１−へブタン１１．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１ｄを加え、プロ
ピレンガスを挿入して５ ｋｇ ／ ｃＡとし、次いで
水素０．４Ｎｌを加えたのち加熱して内湯を７０’Ｃと
した。その後プロピレンを挿入ながら圧力を５ｋｇ／
ｃ４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８５０
ｇを得た。得られたパウダーの極限粘度は１．７８ （
１３５”Ｃテトラリン溶液で測定）であり、沸１１ｎ−
へブタン抽出残率は９８．２％（前用式抽出器を用い、
６時間抽出）であった。Example 1 1-Hebutane 11. Add 300 mg of titanium trichloride catalyst "TGY-24" manufactured by Marubeni Solvay and 1 d of diethylaluminium chloride, insert propylene gas to make the pressure 5 kg/cA, then add 0.4 Nl of hydrogen and heat the inner bath to 70'. It was set as C. Then, while inserting propylene, increase the pressure to 5 kg/
Polymerization was carried out at c4 for 3 hours. Deactivate the catalyst with methanol, wash with water to remove catalyst residue, filter and dry to obtain powder 850.
I got g. The intrinsic viscosity of the obtained powder was 1.78 (
135"C (measured with tetralin solution) and boiling point 11n-
Hebutane extraction residual rate is 98.2% (using a front extractor,
6 hours extraction).
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。On the other hand, syndiotactic polystyrene was obtained by polymerization according to Example 1 of JP-A-62-104818.
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９６．２％であった。The yield was 14.1 g, and the boiling methyl ethyl ketone extraction residue was 96.2%.
上記で得たポリプロピレン１００重量部に対して得られ
たシンジオタクチックポリスチレン０．１重量部、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−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 part by weight of the syndiotactic polystyrene obtained above, 0.02 part by weight of calcium stearate and 0.01 part by weight of 2.6-ditertiary-butyl-4-cresol are mixed with 100 parts by weight of the polypropylene obtained above. Then, a sheet was made by melt pressing and the following physical properties were measured.
・引っ張り降伏強す（ＡＳＴＭ Ｄ６３８−６４Ｔ）
： ３６５ｋｇ／ｃＩａ・曲げ弾性率（ＡＳＴ？ｌロア
９Ｏ−６３） ： ２１０００ｋｇ／ｃ＋Ｉｌ・結晶
化温度： １２１．３°Ｃ
（ＯＳＣを用い、１０°（／ｍｉｎで降温して測定）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／ｃｄ、曲げ弾性率１８０
００ｋｇ／ｃＪ、結晶化温度１１２．５℃と実施例１に
比べ劣っていた。・Tensile yield strength (ASTM D638-64T)
: 365 kg/cIa・Flexural modulus (AST?l Lower 9O-63): 21000 kg/c+Il・Crystallization temperature: 121.3°C (Measured by decreasing the temperature at 10° (/min) using OSC) Comparative Example 1 The same procedure as Example 1 was performed except that the molding was performed without using syndiotactic polystyrene and the physical properties were measured.
Tensile yield strength 330kg/cd, flexural modulus 180
00 kg/cJ, and the crystallization temperature was 112.5°C, which was inferior to Example 1.
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″Ｃで２０時間撹拌処理して水素化した
。’ｌ（−ＮＭＲ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 with palladium (10%) on carbon as a catalyst and stirred at 150''C for 20 hours under a hydrogen stream. Analysis showed that the hydrogenation rate was 85.
%Met.
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
／ｃｊ、曲げ弾性率は２０５００ｋｇ／ｃＪであり、結
晶化温度は１２０．２°Ｃであった。Example 1 was repeated except that this hydrogenated syndiotactic polystyrene was used instead of syndiotactic polystyrene, and the tensile yield strength was 350 kg.
/cj, the flexural modulus was 20500 kg/cJ, and the crystallization temperature was 120.2°C.
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)
物を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 containing syndiotactic polystyrene or its hydride.
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 true JPH01131263A (en) | 1989-05-24 |
| JPH083008B2 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01178505A (en) * | 1987-12-29 | 1989-07-14 | Idemitsu Kosan Co Ltd | Vinylcyclohexane polymer and preparation thereof |
| US5187250A (en) * | 1989-06-05 | 1993-02-16 | Mitsui Toatsu Chemicals, Incorporated | Poly-α-olefins |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62257950A (en) * | 1986-05-06 | 1987-11-10 | Idemitsu Kosan Co Ltd | Thermoplastic resin composition |
-
1987
- 1987-11-17 JP JP62288303A patent/JPH083008B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62257950A (en) * | 1986-05-06 | 1987-11-10 | Idemitsu Kosan Co Ltd | Thermoplastic resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01178505A (en) * | 1987-12-29 | 1989-07-14 | Idemitsu Kosan Co Ltd | Vinylcyclohexane polymer and preparation thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH083008B2 (en) | 1996-01-17 |
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